Thiolactones as additives for vinyl network degradation

Abstract

The introduction of low levels of cleavable comonomer additives in existing vinyl polymerization processes can help produce chemically deconstructable and recoverable variants with other equivalent properties. The present disclosure describes a cleavable comonomer process as a feasible strategy to achieve circulating vinyl polymers. The present disclosure describes examples of copolymers comprising m1 first repeating units of Formula (i); m2 instances of a second repeating unit of formula (iii-A) or (iii-B); and optionally one or more types of additional repeating units. The present disclosure also provides a compound of formula: or a tautomer or salt thereof. The disclosure further describes methods of preparation, compositions, and kits. # imgabs0 #

Description

[0001] Related applications

[0002] This patent application claims priority to U.S. Provisional Patent Application Nos. 63 / 308,492 and 63 / 308,497, filed on February 9, 2022 and February 10, 2022, respectively, the contents of each of which are incorporated herein by reference in their entirety. Background Art

[0003] Materials made from polystyrene (PS) and styrene copolymers are ubiquitous due to their low cost, diverse thermomechanical properties, and adaptability to a wide range of synthesis and processing conditions. Their applications range from bulk consumer goods such as tires and packaging to engineering applications such as coatings and composites. 1 Nevertheless, the strong carbon-carbon bonds that make up the polystyrene backbone lead to environmental persistence and limited opportunities for chemical recycling or upcycling. 2 It can be converted into styrene or thermally degraded into low molecular weight fragments through engineering design. 3 But such processes are energy-intensive, produce complex product mixtures, fail to address environmental persistence concerns, and may not be applicable to all forms of polystyrene (PS, such as copolymers and especially cross-linked variants). Summary of the Invention

[0004] The introduction of low-level cleavable comonomer additives into existing vinyl polymerization processes can facilitate the production of chemically decomposable and recyclable variants with otherwise equivalent properties without requiring new monomer feedstocks that significantly increase costs or alter the manufacturing process, allowing for rapid implementation. This disclosure describes a cleavable comonomer approach as a viable strategy for achieving circular vinyl polymers.

[0005] In some aspects, the present disclosure describes copolymers comprising:

[0006] Examples of m1 first repeating units of formula i:

[0007]

[0008] Examples of m2 second repeating units of formula ii-A or ii-B:

[0009]

[0010]

[0011] optionally one or more types of additional repeating units;

[0012] in:

[0013] The copolymer is substantially free of crosslinks;

[0014] m1 is an integer between 10 and 1,000,000 (inclusive);

[0015] m2 is an integer between 2 and 1,000,000 (inclusive);

[0016] R 1 、R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl;

[0017] Ring A is an aryl group;

[0018] R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a 、-SCN、-SR a 、-SSR a 、-N3、-NO、-N(R a )2、-NO2、-C(=O)R a 、-C(=O)OR a 、-C(=O)SR a 、-C(=O)N(R a )2、-C(=NR a )R a 、-C(=NR a )OR a 、-C(=NR a )SR a 、-C(=NR a )N(R a )2、-S(=O)R a 、-S(=O)OR a 、-S(=O)SR a 、-S(=O)N(R a )2、-S(=O)2R a 、-S(=O)2OR a 、-S(=O)2SR a 、-S(=O)2N(R a )2, -OC(=O)R a 、-OC(=O)OR a 、-OC(=O)SR a 、-OC(=O)N(R a )2、-OC(=NR a )R a 、-OC(=NR a)OR a 、-OC(=NR a )SR a 、-OC(=NR a )N(R a )2、-OS(=O)R a 、-OS(=O)OR a 、-OS(=O)SR a 、-OS(=O)N(R a )2、-OS(=O)2R a 、-OS(=O)2OR a 、-OS(=O)2SR a 、-OS(=O)2N(R a )2、-ON(R a )2、-SC(=O)R a 、-SC(=O)OR a 、-SC(=O)SR a 、-SC(=O)N(R a )2、-SC(=NR a )R a 、-SC(=NR a )OR a 、-SC(=NR a )SR a 、-SC(=NR a )N(R a )2、-NR a C(=O)R a 、-NR a C(=O)OR a 、-NR a C(=O)SR a 、-NR a C(=O)N(R a )2、-NR a C(=NR a )R a 、-NR a C(=NR a )OR a 、-NR a C(=NR a )SR a 、-NR a C(=NR a )N(R a )2、-NR a S(=O)R a 、-NR a S(=O)OR a 、-NR aS(=O)SR a 、-NR a S(=O)N(R a )2、-NR a S(=O)2R a 、-NR a S(=O)2OR a 、-NR a S(=O)2SR a 、-NR a S(=O)2N(R a )2、-Si(R a )3、-Si(R a )2OR a 、-Si(R a )(OR a )2、-Si(OR a )3、-OSi(R a )3、-OSi(R a )2OR a 、-OSi(R a )(OR a )2OR-OSi(OR a )3;

[0019] R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0020] n1 is 0, 1, 2, 3, 4 or 5, as long as the valence allows;

[0021] R 7 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2、-NO2、-C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2、-C(=NR b )R b 、-C(=NR b )ORb 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2、-OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2、-OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)Rb 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b 、-Si(R b )(OR b )2、-Si(OR b )3、-OSi(R b )3、-OSi(R b )2OR b 、-OSi(R b )(OR b )2OR-OSi(OR b )3;

[0022] is alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene;

[0023] n2 is an integer between 0 and 14 (inclusive), as long as the valence permits;

[0024] Each Examples of are independently a single bond or a double bond;

[0025] R 8 Each instance of is independently:

[0026] When attached to a carbon atom: halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2.

[0027] -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2.

[0028] -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、

[0029] -S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、

[0030] -S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、

[0031] -OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b、-OC(=NR b )SR b 、

[0032] -OC(=NR b )N(R b )2、-OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、

[0033] –OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、

[0034] –OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、

[0035] –SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、

[0036] –SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、

[0037] –NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、

[0038] –NR b C(=NR b)SR b ,–NR b C(=NR b )N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b 、

[0039] –NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b 、

[0040] –NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、

[0041] –Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2.

[0042] –OSi(OR b )3, =O, =S or =NR b ;

[0043] When attached to a nitrogen atom: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, –OR b ,–N(R b )2.

[0044] –C(=O)R b 、–C(=O)OR b 、–C(=O)SRb 、–C(=O)N(R b )2、–C(=NR b )R b 、

[0045] –C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、

[0046] –S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、

[0047] –S(=O)2N(R b )2, or a nitrogen protecting group; or

[0048] When attached to a sulfur atom: =O;

[0049] and / or: R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and / or R 8 Two examples of together with their middle atom form a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and

[0050] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0051] The conditions are:

[0052] R 1 、R 2 、R 3 、R 4 , Ring A, R 7and R 8 None contain one or more non-aromatic unsaturated CC bonds;

[0053] any additional monomer does not contain two or more non-aromatic unsaturated CC bonds;

[0054] The second repeat unit does not have the formula: and

[0055] If the first repeating unit has the following formula: Then the second repeat unit does not have the formula:

[0056] In another aspect, the present disclosure provides compounds of the formula:

[0057]

[0058] or a tautomer or salt thereof, wherein:

[0059] X 1 is S or O;

[0060] R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2、-NO2、-C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2、-C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(Rb )2、-OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2、-OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b)SR b ,–NR b C(=NR b )N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b ,–NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0061] R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SRb 、–C(=NR b )N(R b )2、–S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2、–S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)ORb 、 –NR b C(=O)SR b 、 –NR b C(=O)N(R b )2、 –NR b C(=NR b )R b 、 –NR b C(=NR b )OR b 、 –NR b C(=NR b )SR b 、 –NR b C(=NR b )N(R b )2、 –NR b S(=O)R b 、 –NR b S(=O)OR b 、 –NR b S(=O)SR b 、 –NR b S(=O)N(R b )2、 –NR b S(=O)2R b 、 –NR b S(=O)2OR b 、 –NR b S(=O)2SR b 、 –NR b S(=O)2N(R b )2、 –Si(R b )3、 –Si(R b )2OR b 、 –Si(R b )(OR b )2、 –Si(OR b )3、 –OSi(R b )3、 –OSi(R b )2OR b 、 –OSi(R b )(OR b )2或 –OSi(OR b )3;

[0062] R beach instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and

[0063] n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; provided that R 10 and R 11 None contain one or more non-aromatic unsaturated CC bonds.

[0064] In some aspects, the compounds disclosed herein have the formula:

[0065]

[0066] or a tautomer or a salt thereof.

[0067] The present invention also discloses a method for preparing the copolymers described herein, wherein the method comprises polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more types of additional monomers described herein. The present invention also discloses a composition comprising the copolymers described herein, a kit comprising the copolymers described herein or a composition thereof, and instructions for using the copolymers or a composition thereof.

[0068] Typically, cross-linked polymers, especially when the main chain of the cross-linked polymer does not include a decomposable portion (e.g., esters), are difficult to decompose. The introduction of low-level cleavable comonomer additives into cross-linked polymers can promote the production of chemically decomposed and recyclable cross-linked polymers with other equivalent properties without the need for significantly increasing costs or changing new monomer feedstocks for manufacturing processes, which can be rapidly implemented. The present disclosure describes a cleavable comonomer method as a viable strategy for cyclic vinyl polymers. In some aspects, the present disclosure describes copolymers. The present invention further discloses a method for preparing a copolymer as described herein, wherein the method includes polymerizing a first monomer, a second monomer, a third monomer, and optionally one or more types of additional monomers, as described herein. The present disclosure further describes a composition comprising a copolymer as described herein, and a kit comprising a copolymer as described herein or its composition, and instructions for using the copolymer or its composition.

[0069] The copolymers described here could facilitate the creation of chemically deconstructible variants of existing polymers without compromising thermomechanical properties and adhering to existing manufacturing protocols, potentially providing a path to rapidly introduce circularity into otherwise difficult-to-recycle plastics such as polystyrene.

[0070] Details of certain embodiments of the present invention are set forth in the detailed description of certain embodiments, as described below. Other features, objects, and advantages of the present invention will be apparent from the definitions, drawings, examples, clauses, and claims. The aspects described herein are not limited to specific embodiments, methods, apparatus, or configurations and, as such, may, of course, vary. The terminology used herein is for the purpose of describing particular aspects only and, unless expressly defined herein, is not intended to be limiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] These figures are exemplary and do not limit the scope of the present disclosure.

[0072] These figures are exemplary and do not limit the scope of the present disclosure.

[0073] Figure 1A A cleavable comonomer strategy for PS chemical recycling / upcycling is shown. Figure 1B The chemically structured and recyclable PS is shown.

[0074] Figure 2A It shows that the deconstructible PS (F DOT = 2.6, 5.8, 11, 22 and 55% [dPS (F DOT) ]), separation of DOT homopolymer (pDOT) and pure PS control (PS-L), and deconstruction of the former into the corresponding monofunctional OS (Pr-OS (F DOT )) and "oligo-DOT" (oDOT) fragments; a f DOT = molar equivalent of DOT in the monomer feed; b Conversion rate through 1 H NMR analysis was measured using 1,3,5-trimethoxybenzene as an internal standard. c F DOT = molar equivalents of ring-opened DOT-derived units in the isolated polymer (as described in SI 1 H NMR spectrum calculation); d M n = number average molar mass of isolated polymers / oligomers; Figure 2B and 2C Shows dPS(F DOT ) series of partial IR spectra ( Figure 2B ) and part 1 H NMR spectrum ( Figure 2C ). Figure 2D Shows dPS(F DOT ) and pDOT, and the corresponding deconstructed fragment Pr-OS(F DOT ) and oDOT.

[0075] Figure 3 The deconstruction of a model copolymer (dPS(11)) to a bifunctional OS with high-end group fidelity is shown. “Conversion” indicates the consumption of the thioester unit, as indicated by 1 H NMR spectroscopy; M n = number average molar mass; Figure 1. SEC traces of dPS(11) and isolated OS fragments. Figure 2. Representative dPS(11) before (top) and after (bottom) deconstruction. 1 H NMR spectrum.

[0076] Figure 4 It was shown that thiol-OS(11) was oxidatively repolymerized to give rPS(11), whose molecular weight distribution was almost the same as that of dPS(11).

[0077] Figure 5 Shown are circular high molecular weight PS.

[0078] Figures 6A to 6C Shows high M W Thermal and thermomechanical properties of polymers. Figure 6A : DSC trace during the second heating at 10℃ / min; Figure 6B : TGA trace obtained at 20 °C / min; Figure 6C : DMA temperature sweep at constant amplitude and frequency. E' = elastic modulus; E" = loss modulus.

[0079] Figure 7 Three general routes to functionalized DOT derivatives (substituted DOTs) are shown.

[0080] Figure 8A The synthesis of substituted DOT is shown. "dPS" refers to deconstructible PS. Figure 8B The effect of substituents on the copolymerization of styrene with XY-DOT is shown. The consumption of each XY-DOT is plotted against the total monomer conversion. A hypothetical random polymerization is shown as a dashed line with a slope of 1 (i.e., XY-DOT consumption equals the total consumption for the entire polymerization). The curve for unmodified DOT is close to that for the random copolymerization. Fluorine and thioether substituents make XY-DOT more reactive relative to styrene, while methoxy substituents make DOT less reactive. Furthermore, comparing the curves for F-DOT and F2-DOT shows that each benzene ring can be used to tune the reactivity and that the contribution of each ring is additive (also evident when comparing SPr-DOT and SPr-F-DOT).

[0081] Figure 9 Shows the saturated solution of DOT in styrene 1H NMR spectrum (400 MHz, chloroform-d, d1=60s). A saturated solution was prepared as described above.

[0082] Figure 10 Shows the dPS (11) in benzene-d6 (left) and dichloromethane-d2 (right) 1 H NMR spectroscopy, which was used to quantify dyad content (using the former) and F DOT (Use both).

[0083] Figure 11 Shown are SEC traces (normalized by area) of the oligomers separated in the deconstruction studies shown in Table 2 .

[0084] Figure 12 Shows dPS(F DOT ) Two possible mechanisms for forming DTOs during deconstruction.

[0085] Figure 13 The figure above shows that treatment of pDOT with a catalytic amount of thioester (0.3 equivalents each of PrSH and NEt3 relative to the thioester repeat unit) in DMF solution yields 50% DTO after approximately 20 minutes at room temperature, with DTO being the only observable species besides the starting pDOT. After 13 hours, the yield increases to >98%. Figure 13 The lower graph shows that at each time point, the amount of PrSH was the same.

[0086] Figures 14A to 14B The finding that pDOT can be quantitatively deconstructed into a pure small molecule with a catalytic thiolate is expected to have broad implications, but Figure 14A The experiment shown provides more conclusive evidence that the self-immolation effect is effective. After treating a DMF solution of pDOT with NH2Pr (3 equivalents) at room temperature for 1 hour, DTO is formed in 86% yield. The only way DTO is formed here is through intramolecular self-immolation cyclization, such as Figure 14B After 40 h at room temperature, the expected amide product was finally formed in 95% yield via ring opening of DTO. In some experiments, DTO was observed as an intermediate.

[0087] Figure 15A An alternative pathway for chemically cycling PS is shown. Figure 15B Two attempts to recover te-OS(11) by polycondensation are shown.

[0088] Figure 16 A model system of a monofunctional macromolecular disulfide formation is shown.

[0089] Figure 17The number-average degree of polymerization dispersion of fragments repolymerized via a step-growth mechanism involving a mixture of monofunctional and bifunctional OS fragments is shown.

[0090] Figure 18 The molecular weight dispersity of repolymerized chains with a given number of OS segments is shown.

[0091] Figure 19 The effect of the formation of cyclic polymers on the number average molecular weight of the linear repolymerized chains is shown when the initial N value is 10.

[0092] Figure 20 Shown are SEC traces for the synthesis of rPS(2.5)-hMW under standard conditions and at a 50-fold dilution.

[0093] Figures 21A to 21B Shows low M w Basic thermal properties of dPS, pDOT and PS-L. ( Figure 21A )Thermogravimetric analysis (TGA) trace;( Figure 21B ) Differential Scanning Calorimetry (DSC) trace; ( Figure 21C )and( Figure 21D ) were obtained from the decomposition temperature and T g A summary of values.

[0094] Figure 22 The dPS (F) isolated in the solvent screening of entries 1-6 in Table 1 are shown. DOT )of 1 H NMR spectrum (400 MHz, benzene-d6). Spectra normalized to the local maximum of the styrene resonance at 1.6 ppm. TMB = 1,3,5-trimethoxybenzene.

[0095] Figure 23 Showing the separation of XY-dPS samples 1 H NMR spectrum (400 MHz, benzene-d 6) , corresponding to entries 7-11 in Table 1. The spectrum is normalized to the local maximum of the styrene resonance at 1.6 ppm. TMB = 1,3,5-trimethoxybenzene.

[0096] Figure 24 The original PS (PS-L) and dPS with variable composition (dPS(F) corresponding to the entries in Table 2 are shown. DOT ))'s ATR-IR spectrum.

[0097] Figures 25A to 25B The original PS (PS-L), dPS with variable composition (dPS(F)) corresponding to the entries in Table 2 of the main text are shown. DOT )) and DOT homopolymer (pDOT) 1H NMR spectrum (400 MHz, benzene-d6). ( Figure 25A ) spectra (omitting pDOT) were normalized to the local maximum of the styrene resonance at 1.6 ppm, enabling qualitative comparison of the F DOT The spectrum of dPS(11) is shown in bold. ( Figure 25B ) The same spectra (including pDOT) were normalized to the maximum peak intensity between 3.8 and 4.6 ppm, enabling a qualitative comparison of the relative amounts of St-DOT and DOT-DOT dyads.

[0098] Figure 26 The original PS (PS-L), dPS with variable composition (dPS(F)) corresponding to the entries in Table 2 of the main text are shown. DOT )) and SEC traces of DOT homopolymer (pDOT).

[0099] Figures 27A to 27B Shown are SEC traces for the separated polymers shown in Table 1 of the main text (left). The two right traces are fragments after treatment with n-propylamine at room temperature for 3 days (dashed line) and 7 days (solid line).

[0100] Figures 28A to 28B The Pr-OS (F) corresponding to the entries in Table 2 of the main text are shown. DOT) and oDOT 1 H NMR spectrum (400 MHz, benzene-d6). ( Figure 28A ) spectra (oDOT and Pr-OS(55) omitted) are normalized to the local maximum of the styrene resonance at 1.6 ppm, allowing qualitative comparison of end group concentrations. The spectrum of Pr-OS(11) is shown in bold. Figure 28B ) The same spectra (including oDOT and Pr-OS(55)) were normalized to the maximum peak intensity between 4.8 and 5.7 ppm.

[0101] Figure 29 The decomposition of dPS (F) by n-propylamine was shown. DOT ) and correspond to Table 2 in the main text. The intensity of the traces was normalized by area.

[0102] Figure 30 The results show the separation of dPS (11) and the product after decomposition with propylamine (Pr-OS (11)). 1 Comparison of H NMR spectra.

[0103] Figure 31 The results show the separation of dPS (11) and the isolated product (allyl-OS (11)) after decomposition with allylamine. 1 Comparison of H NMR spectra.

[0104] Figure 32The results show the separation of dPS (11) and the isolated product (te-OS (11)) after decomposition with EtSH / DBU. 1 Comparison of H NMR spectra.

[0105] Figure 33 The results show the separation of dPS (11) and the isolated product (thiol-OS (11)) after decomposition with cysteamine hydrochloride / DBU. 1 Comparison of H NMR spectra.

[0106] Figure 34 Deconstruction of dPS (F) with cysteamine hydrochloride / DBU was shown. DOT )-hMW after the isolated oligomer (thiol-(F DOT )-hMW) SEC traces.

[0107] Figure 35 The crude (top) and precipitated (bottom) thiol-OS(2.5)-hMW are shown. 1 H NMR spectrum (400 MHz, benzene-d6).

[0108] Figure 36 The crude (top) and precipitated (bottom) thiol-OS(5.0)-hMW are shown. 1 H NMR spectrum (400 MHz, benzene-d6).

[0109] Figure 37 SEC traces of crude ("aq wkp") and precipitated (black) rPS (11) are shown.

[0110] Figure 38 The isolated rPS(2.5)-hMW (bottom) and the precursor thiol-OS(2.5)-hMW (top) are shown. 1 Comparison of HNMR spectra.

[0111] Figure 39 The isolated rPS(5.0)-hMW (bottom) and the precursor thiol-OS(5.0)-hMW (top) are shown. 1 Comparison of HNMR spectra.

[0112] Figure 40 The results show that rPS(2.5)-hMW and rPS(5.0)-hMW 1 Comparison of H NMR spectra. The spectra were normalized to the local maximum of the styrene resonance at 1.6 ppm.

[0113] Figures 41A to 41B This indicates that lower DOT incorporation levels can produce expected larger fragments. The choice of solvent may affect the degradation to smaller fragments.

[0114] Figure 42 The synthesis of more soluble substituted DOTs is shown. In some experiments, solubility was increased with minimal perturbation of electronic properties.

[0115] Figure 43 The copolymerization mechanism is shown

[0116] Figures 44A to 44B It is shown that the effect of temperature on the reactivity of 2-SBu-DOT may be small between 65° and 105°C. Figure 44A : Reaction diagram. Figure 44B : 2-SBu-DOT (DOT*) conversion curve.

[0117] Figures 45A to 45B The spontaneous homopolymerization of 2-SBu-DOT on the bench is shown. See Roth & Coworkers, Macromolecules, 2020, 53, 539-547. Figure 45A : Reaction diagram. Figure 45B : 1 H NMR results.

[0118] Figure 46 It was shown that molecular weight control can be achieved through nitroxide-mediated polymerization (NMP). See Hawker, et al., JACS, 1999, 121, 16, 3904-3920.

[0119] Figure 47 Three concise pathways for substituted DOT are shown.

[0120] Figure 48A Shown are the synthesis (upper panel) and deconstruction (lower panel) of the cross-linked copolymer. Figure 48B The fragments of network (SPr-te-OS(5)-X) and linear (te-OS(11)) dPS deconstruction are shown. 1 Comparison of characteristic regions of H NMR spectra. Figure 48C Shows Figure 48A The deconstruction product (fragment) of 1 H NMR and SEC results.

[0121] Figure 49 Demonstrated are the common cleavable comonomer strategy for vinyl networks (top) and a “plug-in” cleavable comonomer strategy for vinyl networks (bottom).

[0122] Figure 50 The strategy for preparing the target material "vinyl ester resin" is shown. "1.5" is the number average degree of polymerization of the PEG linker.

[0123] Figure 51Results of a screening of monovinyl diluents for the best combination of solubility, reactivity, and mechanical properties are shown.

[0124] Figure 52 Shown is the synthesis of St / BPAEDA / DOT networks with varying DOT content. Scheme: 1) curing; 2) extraction (for quantification of monomer consumption); 3) drying.

[0125] Figure 53 Shows Figure 52 Degradation experimental results of the resin and network. The results suggest that the BPAEDA:DOT ratio may be important for degradability. "Expt" means "experimental."

[0126] Figure 54 Shows Figure 52 ATR-IR results of the St / BPAEDA / DOT network. The results indicate that higher DOT loading may lead to a higher thioester concentration in the network.

[0127] Figure 55A Shown is the synthesis of BnA / BPAEDA / DOT networks with different DOT contents. Figure 55B Shows Figure 55A Degradation experimental results of resin and network in . Figure 55C Shows Figure 55A ATR-IR results of the BnA / BPAEDA / DOT network.

[0128] Figure 56A Shows Figure 55A Schematic diagram of the degradation of the BnA / BPAEDA / DOT network. Figure 56B All three DOT equivalents were shown to produce degradable (forming homogeneous solutions) materials.The broad molecular weight range can be attributed, at least in part, to the formation of polydisulfides.

[0129] Figure 57 An efficient route to obtain more soluble substituted DOTs is shown.

[0130] Figure 58 Shown are the development towards a solvent-free system with substituted DOT (left panel) and the results of degradation experiments (right panel).

[0131] Figure 59A Shown is the synthesis of BnA / BPAEDA / SPr-F-DOT networks with different SPr-F-DOT contents. Figure 59B Shows Figure 59A Degradation experimental results of resin and network. Figure 59C Shows Figure 59AATR-IR results of the BnA / BPAEDA / SPr-F-DOT network. “DOT*” refers to SPr-F-DOT.

[0132] Figure 60 Shown is the solvent-free synthesis of a BnA / BPAEDA / SBu-F-DOT network.

[0133] definition

[0134] Definitions of specific functional groups and chemical terms are described in more detail below. Chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th edition (inside pages), and specific functional groups are generally defined as described herein. In addition, in Thomas Sorrell, Organic Chemistry, University Science Books, Sausalito, 1999; Smith and March, March's Advanced Organic Chemistry, 5 th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; and Carruthers, Some Modern Methods of Organic Synthesis, 3 rd General principles of organic chemistry, as well as specific functional groups and reactivities, are described in Organic Chemistry: ...

[0135] The compounds described herein may contain one or more asymmetric centers and may therefore exist in various isomeric forms, such as enantiomers and / or diastereomers. For example, the compounds described herein may be in the form of individual enantiomers, diastereomers, or geometric isomers, or may be in the form of mixtures of stereoisomers, including racemic mixtures and mixtures enriched in one or more stereoisomers. Isomers may be separated from the mixture by methods known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC), supercritical fluid chromatography (SFC), and the formation and crystallization of chiral salts; or preferred isomers may be prepared by asymmetric synthesis. See, e.g., Jacques et al., Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen et al., Tetrahedron 33:2725 (1977); Eliel, Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); and Wilen, Tables of Resolving Agents and Optical Resolutions, p. 268 (E.L. Eliel, ed., Univ. of Notre Dame Press, Notre Dame, IN 1972). The present invention further encompasses the compounds described herein as individual isomers substantially free of other isomers, as well as alternatively as mixtures of different isomers.

[0136] In the formula, the key For a single bond, dotted line---for a single bond or does not exist, and the bond or It is a single bond or a double bond.

[0137] Unless otherwise indicated, formulae described herein include compounds that do not contain isotopically enriched atoms as well as compounds that contain isotopically enriched atoms. Compounds containing isotopically enriched atoms are useful, for example, as analytical tools and / or probes in biological assays.

[0138] Term " aliphatic " comprises saturation and undersaturated, non-aromatic, straight chain (i.e. non-branched), side chain, acyclic and cyclic (i.e. carbocyclic) hydrocarbon.In some embodiments, aliphatic group is optionally replaced by one or more functional groups (for example, halogen such as fluorine).As understood by those of ordinary skill in the art, " aliphatic " is intended to include alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl and cycloalkynyl moieties in this article.

[0139] When a range of values ​​("range") is listed, it is intended to encompass every value and subrange within the range. Unless otherwise indicated, a range includes values ​​at both ends of the range. For example, "an integer between 1 and 4" refers to 1, 2, 3, and 4. For example, "C 1–6 "Alkyl" is intended to encompass C1, C2, C3, C4, C5, C6, C 1–6 、C 1–5 、C 1–4 、C 1–3 、C 1–2 、C 2–6 、C 2–5 、C 2–4 、C 2–3 、C 3–6 、C 3–5 、C 3–4 、C 4–6 、C 4–5 and C 5–6 alkyl.

[0140] "Alkyl" refers to a straight-chain or branched saturated hydrocarbon group having 1 to 20 carbon atoms ("C 1–20 In some embodiments, an alkyl group has 1 to 12 carbon atoms ("C 1–12 In some embodiments, an alkyl group has 1 to 10 carbon atoms ("C 1–10 In some embodiments, an alkyl group has 1 to 9 carbon atoms ("C 1–9 In some embodiments, an alkyl group has 1 to 8 carbon atoms ("C 1–8 In some embodiments, an alkyl group has 1 to 7 carbon atoms ("C 1–7 In some embodiments, an alkyl group has 1 to 6 carbon atoms ("C 1–6 In some embodiments, an alkyl group has 1 to 5 carbon atoms ("C 1–5 In some embodiments, an alkyl group has 1 to 4 carbon atoms ("C 1–4 In some embodiments, an alkyl group has 1 to 3 carbon atoms ("C 1–3 In some embodiments, an alkyl group has 1 to 2 carbon atoms ("C 1-2 In some embodiments, an alkyl group has 1 carbon atom ("C1 alkyl"). In some embodiments, an alkyl group has 2 to 6 carbon atoms ("C 2–6 C 1–6Examples of alkyl groups include methyl (C1), ethyl (C2), n-propyl (C3), isopropyl (C3), n-butyl (C4), tert-butyl (C4), sec-butyl (C4), isobutyl (C4), n-pentyl (C5), 3-pentyl (C5), isopentyl (C5), neopentyl (C5), 3-methyl-2-butyl (C5), tert-pentyl (C5), and n-hexyl (C6). Other examples of alkyl groups include n-heptyl (C7), n-octyl (C8), and the like. Unless otherwise specified, each example of alkyl is independently optionally substituted, e.g., unsubstituted ("unsubstituted alkyl") or substituted ("substituted alkyl") with one or more substituents. In certain embodiments, alkyl is unsubstituted C 1–12 Alkyl (e.g., -CH3(Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, e.g., unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr)), unsubstituted butyl (Bu, e.g., unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu or s-Bu), unsubstituted isobutyl (i-Bu)). In certain embodiments, the alkyl group is substituted C 1–12 Alkyl (e.g. substituted C 1-6 Alkyl, such as -CH2F, -CHF2, -CF3, -CH2CH2F, -CH2CHF2, -CH2CF3, or benzyl (Bn). The point of attachment of the alkyl group can be a single bond (such as in -CH3), a double bond (such as in =CH2), or a triple bond (such as in ≡CH). =CH2 and ≡CH moieties are also alkyl.

[0141] The term "heteroalkyl" refers to an alkyl group further comprising at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur, said heteroatom being within (i.e., interposed between adjacent carbon atoms of the parent chain) and / or located at one or more terminal positions of the parent chain. In some embodiments, heteroalkyl refers to a saturated group ("heteroalkyl") having 1-20 carbon atoms and 1 or more heteroatoms within the parent chain. 1–20 Alkyl" or "C 1–20 In some embodiments, heteroalkyl refers to a saturated group having 1-12 carbon atoms and 1 or more heteroatoms within the parent chain ("heteroalkyl"). 1–12 In certain embodiments, heteroalkyl refers to a saturated group having 1-10 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroalkyl”). 1–10 In some embodiments, a heteroalkyl group is a saturated group having 1-9 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroalkyl”). 1–9In some embodiments, a heteroalkyl group is a saturated group having 1-8 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroalkyl”). 1–8 In some embodiments, a heteroalkyl group is a saturated group having 1-7 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroalkyl”). 1–7 In some embodiments, a heteroalkyl group is a saturated group having 1-6 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroalkyl”). 1–6 In some embodiments, a heteroalkyl group is a saturated group having 1 to 5 carbon atoms and 1 or 2 heteroatoms within the parent chain (“heteroalkyl”). 1–5 In some embodiments, a heteroalkyl group is a saturated group having 1 to 4 carbon atoms and 1 or 2 heteroatoms within the parent chain (“heteroalkyl”). 1–4 In some embodiments, a heteroalkyl group is a saturated group having 1 to 3 carbon atoms and 1 heteroatom within the parent chain (“heteroC 1–3 In some embodiments, a heteroalkyl group is a saturated group having 1 to 2 carbon atoms and 1 heteroatom within the parent chain (“heteroC 1–2 In some embodiments, a heteroalkyl group is a saturated group having 1 carbon atom and 1 heteroatom ("heteroC1 alkyl"). In some embodiments, a heteroalkyl group is a saturated group having 2 to 6 carbon atoms and 1 or 2 heteroatoms within the parent chain ("heteroC1 alkyl"). 2-6 Unless otherwise specified, each heteroalkyl group is independently unsubstituted (an “unsubstituted heteroalkyl group”) or substituted (a “substituted heteroalkyl group”) with one or more substituents. In some embodiments, the heteroalkyl group is an unsubstituted heteroalkyl group. 1–10 In some embodiments, heteroalkyl is substituted heteroC 1–10 alkyl.

[0142] In some embodiments, the alkyl group is substituted with one or more halogens. A "perhaloalkyl" is a substituted alkyl group as defined herein in which all hydrogen atoms are independently replaced by halogens such as fluorine, bromine, chlorine, or iodine. In some embodiments, the alkyl moiety has 1 to 8 carbon atoms ("C 1–8 In some embodiments, the alkyl moiety has 1 to 6 carbon atoms ("C 1–6 In some embodiments, the alkyl moiety has 1 to 4 carbon atoms ("C 1–4 In some embodiments, the alkyl moiety has 1 to 3 carbon atoms ("C 1–3 In some embodiments, the alkyl moiety has 1 to 2 carbon atoms ("C 1–2In some embodiments, all hydrogen atoms are replaced by fluorine. In some embodiments, all hydrogen atoms are replaced by chlorine. Examples of perhaloalkyl groups include -CF3, -CF2CF3, -CF2CF2CF3, -CCl3, -CFCl2, -CF2Cl, and the like.

[0143] "Alkenyl" refers to a straight or branched chain hydrocarbon radical ("C 2-20 In some embodiments, an alkenyl group has 2 to 10 carbon atoms ("C 2-10 In some embodiments, an alkenyl group has 2 to 9 carbon atoms ("C 2-9 In some embodiments, an alkenyl group has 2 to 8 carbon atoms ("C 2-8 In some embodiments, an alkenyl group has 2 to 7 carbon atoms ("C 2-7 In some embodiments, an alkenyl group has 2 to 6 carbon atoms ("C 2-6 In some embodiments, an alkenyl group has 2 to 5 carbon atoms ("C 2-5 In some embodiments, an alkenyl group has 2 to 4 carbon atoms ("C 2-4 In some embodiments, an alkenyl group has 2 to 3 carbon atoms ("C 2-3 In some embodiments, an alkenyl group has 2 carbon atoms ("C2 alkenyl"). The one or more carbon-carbon double bonds can be internal (as in 2-butenyl) or terminal (as in 1-butenyl). C 2-4 Examples of alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2-propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), butadienyl (C4), and the like. 2-6 Examples of alkenyl groups include the above-mentioned C 2-4 In some embodiments, alkenyl is an unsubstituted C 1-4, C 1-6, C 1-8, C 1-9, C 2-10, C 3-11, C 3-12, C 3-13, C 3-14, C 3-15, C 3-16, C 3-17, C 3-18, C 3-19, C 4-20, C 4-32, C 4-33, C 4-44, C 4-50, C 4-6, C 4-7, C 4-8, C 4-9, C 4-10, C 4-11, C 4-12, C 4-13, C 4-14, C 4-15, C 4-16, C 4-17, C 4-18, C 4-19, C 4-20, C 4-21, C 4-22, 2-10 In certain embodiments, alkenyl is a substituted C 2-10 In alkenyl, a C=C double bond with unspecified stereochemistry (e.g., -CH=CHCH3 or ) may be in the (E)- or (Z)-configuration.

[0144] The term "heteroalkenyl" refers to an alkenyl group further comprising at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur, said heteroatom being within (i.e., interposed between adjacent carbon atoms of the parent chain) and / or located at one or more terminal positions of the parent chain. In some embodiments, heteroalkenyl refers to a group having 2 to 20 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain ("heteroalkenyl"). 2-20 Alkenyl" or "C 2-20 In certain embodiments, heteroalkenyl refers to a group having 2 to 12 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain ("heteroC 2-12 In certain embodiments, heteroalkenyl refers to a group having 2 to 10 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain ("heteroC 2-10 In some embodiments, a heteroalkenyl group has 2 to 9 carbon atoms, at least one double bond, and 1 or more heteroatoms (“heteroC 2-9 In some embodiments, a heteroalkenyl group has 2 to 8 carbon atoms, at least one double bond, and 1 or more heteroatoms (“heteroC 2-8 In some embodiments, a heteroalkenyl group has 2 to 7 carbon atoms, at least one double bond, and 1 or more heteroatoms (“heteroC 2-7 In some embodiments, a heteroalkenyl group has 2 to 6 carbon atoms, at least one double bond, and 1 or more heteroatoms (“heteroC 2-6 In some embodiments, a heteroalkenyl group has 2 to 5 carbon atoms, at least one double bond, and 1 or 2 heteroatoms ("heteroC 2-5 In some embodiments, a heteroalkenyl group has 2 to 4 carbon atoms, at least one double bond, and 1 or 2 heteroatoms ("heteroC 2-4 In some embodiments, a heteroalkenyl group has 2 to 3 carbon atoms, at least one double bond, and 1 heteroatom within the parent chain (“heteroC 2-3 In some embodiments, a heteroalkenyl group has 2 to 6 carbon atoms, at least one double bond, and 1 or 2 heteroatoms (“heteroC 2-6 Unless otherwise specified, each instance of a heteroalkenyl group is independently unsubstituted (an “unsubstituted heteroalkenyl”) or substituted (a “substituted heteroalkenyl”) with one or more substituents. In some embodiments, a heteroalkenyl group is an unsubstituted heteroC 2-20 In some embodiments, heteroalkenyl is substituted heteroC 2-20 Alkenyl.

[0145] "Alkynyl" refers to a straight or branched chain hydrocarbon radical ("C 2–20 In certain embodiments, an alkynyl group does not contain any double bonds. In some embodiments, an alkynyl group has 2 to 10 carbon atoms ("C 2–10 In some embodiments, an alkynyl group has 2 to 9 carbon atoms ("C 2–9 In some embodiments, an alkynyl group has 2 to 8 carbon atoms ("C 2–8 In some embodiments, an alkynyl group has 2 to 7 carbon atoms ("C 2–7 In some embodiments, an alkynyl group has 2 to 6 carbon atoms ("C 2–6 In some embodiments, an alkynyl group has 2 to 5 carbon atoms ("C 2–5 In some embodiments, an alkynyl group has 2 to 4 carbon atoms ("C 2–4 In some embodiments, an alkynyl group has 2 to 3 carbon atoms ("C 2–3 In some embodiments, an alkynyl group has 2 carbon atoms ("C2 alkynyl"). The one or more carbon-carbon triple bonds can be internal (as in 2-butynyl) or terminal (as in 1-butynyl). C 2–4 Examples of alkynyl groups include, but are not limited to, ethynyl (C2), 1-propynyl (C3), 2-propynyl (C3), 1-butynyl (C4), 2-butynyl (C4), and the like. 2–6 Examples of alkenyl groups include the above-mentioned C 2–4 Alkynyl and pentynyl (C5), hexynyl (C6), etc. Additional examples of alkynyl include heptynyl (C7), octynyl (C8), etc. Unless otherwise specified, each instance of alkynyl is independently optionally substituted, e.g., unsubstituted (“unsubstituted alkynyl”) or substituted with one or more substituents (“substituted alkynyl”). In certain embodiments, alkynyl is unsubstituted C 2–10 In certain embodiments, the alkynyl group is a substituted C 2–10 Alkynyl.

[0146] The term "heteroalkynyl" refers to an alkynyl group further comprising at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur, said heteroatom being within (i.e., interposed between adjacent carbon atoms of the parent chain) and / or located at one or more terminal positions of the parent chain. In some embodiments, heteroalkynyl refers to a group having 2 to 20 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain ("heteroalkynyl").2-20 Alkynyl" or "C 2-20 In some embodiments, heteroalkynyl refers to a group having 2 to 12 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain ("heteroalkynyl"). 2-12 In some embodiments, heteroalkynyl refers to a group having 2 to 10 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain ("heteroalkynyl"). 2-10 In some embodiments, a heteroalkynyl group has 2 to 9 carbon atoms, at least one triple bond, and 1 or more heteroatoms (“heteroC 2–9 In some embodiments, a heteroalkynyl group has 2 to 8 carbon atoms, at least one triple bond, and 1 or more heteroatoms (“heteroC 2-8 In some embodiments, a heteroalkynyl group has 2 to 7 carbon atoms, at least one triple bond, and 1 or more heteroatoms (“heteroC 2–7 In some embodiments, a heteroalkynyl group has 2 to 6 carbon atoms, at least one triple bond, and 1 or more heteroatoms (“heteroC 2-6 In some embodiments, a heteroalkynyl group has 2 to 5 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms ("heteroC 2-5 In some embodiments, a heteroalkynyl group has 2 to 4 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms ("heteroC 2-4 In some embodiments, a heteroalkynyl group has 2 to 3 carbon atoms, at least one triple bond, and 1 heteroatom within the parent chain (“heteroC 2-3 In some embodiments, a heteroalkynyl group has 2 to 6 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms (“heteroC 2-6 Unless otherwise specified, each instance of a heteroalkynyl group is independently unsubstituted (an “unsubstituted heteroalkynyl”) or substituted (a “substituted heteroalkynyl”) with one or more substituents. In some embodiments, a heteroalkynyl group is an unsubstituted heteroC 2-10 In some embodiments, heteroalkynyl is substituted heteroC 2-10 Alkynyl.

[0147] "Carbocyclyl" or "carbocyclic" refers to a non-aromatic ring system having 3 to 13 ring carbon atoms ("C 3–13 In some embodiments, the carbocyclyl group has 3 to 8 ring carbon atoms ("C 3–8 In some embodiments, a carbocyclyl group has 3 to 7 ring carbon atoms ("C 3-7In some embodiments, a carbocyclyl group has 3 to 6 ring carbon atoms ("C 3–6 In some embodiments, a carbocyclyl group has 5 to 10 ring carbon atoms ("C 5–10 Carbocyclyl”). Exemplary C 3–6 Carbocyclic groups include, but are not limited to, cyclopropyl (C3), cyclopropenyl (C3), cyclobutyl (C4), cyclobutenyl (C4), cyclopentyl (C5), cyclopentenyl (C5), cyclohexyl (C6), cyclohexenyl (C6), cyclohexadienyl (C6), and the like. 3-8 Carbocyclic groups include but are not limited to the above C 3-6 Carbocyclic groups and cycloheptyl (C7), cycloheptenyl (C7), cycloheptadienyl (C7), cycloheptatrienyl (C7), cyclooctyl (C8), cyclooctenyl (C8), bicyclo [2.2.1] heptyl (C7), bicyclo [2.2.2] octyl (C8), etc. Exemplary C 3–10 Carbocyclic groups include the above-mentioned C 3–8 Carbocyclic groups and cyclononyl (C9), cyclononenyl (C9), cyclodecyl (C 10 ), cyclodecenyl (C 10 ), octahydro-1H-indenyl (C9), decahydronaphthyl (C 10 ), spiro[4.5]decyl (C 10 ) and the like. As illustrated in the foregoing examples, in certain embodiments, a carbocyclyl is monocyclic ("monocyclic carbocyclyl") or contains a fused, bridged, or spirocyclic ring system, such as a bicyclic ring system ("bicyclic carbocyclyl"). A carbocyclyl may be saturated, and a saturated carbocyclyl is referred to as a "cycloalkyl." In some embodiments, a carbocyclyl is a monocyclic saturated carbocyclyl having 3 to 10 ring carbon atoms ("C 3–10 In some embodiments, a cycloalkyl group has 3 to 8 ring carbon atoms ("C 3–8 In some embodiments, a cycloalkyl group has 3 to 6 ring carbon atoms ("C 3–6 In some embodiments, a cycloalkyl group has 5 to 6 ring carbon atoms ("C 5–6 In some embodiments, a cycloalkyl group has 5 to 10 ring carbon atoms ("C 5–10 Cycloalkyl”). C 5–6 Examples of cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C5). 3–6 Examples of the cycloalkyl group include the above-mentioned C 5–6 Cycloalkyl as well as cyclopropyl (C3) and cyclobutyl (C4). 3–8 Examples of the cycloalkyl group include the above-mentioned C 3–6Cycloalkyl and cycloheptyl (C7) and cyclooctyl (C8). Unless otherwise specified, each instance of cycloalkyl is independently unsubstituted (“unsubstituted cycloalkyl”) or substituted (“substituted cycloalkyl”) with one or more substituents. In certain embodiments, cycloalkyl is unsubstituted C 3–10 In certain embodiments, the cycloalkyl group is a substituted C 3–10 Cycloalkyl. A carbocyclyl group may be partially unsaturated. A carbocyclyl group may contain zero, one or more (e.g., two, three, or four, where valence permits) C=C double bonds in all rings of a non-aromatic or heteroaromatic carbocyclic ring system. A carbocyclyl group containing one or more (e.g., two or three, where valence permits) C=C double bonds in a carbocyclic ring is referred to as a "cycloalkenyl group." A carbocyclyl group containing one or more (e.g., two or three, where valence permits) C≡C triple bonds in a carbocyclic ring is referred to as a "cycloalkynyl group." Carbocyclyl groups include aryl groups. "Carbocyclyl" also includes ring systems in which a carbocyclic ring as defined above is fused to one or more aryl or heteroaryl groups, where the point of attachment is on the carbocyclic ring, and in this case, the carbon number still refers to the number of carbons in the carbocyclic ring system. Unless otherwise specified, each instance of a carbocyclyl group is independently optionally substituted, e.g., unsubstituted ("unsubstituted carbocyclyl"), or substituted ("substituted carbocyclyl") with one or more substituents. In certain embodiments, the carbocyclyl group is an unsubstituted C 3–10 In certain embodiments, the carbocyclyl group is a substituted C 3–10 In certain embodiments, the carbocyclyl group is a substituted or unsubstituted 3- to 7-membered monocyclic ring. In certain embodiments, the carbocyclyl group is a substituted or unsubstituted 5- to 13-membered bicyclic ring.

[0148] In some embodiments, a "carbocyclyl" is a monocyclic saturated carbocyclyl ("C 3–10 In some embodiments, a cycloalkyl group has 3 to 8 ring carbon atoms ("C 3–8 In some embodiments, a cycloalkyl group has 3 to 6 ring carbon atoms ("C 3–6 In some embodiments, a cycloalkyl group has 5 to 6 ring carbon atoms ("C 5–6 In some embodiments, a cycloalkyl group has 5 to 10 ring carbon atoms ("C 5–10 Cycloalkyl”). C 5–6 Examples of cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C5). 3–6 Examples of the cycloalkyl group include the above-mentioned C 5–6 Cycloalkyl as well as cyclopropyl (C3) and cyclobutyl (C4). 3–8 Examples of the cycloalkyl group include the above-mentioned C 3–6Cycloalkyl and cycloheptyl (C7) and cyclooctyl (C8). Unless otherwise specified, each instance of cycloalkyl is independently unsubstituted (“unsubstituted cycloalkyl”) or substituted (“substituted cycloalkyl”) with one or more substituents. In certain embodiments, cycloalkyl is unsubstituted C 3–10 In certain embodiments, the cycloalkyl group is a substituted C 3–10 Cycloalkyl.

[0149] "Heterocyclyl" or "heterocyclic" refers to a radical of a 3- to 13-membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("3-13 membered heterocyclyl"). In heterocyclyl groups containing one or more nitrogen atoms, the point of attachment may be a carbon or nitrogen atom, as valence permits. A heterocyclyl group may be monocyclic ("monocyclic heterocyclyl") or a fused, bridged, or spiro ring system, such as a bicyclic ring system ("bicyclic heterocyclyl"). A heterocyclyl group may be saturated or partially unsaturated. A heterocyclyl group may contain zero, one or more (e.g., two, three, or four, as valence permits) double bonds in all non-aromatic or heteroaromatic rings of the heterocyclyl group. Partially unsaturated heterocyclyl groups include heteroaryls. Heterocyclyl bicyclic ring systems may contain one or more heteroatoms in one or both rings. "Heterocyclyl" also includes ring systems in which a heterocycle as defined above is fused to one or more carbocyclyl groups, wherein the point of attachment is on the carbocyclyl or heterocyclyl ring, or ring systems in which a heterocycle as defined above is fused to one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocycle, and in this case, the number of ring atoms still refers to the number of ring atoms in the heterocycle system. Unless otherwise specified, each instance of a heterocyclyl group is independently optionally substituted, e.g., unsubstituted ("unsubstituted heterocyclyl") or substituted ("substituted heterocyclyl") with one or more substituents. In certain embodiments, a heterocyclyl group is an unsubstituted 3- to 10-membered heterocyclyl group. In certain embodiments, a heterocyclyl group is a substituted 3- to 10-membered heterocyclyl group. In certain embodiments, a heterocyclyl group is a substituted or unsubstituted 3- to 7-membered monocyclic ring. In certain embodiments, a heterocyclyl group is a substituted or unsubstituted 5- to 13-membered bicyclic ring.

[0150] In some embodiments, the heterocyclyl group is a 5-10 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-10 membered heterocyclyl”). In some embodiments, the heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-8 membered heterocyclyl”). In some embodiments, the heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-6 membered heterocyclyl”). In some embodiments, the 5-6 membered heterocyclyl group has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heterocyclyl group has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heterocyclyl group has one ring heteroatom selected from nitrogen, oxygen, and sulfur.

[0151] Exemplary 3-membered heterocyclic groups containing one heteroatom include aziridine, oxirane, and thiirane. Exemplary 4-membered heterocyclic groups containing one heteroatom include azetidinyl, oxetanyl, and thiirane. Exemplary 5-membered heterocyclic groups containing one heteroatom include tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione. Exemplary 5-membered heterocyclic groups containing two heteroatoms include dioxolanyl, oxathiolanyl, dithiolanyl, and oxazolidin-2-one. Exemplary 5-membered heterocyclic groups containing three heteroatoms include triazolinyl, oxadiazolinyl, and thiadiazolinyl. Exemplary 6-membered heterocyclic groups containing one heteroatom include piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thiohexyl. Exemplary 6-membered heterocyclic groups containing two heteroatoms include piperazinyl, morpholinyl, dithiohexyl and dioxanyl. Exemplary 6-membered heterocyclic groups containing two heteroatoms include triazinyl. Exemplary 7-membered heterocyclic groups containing one heteroatom include azepanyl, oxepanyl and thiepanyl. Exemplary 8-membered heterocyclic groups containing one heteroatom include azocanyl, oxocanyl and thiocanyl. Exemplary 5-membered heterocyclic groups fused to a C6 aromatic ring (also referred to herein as 5,6-bicyclic heterocycles) include dihydroindolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, benzoxazolinone and the like. Exemplary 6-membered heterocyclic groups fused to an aromatic ring (also referred to herein as 6,6-bicyclic heterocycles) include tetrahydroquinolinyl, tetrahydroisoquinolinyl and the like.

[0152] "Aryl" refers to a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in the ring array) having 6-14 ring carbon atoms and no heteroatoms ("C6-14 In some embodiments, an aryl group has 6 ring carbon atoms ("C6 aryl"; e.g., phenyl). In some embodiments, an aryl group has 10 ring carbon atoms ("C 10 "Aryl"; for example, naphthyl, such as 1-naphthyl and 2-naphthyl). In some embodiments, an aryl group has 14 ring carbon atoms ("C 14 "Aryl"; for example, anthracenyl). "Aryl" also includes ring systems in which an aryl ring as defined above is fused to one or more carbocyclyl or heterocyclyl groups, wherein the radical or point of attachment is on the aryl ring, and in this case, the number of carbon atoms still refers to the number of carbon atoms in the aryl ring system. Unless otherwise specified, each instance of aryl is independently optionally substituted, e.g., unsubstituted ("unsubstituted aryl") or substituted with one or more substituents ("substituted aryl"). In certain embodiments, aryl is unsubstituted C 6–14 In certain embodiments, aryl is substituted C 6–14 Aryl.

[0153] "Heteroaryl" refers to a radical of a 5-10 membered monocyclic or bicyclic 4n+2 aromatic ring system (e.g., having 6 or 10 pi electrons shared in the ring array) having ring carbon atoms and 1-4 ring heteroatoms in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-10 membered heteroaryl"). In heteroaryl groups containing one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valence permits. Heteroaryl bicyclic ring systems can contain one or more heteroatoms in one or both rings. "Heteroaryl" includes ring systems in which a heteroaryl ring as defined above is fused to one or more carbocyclyl or heterocyclyl groups, wherein the point of attachment is on the heteroaryl ring, and in this case, the number of ring atoms still refers to the number of ring atoms in the heteroaryl ring system. "Heteroaryl" also includes ring systems in which a heteroaryl ring, as defined above, is fused to one or more aryl groups, wherein the point of attachment is on the aryl or heteroaryl ring, and in this case, the number of ring atoms refers to the number of ring atoms in the fused (aryl / heteroaryl) ring system. In bicyclic heteroaryl groups in which one ring does not contain heteroatoms (e.g., indolyl, quinolinyl, carbazolyl, etc.), the point of attachment can be on either ring, for example, on the heteroatom-containing ring (e.g., 2-indolyl) or on the non-heteroatom-containing ring (e.g., 5-indolyl).

[0154] In some embodiments, heteroaryl is a 5-10 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-10 membered heteroaryl”). In some embodiments, heteroaryl is a 5-8 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-8 membered heteroaryl”). In some embodiments, heteroaryl is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-6 membered heteroaryl”). In some embodiments, the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl group has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur. Unless otherwise specified, each instance of a heteroaryl group is independently optionally substituted, e.g., unsubstituted (an “unsubstituted heteroaryl”) or substituted (a “substituted heteroaryl”) with one or more substituents. In certain embodiments, a heteroaryl group is an unsubstituted 5-14 membered heteroaryl group. In certain embodiments, a heteroaryl group is a substituted 5-14 membered heteroaryl group.

[0155] Exemplary 5-membered heteroaryl groups containing one heteroatom include pyrrolyl, furanyl, and thienyl. Exemplary 5-membered heteroaryl groups containing two heteroatoms include imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing four heteroatoms include tetrazolyl. Exemplary 6-membered heteroaryl groups containing one heteroatom include pyridinyl. Exemplary 6-membered heteroaryl groups containing two heteroatoms include pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include triazinyl and tetrazinyl, respectively. Exemplary 7-membered heteroaryl groups containing one heteroatom include azepine, oxepinyl, and thiepine. Exemplary 5,6-bicyclic heteroaryl groups include indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, indolizinyl, and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl.

[0156] "Partially unsaturated" refers to a group that contains at least one double or triple bond. The term "partially unsaturated" is intended to include rings with multiple sites of unsaturation, but is not intended to include aromatic groups (e.g., aryl or heteroaryl) as defined herein. Similarly, "saturated" refers to a group that contains no double or triple bonds (i.e., contains all single bonds).

[0157] In some embodiments, aliphatic, alkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups as defined herein are optionally substituted (e.g., "substituted" or "unsubstituted" alkyl, "substituted" or "unsubstituted" alkenyl, "substituted" or "unsubstituted" alkynyl, "substituted" or "unsubstituted" carbocyclyl, "substituted" or "unsubstituted" heterocyclyl, "substituted" or "unsubstituted" aryl, or "substituted" or "unsubstituted" heteroaryl). In some embodiments, heteroalkyl, heteroalkenyl, and heteroalkynyl groups are optionally substituted. In general, the term "substituted," whether preceded by the term "optionally" or not, means that at least one hydrogen atom present on a group (e.g., a carbon or nitrogen atom) is replaced with a permissible substituent (e.g., a substituent that, upon substitution, forms a stable compound, e.g., the compound does not spontaneously undergo a transformation such as a rearrangement, cyclization, elimination, or other reaction). Unless otherwise indicated, a "substituted" group has a substituent at one or more substitutable positions of the group, and when more than one position is substituted in any given structure, the substituent is the same or different at each position. The term "substituted" is intended to include substitution with all permissible substituents of an organic compound (resulting in any substituent described herein that forms a stable compound). The present invention includes any and all such combinations to obtain stable compounds. For purposes of the present invention, a heteroatom (e.g., nitrogen) may have a hydrogen substituent and / or any suitable substituent described herein that satisfies the valence of the heteroatom and forms a stable group.

[0158] Exemplary carbon atom substituents include halogen, -CN, -NO2, -N3, -SO2H, -SO3H, -OH, -OR aa 、-ON(R bb )2、-N(R bb )2、-N(R bb )3 + X - 、-N(OR cc )R bb 、-SH、-SR aa 、-SSR cc 、-C(=O)R aa 、-CO2H、-CHO、-C(OR cc )2, -CO2R aa 、-OC(=O)R aa 、-OCO2Raa 、-C(=O)N(R bb )2、-OC(=O)N(R bb )2、-NR bb C(=O)R aa 、-NR bb CO2R aa 、-NR bb C(=O)N(R bb )2、-C(=NR bb )R aa 、-C(=NR bb )OR aa 、-OC(=NR bb )R aa 、-OC(=NR bb )OR aa 、-C(=NR bb )N(R bb )2、-OC(=NR bb )N(R bb )2、-NR bb C(=NR bb )N(R bb )2、-C(=O)NR bb SO2R aa 、-NR bb SO2R aa 、-SO2N(R bb )2、-SO2R aa 、-SO2OR aa 、-OSO2R aa 、-S(=O)R aa 、-OS(=O)R aa 、-Si(R aa )3、-OSi(R aa )3、-C(=S)N(R bb )2、-C(=O)SR aa 、-C(=S)SR aa 、-SC(=S)SR aa 、-SC(=O)SR aa 、-OC(=O)SR aa 、-SC(=O)OR aa 、-SC(=O)R aa 、-P(=O)(R aa )2、-P(=O)(OR cc )2、-OP(=O)(R aa )2、-OP(=O)(OR cc )2、-P(=O)(N(R bb)2)2、-OP(=O)(N(R bb )2)2、-NR bb P(=O)(R aa )2、-NR bb P(=O)(OR cc )2、-NR bb P(=O)(N(R bb )2)2、-P(R cc )2、-P(OR cc )2、-P(R cc )3 + X - 、-P(OR cc )3 + X - 、-P(R cc )4、-P(OR cc )4、-OP(R cc )2、-OP(R cc )3 + X - 、-OP(OR cc )2、-OP(OR cc )3 + X - 、-OP(R cc )4、-OP(OR cc )4、-B(R aa )2、-B(OR cc )2, -BR aa (OR cc ), C 1-10 Alkyl, C 1-10 Perhalogenated alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, hetero C 1-10 Alkyl, hetero C 2-10 Alkenyl, hetero C 2-10 Alkynyl, C 3-10 Carbocyclic group, 3-14 membered heterocyclic group, C 6-14 Aryl and 5-14 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl is independently replaced by 0, 1, 2, 3, 4 or 5 R dd substituted by a group; wherein X - is the counter ion;

[0159] Or the two geminal hydrogens on the carbon atom are replaced by groups =O, =S, =NN(R bb )2, =NNR bb C(=O)R aa 、=NNR bb C(=O)ORaa 、=NNR bb S(=O)2R aa 、=NR bb or = NOR cc Replacement;

[0160] R aa Each instance of is independently selected from C 1-10 Alkyl, C 1-10 Perhalogenated alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, hetero C 1-10 Alkyl, hetero C 2-10 Alkenyl, hetero C 2-10 Alkynyl, C 3-10 Carbocyclic group, 3-14 membered heterocyclic group, C 6-14 Aryl and 5-14 membered heteroaryl, or two R aa The groups are connected to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd substituted by a group;

[0161] R bb Each instance of is independently selected from hydrogen, -OH, -OR aa 、-N(R cc )2, -CN, -C(=O)R aa 、-C(=O)N(R cc )2, -CO2R aa 、-SO2R aa 、-C(=NR cc )OR aa 、-C(=NR cc )N(R cc )2、-SO2N(R cc )2, -SO2R cc 、-SO2OR cc 、-SOR aa 、-C(=S)N(R cc )2, -C(=O)SR cc 、-C(=S)SR cc 、-P(=O)(R aa )2、-P(=O)(OR cc )2、-P(=O)(N(R cc )2)2、C 1-10 Alkyl, C 1-10 Perhalogenated alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, hetero C 1-10Alkyl, hetero C 2-10 Alkenyl, hetero C 2-10 Alkynyl, C 3-10 Carbocyclic group, 3-14 membered heterocyclic group, C 6-14 Aryl and 5-14 membered heteroaryl, or two R bb The groups are connected to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd substituted by a group; wherein X - is the counter ion;

[0162] R cc Each instance of is independently selected from hydrogen, C 1-10 Alkyl, C 1-10 Perhalogenated alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, hetero C 1-10 Alkyl, hetero C 2-10 Alkenyl, hetero C 2-10 Alkynyl, C 3-10 Carbocyclic group, 3-14 membered heterocyclic group, C 6-14 Aryl and 5-14 membered heteroaryl, or two R cc The groups are connected to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd substituted by a group;

[0163] R dd Each instance of is independently selected from halogen, -CN, -NO2, -N3, -SO2H, -SO3H, -OH, -OR ee 、-ON(R ff )2、-N(R ff )2、-N(R ff )3 + X - 、-N(OR ee )R ff 、-SH、-SR ee 、-SSR ee 、-C(=O)R ee 、-CO2H、-CO2R ee 、-OC(=O)R ee 、-OCO2R ee 、-C(=O)N(R ff )2、-OC(=O)N(R ff )2、-NR ff C(=O)Ree 、-NR ff CO2R ee 、-NR ff C(=O)N(R ff )2、-C(=NR ff )OR ee 、-OC(=NR ff )R ee 、-OC(=NR ff )OR ee 、-C(=NR ff )N(R ff )2、-OC(=NR ff )N(R ff )2、-NR ff C(=NR ff )N(R ff )2、-NR ff SO2R ee 、-SO2N(R ff )2, -SO2R ee 、-SO2OR ee 、-OSO2R ee 、-S(=O)R ee 、-Si(R ee )3、-OSi(R ee )3、-C(=S)N(R ff )2, -C(=O)SR ee 、-C(=S)SR ee 、-SC(=S)SR ee 、-P(=O)(OR ee )2、-P(=O)(R ee )2、-OP(=O)(R ee )2、-OP(=O)(OR ee )2、C 1-6 Alkyl, C 1-6 Perhalogenated alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, hetero C 1-6 Alkyl, hetero C 2-6 Alkenyl, hetero C 2-6 Alkynyl, C 3-10 Carbocyclic group, 3-10 membered heterocyclic group, C 6-10 Aryl, 5-10 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl are independently replaced by 0, 1, 2, 3, 4 or 5 R gg group, or two geminal R dd Substituents may be linked to form =O or =S; wherein X -is the counter ion;

[0164] R ee Each instance of is independently selected from C 1-6 Alkyl, C 1-6 Perhalogenated alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, hetero C 1-6 Alkyl, hetero C 2-6 Alkenyl, hetero C 2-6 Alkynyl, C 3-10 Carbocyclic group, C 6-10 aryl, 3-10 membered heterocyclyl and 3-10 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl is independently replaced by 0, 1, 2, 3, 4 or 5 R gg substituted by a group;

[0165] R ff Each instance of is independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Perhalogenated alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, hetero C 1-6 Alkyl, hetero C 2-6 Alkenyl, hetero C 2-6 Alkynyl, C 3-10 Carbocyclic group, 3-10 membered heterocyclic group, C 6-10 Aryl and 5-10 membered heteroaryl, or two R ff The groups are connected to form a 3-10 membered heterocyclyl or 5-10 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R gg substituted with a group; and

[0166] R gg Each instance of is independently selected from halogen, -CN, -NO2, -N3, -SO2H, -SO3H, -OH, -OC 1-6 Alkyl, -ON(C 1-6 Alkyl)2, -N(C 1-6 Alkyl)2, -N(C 1-6 Alkyl)3 + X - 、-NH(C 1-6 Alkyl)2 + X - 、-NH2(C 1-6 alkyl) + X - 、-NH3 + X - 、-N(OC 1-6Alkyl)(C 1-6 Alkyl), -N(OH)(C 1-6 Alkyl), -NH(OH), -SH, -SC 1-6 Alkyl, -SS(C 1-6 alkyl), -C(=O)(C 1-6 alkyl), -CO2H, -CO2(C 1-6 alkyl), -OC(=O)(C 1-6 Alkyl), -OCO2(C 1-6 alkyl), -C(=O)NH2, -C(=O)N(C 1-6 alkyl)2, -OC(=O)NH(C 1-6 alkyl), -NHC(=O)(C 1-6 Alkyl), -N(C 1-6 alkyl)C(=O)(C 1-6 Alkyl), -NHCO2(C 1-6 alkyl), -NHC(=O)N(C 1-6 Alkyl)2, -NHC(=O)NH(C 1-6 alkyl), -NHC(=O)NH2, -C(=NH)O(C 1-6 alkyl), -OC(=NH)(C 1-6 alkyl), -OC(=NH)OC 1-6 Alkyl, -C(=NH)N(C 1-6 Alkyl)2, -C(=NH)NH(C 1-6 alkyl), -C(=NH)NH2, -OC(=NH)N(C 1-6 Alkyl)2, -OC(NH)NH(C 1-6 alkyl), -OC(NH)NH2, -NHC(NH)N(C 1-6 Alkyl)2, -NHC(=NH)NH2, -NHSO2(C 1-6 Alkyl), -SO2N(C 1-6 Alkyl)2, -SO2NH(C 1-6 alkyl), -SO2NH2, -SO2C 1-6 Alkyl, -SO2OC 1-6 Alkyl, -OSO2C 1-6 Alkyl, -SOC 1-6 Alkyl, -Si(C 1-6 alkyl)3, -OSi(C 1-6 alkyl)3-C(=S)N(C 1-6 alkyl)2、C(=S)NH(C 1-6 alkyl), C(=S)NH2, -C(=O)S(C 1-6alkyl), -C(=S)SC 1-6 Alkyl, -SC(=S)SC 1-6 Alkyl, -P(=O)(OC 1-6 alkyl)2, -P(=O)(C 1-6 alkyl)2, -OP(=O)(C 1-6 alkyl)2, -OP(=O)(OC 1-6 Alkyl)2, C 1-6 Alkyl, C 1-6 Perhalogenated alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, hetero C 1-6 Alkyl, hetero C 2-6 Alkenyl, hetero C 2-6 Alkynyl, C 3-10 Carbocyclic group, C 6-10 Aryl, 3-10 membered heterocyclyl, 5-10 membered heteroaryl; or two geminal R gg Substituents may be linked to form =O or =S; wherein X – For the counter ion.

[0167] In certain embodiments, the carbon atom substituents are independently halogen, substituted (eg, substituted with one or more halogens), or unsubstituted C 1-6 Alkyl, -OR aa 、-SR aa 、-N(R bb )2, –CN, –SCN, –NO2, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb )2, -OC(=O)R aa 、-OCO2R aa 、-OC(=O)N(R bb )2、-NR bb C(=O)R aa 、-NR bb CO2R aa or -NR bb C(=O)N(R bb ) 2. In certain embodiments, the carbon atom substituents are independently halogen, substituted (eg, substituted with one or more halogens), or unsubstituted C 1-6 Alkyl, -OR aa 、-SR aa 、-N(R bb )2, –CN, –SCN, –NO2, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb )2, -OC(=O)Raa 、-OCO2R aa 、-OC(=O)N(R bb )2、-NR bb C(=O)R aa 、-NR bb CO2R aa or -NR bb C(=O)N(R bb )2, where R aa is halogen, substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 alkyl, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom (e.g., acetamidomethyl, t-Bu, 3-nitro-2-pyridinesulfinyl, 2-pyridine-sulfinyl, or triphenylmethyl); and each R bb are independently hydrogen, substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 In certain embodiments, the carbon atom substituents are independently halogen, substituted (e.g., substituted with one or more halogens), or unsubstituted C 1-6 Alkyl, -OR aa 、-SR aa 、-N(R bb )2, -CN, -SCN or -NO2. In certain embodiments, the carbon atom substituents are independently halogen, substituted (e.g., substituted with one or more halogen moieties) or unsubstituted C 1-6 Alkyl, -OR aa 、-SR aa 、-N(R bb )2, –CN, –SCN or –NO2, where R aa is hydrogen, substituted (e.g., substituted by one or more halogens) or unsubstituted C 1-6 alkyl, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom (e.g., acetamidomethyl, t-Bu, 3-nitro-2-pyridinesulfinyl, 2-pyridine-sulfinyl, or triphenylmethyl); and each R bb are independently hydrogen, substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 Alkyl or nitrogen protecting group.

[0168] A "counterion" or "anionic counterion" is a negatively charged group that associates with a positively charged group to maintain electrical neutrality. Anionic counterions can be monovalent (i.e., contain one formal negative charge). Anionic counterions can also be multivalent (i.e., contain more than one formal negative charge), such as divalent or trivalent. Exemplary counterions include halide ions (e.g., F – 、Cl– Br – , I – )、NO3 – 、ClO4 – OH – 、H2PO4 – 、HCO3 - 、HSO4 – , sulfonate ions (e.g., methanesulfonate, trifluoromethanesulfonate, p-toluenesulfonate, benzenesulfonate, 10-camphorsulfonate, naphthalene-2-sulfonate, naphthalene-1-sulfonic acid-5-sulfonate, ethane-1-sulfonic acid-2-sulfonate, etc.), carboxylate ions (e.g., acetate, propionate, benzoate, glycerate, lactate, tartrate, glycolate, gluconate, etc.), BF4 - PF4 – PF6 – 、AsF6 – 、SbF6 – 、B[3,5-(CF3)2C6H3]4] – 、B(C6F5)4 - , BPh4 – 、Al(OC(CF3)3)4 – and carborane anions (e.g. CB 11 H 12 – or (HCB 11 Me5Br6) – ). Exemplary counterions that may be multivalent include CO3 2- 、HPO4 2- PO4 3- 、B4O7 2- 、SO4 2- 、S2O3 2- , carboxylate anions (e.g., tartrate, citrate, fumarate, maleate, malate, malonate, gluconate, succinate, glutarate, adipate, pimelate, suberate, azelaic acid, sebacate, salicylate, phthalate, aspartate, glutamate, etc.) and carborane.

[0169] "Halo" or "halogen" refers to fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), or iodine (iodo, -I).

[0170] Where valence permits, the nitrogen atoms may be substituted or unsubstituted and include primary, secondary, tertiary, and quaternary nitrogen atoms. Exemplary nitrogen atom substituents include hydrogen, -OH, -OR aa 、-N(R cc )2, -CN, -C(=O)R aa、-C(=O)N(R cc )2, -CO2R aa 、-SO2R aa 、-C(=NR bb )R aa 、-C(=NR cc )OR aa 、-C(=NR cc )N(R cc )2、-SO2N(R cc )2, -SO2R cc 、-SO2OR cc 、-SOR aa 、-C(=S)N(R cc )2, -C(=O)SR cc 、-C(=S)SR cc 、-P(=O)(OR cc )2、-P(=O)(R aa )2、-P(=O)(N(R cc )2)2、C 1-10 Alkyl, C 1-10 Perhalogenated alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, hetero C 1-10 Alkyl, hetero C 2-10 Alkenyl, hetero C 2-10 Alkynyl, C 3-10 Carbocyclic group, 3-14 membered heterocyclic group, C 6-14 Aryl and 5-14 membered heteroaryl, or two R groups connected to the N atom cc The groups are combined to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd group, and wherein R aa 、R bb 、R cc and R dd As defined above.

[0171] In certain embodiments, nitrogen atom substituents are independently substituted (eg, with one or more halogens) or unsubstituted C 1-6 Alkyl, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb ) 2, or a nitrogen protecting group. In certain embodiments, the nitrogen atom substituents are independently substituted (e.g., substituted with one or more halogens) or unsubstituted C 1-6 Alkyl, -C(=O)Raa 、-CO2R aa 、-C(=O)N(R bb ) 2, or a nitrogen protecting group, wherein R aa is hydrogen, substituted (e.g., substituted by one or more halogens) or unsubstituted C 1-6 alkyl, or when attached to an oxygen atom, an oxygen protecting group; and each R bb are independently hydrogen, substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 In certain embodiments, the nitrogen atom substituents are independently substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 Alkyl or nitrogen protecting group.

[0172] In certain embodiments, the substituent present on the nitrogen atom is a nitrogen protecting group (also known as an amino protecting group). Nitrogen protecting groups include -OH, -OR aa ,–N(R cc )2, –C(=O)R aa 、–C(=O)N(R cc 2. –CO2R aa ,–SO2R aa 、–C(=NR cc )R aa 、–C(=NR cc )OR aa 、–C(=NR cc )N(R cc )2、–SO2N(R cc )2. –SO2R cc ,–SO2OR cc ,–SOR aa 、–C(=S)N(R cc )2, –C(=O)SR cc , –C(=S)SR cc 、C 1–10 Alkyl (e.g., aralkyl, heteroaralkyl), C 2–10 Alkenyl, C 2–10 Alkynyl, C 3–10 Carbocyclic, 3–14 membered heterocyclic, C 6–14 Aryl and 5-14 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, aralkyl, aryl and heteroaryl is independently replaced by 0, 1, 2, 3, 4 or 5 R dd group, and wherein R aa 、R bb 、R cc and R ddAs defined herein. Nitrogen protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, TW Greene and PGM Wuts, 3rd edition, John Wiley & Sons, 1999, which is incorporated herein by reference.

[0173] Amide nitrogen protecting groups (e.g., -C(=O)R aa ) include formamide, acetamide, chloroacetamide, trichloroacetamide, trifluoroacetamide, phenylacetamide, 3-phenylpropionamide, picolinamide, pyridine-2-carboxamide, N-benzoylphenylalanyl derivatives, benzamide, p-phenylbenzamide, o-nitrophenylacetamide, o-nitrophenoxyacetamide, acetoacetamide, (N'-dithiobenzyloxyacylamino)acetamide, 3-(p-hydroxyphenyl)propionamide, 3-(o-nitrophenyl)propionamide, 2-methyl-2-(o-nitrophenoxy)propionamide, 2-methyl-2-(o-phenylazophenoxy)propionamide, 4-chlorobutanamide, 3-methyl-3-nitrobutanamide, o-nitrocinnamamide, N-acetylmethionine, o-nitrobenzamide, and o-(benzoyloxymethyl)benzamide.

[0174] Carbamate nitrogen protecting groups (e.g., -C(=O)OR aa) include methyl carbamate, ethyl carbamate, 9-fluorenylmethyl carbamate (Fmoc), 9-(2-sulfo)fluorenylmethyl carbamate, 9-(2,7-dibromo)fluorenylmethyl carbamate, 2,7-di-tert-butyl-[9-(10,10-dioxo-10,10,10,10-tetrahydrothioxanthenyl)]methyl carbamate (DBD-Tmoc), 4-methoxyphenacyl carbamate (Phenoc), 2,2,2-trichloroethyl carbamate (Troc), 2-trimethylsilylethyl carbamate (Teoc), 2-phenylethyl carbamate (hZ), 1-(1-adamantyl)-1-methylethyl carbamate (Adpo c), 1,1-dimethyl-2-haloethyl carbamate, 1,1-dimethyl-2,2-dibromoethyl carbamate (DB–t–BOC), 1,1-dimethyl-2,2,2-trichloroethyl carbamate (TCBOC), 1-methyl-1-(4-biphenylyl)ethyl carbamate (Bpoc), 1-(3,5-di-tert-butylphenyl)-1-methylethyl carbamate (t–Bumeoc), 2-(2'- and 4'-pyridyl)ethyl carbamate (Pyoc), 2-(N,N-dicyclohexylcarboxamido)ethyl carbamate, tert-butyl carbamate (BOC), 1-adamantyl carbamate (Adoc), vinyl carbamate (Voc ), allyl carbamate (Alloc), 1-isopropylallyl carbamate (Ipaoc), cinnamyl carbamate (Coc), 4-nitrocinnamyl carbamate (Noc), 8-quinolinyl carbamate, N-hydroxypiperidinyl carbamate, alkyl dithiocarbamates, benzyl carbamate (Cbz), p-methoxybenzyl carbamate (Moz), p-nitrobenzyl carbamate, p-bromobenzyl carbamate, p-chlorobenzyl carbamate, 2,4-dichlorobenzyl carbamate, 4-methylsulfinylbenzyl carbamate (Msz), 9-anthrylmethyl carbamate, diphenylmethyl carbamate, 2-methylthioethyl carbamate, 2-methylsulfonyl carbamate Acylethyl ester, 2-(p-toluenesulfonyl)ethyl carbamate, [2-(1,3-dithianyl)]methyl carbamate (Dmoc), 4-methylthienyl carbamate (Mtpc), 2,4-dimethylthienyl carbamate (Bmpc), 2-phosphoniumethyl carbamate (Peoc), 2-triphenylphosphoniumisopropyl carbamate (Ppoc), 1,1-dimethyl-2-cyanoethyl carbamate, m-chloro-p-acyloxybenzyl carbamate, p-(dihydroxyboryl)benzyl carbamate, 5-benzisoxazolylmethyl carbamate, 2-(trifluoromethyl)-6-chromonylmethyl carbamate (Tcroc), m-nitrophenyl carbamate, 3,5-dimethoxybenzyl ester, o-nitrobenzyl carbamate, 3,4-dimethoxy-6-nitrobenzyl carbamate, phenyl (o-nitrophenyl) methyl carbamate, tert-amyl carbamate, S-benzyl thiocarbamate, p-cyanobenzyl carbamate, cyclobutyl carbamate, cyclohexyl carbamate, cyclopentyl carbamate, cyclopropyl methyl carbamate, p-decyloxybenzyl carbamate, 2,2-dimethoxyacylvinyl carbamate, o-(N,N-dimethylformamido)benzyl carbamate, 1,1-dimethyl-3-(N,N-dimethylformamido)propyl carbamate, 1,1-dimethylpropynyl carbamate, di(2-pyridyl)methyl carbamate, 2-furylmethyl carbamate, 2-iodocarbamate Ethyl ester, isobornyl carbamate, isobutyl carbamate, isonicotinoyl carbamate, p-(p'-methoxyphenylazo)benzyl carbamate, 1-methylcyclobutyl carbamate, 1-methylcyclohexyl carbamate, 1-methyl-1-cyclopropylmethyl carbamate, 1-methyl-1-(3,5-dimethoxyphenyl)ethyl carbamate, 1-methyl-1-(p-phenylazophenyl)ethyl carbamate, 1-methyl-1-phenylethyl carbamate, 1-methyl-1-(4-pyridyl)ethyl carbamate, phenyl carbamate, p-(phenylazo)benzyl carbamate, 2,4,6-tri-tert-butylphenyl carbamate, 4-(trimethylammonium)benzyl carbamate, and 2,4,6-trimethylbenzyl carbamate.

[0175] Sulfonamide nitrogen protecting group (e.g. -S(=O)2R aa ) include p-toluenesulfonamide (Ts), benzenesulfonamide, 2,3,6-trimethyl-4-methoxybenzenesulfonamide (Mtr), 2,4,6-trimethoxybenzenesulfonamide (Mtb), 2,6-dimethyl-4-methoxybenzenesulfonamide (Pme), 2,3,5,6-tetramethyl-4-methoxybenzenesulfonamide (Mte), 4-methoxybenzenesulfonamide (Mbs), 2,4,6-trimethylbenzenesulfonamide (Mts), 2,6-dimethoxy-4-methylbenzenesulfonamide (iMds), 2,2,5,7,8-pentamethylchroman-6-sulfonamide (Pmc), methanesulfonamide (Ms), β-trimethylsilylethanesulfonamide (SES), 9-anthracenesulfonamide, 4-(4',8'-dimethoxynaphthylmethyl)benzenesulfonamide (DNMBS), benzylsulfonamide, trifluoromethylsulfonamide and phenacylmethylsulfonamide.

[0176] Other nitrogen protecting groups include phenothiazinyl-(10)-acyl derivatives, N'-toluenesulfonylaminoacyl derivatives, N'-phenylaminothioacyl derivatives, N-benzoylphenylalanyl derivatives, N-acetylmethionine derivatives, 4,5-diphenyl-3-oxazolin-2-one, N-phthalimide, N-dithiosuccinimide (Dts), N-2,3-diphenylmaleimide, N-2,5-dimethylpyrrole, N-1,1,4,4-tetramethyldisilazide adduct (STABASE), 5-substituted 1,3-dimethyl-1,3,5-triazacyclohexan-2-one, 5-substituted 1,3-dibenzyl-1,3,5-triazacyclohexan-2-one, 1-substituted 3,5-dinitro-4-pyridone, N-methylamine, N-allylamine, N-[2-(trimethylsilyl)ethoxy]methylamine (SEM), N-3-acetoxypropylamine, N-(1-isopropyl-4-nitro-2-oxo-3-pyrrolidin-3-yl)amine, quaternary ammonium salts, N-benzylamine, N-di(4-methoxyphenyl)methylamine, N-5-dibenzosuberylamine, N-triphenylmethylamine (Tr), N-[(4-methoxyphenyl)diphenylmethyl]amine (MMTr), N-9-phenylfluorenylamine (PhF), N-2,7- Dichloro-9-fluorenylmethyleneamine, N-ferrocenylmethylamino (Fcm), N-2-pyridylmethylamino N'-oxide, N-1,1-dimethylthiomethyleneamine, N-benzylideneamine, N-p-methoxybenzylideneamine, N-diphenylmethyleneamine, N-[(2-pyridyl)mesityl]methyleneamine, N-(N',N'-dimethylaminomethylene)amine, N,N'-isopropylidenediamine, N-p-nitrobenzylideneamine, N-salicylideneamine, N-5-chlorosalicylideneamine, N-(5-chloro-2-hydroxyphenyl)phenylmethyleneamine, N-cyclohexyleneamine, N-(5,5-dimethyl-3-oxo-1-cyclohexenyl)amine , N-borane derivatives, N-diphenylboronic acid derivatives, N-[phenyl(pentaacylchromium- or tungsten)acyl]amine, N-copper chelates, N-zinc chelates, N-nitroamines, N-nitrosoamines, amine N-oxides, diphenylphosphinamide (Dpp), dimethylphosphinothioamide (Mpt), diphenylphosphinothioamide (Ppt), dialkylphosphoramidates, dibenzylphosphoramidates, diphenylphosphoramidates, benzenesulfenamide, o-nitrobenzenesulfenamide (Nps), 2,4-dinitrobenzenesulfenamide, pentachlorobenzenesulfenamide, 2-nitro-4-methoxybenzenesulfenamide, triphenylmethylsulfenamide, and 3-nitropyridinesulfenamide (Npys).

[0177] In certain embodiments, the nitrogen protecting group is Bn, Boc, Cbz, Fmoc, trifluoroacetyl, triphenylmethyl, acetyl, or Ts.

[0178] In certain embodiments, oxygen atom substituents are independently substituted (eg, with one or more halogens) or unsubstituted C 1-6 Alkyl, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb ) 2 or oxygen protecting groups. In certain embodiments, the oxygen atom substituents are independently substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 Alkyl, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb )2 or oxygen protecting group, wherein R aa is hydrogen, substituted (e.g., substituted by one or more halogens) or unsubstituted C 1-6 alkyl, or when attached to an oxygen atom, an oxygen protecting group; and each R bb are independently hydrogen, substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 In certain embodiments, the oxygen atom substituents are independently substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 Alkyl or oxygen protecting groups.

[0179] In certain embodiments, the substituent present on the oxygen atom is an oxygen protecting group (also referred to herein as a "hydroxy protecting group"). Oxygen protecting groups include: -R aa 、-N(R bb )2, -C(=O)SR aa 、-C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb )2、-C(=NR bb )R aa 、-C(=NR bb )OR aa 、-C(=NR bb )N(R bb )2、-S(=O)R aa 、-SO2R aa 、-Si(R aa )3、-P(R cc )2、-P(R cc )3 + X - 、-P(OR cc )2、-P(OR cc )3 + X - 、-P(=O)(R aa)2、-P(=O)(OR cc )2 and -P(=O)(N(R bb )2)2, where X - 、R aa 、R bb and R cc As defined herein. Oxygen protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, TW Greene and PGM Wuts, 3rd edition, John Wiley & Sons, 1999, which is incorporated herein by reference.

[0180] Exemplary oxygen protecting groups include methyl, methoxymethyl (MOM), methylthiomethyl (MTM), tert-butylthiomethyl, (phenyldimethylsilyl)methoxymethyl (SMOM), benzyloxymethyl (BOM), p-methoxybenzyloxymethyl (PMBM), (4-methoxyphenoxy)methyl (p-AOM), guaiacolmethyl (GUM), tert-butoxymethyl, 4-pentenyloxymethyl (POM), silyloxymethyl, 2-methoxyethoxymethyl (MEM), 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, 2-(trimethylsilyl)ethoxymethyl (SEMOR), tetrahydropyranyl (THP), 3-bromotetrahydropyranyl (THP), pyranyl, tetrahydrothiopyranyl, 1-methoxycyclohexyl, 4-methoxytetrahydropyranyl (MTHP), 4-methoxytetrahydrothiopyranyl, 4-methoxytetrahydrothiopyranyl S,S-dioxide, 1-[(2-chloro-4-methyl)phenyl]-4-methoxypiperidin-4-yl (CTMP), 1,4-dioxan-2-yl, tetrahydrofuranyl, tetrahydrothiophenyl, 2,3,3a,4,5,6,7,7a-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl, 1-ethoxyethyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, 1-methyl-1-benzyloxyethyl, 1-methyl 1-Benzyloxy-2-fluoroethyl, 2,2,2-trichloroethyl, 2-trimethylsilylethyl, 2-(phenylhydrogenseleno)ethyl, tert-butyl, allyl, p-chlorophenyl, p-methoxyphenyl, 2,4-dinitrophenyl, benzyl (Bn), p-methoxybenzyl, 3,4-dimethoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, p-halobenzyl, 2,6-dichlorobenzyl, p-cyanobenzyl, p-phenylbenzyl, 2-picolyl, 4-picolyl, 3-methyl-2-picolyl N-oxide, diphenylmethyl, p,p'-dinitrodiphenylmethyl, 5-dibenzocycloheptatrienyl, triphenylmethyl, α-naphthyldiphenylmethyl, p-methoxyphenyldiphenylmethyl, di(p-methoxyphenyl) phenylmethyl, tris(p-methoxyphenyl)methyl, 4-(4′-bromobenzoylmethoxyphenyl)diphenylmethyl, 4,4′,4″-tris(4,5-dichlorophthalimidophenyl)methyl, 4,4′,4″-tris(levulinyloxyphenyl)methyl, 4,4′,4″-tris(benzoyloxyphenyl)methyl, 3-(imidazol-1-yl)bis(4′,4″-dimethoxyphenyl)methyl, 1,1-bis(4-methoxyphenyl)-1′-pyrenylmethyl, 9-anthryl, 9-(9-phenyl)xanthenyl, 9-(9-phenyl-10-oxo)anthryl, 1,3-benzodisulfuran-2-yl, benzisothiazolyl S,S-dioxide, trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), dimethylisopropylsilyl (IPDMS), diethylisopropylsilyl (DEIPS), dimethylhexylsilyl, tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), tribenzylsilyl, tri-p-xylylsilyl, triphenylsilyl, diphenylmethylsilyl (DPMS), tert-butylmethoxyphenylsilyl (TBMPS), formate, benzoylformate, acetate, chloroacetate, dichloroacetate, trichloroacetate, trifluoroacetate, methoxyacetate, triphenylmethane oxyacetate, phenoxyacetate, p-chlorophenoxyacetate, 3-phenylpropionate, 4-oxopentanoate (levulinic acid ester), 4,4-(ethylenedithio)pentanoate (levulinic acid dithioacetal), pivalate, adamantate, crotonate, 4-methoxycrotonate, benzoate, p-phenylbenzoate, 2,4,6-trimethylbenzoate (mesitoate), alkyl methyl carbonate, 9-fluorenylmethyl carbonate (Fmoc), alkyl ethyl carbonate, alkyl 2,2,2-trichloroethyl carbonate (Troc), 2-(trimethylsilyl)ethyl carbonate (TMSEC), 2-(phenylsulfonyl)ethyl carbonate (Psec), 2-(triphenylsilyl)ethyl carbonate phosphonium)ethyl carbonate (Peoc), alkyl isobutyl carbonate, alkyl vinyl carbonate, alkyl allyl carbonate, alkyl p-nitrophenyl carbonate, alkyl benzyl carbonate, alkyl p-methoxybenzyl carbonate, alkyl 3,4-dimethoxybenzyl carbonate, alkyl o-nitrobenzyl carbonate, alkyl p-nitrobenzyl carbonate, alkyl S-benzylthiocarbonate, 4-ethoxy-1-naphthyl carbonate, methyl dithiocarbonate, 2-iodobenzoate, 4-azidobutyrate, 4-nitro-4-methylpentanoate, o-(dibromomethyl)benzoate, 2-formylbenzenesulfonate, 2-(methylthiomethoxy)ethyl, 4-(methylthiomethoxy)butyrate, 2-(methylthiomethoxymethyl)benzoate , 2,6-dichloro-4-methylphenoxyacetate, 2,6-dichloro-4-(1,1,3,3-tetramethylbutyl)phenoxyacetate, 2,4-bis(1,1-dimethylpropyl)phenoxyacetate, chlorodiphenylacetate, isobutyrate, monosuccinate, (E)-2-methyl-2-butenoate, o-(methoxyacyl)benzoate, α-naphthoate, nitrate, alkyl N,N,N',N'-tetramethylphosphorodiamidate, alkyl N-phenylcarbamate, borate, dimethylphosphinothioate, alkyl 2,4-dinitrophenylsulfenate, sulfate, methanesulfonate (mesylate), benzylsulfonate and toluenesulfonate (Ts).

[0181] In certain embodiments, the oxygen protecting group is silyl, TBDPS, TBDMS, TIPS, TES, TMS, MOM, THP, t-Bu, Bn, allyl, acetyl, pivaloyl, or benzoyl.

[0182] In certain embodiments, the sulfur atom substituents are independently substituted (eg, with one or more halogens) or unsubstituted C 1-6 Alkyl, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb ) 2, or a sulfur protecting group. In certain embodiments, the sulfur atom substituents are independently substituted (e.g., substituted with one or more halogens) or unsubstituted C 1-6 Alkyl, -C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb ) 2, or a sulfur protecting group, wherein R aa is hydrogen, substituted (e.g., substituted by one or more halogens) or unsubstituted C 1-6 alkyl, or when attached to an oxygen atom, an oxygen protecting group; and each R bb are independently hydrogen, substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 In certain embodiments, the sulfur atom substituents are independently substituted (eg, substituted with one or more halogens) or unsubstituted C 1-6 Alkyl or sulfur protecting group.

[0183] In certain embodiments, the substituent present on the sulfur atom is a sulfur protecting group (also known as a "thiol protecting group"). Sulfur protecting groups include: -R aa 、-N(R bb )2, -C(=O)SR aa 、-C(=O)R aa 、-CO2R aa 、-C(=O)N(R bb )2、-C(=NR bb )R aa 、-C(=NR bb )OR aa 、-C(=NR bb )N(R bb )2、-S(=O)R aa 、-SO2R aa 、-Si(R aa )3、-P(R cc )2、-P(R cc )3 +X - 、-P(OR cc )2、-P(OR cc )3 + X - 、-P(=O)(R aa )2、-P(=O)(OR cc )2 and -P(=O)(N(R bb )2)2, where R aa 、R bb and R cc As defined herein. Sulfur protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, TW Greene and PGM Wuts, 3rd edition, John Wiley & Sons, 1999, which is incorporated herein by reference. In certain embodiments, the sulfur protecting group is acetamidomethyl, t-Bu, 3-nitro-2-pyridinesulfinyl, 2-pyridine-sulfinyl, or triphenylmethyl.

[0184] The "molecular weight" of –R (where –R is any monovalent moiety) is calculated by subtracting the atomic weight of the hydrogen atoms from the molecular weight of the molecule R–H. The "molecular weight" of –L– (where –L– is any divalent moiety) is calculated by subtracting the total atomic weight of the two hydrogen atoms from the molecular weight of the molecule H–L–H.

[0185] In certain embodiments, the molecular weight of the substituent is less than 200, less than 150, less than 100, less than 50 or less than 25g / mol. In certain embodiments, the substituent is composed of carbon, hydrogen, fluorine, chlorine, bromine, iodine, oxygen, sulphur, nitrogen and / or silicon atoms. In certain embodiments, the substituent is composed of carbon, hydrogen, fluorine, chlorine, bromine and / or iodine atoms. In certain embodiments, the substituent is composed of carbon, hydrogen and / or fluorine atoms. In certain embodiments, the substituent does not include one or more, two or more or three or more hydrogen bond donors. In certain embodiments, the substituent does not include one or more, two or more or three or more hydrogen bond acceptors.

[0186] The term "leaving group" has its common meaning in the field of synthetic organic chemistry, and refers to an atom or group that can be substituted by a nucleophilic reagent. Examples of suitable leaving groups include halogen (e.g., F, Cl, Br, or I (iodine)), alkoxycarbonyloxy, aryloxycarbonyloxy, alkanesulfonyloxy, arenesulfonyloxy, alkylcarbonyloxy (e.g., acetoxy), arylcarbonyloxy, aryloxy, methoxy, N, O-dimethylhydroxyamino, 9-phenylxanthenyl (pixyl) and haloformate. In some cases, the leaving group is a sulfonate group, such as toluenesulfonate (tosylate, -OTs), methanesulfonate (mesylate, -OMs), bromophenylsulfonyloxy (bromophenylsulfonate, -OBs), -OS(=O)2(CF2)3CF3 (perfluorobutanesulfonate, -ONf) or trifluoromethanesulfonate (triflate, -OTf). In some cases, the leaving group is bromophenylsulfonate, such as bromophenylsulfonyloxy. In some cases, the leaving group is nitrobenzenesulfonate, such as 2-nitrobenzenesulfonyloxy. In some embodiments, the leaving group is a sulfonate-containing group. In some embodiments, the leaving group is tosylate. The leaving group can also be a phosphine oxide (e.g., formed during the Mitsunobu reaction) or an internal leaving group such as an epoxide or a cyclic sulfate. Other examples of leaving groups are water, ammonia, alcohols, ether moieties, thioether moieties, zinc halides, magnesium moieties, diazonium salts, and copper moieties.

[0187] The term "salt" refers to an ionic compound produced by the neutralization reaction of an acid and a base. A salt is composed of one or more cations (positively charged ions) and one or more anions (negative ions), so that the salt is electrically neutral (no net charge). Salts of the compounds of the present invention include those derived from inorganic and organic acids and inorganic and organic bases. Examples of acid addition salts are salts of amino groups formed with inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, and perchloric acid, or with organic acids such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, or malonic acid, or by using other methods known in the art, such as ion exchange. Other salts include adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate, and the like. Salts derived from appropriate bases include alkali metal salts, alkaline earth metal salts, ammonium salts and N + (C 1-4 Alkyl)4 - Representative alkali metal or alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, and the like. Other salts include salts of ammonium, quaternary ammonium, and amine cations formed using counterions such as halides, hydroxides, carboxylates, sulfates, phosphates, nitrates, lower alkyl sulfonates, and aryl sulfonates.

[0188] "Compounds" include, for example, small molecules and macromolecules. Macromolecules include, for example, polymers, peptides, proteins, carbohydrates, monosaccharides, oligosaccharides, polysaccharides, nucleoproteins, mucins, lipoproteins, synthetic polypeptides or proteins, glycoproteins, steroids, nucleic acids, DNA, RNA, nucleotides, nucleosides, oligonucleotides, antisense oligonucleotides, lipids, hormones, vitamins, and cells.

[0189] The term "small molecule" refers to a molecule with a relatively low molecular weight, whether naturally occurring or artificially produced (e.g., by chemical synthesis). Typically, a small molecule is an organic compound (i.e., it contains carbon). A small molecule may comprise multiple carbon-carbon bonds, stereocenters, and other functional groups (e.g., amines, hydroxyls, carbonyls, and heterocycles). In certain embodiments, the molecular weight of a small molecule is no more than 2,000 g / mol. In certain embodiments, the molecular weight of a small molecule is no more than 1,500 g / mol. In certain embodiments, the molecular weight of a small molecule is no more than 1,000 g / mol, no more than 900 g / mol, no more than 800 g / mol, no more than 700 g / mol, no more than 600 g / mol, no more than 500 g / mol, no more than 400 g / mol, no more than 300 g / mol, no more than 200 g / mol, or no more than 100 g / mol. In certain embodiments, the molecular weight of the small molecule is at least 100 g / mol, at least 200 g / mol, at least 300 g / mol, at least 400 g / mol, at least 500 g / mol, at least 600 g / mol, at least 700 g / mol, at least 800 g / mol, or at least 900 g / mol, or at least 1,000 g / mol. Combinations of the above ranges (e.g., at least 200 g / mol and no more than 500 g / mol) are also possible. In certain embodiments, the small molecule is a therapeutically active agent, such as a drug (e.g., a molecule approved by the U.S. Food and Drug Administration under the provisions of the Code of Federal Regulations (CFR)). The small molecule can also be complexed with one or more metal atoms and / or metal ions. In this case, the small molecule is also referred to as an "organometallic small molecule." Preferred small molecules are biologically active because they produce biological effects in animals (preferably mammals, more preferably humans). Small molecules include radionuclides and imaging agents. In certain embodiments, the small molecule is a drug. Preferably, but not necessarily, the drug has been identified by a relevant government agency or regulatory agency as safe and effective for use in humans or animals. For example, the FDA lists drugs approved for human use at 21 CFR §§ 330.5, 331 to 361, and 440 to 460, which are incorporated herein by reference; the FDA lists veterinary drugs at 21 CFR §§ 500 to 589, which are incorporated herein by reference. All listed drugs are considered acceptable for use according to the present invention.

[0190] The term "polymer" refers to a compound comprising eleven or more covalently linked repeating units. In certain embodiments, the polymer is naturally occurring. In certain embodiments, the polymer is synthetic (e.g., not naturally occurring). In certain embodiments, the polymer has a molecular weight of WIn certain embodiments, the M of the polymer is 1,000 to 2,000 g / mol, 2,000 to 10,000 g / mol, 10,000 to 30,000 g / mol, 30,000 to 100,000 g / mol, 100,000 to 300,000 g / mol, 300,000 to 1,000,000 g / mol (inclusive). W Between 2,000 and 1,000,000 g / mol (inclusive).

[0191] The term "average molecular weight" may encompass the number average molecular weight (M n ), weight average molecular weight (M w ), higher average molecular weight (M z or M z +1), average molecular weight (M) determined by GPC / SEC (gel permeation chromatography / size exclusion chromatography) p ) and viscosity average molecular weight (M v The average molecular weight may also refer to the average molecular weight determined by gel permeation chromatography. The average molecular weight may also refer to the average molecular weight determined by gel permeation chromatography.

[0192] The term "degree of polymerization" (DP) refers to the number of repeating units in a polymer. In certain embodiments, DP is determined by chromatography (e.g., gel permeation chromatography). For homopolymers, DP refers to the number of repeating units contained in the homopolymer. For a copolymer of two types of monomers (e.g., a first monomer and a second monomer), wherein the molar ratio of the two types of monomers is about 1:1, DP refers to the number of repeating units of either of the two types of monomers contained in the copolymer. For a copolymer of two types of monomers (e.g., a first monomer and a second monomer), wherein the molar ratio of the two types of monomers is not about 1:1, two DPs can be used. The first DP refers to the number of repeating units of the first monomer contained in the copolymer, and the second DP refers to the number of repeating units of the second monomer contained in the copolymer. Unless otherwise indicated, a DP of "xx" (wherein xx is an integer) refers to the number of repeating units of either of the two types of monomers in a copolymer of two types of monomers (e.g., a first monomer and a second monomer), wherein the molar ratio of the two types of monomers is about 1:1. Unless otherwise indicated, a DP of "xx-yy" (wherein xx and yy are integers) refers to a copolymer of two types of monomers (e.g., a first monomer and a second monomer) wherein xx is the number of repeating units of the first monomer and yy is the number of repeating units of the second monomer, wherein the molar ratio of the two types of monomers is not about 1:1.

[0193] The term "ring-opening metathesis polymerization (ROMP)" refers to an olefin metathesis chain growth polymerization driven by the relief of ring strain in a cyclic olefin (eg, norbornene or cyclopentene). The catalysts used in the ROMP reaction ("metathesis catalysts") include RuCl3 / alcohol mixtures, bis(cyclopentadienyl)dimethyl zirconium(IV), [1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II) dichloride, [1,3-bis(2-methylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II) dichloride, [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][3-(2-pyridyl)propylidene]ruthenium(II) dichloride, (3-methyl-2-butenylidene)bis(tricyclopentylphosphine)ruthenium(II) dichloride, [1,3-bis(2-methylphenyl)-2-imidazolidinylidene](2-isopropyloxyphenylmethylene)ruthenium(II) dichloride (Grubbs C571), (benzylidene)bis(tricyclohexylphosphine)dichlororuthenium(II) (Grubbs I), [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)dichlororuthenium(II) (Grubbs II), and [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)bis(3-bromopyridinium)dichlororuthenium(II) (Grubbs III).

[0194] The term "v / v" refers to a volume ratio and is used herein to refer to the concentration of monomers. Unless otherwise specified, the percentage concentration of a second monomer in a first monomer is expressed as v / v. For example, a mixture of a first monomer and 10% of a second monomer refers to a mixture of the first monomer and the second monomer, wherein the volume of the second monomer is 10% of the total volume of the first and second monomers.

[0195] It is not intended that the present invention be limited in any manner by the foregoing list of exemplary substituents.Additional terms may be defined in other sections of this disclosure. DETAILED DESCRIPTION

[0196] Many common polymers, particularly vinyl polymers such as polystyrene, are inherently difficult to chemically recycle and are persistent to the environment. The introduction of low levels of cleavable comonomer additives into existing vinyl polymerization processes could facilitate the production of chemically deconstructible and recyclable variants with otherwise equivalent properties without requiring new monomer feedstocks that significantly increase the cost or change the manufacturing process. Disclosed herein are cleavable comonomer additives that allow the chemical deconstruction and recycling of polystyrene, one of the most common commodity polymers. Deconstructible PS of varying molar masses with varying amounts of randomly associated thioester backbone linkages can be selectively depolymerized to produce well-defined thiol-terminated fragments that are amenable to oxidative repolymerization to produce recycled polystyrene of nearly identical molar mass to the parent material in excellent yields. The thermomechanical properties of the deconstructible polystyrene and its recycled products are very similar to those of virgin polystyrene.

[0197] Polymer and preparation method, composition and kit thereof

[0198] In certain aspects, the present disclosure relates to copolymers comprising:

[0199] Examples of m1 first repeating units of formula i:

[0200]

[0201] Examples of m2 second repeating units of formula ii-A or ii-B:

[0202]

[0203] optionally one or more types of additional repeating units;

[0204] in:

[0205] The copolymer is substantially free of crosslinks;

[0206] m1 is an integer between 10 and 1,000,000 (inclusive);

[0207] m2 is an integer between 2 and 1,000,000 (inclusive);

[0208] R 1 、R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl;

[0209] Ring A is an aryl group;

[0210] R 4Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a ,–SCN,–SR a 、–SSR a 、–N3、–NO、–N(R a )2、–NO2、–C(=O)R a 、–C(=O)OR a 、–C(=O)SR a 、–C(=O)N(R a )2、–C(=NR a )R a 、–C(=NR a )OR a 、–C(=NR a )SR a 、–C(=NR a )N(R a )2, –S(=O)R a 、–S(=O)OR a 、–S(=O)SR a 、–S(=O)N(R a )2, –S(=O)2R a 、–S(=O)2OR a 、–S(=O)2SR a 、–S(=O)2N(R a )2, –OC(=O)R a 、–OC(=O)OR a 、–OC(=O)SR a 、–OC(=O)N(R a )2、–OC(=NR a )R a 、–OC(=NR a )OR a 、–OC(=NR a )SR a 、–OC(=NR a )N(R a )2. –OS(=O)R a 、–OS(=O)OR a 、–OS(=O)SR a 、–OS(=O)N(R a )2, –OS(=O)2R a 、–OS(=O)2OR a 、–OS(=O)2SR a 、–OS(=O)2N(Ra )2、–ON(R a )2、–SC(=O)R a 、–SC(=O)OR a 、–SC(=O)SR a 、–SC(=O)N(R a )2、–SC(=NR a )R a 、–SC(=NR a )OR a 、–SC(=NR a )SR a 、–SC(=NR a )N(R a )2、–NR a C(=O)R a 、–NR a C(=O)OR a 、–NR a C(=O)SR a 、–NR a C(=O)N(R a )2、–NR a C(=NR a )R a 、–NR a C(=NR a )OR a 、–NR a C(=NR a )SR a 、–NR a C(=NR a )N(R a )2、–NR a S(=O)R a 、–NR a S(=O)OR a 、–NR a S(=O)SR a 、–NR a S(=O)N(R a )2、–NR a S(=O)2R a 、–NR a S(=O)2OR a 、–NR a S(=O)2SR a 、–NR a S(=O)2N(R a )2、–Si(R a )3、–Si(R a )2OR a 、–Si(Ra )(OR a )2、–Si(OR a )3. –OSi(R a )3. –OSi(R a )2OR a 、–OSi(R a )(OR a )2OR–OSi(OR a )3;

[0211] R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0212] n1 is 0, 1, 2, 3, 4 or 5, as long as the valence allows;

[0213] R 7 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2, –OC(=O)Rb 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NRb C(=NR b )N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b ,–NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0214] is alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene;

[0215] n2 is an integer between 0 and 14 (including the endpoint values), as long as the valence allows

[0216] Each Examples of are independently a single bond or a double bond;

[0217] R 8 Each instance of is independently:

[0218] When attached to a carbon atom: halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, –CN, –OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2.

[0219] –NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、

[0220] –C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2、–S(=O)R b 、

[0221] –S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2、–S(=O)2R b 、–S(=O)2OR b 、

[0222] –S(=O)2SR b 、–S(=O)2N(R b )2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、

[0223] –OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、

[0224] –OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、

[0225] –OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SRb 、

[0226] –OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、

[0227] –SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、

[0228] –SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、

[0229] –NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、

[0230] –NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、

[0231] –NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b,–NR b S(=O)2OR b 、

[0232] –NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、

[0233] –Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2.

[0234] –OSi(OR b )3, =O, =S or =NR b ;

[0235] When attached to a nitrogen atom: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, –OR b ,–N(R b )2.

[0236] –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、

[0237] –C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、

[0238] –S(=O)SRb 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、

[0239] –S(=O)2N(R b )2, or a nitrogen protecting group; or

[0240] When attached to a sulfur atom: =O;

[0241] and / or: R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and / or R 8 Two examples of together with their middle atom form a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and

[0242] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0243] The conditions are:

[0244] R 1 、R 2 、R 3 、R 4 , Ring A, R 7 and R 8 None contain one or more non-aromatic unsaturated CC bonds;

[0245] any additional monomer does not contain two or more non-aromatic unsaturated CC bonds;

[0246] The second repeat unit does not have the formula: and

[0247] If the first repeating unit has the following formula: Then the second repeat unit does not have the formula:

[0248] In certain embodiments, the copolymers described herein are prepared by a process comprising polymerizing a first monomer, a second monomer, and optionally one or more types of additional monomers, wherein:

[0249] The first monomer has formula I:

[0250]

[0251] or a tautomer or salt thereof; and

[0252] The second monomer has formula II-A or II-B:

[0253]

[0254] or a tautomer or salt thereof, wherein is ring B, and ring B is a heterocycle;

[0255] The conditions are:

[0256] Ring B does not contain one or more non-aromatic unsaturated CC bonds;

[0257] The second monomer does not have the formula:

[0258]

[0259] or a tautomer thereof; and

[0260] If the first monomer is unsubstituted styrene, then the second monomer does not have the formula:

[0261]

[0262] or a tautomer thereof.In certain embodiments, the copolymer is prepared by polymerizing the first monomer, the second monomer, and optionally one or more types of the additional monomer.

[0263] In another aspect, the present disclosure provides a method of preparing a copolymer, comprising polymerizing the first monomer, the second monomer, and optionally one or more types of the additional monomers.

[0264] The copolymers described herein comprise m1 examples of first repeating units of formula i: In certain embodiments, formula (i) comprises a substituent R 1 、R 2 and R 3 In certain embodiments, R 1 、R 2 and R 3 Each is independently hydrogen, halogen, or substituted or unsubstituted alkyl.

[0265] In certain embodiments, formula (i) contains a substituent R 4 In certain embodiments, R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a ,–SCN,–SR a 、–SSR a 、–N3、–NO、–N(R a )2、–NO2、–C(=O)R a 、–C(=O)OR a 、–C(=O)SR a 、–C(=O)N(R a )2、–C(=NR a )R a 、–C(=NR a )OR a 、–C(=NR a )SR a 、–C(=NR a )N(R a )2, –S(=O)R a 、–S(=O)OR a 、–S(=O)SR a 、–S(=O)N(R a )2, –S(=O)2R a 、–S(=O)2OR a 、–S(=O)2SR a 、–S(=O)2N(R a )2, –OC(=O)R a 、–OC(=O)OR a 、–OC(=O)SR a 、–OC(=O)N(R a )2、–OC(=NR a )R a 、–OC(=NR a )OR a 、–OC(=NR a )SR a 、–OC(=NR a )N(R a )2. –OS(=O)R a 、–OS(=O)OR a 、–OS(=O)SR a 、–OS(=O)N(R a )2, –OS(=O)2Ra 、–OS(=O)2OR a 、–OS(=O)2SR a 、–OS(=O)2N(R a )2、–ON(R a )2、–SC(=O)R a 、–SC(=O)OR a 、–SC(=O)SR a 、–SC(=O)N(R a )2、–SC(=NR a )R a 、–SC(=NR a )OR a 、–SC(=NR a )SR a 、–SC(=NR a )N(R a )2、–NR a C(=O)R a 、–NR a C(=O)OR a 、–NR a C(=O)SR a 、–NR a C(=O)N(R a )2、–NR a C(=NR a )R a 、–NR a C(=NR a )OR a 、–NR a C(=NR a )SR a 、–NR a C(=NR a )N(R a )2、–NR a S(=O)R a 、–NR a S(=O)OR a 、–NR a S(=O)SR a 、–NR a S(=O)N(R a )2、–NR a S(=O)2R a 、–NR a S(=O)2OR a 、–NR a S(=O)2SR a 、–NR a S(=O)2N(Ra )2、–Si(R a )3, –Si(R a )2OR a 、–Si(R a )(OR a )2、–Si(OR a )3. –OSi(R a )3. –OSi(R a )2OR a 、–OSi(R a )(OR a )2OR–OSi(OR a )3;

[0266] R a Each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom.

[0267] In certain embodiments, R 4 At least one example of is halogen (eg, F). In certain embodiments, R 4 At least one example is a substituted or unsubstituted alkyl group (e.g., an unsubstituted C 1-6 alkyl, e.g., Me).

[0268] In certain embodiments, Ring A is aryl. In certain embodiments, Ring A is phenyl.

[0269] In certain embodiments, n1 is 0. In certain embodiments, n1 is 1.

[0270] In another aspect, the present disclosure describes a copolymer comprising:

[0271] Examples of m1 first repeating units of formula i':

[0272]

[0273] Examples of m2 second repeating units of formula ii-A or ii-B:

[0274]

[0275] m3' examples of cross-linking groups, wherein the cross-linking group is a multivalent group of a small molecule, wherein the multivalent group is at least tetravalent; and

[0276] optionally one or more types of additional repeating units;

[0277] in:

[0278] The copolymer is substantially cross-linked;

[0279] m1 is an integer between 10 and 1,000,000 (inclusive);

[0280] m2 is an integer between 2 and 1,000,000 (inclusive);

[0281] R 1 、R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl;

[0282] R 4 ' is halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a ,–SCN,–SR a 、–SSR a 、–N3、–NO、–N(R a )2、–NO2、–C(=O)R a 、–C(=O)OR a 、–C(=O)SR a 、–C(=O)N(R a )2、–C(=NR a )R a 、–C(=NR a )OR a 、–C(=NR a )SR a 、–C(=NR a )N(R a )2, –S(=O)R a 、–S(=O)OR a 、–S(=O)SR a 、–S(=O)N(R a )2, –S(=O)2R a 、–S(=O)2OR a 、–S(=O)2SR a 、–S(=O)2N(R a )2, –OC(=O)R a 、–OC(=O)OR a 、–OC(=O)SR a 、–OC(=O)N(R a )2、–OC(=NR a )R a 、–OC(=NR a)OR a 、–OC(=NR a )SR a 、–OC(=NR a )N(R a )2、–OS(=O)R a 、–OS(=O)OR a 、–OS(=O)SR a 、–OS(=O)N(R a )2、–OS(=O)2R a 、–OS(=O)2OR a 、–OS(=O)2SR a 、–OS(=O)2N(R a )2、–ON(R a )2、–SC(=O)R a 、–SC(=O)OR a 、–SC(=O)SR a 、–SC(=O)N(R a )2、–SC(=NR a )R a 、–SC(=NR a )OR a 、–SC(=NR a )SR a 、–SC(=NR a )N(R a )2、–NR a C(=O)R a 、–NR a C(=O)OR a 、–NR a C(=O)SR a 、–NR a C(=O)N(R a )2、–NR a C(=NR a )R a 、–NR a C(=NR a )OR a 、–NR a C(=NR a )SR a 、–NR a C(=NR a )N(R a )2、–NR a S(=O)R a 、–NR a S(=O)OR a 、–NR aS(=O)SR a ,–NR a S(=O)N(R a )2. –NR a S(=O)2R a ,–NR a S(=O)2OR a ,–NR a S(=O)2SR a ,–NR a S(=O)2N(R a )2、–Si(R a )3, –Si(R a )2OR a 、–Si(R a )(OR a )2、–Si(OR a )3. –OSi(R a )3. –OSi(R a )2OR a 、–OSi(R a )(OR a )2OR–OSi(OR a )3;

[0283] R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0284] R 7 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b、–C(=NR b )N(R b )2、–S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2、–S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NRb C(=O)SR b ,–NR b C(=O)N(R b )2. –NR b C(=NR b )R b ,–NR b C(=NR b )OR b ,–NR b C(=NR b )SR b ,–NR b C(=NR b )N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b ,–NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0285] is alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene;

[0286] n2 is an integer between 0 and 14 (inclusive), as long as the valence permits;

[0287] Each Examples of are independently a single bond or a double bond;

[0288] R 8 Each instance of is independently:

[0289] When attached to a carbon atom: halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, –CN, –OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2.

[0290] –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2.

[0291] –C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、

[0292] –S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、

[0293] –S(=O)2SR b 、–S(=O)2N(R b )2, –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、

[0294] –OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、

[0295] –OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、

[0296] –OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、

[0297] –OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、

[0298] –SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、

[0299] –SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、

[0300] –NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、

[0301] –NR b C(=NR b )SR b 、–NR b C(=NR b)N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b 、

[0302] –NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b 、

[0303] –NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、

[0304] –Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2.

[0305] –OSi(OR b )3, =O, =S or =NR b ;

[0306] When attached to a nitrogen atom: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, –OR b ,–N(R b )2.

[0307] –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b)R b 、

[0308] –C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、

[0309] –S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、

[0310] –S(=O)2N(R b )2, or a nitrogen protecting group; or

[0311] When attached to a sulfur atom: =O;

[0312] and / or: R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and / or R 8 Two examples of together with their middle atom form a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and

[0313] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0314] Provided that if the first repeat unit has the formula: And the cross-linking group has the following formula: Then the second repeat unit does not have the formula:

[0315] In certain embodiments, the copolymer is prepared by a process of polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more of the additional monomers, wherein:

[0316] The first monomer has formula I':

[0317]

[0318] or a tautomer or salt thereof;

[0319] The second monomer has formula II-A or II-B:

[0320]

[0321] or a tautomer or salt thereof, wherein is Ring B, and Ring B is a heterocycle; and

[0322] The third monomer is a small molecule containing two or more non-aromatic unsaturated C—C bonds;

[0323] with the proviso that if the first monomer is unsubstituted styrene and the third monomer is unsubstituted 1,4-divinylbenzene, then the second monomer does not have the formula: or a tautomer thereof.

[0324] In certain embodiments, the method includes polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more types of the additional monomers.

[0325] The copolymers described herein comprise m1 examples of first repeating units of formula i': In certain embodiments, the repeating unit of formula (i') contains a substituent R 1 、R 2 or R 3 In certain embodiments, R 1 、R 2 and R 3 Each is independently hydrogen, halogen, or substituted or unsubstituted alkyl.

[0326] In certain embodiments, R 4 ' is halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a 、-SCN、-SR a 、-SSR a 、-N3、-NO、-N(R a )2、-NO2、-C(=O)R a 、-C(=O)ORa 、-C(=O)SR a 、-C(=O)N(R a )2、-C(=NR a )R a 、-C(=NR a )OR a 、-C(=NR a )SR a 、-C(=NR a )N(R a )2、-S(=O)R a 、-S(=O)OR a 、-S(=O)SR a 、-S(=O)N(R a )2、-S(=O)2R a 、-S(=O)2OR a 、-S(=O)2SR a 、-S(=O)2N(R a )2、-OC(=O)R a 、-OC(=O)OR a 、-OC(=O)SR a 、-OC(=O)N(R a )2、-OC(=NR a )R a 、-OC(=NR a )OR a 、-OC(=NR a )SR a 、-OC(=NR a )N(R a )2、-OS(=O)R a 、-OS(=O)OR a 、-OS(=O)SR a 、-OS(=O)N(R a )2、-OS(=O)2R a 、-OS(=O)2OR a 、-OS(=O)2SR a 、-OS(=O)2N(R a )2、-ON(R a )2、-SC(=O)R a 、-SC(=O)OR a 、-SC(=O)SR a 、-SC(=O)N(R a )2、-SC(=NR a )R a 、-SC(=NR a )ORa , -SC(=NR a )SR a , -SC(=NR a )N(R a )2, -NR a C(=O)R a , -NR a C(=O)OR a , -NR a C(=O)SR a , -NR a C(=O)N(R a )2, -NR a C(=NR a )R a , -NR a C(=NR a )OR a , -NR a C(=NR a )SR a , -NR a C(=NR a )N(R a )2, -NR a S(=O)R a , -NR a S(=O)OR a , -NR a S(=O)SR a , -NR a S(=O)N(R a )2, -NR a S(=O)2R a , -NR a S(=O)2OR a , -NR a S(=O)2SR a , -NR a S(=O)2N(R a )2, -Si(R a )3, -Si(R a )2OR a , -Si(R a )(OR a )2, -Si(OR a )3, -OSi(R a )3, -OSi(R a )2OR a , -OSi(R a )(OR a )2 or -OSi(OR a )3;

[0327] R a Each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom. In certain embodiments, R 4 ' is -C(=O)OR a In certain embodiments, R 4 ' is -C(=O)N(R a )2, provided that at least one R a In certain embodiments, at least one R a is a substituted or unsubstituted alkyl group. In certain embodiments, at least one R a is a substituted or unsubstituted alkyl group.

[0328] In certain embodiments, R 4 ' is a substituted or unsubstituted phenyl group. In certain embodiments, R 4 ' is unsubstituted phenyl. In certain embodiments, R 4 ' is halogen (e.g., F). In certain embodiments, R 4 ' is a substituted or unsubstituted alkyl group (e.g., an unsubstituted C 1-6 alkyl, e.g., Me).

[0329] In certain embodiments, R 1 、R 2 、R 3 、R 4 '、R 7 、R 8 Neither Ring B nor Ring B contains one or more non-aromatic unsaturated CC bonds.

[0330] In certain embodiments, Formula I' has the following formula;

[0331]

[0332] In certain embodiments, the first repeating unit has the formula:

[0333] or

[0334] The first monomer is unsubstituted styrene.

[0335] The copolymers described herein comprise m2 examples of the second repeating unit of formula ii-A or ii-B:

[0336]

[0337] In certain embodiments, is an alkylene group, preferably, C 2-5 In certain embodiments, In certain embodiments, In certain embodiments, In certain embodiments, In certain embodiments, In certain embodiments, In certain embodiments, In certain embodiments, In certain embodiments, is a heteroalkylene group wherein the backbone atoms are 1, 2, 3, 4, 5, 6, or 7 carbon atoms and 1 or 2 oxygen atoms.

[0338] In certain embodiments, Ring B is a monocyclic heterocycle. In certain embodiments, Ring B has the formula

[0339] In certain embodiments, R 7 Each instance of is hydrogen. In certain embodiments, R 7 At least one example of is hydrogen. In certain embodiments, R 7 At least one example of is halogen (eg, F). In certain embodiments, R 7 At least one example is a substituted or unsubstituted alkyl group (e.g., an unsubstituted C 1-6 alkyl, e.g., Me).

[0340] In certain embodiments, n2 is 0. In certain embodiments, n2 is 1. In certain embodiments, n2 is 2.

[0341] In certain embodiments, R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and / or R 8 Two examples of and their middle atom together form a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. In certain embodiments, R 9 or R 7 An example and R 8An example of R is formed together with its middle atom to form a substituted or unsubstituted phenyl group, and / or R 8 The two examples of are taken together with their middle atoms to form a substituted or unsubstituted phenyl group.

[0342] In certain embodiments, the second repeat unit has the formula:

[0343]

[0344] or

[0345] The second monomer has the formula:

[0346]

[0347] or a tautomer or salt thereof;

[0348] in:

[0349] R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2、-NO2、-C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2、-C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b、-OC(=O)SR b 、-OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2、-OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(Rb )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b 、-Si(R b )(OR b )2、-Si(OR b )3、-OSi(R b )3、-OSi(R b )2OR b 、-OSi(R b )(OR b )2OR-OSi(OR b )3;

[0350] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and

[0351] n3 is 0, 1, 2, 3, or 4;

[0352] The condition is R 10 In certain embodiments, the second repeating unit has the following formula: Or the second monomer has the formula: or a tautomer or salt thereof; wherein:

[0353] R 10Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2、-NO2、-C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2、-C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2, -OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(Rb )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b 、–Si(Rb )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0354] R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2, –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b)2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0355] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and

[0356] n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; provided that R 10 and R 11 In certain embodiments, the second repeating unit has the following formula:

[0357]

[0358] or

[0359] The second monomer has the formula:

[0360]

[0361] or a tautomer or a salt thereof.

[0362] In certain embodiments, X 1 For S.

[0363] In certain embodiments, wherein n3 is 1. In certain embodiments, wherein n3 is 2.

[0364] In certain embodiments, wherein n4 is 1. In certain embodiments, wherein n4 is 2.

[0365] In certain embodiments, R 10 or R 11 In certain embodiments, at least one example of R is substituted or unsubstituted alkyl, -O(substituted or unsubstituted alkyl), or -S(substituted or unsubstituted alkyl). 10 or R 11 At least one example is substituted or unsubstituted C 2-6 Alkyl, -O (substituted or unsubstituted C 2-6 Alkyl) or -S (substituted or unsubstituted C 2-6 In certain embodiments, R 10 or R 11 At least one example is substituted or unsubstituted C 2-6 Alkyl, -O (substituted or unsubstituted C 1-6 Alkyl) or -S (substituted or unsubstituted C 1-6 In certain embodiments, R 10 or R 11 At least one example of is halogen, preferably fluorine. In certain embodiments, R 10 or R 11 At least one instance of which is unsubstituted C 2-6 Alkyl, -O(unsubstituted C 1-6 Alkyl) or -S(unsubstituted C 1-6 In certain embodiments, R 10 or R 11 At least one instance of -OR b In certain embodiments, R 10 or R 11 At least one example of is -O(substituted or unsubstituted alkyl). In certain embodiments, R 10 or R 11 At least one example of -O(unsubstituted C 1-6 In certain embodiments, R 10 or R 11 At least one instance of -SR b In certain embodiments, R 10 or R 11 At least one example of is -S(substituted or unsubstituted alkyl). In certain embodiments, R 10 or R 11At least one example is -S (unsubstituted C 1-6 In certain embodiments, R 10 or R 11 At least one example is -S (unsubstituted C 3-6 alkyl).

[0366] In certain embodiments, the second repeat unit has the formula:

[0367]

[0368] or

[0369] The second monomer has the formula:

[0370]

[0371] or a tautomer or salt thereof. In certain embodiments, the second repeating unit has the formula: Or the second monomer has the formula: In certain embodiments, the second monomer has the formula:

[0372]

[0373] or a tautomer or a salt thereof.

[0374] In certain embodiments, the second repeat unit does not have the formula:

[0375] or

[0376] The second monomer does not have the formula:

[0377]

[0378] In certain embodiments, the second repeat unit does not have the formula:

[0379] or

[0380] The second monomer does not have the formula:

[0381]

[0382] or a tautomer thereof.

[0383] In certain embodiments, the second repeat unit does not have the formula:

[0384] or

[0385] The second monomer does not have the formula:

[0386]

[0387] or a tautomer thereof.

[0388] In certain embodiments, the cross-linking group is a multivalent group of a small molecule. In certain embodiments, the multivalent group is at least tetravalent. In certain embodiments, the cross-linking group or the third monomer does not contain -C(=O)O- or -OC(=O)- in the main chain. In certain embodiments, the cross-linking group or the third monomer only contains carbon atoms in the main chain. In certain embodiments, the third monomer includes (non-aromatic C=C or non-aromatic C≡C)-L 1 '-(non-aromatic C=C or non-aromatic C≡C), where L 1 ' is substituted or unsubstituted C 1-1000 Alkylene, substituted or unsubstituted C 2-1000 Alkenylene, substituted or unsubstituted C 2-1000 Alkynylidene, substituted or unsubstituted C 1-1000 Heteroalkylene, substituted or unsubstituted C 2-1000 Heteroalkenylene, substituted or unsubstituted C 2-1000 Heteroalkynylene, optionally wherein the C 1-1000 Alkylene, C 2-1000 Alkenylene, C 2-1000 Alkynylidene, C 1-1000 Heteroalkylene, C 2-1000 Heteroalkenylene, or C 2-1000 One or more backbone carbon atoms of the heteroalkynylene group are optionally replaced by a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group. In certain embodiments, the crosslinking group has the formula:

[0389] or

[0390] The third monomer has the formula:

[0391] or a tautomer or salt thereof, wherein R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each is independently hydrogen, halogen, or substituted or unsubstituted alkyl. In certain embodiments, R 12 、R 13 、R 14 、R 15 、R 16 and R17 Each is hydrogen.

[0392] In certain embodiments, L 1 ' is substituted or unsubstituted C 1-1000 Heteroalkylene, optionally wherein the C 1-1000 One or more backbone carbon atoms of the heteroalkylene group are replaced by a substituted or unsubstituted arylene group. 1 ' is substituted or unsubstituted C 10-100 Heteroalkylene, optionally wherein one or more (e.g., 2 or 3) C 10-100 The backbone carbon atoms of the heteroalkylene group are independently replaced by substituted or unsubstituted arylene groups. 1 ' is substituted or unsubstituted C 10-50 Heteroalkylene, optionally wherein one or more (e.g., 2 or 3) C 10-50 The backbone carbon atoms of the heteroalkylene are independently replaced by substituted or unsubstituted phenylene. In certain embodiments, the backbone heteroatom of the heteroalkylene is oxygen. In certain embodiments, the optional substituents of the heteroalkylene are halogen (e.g., F), substituted or unsubstituted alkyl (e.g., unsubstituted C 1-6 Alkyl, for example, Me) or -O(substituted or unsubstituted alkyl) (for example, -O(unsubstituted C 1-6 In certain embodiments, L 1 'Has the following formula:

[0393]

[0394] wherein each instance of n is independently 1, 2, 3, 4, or 5. In certain embodiments, the crosslinking group has the formula:

[0395] or

[0396] The third monomer has the formula:

[0397]

[0398] or a salt thereof, wherein each instance of n is independently 1, 2, 3, 4, or 5. In certain embodiments, L 1 ' is a substituted or unsubstituted arylene group. In certain embodiments, L 1 ' is an unsubstituted 1,4-phenylene group.

[0399] In certain embodiments, the molar ratio of the first repeating unit to the cross-linking group or the molar ratio of the first monomer to the third monomer is between 2:1 and 10:1, between 10:1 and 30:1, or between 30:1 and 100:1 (including endpoints).

[0400] In certain embodiments, the degree of crosslinking is between 0.1% and 0.3%, between 0.3% and 1%, between 1% and 3%, between 3% and 10%, between 10% and 20%, or between 20% and 50%, inclusive, on a mol:mol basis. In certain embodiments, the degree of crosslinking is between 1% and 10%, inclusive, on a mol:mol basis.

[0401] In certain embodiments, the additional repeating units or additional monomers, if present, do not comprise —C(═O)O— or —OC(═O)— in the backbone. In certain embodiments, the additional repeating units or additional monomers, if present, comprise only carbon atoms in the backbone.

[0402] In certain embodiments, the polymerization step further comprises a free radical initiator. In certain embodiments, the free radical initiator is a halogen (e.g., Cl 2 ), an azo compound, an organic peroxide, or an inorganic peroxide. In certain embodiments, the free radical initiator is azobisisobutyronitrile.

[0403] In certain embodiments, the polymerization step further comprises a solvent. In certain embodiments, the polymerization step is substantially free of (e.g., by weight, between 90% and 95%, between 95% and 97%, between 97% and 99% or between 99% and 99.9%, including endpoint values, substantially free of) solvent. In certain embodiments, the solvent is substantially a single solvent. In certain embodiments, the solvent is a mixture of two or more (e.g., three) solvents (e.g., the solvent described in this paragraph). In certain embodiments, the solvent is an organic solvent. In certain embodiments, the solvent is an aprotic solvent. In certain embodiments, the solvent is an ether solvent. In certain embodiments, the solvent is a ketone solvent. In certain embodiments, the solvent is an alkane solvent. In certain embodiments, the solvent is an alcohol solvent. In certain embodiments, the solvent is an aromatic organic solvent. In certain embodiments, the solvent is benzene, toluene, o-xylene, m-xylene or p-xylene, or a mixture thereof. In certain embodiments, the solvent is a non-aromatic organic solvent. In certain embodiments, the solvent is acetonitrile, dioxane or tetrahydrofuran, or a mixture thereof. In certain embodiments, the solvent is acetonitrile. In certain embodiments, the first solvent is acetone, chloroform, dichloromethane, ether, ethyl acetate, methyl tert-butyl ether or 2-methyltetrahydrofuran, or a mixture thereof. In certain embodiments, the solvent is an inorganic solvent. In certain embodiments, the boiling point of the solvent at about 1 atm is between 30 and 50° C., between 50 and 70° C., between 70 and 100° C., between 100 and 130° C., between 130 and 160° C., or between 160 and 200° C. (inclusive of the endpoint values).

[0404] In certain embodiments, the temperature of the polymerization step is between 25 and 150° C., between 50 and 150° C., or between 70 and 120° C. (inclusive). In certain embodiments, the duration of the polymerization step is between 1 and 3 hours, between 3 and 8 hours, between 8 and 24 hours, between 1 and 3 days, or between 3 and 7 days (inclusive).

[0405] In certain embodiments, the mol ratio of the first repeating unit to the second repeating unit or the mol ratio of the first monomer to the second monomer is between 1: 1 and 3: 1, between 3: 1 and 10: 1, between 10: 1 and 30: 1, between 30: 1 and 100: 1, or between 100: 1 and 300: 1 (including endpoint values). In certain embodiments, the mol ratio of the first repeating unit to the second repeating unit or the mol ratio of the first monomer to the second monomer is between 3: 1 and 30: 1 (including endpoint values). In certain embodiments, the mol ratio of the first repeating unit to the second repeating unit or the mol ratio of the first monomer to the second monomer is between 30: 1 and 100: 1 (including endpoint values).

[0406] In certain embodiments, the copolymer is a random copolymer. In certain embodiments, the copolymer is a block copolymer.

[0407] In another aspect, the present disclosure provides compounds of the formula:

[0408]

[0409] or a tautomer or salt thereof, wherein:

[0410] X 1 is S or O;

[0411] R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2、-NO2、-C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2、-C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2、-OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0412] R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b、–S(=O)2SR b 、–S(=O)2N(R b )2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b,–NR b C(=NR b )SR b ,–NR b C(=NR b )N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b ,–NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0413] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and

[0414] n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; provided that R 10 and R 11 None contain one or more non-aromatic unsaturated CC bonds.

[0415] In certain embodiments, the compound has the formula:

[0416]

[0417] or a tautomer or a salt thereof.

[0418] In certain embodiments, n3 is 1. In certain embodiments, n4 is 1.

[0419] In certain embodiments, R 10 or R 11 is substituted or unsubstituted alkyl, -O(substituted or unsubstituted alkyl) or -S(substituted or unsubstituted alkyl). In certain embodiments, R 10 or R 11 is substituted or unsubstituted C 2-6 Alkyl, -O (substituted or unsubstituted C 2-6 Alkyl) or -S (substituted or unsubstituted C 2-6 alkyl).

[0420] In certain embodiments, the compound has the formula:

[0421]

[0422] or a tautomer or a salt thereof.

[0423] In another aspect, the present disclosure provides a homopolymer of the formula:

[0424]

[0425] or a salt thereof, wherein:

[0426] m1 is an integer between 10 and 1,000,000 (inclusive);

[0427] R 1 、R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl;

[0428] Ring A is an aryl group;

[0429] R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a 、-SCN、-SR a 、-SSR a 、-N3、-NO、-N(R a )2、-NO2、-C(=O)R a 、-C(=O)OR a 、-C(=O)SRa 、-C(=O)N(R a )2、-C(=NR a )R a 、-C(=NR a )OR a 、-C(=NR a )SR a 、-C(=NR a )N(R a )2、-S(=O)R a 、-S(=O)OR a 、-S(=O)SR a 、-S(=O)N(R a )2、-S(=O)2R a 、-S(=O)2OR a 、-S(=O)2SR a 、-S(=O)2N(R a )2、-OC(=O)R a 、-OC(=O)OR a 、-OC(=O)SR a 、-OC(=O)N(R a )2、-OC(=NR a )R a 、-OC(=NR a )OR a 、-OC(=NR a )SR a 、-OC(=NR a )N(R a )2、-OS(=O)R a 、-OS(=O)OR a 、-OS(=O)SR a 、-OS(=O)N(R a )2、-OS(=O)2R a 、-OS(=O)2OR a 、-OS(=O)2SR a 、-OS(=O)2N(R a )2、-ON(R a )2、-SC(=O)R a 、-SC(=O)OR a 、-SC(=O)SR a 、-SC(=O)N(R a )2、-SC(=NR a )R a 、-SC(=NR a )OR a 、-SC(=NRa )SR a 、 -SC(=NR a )N(R a )2、 -NR a C(=O)R a 、 -NR a C(=O)OR a 、 -NR a C(=O)SR a 、 -NR a C(=O)N(R a )2、 -NR a C(=NR a )R a 、 -NR a C(=NR a )OR a 、 -NR a C(=NR a )SR a 、 -NR a C(=NR a )N(R a )2、 -NR a S(=O)R a 、 -NR a S(=O)OR a 、 -NR a S(=O)SR a 、 -NR a S(=O)N(R a )2、 -NR a S(=O)2R a 、 -NR a S(=O)2OR a 、 -NR a S(=O)2SR a 、 -NR a S(=O)2N(R a )2、 -Si(R a )3、 -Si(R a )2OR a 、 -Si(R a )(OR a )2、 -Si(OR a )3、 -OSi(R a )3、 -OSi(R a )2OR a 、 -OSi(R a )(OR a )2或 -OSi(OR a )3;

[0430] Ra each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0431] n1 is 0, 1, 2, 3, 4 or 5, as long as the valence allows;

[0432] R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2, –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NRb )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NRb S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0433] R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b)2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SRb 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b 、-Si(R b )(OR b )2、-Si(OR b )3、-OSi(R b )3、-OSi(R b )2OR b 、-OSi(R b )(OR b )2OR-OSi(OR b )3;

[0434] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0435] n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; and

[0436] L 1 is a substituted or unsubstituted alkylene group or a substituted or unsubstituted heteroalkylene group;

[0437] The conditions are:

[0438] The condition is R 1 、R 2 、R3 、R 4 , Ring A, R 10 、R 11 and L 1 The alkylene glycols do not contain one or more non-aromatic unsaturated CC bonds.

[0439] In another aspect, the present disclosure provides a method for preparing a homopolymer comprising reacting a copolymer with a compound of the formula:

[0440] HS-L 1 -NH2,

[0441] or a salt thereof.

[0442] In certain embodiments, the homopolymer has the formula:

[0443]

[0444] or a salt thereof.

[0445] In certain embodiments, the homopolymer has the formula:

[0446]

[0447] or a salt thereof.

[0448] In another aspect, the present disclosure provides copolymers comprising m3 instances of repeating units of formula III:

[0449]

[0450] in:

[0451] m3 is an integer between 10 and 10,000 (inclusive);

[0452] Each instance of m1 is independently an integer between 10 and 1,000,000 (inclusive);

[0453] R 1 、R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl;

[0454] Ring A is an aryl group;

[0455] R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a 、-SCN、-SR a 、-SSR a、-N3、-NO、-N(R a )2、-NO2、-C(=O)R a 、-C(=O)OR a 、-C(=O)SR a 、-C(=O)N(R a )2、-C(=NR a )R a 、-C(=NR a )OR a 、-C(=NR a )SR a 、-C(=NR a )N(R a )2、-S(=O)R a 、-S(=O)OR a 、-S(=O)SR a 、-S(=O)N(R a )2、-S(=O)2R a 、-S(=O)2OR a 、-S(=O)2SR a 、-S(=O)2N(R a )2、-OC(=O)R a 、-OC(=O)OR a 、-OC(=O)SR a 、-OC(=O)N(R a )2、-OC(=NR a )R a 、-OC(=NR a )OR a 、-OC(=NR a )SR a 、-OC(=NR a )N(R a )2、-OS(=O)R a 、-OS(=O)OR a 、-OS(=O)SR a 、-OS(=O)N(R a )2、-OS(=O)2R a 、-OS(=O)2OR a 、-OS(=O)2SR a 、-OS(=O)2N(R a )2、-ON(R a )2、-SC(=O)R a 、-SC(=O)OR a 、-SC(=O)SR a 、-SC(=O)N(R a)2、-SC(=NR a )R a 、-SC(=NR a )OR a 、-SC(=NR a )SR a 、-SC(=NR a )N(R a )2、-NR a C(=O)R a 、-NR a C(=O)OR a 、-NR a C(=O)SR a 、-NR a C(=O)N(R a )2、-NR a C(=NR a )R a 、-NR a C(=NR a )OR a 、-NR a C(=NR a )SR a 、-NR a C(=NR a )N(R a )2、-NR a S(=O)R a 、-NR a S(=O)OR a 、-NR a S(=O)SR a 、–NR a S(=O)N(R a )2、–NR a S(=O)2R a 、–NR a S(=O)2OR a 、–NR a S(=O)2SR a 、–NR a S(=O)2N(R a )2、–Si(R a )3、–Si(R a )2OR a 、–Si(R a )(OR a )2、–Si(OR a )3、–OSi(R a )3、–OSi(R a )2OR a 、–OSi(Ra )(OR a )2OR–OSi(OR a )3;

[0456] R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0457] n1 is 0, 1, 2, 3, 4 or 5, as long as the valence allows;

[0458] R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2, –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b,–NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0459] R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b )2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2, –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b)2、–S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2、–OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NRb C(=NR b )OR b ,–NR b C(=NR b )SR b ,–NR b C(=NR b )N(R b )2. –NR b S(=O)R b ,–NR b S(=O)OR b ,–NR b S(=O)SR b ,–NR b S(=O)N(R b )2. –NR b S(=O)2R b ,–NR b S(=O)2OR b ,–NR b S(=O)2SR b ,–NR b S(=O)2N(R b )2、–Si(R b )3, –Si(R b )2OR b 、–Si(R b )(OR b )2、–Si(OR b )3. –OSi(R b )3. –OSi(R b )2OR b 、–OSi(R b )(OR b )2OR–OSi(OR b )3;

[0460] R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0461] n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; and

[0462] L 1 is a substituted or unsubstituted alkylene group or a substituted or unsubstituted heteroalkylene group;

[0463] The condition is R 1 、R 2 、R 3 、R 4 , Ring A, R 10 、R 11 and L 1 The alkylene glycols do not contain one or more non-aromatic unsaturated CC bonds.

[0464] In another aspect, the present disclosure provides a method for preparing a copolymer comprising polymerizing the homopolymer in the presence of I2 and a HI scavenger.

[0465] In certain embodiments, the HI scavenger is a base. In certain embodiments, the base is an aromatic amine, preferably pyridine.

[0466] In certain embodiments, the base is 1,5,7-triazabicyclo(4.4.0)dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo(4.4.0)dec-5-ene (MTBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,1,3,3-tetramethylguanidine (TMG), quinuclidine, 2,2,6,6-tetramethylpiperidine (TMP), pentamethylpiperidine (PMP), tributylamine, triethylamine, 1,4-diazabicyclo[2.2.2]octane (TED), collidine, or 2,6-lutidine (2,6-dimethylpyridine).

[0467] In certain embodiments, Formula iii is:

[0468]

[0469] In certain embodiments, Formula iii is:

[0470]

[0471] In certain embodiments, L 1 is a substituted or unsubstituted alkylene group. 1 For unsubstituted C 2-6 Alkylene.

[0472] In another aspect, the present disclosure provides a copolymer comprising:

[0473] Examples of m1 first repeating units of formula i':

[0474]

[0475] Examples of m2 second repeating units of formula ii-A or ii-B:

[0476]

[0477] m3' examples of cross-linking groups, wherein the cross-linking groups are multivalent groups of small molecules, wherein the multivalent groups are at least tetravalent; and

[0478] optionally one or more types of additional repeating units;

[0479] in:

[0480] The copolymer is substantially cross-linked;

[0481] m1 is an integer between 10 and 1,000,000 (inclusive);

[0482] m2 is an integer between 2 and 1,000,000 (inclusive);

[0483] R 1 、R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl;

[0484] R 4 ' is halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a ,–SCN,–SR a 、–SSR a 、–N3、–NO、–N(R a )2、–NO2、–C(=O)R a 、–C(=O)OR a 、–C(=O)SR a 、–C(=O)N(R a )2、–C(=NR a )R a 、–C(=NR a )OR a 、–C(=NR a )SR a 、–C(=NR a )N(R a )2, –S(=O)R a 、–S(=O)OR a 、–S(=O)SR a 、–S(=O)N(R a )2, –S(=O)2R a 、–S(=O)2ORa 、–S(=O)2SR a 、–S(=O)2N(R a )2、–OC(=O)R a 、–OC(=O)OR a 、–OC(=O)SR a 、–OC(=O)N(R a )2、–OC(=NR a )R a 、–OC(=NR a )OR a 、–OC(=NR a )SR a 、–OC(=NR a )N(R a )2、–OS(=O)R a 、–OS(=O)OR a 、–OS(=O)SR a 、–OS(=O)N(R a )2、–OS(=O)2R a 、–OS(=O)2OR a 、–OS(=O)2SR a 、–OS(=O)2N(R a )2、–ON(R a )2、–SC(=O)R a 、–SC(=O)OR a 、–SC(=O)SR a 、–SC(=O)N(R a )2、–SC(=NR a )R a 、–SC(=NR a )OR a 、–SC(=NR a )SR a 、–SC(=NR a )N(R a )2、–NR a C(=O)R a 、–NR a C(=O)OR a 、–NR a C(=O)SR a 、–NR a C(=O)N(R a )2、–NR a C(=NR a )R a 、–NR a C(=NR a )ORa ,–NR a C(=NR a )SR a ,–NR a C(=NR a )N(R a )2. –NR a S(=O)R a ,–NR a S(=O)OR a ,–NR a S(=O)SR a ,–NR a S(=O)N(R a )2. –NR a S(=O)2R a ,–NR a S(=O)2OR a ,–NR a S(=O)2SR a ,–NR a S(=O)2N(R a )2、–Si(R a )3, –Si(R a )2OR a 、–Si(R a )(OR a )2、–Si(OR a )3. –OSi(R a )3. –OSi(R a )2OR a 、–OSi(R a )(OR a )2OR–OSi(OR a )3;

[0485] R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0486] R 7 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b ,–SCN,–SR b 、–SSR b 、–N3、–NO、–N(R b)2、–NO2、–C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、–C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2、–S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2、–S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2、–OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2、–OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2、–OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )Rb 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b 、-Si(R b )(OR b )2、-Si(OR b )3、-OSi(R b )3、-OSi(R b )2OR b 、-OSi(R b )(OR b)2OR-OSi(OR b )3;

[0487] is alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene;

[0488] n2 is an integer between 0 and 14 (inclusive), as long as the valence permits;

[0489] Each Examples of are independently a single bond or a double bond;

[0490] R 8 Each instance of is independently:

[0491] When attached to a carbon atom: halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2.

[0492] -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2.

[0493] -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、

[0494] -S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、

[0495] -S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)ORb 、-OC(=O)SR b 、

[0496] -OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、

[0497] -OC(=NR b )N(R b )2、-OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、

[0498] -OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、

[0499] -OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、

[0500] -SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、

[0501] -SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、

[0502] -NR b C(=O)N(R b)2, -NR b C(=NR b )R b , -NR b C(=NR b )OR b ,

[0503] -NR b C(=NR b )SR b , -NR b C(=NR b )N(R b ), 2, -NR b S(=O)R b , -NR b S(=O)OR b ,

[0504] -NR b S(=O)SR b , -NR b S(=O)N(R b ), 2, -NR b S(=O)2R b , -NR b S(=O)2OR b ,

[0505] -NR b S(=O)2SR b , -NR b S(=O)2N(R b ), 3, -Si(R b ), 3, -Si(R b ), 2, OR b ,

[0506] -Si(R b )(OR b ), 2, -Si(OR b ), 3, -OSi(R b ), 3, -OSi(R b ), 2, OR b , -OSi(R b )(OR b ), 2,

[0507] -OSi(OR b ), 3, =O, =S or =NR b ;

[0508] When attached to a nitrogen atom: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -OR b 、-N(R b )2.

[0509] -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2、-C(=NR b )R b 、

[0510] -C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、

[0511] -S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、

[0512] -S(=O)2N(R b )2, or a nitrogen protecting group; or

[0513] When attached to a sulfur atom: =O;

[0514] and / or: R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and / or R 8 Two examples of together with their middle atom form a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl; and

[0515] R beach instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom;

[0516] Provided that if the first repeat unit has the formula: And the cross-linking group has the following formula: Then the second repeat unit does not have the formula:

[0517] In certain embodiments, the copolymer is prepared by a process of polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more of the additional monomers, wherein:

[0518] The first monomer has formula I':

[0519]

[0520] or a tautomer or salt thereof;

[0521] The second monomer has formula II-A or II-B:

[0522]

[0523] or a tautomer or salt thereof, wherein is Ring B, and Ring B is a heterocycle; and

[0524] The third monomer is a small molecule containing two or more non-aromatic unsaturated C—C bonds;

[0525] with the proviso that if the first monomer is unsubstituted styrene and the third monomer is unsubstituted 1,4-divinylbenzene, then the second monomer does not have the formula: or a tautomer thereof.

[0526] In another aspect, the present disclosure provides a method of preparing a copolymer, comprising polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more types of the additional monomers.

[0527] In certain embodiments, the cross-linking group or the third monomer does not include -C(=O)O- or -OC(=O)- in the backbone.

[0528] In certain embodiments, the cross-linking group or third monomer comprises only carbon atoms in the backbone.

[0529] In certain embodiments, the third monomer comprises (non-aromatic C=C or non-aromatic C≡C)-L 1 '-(non-aromatic C=C or non-aromatic C≡C), where L 1 ' is substituted or unsubstituted C 1-1000 Alkylene, substituted or unsubstituted C 2-1000 Alkenylene, substituted or unsubstituted C 2-1000 Alkynylidene, substituted or unsubstituted C 1-1000 Heteroalkylene, substituted or unsubstituted C 2-1000 Heteroalkenylene, substituted or unsubstituted C 2-1000 Heteroalkynylene, optionally wherein the C 1-1000 Alkylene, C 2-1000 Alkenylene, C 2-1000 Alkynylidene, C 1-1000 Heteroalkylene, C 2-1000 Heteroalkenylene, or C 2-1000 One or more backbone carbon atoms of a heteroalkynylene group is replaced by a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0530] In certain embodiments, the crosslinking group has the formula:

[0531] or

[0532] The third monomer has the formula:

[0533]

[0534] or a tautomer or salt thereof, wherein R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each is independently hydrogen, halogen, or substituted or unsubstituted alkyl.

[0535] In certain embodiments, R 12 、R 13 、R 14 、R 15 、R 16 and R 17 Each is hydrogen.

[0536] In certain embodiments, L 1 ' is substituted or unsubstituted C 1-1000 Heteroalkylene, optionally wherein the C 1-1000 One or more backbone carbon atoms of a heteroalkylene group is replaced by a substituted or unsubstituted arylene group.

[0537] In certain embodiments, L 1 ' is substituted or unsubstituted C 10-100 Heteroalkylene, optionally wherein the C 10-100 One or more backbone carbon atoms of the heteroalkylene group are replaced by a substituted or unsubstituted arylene group. 1 ' is substituted or unsubstituted C 10-50 Heteroalkylene, optionally wherein the C 10-50 One or more backbone carbon atoms of the heteroalkylene group is replaced by a substituted or unsubstituted phenylene group.

[0538] In certain embodiments, L 1 'Has the following formula:

[0539]

[0540] wherein each instance of n is independently 1, 2, 3, 4, or 5.

[0541] In certain embodiments, the crosslinking group has the formula:

[0542] or

[0543] The third monomer has the formula:

[0544]

[0545] or a salt thereof, wherein each instance of n is independently 1, 2, 3, 4 or 5.

[0546] In certain embodiments, L 1 ' is a substituted or unsubstituted arylene group. In certain embodiments, L 1 ' is an unsubstituted 1,4-phenylene group.

[0547] In certain embodiments, m1 is an integer between 30 and 3,000, inclusive. In certain embodiments, m1 is an integer between 10 and 30, between 30 and 100, between 100 and 300, between 300 and 1,000, between 1,000 and 3,000, between 3,000 and 10,000, between 10,000 and 100,000, or between 100,000 and 1,000,000, inclusive.

[0548] In certain embodiments, m2 is an integer between 3 and 300, inclusive. In certain embodiments, m2 is an integer between 2 and 10, between 10 and 30, between 30 and 100, between 100 and 300, between 300 and 1,000, between 1,000 and 3,000, between 3,000 and 10,000, between 10,000 and 100,000, or between 100,000 and 1,000,000, inclusive.

[0549] In certain embodiments, m3 is an integer between 30 and 3,000, inclusive. In certain embodiments, m3 is an integer between 10 and 30, between 30 and 100, between 100 and 300, between 300 and 1,000, between 1,000 and 3,000, or between 3,000 and 10,000, inclusive.

[0550] In certain embodiments, R 1 In certain embodiments, R 1 is a substituted or unsubstituted alkyl group. 1 For unsubstituted C 1-6 In certain embodiments, R 1 is a halogen (eg, F).

[0551] In certain embodiments, R 2 In certain embodiments, R 2 is a substituted or unsubstituted alkyl group. 2 For unsubstituted C 1-6 In certain embodiments, R 2 is a halogen (eg, F).

[0552] In certain embodiments, R 3 In certain embodiments, R 3 is a substituted or unsubstituted alkyl group. 3 is a substituted or unsubstituted alkyl group. 3 For unsubstituted C 1-6 In certain embodiments, R 3 is a halogen (eg, F).

[0553] In certain embodiments, R 4 ' is –C(=O)OR a ;

[0554] where Ra is a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0555] In certain embodiments, R 4 ' is –C(=O)N(R a )2;

[0556] Each R a are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

[0557] The condition is that at least one R a Not hydrogen.

[0558] In certain embodiments, at least one R a is a substituted or unsubstituted alkyl group. In certain embodiments, at least one R a For unsubstituted C 1-6 Alkyl (e.g., Me, Et, i-Pr).

[0559] In certain embodiments, R 4 ' is a substituted or unsubstituted phenyl group. In certain embodiments, R 4 ' is not substituted or unsubstituted phenyl. In certain embodiments, R 4 ' is unsubstituted phenyl. In certain embodiments, R 4 ' is not an unsubstituted phenyl group.

[0560] In certain embodiments, R 1 、R 2 、R 3 、R 4 '、R 7 、R 8 Neither Ring B nor Ring B contains one or more non-aromatic unsaturated CC bonds.

[0561] In certain embodiments, Formula I' is

[0562]

[0563] In certain embodiments, the molar ratio of the first repeating unit to the cross-linking group or the molar ratio of the first monomer to the third monomer is between 2:1 and 10:1, between 10:1 and 30:1, or between 30:1 and 100:1 (including endpoints).

[0564] In certain embodiments, the degree of crosslinking is between 0.1% and 0.3%, between 0.3% and 1%, between 1% and 3%, between 3% and 10%, between 10% and 20%, or between 20% and 50%, inclusive, on a mol:mol basis. In certain embodiments, the degree of crosslinking is between 1% and 10%, inclusive, on a mol:mol basis. In certain embodiments, the degree of crosslinking is between 20% and 30%, between 30% and 40%, or between 40% and 50%, inclusive, on a mol:mol basis.

[0565] In certain embodiments, the degree of cross-linking is less than 0.1% (molar ratio). In certain embodiments, the degree of cross-linking is between 0.001% and 0.01% or between 0.01% and 0.1% (molar ratio, exclusive of endpoints).

[0566] In certain embodiments, the degree of crosslinking is determined by the consumption of monomers that are polymerized to form the copolymer. In certain embodiments, the degree of crosslinking is determined by nuclear magnetic resonance spectroscopy (NMR, such as single-sided NMR). In certain embodiments, the degree of crosslinking is determined by a swelling test.

[0567] In another aspect, the present disclosure provides a homopolymer prepared by a process comprising polymerizing a compound described herein, or a tautomer or salt thereof.

[0568] In certain embodiments, the number average molecular weight of the copolymer or homopolymer measured by gel permeation chromatography is between 20kDa and 100kDa, between 100kDa and 300kDa, between 300kDa and 1,000kDa, between 1,000kDa and 3,000kDa, or between 3,000kDa and 10,000kDa. In certain embodiments, the number average molecular weight of the copolymer or homopolymer measured by gel permeation chromatography is between 300Da and 7kDa (including endpoint values). In certain embodiments, the number average molecular weight of the copolymer or homopolymer measured by gel permeation chromatography is between 7kDa and 100kDa (including endpoint values). In certain embodiments, the number average molecular weight of the copolymer or homopolymer measured by gel permeation chromatography is between 100kDa and 3,000kDa (including endpoint values).

[0569] In certain embodiments, the copolymer or homopolymer is degradable.In certain embodiments, the copolymer or homopolymer is degradable after reaction with a nucleophile.

[0570] Further disclosed herein are methods of degrading a copolymer or homopolymer described herein, comprising reacting the copolymer or homopolymer with a nucleophile. In certain embodiments, the nucleophile degrades the copolymer or homopolymer under ambient conditions.

[0571] In certain embodiments, the nucleophile is an amine. In certain embodiments, the nucleophile is an organic amine. In certain embodiments, the nucleophile is an organic aliphatic amine. In certain embodiments, the nucleophile is an organic aromatic amine. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl)2-NH. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl)-NH2. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl)-NH2, preferably (unsubstituted C 2-6 In certain embodiments, the nucleophile is (alkyl substituted with at least -SH)-NH2, preferably HS-(CH2) 2-6 In certain embodiments, the nucleophile is a thiol. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl)-SH, preferably (unsubstituted C 2-6 In certain embodiments, the nucleophile is a small molecule.

[0572] In certain embodiments, the average molecular weight of the copolymer is from 10kDa to 10,000kDa (inclusive). In certain embodiments, the average molecular weight of the copolymer is from 10kDa to 30kDa, from 30kDa to 100kDa, from 100kDa to 1,000kDa, from 1,000kDa to 10,000kDa, or from 10,000kDa to 100,000kDa (inclusive). In certain embodiments, the average molecular weight of the copolymer is from 10kDa to 100kDa (inclusive). In certain embodiments, the average molecular weight is determined by gel permeation chromatography. In certain embodiments, the average molecular weight of the copolymer determined by gel permeation chromatography is from 10kDa to 100,000kDa (inclusive). In certain embodiments, the number average degree of polymerization is from 2 to 1,000 (inclusive) relative to the first monomer; and the number average degree of polymerization is from 2 to 1,000 (inclusive) relative to the second monomer. In certain embodiments, the number average degree of polymerization is from 10 to 200 (inclusive) relative to the first monomer; and the number average degree of polymerization is from 10 to 200 (inclusive) relative to the second monomer. In certain embodiments, the number average degree of polymerization is from 15 to 100 (inclusive) relative to the first monomer; and the number average degree of polymerization is from 15 to 100 (inclusive) relative to the second monomer. In certain embodiments, the number average degree of polymerization is from 2 to 1,000, 10 to 1,000, 100 to 1,000, 2 to 100, 10 to 100, 2 to 10 (inclusive) relative to the first monomer. In certain embodiments, the number average degree of polymerization is from 2 to 1,000, 10 to 1,000, 100 to 1,000, 2 to 100, 10 to 100, 2 to 10 (inclusive) relative to the second monomer.

[0573] In certain embodiments, the dispersity of the copolymer 1 to 2, 1.1 to 2, 1.3 to 2, 1.5 to 2, 1.1 to 1.5, 1.1 to 1.3, 1.3 to 2, 1.3 to 1.5, 1.5 to 2 (inclusive).

[0574] In another aspect, the present disclosure provides a composition comprising:

[0575] copolymers; and

[0576] Optionally, an excipient.

[0577] In another aspect, the present disclosure provides a composition comprising:

[0578] compound, or a tautomer or salt thereof; and

[0579] Optionally, an excipient.

[0580] In another aspect, the present disclosure provides a composition comprising:

[0581] homopolymers; and

[0582] Optionally, an excipient.

[0583] The compositions described herein can be prepared by any method known in the art. Generally speaking, such preparation methods include combining the polymer with an excipient and / or one or more other auxiliary ingredients by copolymers, and then, if necessary and / or desired, molding and / or packaging the product into the desired units. In certain embodiments, disclosed herein are compositions comprising copolymers described herein and optional excipients. In certain embodiments, disclosed herein are compositions comprising compounds described herein or their tautomers or salts; and optional excipients. In certain embodiments, disclosed herein are compositions comprising homopolymers described herein; and optional excipients. In certain embodiments, the excipient is a pharmaceutically acceptable excipient (e.g., water).

[0584] On the other hand, the present disclosure describes a kit comprising a copolymer, compound or composition as described herein; and instructions for use of the copolymer, compound, homopolymer or composition. In certain embodiments, the kit comprises a copolymer or composition as described herein; and instructions for use of the copolymer or composition. In certain embodiments, the kit comprises a compound or its tautomer or salt as described herein or a composition as described herein; and instructions for use of the compound, tautomer, salt or composition. In certain embodiments, the kit comprises a homopolymer or composition as described herein; and instructions for use of the homopolymer or composition. The kit can be commercial packaging or reagent packaging. The kit can also include a container (e.g., a vial, an ampoule, a bottle, a syringe and / or a dispenser packaging, or other suitable container). In certain embodiments, the kit also includes instructions for use of the copolymer (e.g., a degradation copolymer and / or a reconstruction copolymer).

[0585] Example

[0586] In order to more fully understand the present disclosure, the following examples are listed below.The synthetic and biological examples described in this application are used to illustrate the compounds, pharmaceutical compositions and methods provided herein and should not be construed in any way to limit the scope thereof.

[0587] Example 1.

[0588] Many common polymers, particularly vinyl polymers like polystyrene, are inherently difficult to chemically recycle and environmentally persistent. The introduction of low levels of cleavable comonomer additives into existing vinyl polymerization processes could facilitate the production of chemically deconstructible and recyclable variants with otherwise equivalent properties without significantly increasing the cost or requiring new monomer feedstocks for manufacturing process changes, allowing for rapid implementation. Here, we report cleavable comonomer additives that allow the chemical deconstruction and recycling of polystyrene (PS), one of the most common commodity polymers. Deconstructible PS with varying molar masses (∼20–300 kDa) and containing varying amounts of randomly incorporated thioester backbone linkages (2.5–100 mol %) can be selectively depolymerized to produce well-defined thiol-terminated fragments (<10 kDa) that are amenable to oxidative repolymerization to generate recycled PS of nearly identical molar mass to the parent material in excellent yields (80–95%). The thermomechanical properties of the deconstructible PS (containing 2.5 mol % cleavable linkages) and its recycled products are very similar to those of virgin PS. This study establishes the cleavable comonomer approach as a viable strategy for recycling vinyl polymers.

[0589] We explore cleavable comonomers as additives to create chemically deconstructible variants of existing polymers without compromising thermomechanical properties and following existing manufacturing protocols, which we believe offers a path to rapidly introduce circularity into otherwise difficult-to-recycle plastics. 4–6 With suitable comonomers, this strategy can be naturally integrated into the existing PS production infrastructure ( Figure 1A ), the infrastructure has relied heavily on copolymerization to tune material properties. In fact, although many efforts have been made to synthesize chemically cleavable vinyl polymers (including PS) through comonomer methods, 7–13 , forming a closed loop cycle to produce recycled variants has proven difficult to achieve. Rimmer and Ebdon made significant contributions to the chemical recycling of PS by demonstrating that the olefin backbone of styrene-butadiene copolymers can be cleaved by ozonolysis; 9 However, the harsh conditions can produce unwanted byproducts and are difficult to scale up, and no efforts at repolymerization have been discussed. Many reports describe the synthesis of 2-hydroxy-2-pyrrolidone by free radical ring-opening polymerization (rROP). 14,15 The cleavable ester was introduced into the PS backbone by co-polymerization with cyclic ketene acetal (CKA); 10-13 However, due to the unfavorable reactivity ratio between styrene and CKA comonomers, these copolymers always have a strong composition gradient, which makes it impossible to deconstruct PS into low molecular weight, reusable fragments. Meanwhile, other cleavable comonomer classes of rROP, such as thiolactones, have been reported. 16,17It does not copolymerize with styrene at all; however, during the preparation of this paper, we discovered that the thiolactone dibenzo[c,e]oxepin-5(7H)-thione (DOT) can be incorporated into PS under emulsion polymerization conditions to produce degradable latex particles. 18 Nevertheless, despite the various copolymer compositions 14-22 Significant progress has been made in the development of rROP, and attempts have been made to repolymerize oligomeric fragments obtained by other means. 23-25 , but to our knowledge, recycling via a comonomer approach (i.e., producing recycled materials with comparable properties) has not yet been demonstrated for any vinyl polymer.

[0590] Here, we achieve chemically recyclable PS via a cleavable comonomer strategy. We show that DOT and a novel DOT derivative (XY-DOT) can undergo near-random copolymerization with styrene under standard free radical polymerization conditions to generate PS with backbone thioesters over a range of molar masses (~20-300 kDa) and comonomer compositions (2.5-100%). Treatment of these polymers with mild, readily available thiols, aminothiols, or allylamines allows their quantitative deconstruction into well-defined telechelic oligomeric fragments (<10 kDa) suitable for repolymerization. We demonstrate the ring-closing deconstruction and oxidative repolymerization of a high molecular weight (300 kDa) PS containing 2.5% DOT, yielding recycled PS with equivalent molar mass and thermomechanical properties to the original PS.

[0591] Synthesis of deconstructible PS with arbitrary composition and tunable microstructure.

[0592] Although it was previously reported that DOT cannot effectively copolymerize with styrene, 16 However, the structural similarity between DOT and thioesters known to cause chain transfer in styrene polymerization is 26 This inspired us to explore the conditions for styrene / DOT copolymerization in more detail. Suspecting that substituents might provide a way to tune the copolymerization of DOT with styrene, we synthesized and screened a small library of DOT derivatives (XY-DOT) for their ability to copolymerize with styrene under free radical conditions using AIBN initiator and six solvents of varying polarity (Table 1). Remarkably, substantial incorporation of XY-DOT into the copolymers was observed in all cases. Furthermore, the mole fraction of incorporated XY-DOT (F X-Y-DOT* ) varies depending on the solvent and DOT substituents, providing orthogonal control to systematically tune copolymer composition / microstructure ( Figures 8A to 8B When polymerized in toluene-d8, the consumption of styrene and unmodified DOT was equal, indicating that bulk polymerization (with a dielectric constant similar to toluene) can yield high molecular weight random copolymers.

[0593]

[0594]

[0595] Table 1. Copolymerization of styrene and XY-DOT (molar ratio approximately 10:1) in various solvents. All experiments were performed in a J-Young NMR tube with 1-2 mol% AIBN initiator and styrene concentrations of 1-2 M at 70°C for 18-30 h. a Conversion rate through 1 H NMR analysis was measured using 1,3,5-trimethoxybenzene as an internal standard. b The molar equivalent of XY-DOT in the monomer feed; c the molar equivalents of XY-DOT-derived units in the isolated polymer; d number-average molar mass of the isolated polymers; e The molar mass dispersion of the isolated polymers was determined by following this procedure but substituting 1,1′-azobis(cyanocyclohexane) (ACHN) for AIBN due to its slower decomposition half-life (t 1 / 2 = 10 hours, 88 ° C), so a higher monomer conversion rate can be achieved, and F DOT =2.6-55%(dPS(F DOT) , Figures 2A to 2D ) and F DOT = 100% (ie, DOT homopolymer, pDOT) copolymers. Size exclusion chromatography (SEC) showed that for relatively low DOT incorporation levels (F DOT =2.6-11%), which is most relevant to the following recovery studies, and M n Similar to the PS homopolymer (PS-L) prepared under the same conditions. DOT The larger molar masses observed for >11% can be partially explained by the larger mass of DOT (2.2 times that of styrene), but may also reflect differences in the termination mechanism or errors in the SEC calibration due to deviations in copolymer composition from PS.

[0596] ATR-IR( Figure 2B ) and NMR( Figure 2C ) Spectral and deconstructive studies( Figure 2A and 2D ) supports the incorporation of thioesters into the backbone of each deconstructible PS. In the former, the C=O stretching (~1620-1700 cm -1 ) and the peak intensity associated with F DOT At the same time, in the 3.7-4.7ppm area 1 H NMR resonance (with 1H- 13 C heteronuclear multiple bond correlation (HMBC) assigned to the protons adjacent to the thioester functional group) was used to measure F DOT and provide insights into the microstructure of the copolymers. It is noteworthy that these studies show that for all tested compositions F DOT≈ f DOT These copolymers were deconstructed by thioester cleavage using n-propylamine ( Figure 2A and 2D ), which in all cases yielded narrowly dispersed The oligomers were prepared with predictable molar masses based on the random copolymerization hypothesis. Taken together, these results provide strong evidence for the near-random copolymerization of DOT and styrene under these conditions, thereby providing a route to obtaining chemically decomposable PS analogs.

[0597] Mild and selective chemical deconstruction of dPS into bifunctional oligostyrene fragments.

[0598] A key challenge hindering the chemical cyclization of vinyl polymers via cleavable comonomer approaches is the development of mild yet selective deconstruction conditions that provide α,ω-functionalized, well-defined oligomeric products suitable for repolymerization in high yield and purity. Here, we hypothesize that the use of thiolate or bifunctional amine nucleophiles for PS deconstruction could address these challenges. Under optimized conditions, treatment of dPS (11) with any of three readily available cleavage agents—allylamine, ethanethiol, or cysteamine—(Scheme 2) afforded the α,ω-functionalized oligostyrene fragments allyl-OS (11), te-OS (11), and thiol-OS (11), respectively, in high yield and purity. These products differ only in the nature of the α-terminal reactive group (allyl, thioester, and thiol, respectively), and in principle, each is amenable to step-growth repolymerization. It is well known that polar solvents are most favorable for thioester cleavage; 27 In fact, DMF is an excellent solvent for these deconstruction reactions (Table 2 and Figure 11 ). However, it is worth noting that pure allylamine and ethanethiol are most effective for the synthesis of allyl-OS(11) and -OS(11), thus avoiding the use of additional organic solvents.

[0599] The extent of thioester cleavage is determined by 1 Quantitative analysis by H NMR spectroscopy ( Figure 3, Inset 2). Upon thioester cleavage, the resonances of the methine and methylene protons α to the thioester functionality in the polymer (4.3-4.7 ppm and 3.8-4.2 ppm, respectively, in benzene-d6) shifted upfield to 3.3-3.8 ppm, indicating the formation of a thiol functionality. In the case of allyl-OS(11) and thiol-OS(11), all observable fragments had the structures shown in Figure 2, and the end group concentrations matched those expected from the thioester functionality in the polymer, indicating that the yields of the desired deconstructed products were quantitative. In contrast, the yield of oligomeric te-OS(11) was 94% (by mass) and that of dibenzo[c,e]thiol-5(7H)-one (DTO) was 6%. The latter may arise from the cyclization of the putative species A or from the self-decomposition of the DOT-DOT dyad in the copolymer backbone. 28 process( Figure 12 pDOT undergoes self-decomposition to form DTO (yield > 98%) ( Figure 13 and 14A 14B), which strongly suggests that a self-decomposition mechanism could be at work. DTO is expected to be inert under many feasible repolymerization strategies, so its removal before repolymerization may not be necessary.

[0600] Repolymerization of oligostyrene fragments to generate recycled PS

[0601] Next, we sought new conditions for the polymerization of bifunctional fragments to regenerate PS. We first explored the polycondensation of te-OS(11) by removing ethanethiol ( Figures 15A to 15B ), which could in principle provide pristine dPS(11); however, we observed only a two-fold increase in molecular weight, suggesting that this route may be feasible but requires further optimization. Meanwhile, initial success in the oxidative polymerization of thiol-OS(11) ( Figure 4 ) motivated us to explore this approach more deeply, as this step-growth coupling would be atom-economical and potentially applicable to a variety of conditions under which thiol / disulfide redox couples can be manipulated. Furthermore, the precedent for the polycondensation of thiol-terminated PS provided a starting point. 29,30

[0602] First, disulfide bond formation conditions were optimized using small molecule and monofunctional macromolecular models (Table 3 and Figures 15A to 15B ). In the case of pyridine as HI scavenger, the use of I2 as oxidant can obtain quantitative yields and is fast, convenient and reliable. In fact, the treatment of thiol-OS (11) (M n =1.1 kDa) was reacted with these reagents in dichloromethane solvent and then precipitated from methanol to obtain the recovered polymer rPS (11) (M n=12.3 kDa), with an isolated yield of 89%. The molecular weight distribution of rPS (11) is almost the same as that of dPS (11); M n The slight increase in M ​​may be attributed to the intercalating groups from the cleavage reagent. Theoretical considerations suggest that the presence of monofunctional fragments in the thiol-OS (11) originating from the terminal groups in dPS (11) will n The limit is the mass of the original dPS (11) plus the mass of the cleavage reagent. This "molecular weight memory" effect indicates that recovered PS can be generated in excellent yields from deconstructed PS. Ten grams of chemically recoverable high molecular weight PS were synthesized.

[0603] Having demonstrated proof-of-concept for the chemical recycling of relatively low-molecular-weight PS on a small scale, we next sought to apply a similar workflow to the larger scale of high-molecular-weight PS ( Figure 5 ), since the useful thermomechanical properties of PS appear around 10 times the entanglement molecular weight, i.e., ~18 kDa. 31 Therefore, we screened the conditions for obtaining high molecular weight deconstructible PS (Table 4). Notably, when a bulk mixture of styrene and DOT was heated at 130 °C for 15 h in the absence of an exogenous initiator, 15-20 g of each of dPS(2.5)-hMW and dPS(5.0)-hMW were isolated, with molecular weights of 312 and 248 kDa, respectively, and f DOT =F DOT These samples were deconstructed into thiol-OS(2.5)-hMW and thiol-OS(5.0)-hMW with an isolated yield of >98%, affording M w =9.1 and 4.5 kDa, Finally, these crude fragments were oxidatively repolymerized to obtain rPS(2.5)-hMW and rPS(5.0)-hMW without any purification, in which the M of dPS(2.5)-hMW and dPS(5.0)-hMW were recovered respectively. w The values ​​of rPS(2.5)-hMW and rPS(5.0)-hMW were 68% (212 kDa) and 62% (154 kDa) of the original values. If the OS fragment was first precipitated from methanol, these values ​​increased to a remarkable 94% (292 kDa) and 116% (287 kDa), probably due to the removal of small molecule impurities that hindered the step-growth repolymerization process. The total isolated yield of rPS(2.5)-hMW and rPS(5.0)-hMW from the deconstruction / precipitation / recovery cycle was 80–85%. This yield increased to 90–95% if the intermediate precipitation was abandoned. The SEC trace of the recovered PS sample showed some tailing to lower molecular weights, which may be attributed to the formation of cyclic polymers during the oxidative repolymerization process ( Figure 20). Nevertheless, these results demonstrate that it is possible to synthesize high-molecular-weight deconstructable PS on a decagram scale under industrially relevant batch conditions, deconstruct these polymers into low-mass fragments, and repolymerize them under mild conditions to generate recycled PS with nearly equivalent molar masses in excellent yields.

[0604] “PS-like” thermal and thermomechanical properties at low comonomer loading.

[0605] Differential scanning calorimetry (DSC, Figure 4 a) and thermogravimetric analysis (TGA, Figure 6B ; See Figures 21A to 21D For the whole series of low M w Similar studies of dPS polymers) probed high M w Thermal properties of polymers. The same glass transition temperature (T g ) is 107°C. The T g The values ​​decreased only slightly (103°C and 100°C for rPS(2.5)-hMW and rPS(5.0)-hMW, respectively). The thermal decomposition temperature (T d,5％ ), the thermal decomposition temperatures of the deconstructible PS samples (dPS(2.5)-hMW and dPS(5.0)-hMW were 378 and 372 °C, respectively) were slightly lower than those of PS-hMW (408 °C), while the thermal decomposition temperatures of the recovered PS samples were further reduced to 360 and 337 °C for rPS(2.5)-hMW and rPS(5.0)-hMW, respectively. Although T d,5％ The values ​​decreased slightly, but all polymers retained an excellent thermal processing window, ranging from a low of 237 °C for rPS(5.0)-hMW to a high of 271 °C for dPS(2.5)-hMW (and 301 °C for PS-hMW).

[0606] Given that dPS2.5-hMW and rPS2.5-hMW exhibited similar thermal properties to pristine PS and that these samples involved the lowest cleavable comonomer loading, which is advantageous from a manufacturing perspective, we investigated their thermomechanical properties using dynamic mechanical analysis (DMA) ( Figure 6C ). Compression-molded rectangular bars of each sample showed nearly identical temperature sweep curves compared to pristine, indestructible PS-hMW. The elastic modulus (E′) ranged from 1.9–2.7 GPa, which is comparable to the reported values ​​for pristine PS (1–3 GPa 32 ) is very consistent.

[0607] This paper shows that cleavable comonomers can be used to impart chemical circularity to the commodity polymer polystyrene. Looking ahead, this concept has several implications for sustainable polymer design. First, it provides a roadmap for developing “drop-in” additives compatible with current polymerization techniques (e.g., free-radical polymerization) that can leverage existing infrastructure, potentially facilitating rapid adoption compared to systems that rely on new chemistries. Second, because the properties of deconstructible copolymers prepared using cleavable comonomers can be very similar to those of the virgin material, they could avoid the property-sustainability trade-offs that plague many attempts to deploy novel polymers. Third, while we demonstrate these concepts here for PS, we expect them to be broadly applicable to other vinyl polymers prepared using free-radical polymerization. Furthermore, cleavable comonomers can potentially be designed for any polymer chemistry of interest, which will provide numerous opportunities for fundamental synthetic, theoretical, and analytical advances in polymer science.

[0608] General Considerations

[0609] Unless otherwise noted, all reactions were performed in dry solvents under nitrogen using standard Schlenk techniques or in a glove box. "Room temperature," "RT," or "ambient temperature" refers to ~22° C. Unless otherwise noted, reaction temperatures represent oil bath temperature (fully submerged, stirred solutions).

[0610] Materials and purification methods

[0611] Styrene purification

[0612] Styrene was purchased from Sigma Aldrich ( >=99%; SKU: S4972). Store at ~2°C and use within 3 months of purchase. Before each use, remove the stabilizer (4-tert-butylcatechol) immediately as follows. Fill a syringe with basic alumina equal to the mass of styrene to be purified. Dissolve the alumina plug with styrene, then elute one column volume of styrene and discard. Then, collect the desired mass of styrene and use immediately.

[0613] Reagent / solvent sources and purification

[0614] N,N-Dimethylformamide (DMF) for polymer deconstruction was purchased from Alfa Aesar (stock number: 43465, anhydrous, amine-free, 99.9%) and transferred to a The flask was filled with 4% 4-nitropropionitrile (2-nitropropionitrile) molecular sieves (5% by mass) and 3-5% of the volume was removed under vacuum to remove O2 and residual amine. Cysteamine hydrochloride was recrystallized from anhydrous EtOH and stored in a desiccator. 2,2′-Azobis(2-methylpropionitrile) (AIBN) and 1,1′-azobis(cyanocyclohexane) (ACHN) were recrystallized from MeOH and anhydrous EtOH, respectively, and stored at ~2°C. Lawesson reagent was purchased from Oakwood Chemical and used as received. All other reagents and solvents were purchased from commercial suppliers and used as received.

[0615] Chromatography

[0616] Column chromatography was performed using Fischer Chemical 40–63 μm, 230–400 mesh silica gel. Preparative thin-layer chromatography (preparative TLC) was performed using Analtech Silica Gel GF UNIPLATES (1000 μm, 20 x 20 cm). For preparative TLC, a typical procedure involves loading 35–50 mg of material onto one side of the plate and allowing the solvent front to elute to halfway (i.e., 70–100 mg can be separated per plate).

[0617] precipitation

[0618] The polymer precipitation performed in this study was generally carried out as follows. The crude polymer was dissolved in CH2Cl2 (low M w The sample is about 10mL / g, high M w The precipitate is collected on a sintered funnel of medium porosity and the solid is quantitatively transferred to the sintered funnel with the aid of additional MeOH. The solid is allowed to dry in a stream of air over the sintered funnel for approximately 1 hour, and this procedure is then repeated the number of times indicated. To avoid excessive mechanical losses, especially on a small scale, the precipitated solid is quantitatively recombined with CH2Cl2 before each subsequent precipitation. After the final precipitation, the residual solvent is removed from the sample under high vacuum until the mass remains constant (>12 hours at room temperature or 3 hours at 50°C are usually effective).

[0619] Analytical methods

[0620] Nuclear magnetic resonance (NMR) spectroscopy

[0621] Unless otherwise stated, NMR spectra were obtained at ambient temperature (-22°C) at the MIT Chemistry Department Instrumentation Facility using a Bruker AVANCE III DRX 400 or Neo 500 spectrometer. Chemical shifts (δ) are in ppm and are referenced to 1 HNMR spectrum (chloroform-dδ=7.26ppm, benzene-d6δ=7.16, dichloromethane-d2δ=5.32, toluene-d8δ=2.09) and 13 C{ 1 Residual solvent peak in H} NMR spectrum (chloroform-dδ=77.16 ppm).

[0622] High-resolution mass spectrometry (HRMS)

[0623] HRMS measurements were performed on a JEOL AccuTOF system at the MIT Department of Chemistry Instrumentation Facility.

[0624] Size Exclusion Chromatography (SEC)

[0625] Analytical gel permeation chromatography was performed on a Tosoh EcoSEC HLC-8320 equipped with dual TSKgel SuperH3000 columns and an ethanol-stabilized chloroform mobile phase. The sample concentration was approximately 1 mg / mL. Samples were filtered through a 0.2 μm PTFE syringe filter before injection into the instrument. Molecular weight values ​​were calculated using linear polystyrene calibration standards. All SEC traces were referenced to a toluene internal standard.

[0626] Thermogravimetric analysis (TGA)

[0627] TGA studies were performed on approximately 2-3 mg of sample. The analysis was performed on a TGA / DSC 2STAR system (Mettler-Toledo) equipped with a gas controller GC 200Star system. The studies were performed under a constant nitrogen flow with a temperature gradient of 20°C / min.

[0628] Differential Scanning Calorimetry (DSC)

[0629] DSC studies were performed on approximately 6-8 mg of sample. The analysis was performed on a TGA / DSC 2STAR system (Mettler-Toledo) equipped with an RCS1-3277 DSC unit and a DSC1-0107 cooling system. Each sample was sealed in an aluminum pan and subjected to three heating / cooling cycles from -20°C to 200°C at a rate of 10°C / min. T was recorded from the second heating ramp using the maximum absolute value of the derivative of the heat flow with respect to temperature. g The DSC traces for the second and third heating cycles are identical for all samples reported in this paper.

[0630] Dynamic Mechanical Analysis (DMA)

[0631] DMA was performed on a Discovery DMA 850 system (TA). Tensile tests were performed on samples with dimensions of approximately 2.5 x 1.0 x 12 mm (w x t x l) prepared as described below. Measurements were recorded at a frequency of 1 Hz and a strain amplitude of 0.1% over a temperature range of 40–180°C, a heating rate of 3°C / min, a data sampling interval of 3 s / pt, using a force tracking of 125% and a preload of 0.01 N. Data were collected using Trios software and exported to Microsoft Excel for analysis. Experiments were performed at the MIT NanoTech Institute. Modulus values ​​reported in the main text are for measurements performed at 40°C.

[0632] Compression Molding for DMA Sample Preparation

[0633] DMA rectangular rods were prepared by compression molding a MeOH-precipitated sample. The solid was repeatedly pressed into discs with a diameter of 28 mm and a thickness of 1.5 mm. First, eight circular samples were prepared by filling a mold with PS and pressing at 4 tons of pressure at 50°C for 1 minute. Next, each of these samples was combined with another sample under the same conditions to produce four samples. This process was repeated once to produce two discs, which were then pressed together at 130°C at 4 tons of pressure for 10 minutes to produce a single transparent disc. Rectangular rods were cut from this disc and polished to a uniform consistency.

[0634] Evidence of polymer stability under processing conditions

[0635] The stability of each polymer (PS-hMW, dPS(2.5)-hMW, and rPS(2.5)-hMW) under the above compression molding conditions was evaluated by SEC analysis of the materials before and after processing. In all cases, the molecular weight distribution showed no detectable changes.

[0636] General route to functionalized DOT derivatives with modified reactivity and solubility.

[0637] Three different DOT functionalization strategies were developed, all ultimately using Lawesson's reagent for thiolation to generate the desired DOT derivatives ( Figure 7 These differ only in the details of the synthesis of DOT derivatives from dibenzo[c,e]oxepin-5(7H)-one (DOO) precursors.

[0638] Determination of the solubility of DOT in styrene

[0639] As described in this article, through 1The solubility of DOT in styrene at 22°C was determined by H NMR spectroscopy to be 1.0 molar equivalent of DOT per 35 molar equivalents of styrene. First, a saturated solution of DOT in styrene was prepared. To a vial containing 20 mg (0.088 mmol) of freshly recrystallized DOT was added 145 mg (16 equivalents) of styrene. The mixture was vortexed for approximately 5 minutes and then allowed to stand for 10 minutes. A large amount of solid DOT remained. The mixture was passed through a 0.2 micron filter into an NMR tube (the temperature during filtration was 22°C). The mixture was then diluted with chloroform-d and quantitatively analyzed by 1 H NMR spectroscopy was used for analysis ( Figure 9 ).

[0640] pass 1 H NMR spectroscopy to measure the diad content and F DOT

[0641] This article describes in detail the use of 1 H NMR spectroscopy (using Figure 10 shown 1 H NMR spectrum) of dPS (11) DOT The measurement protocol and for all dPS prepared herein (F DOT ) and dPS(F DOT )-hMW samples are identical. Overlapping of the chemical shifts of styrene and DOT units requires an indirect method. Due to the resonance of the methyl and methylene alpha ( Figure 10 H in 1 and H 2 / H 2 ') do not overlap with the styrene resonances, so they are used to quantify the ring-opened DOT content. This calculation requires knowledge of the methine (H 1 ) and methylene (H 2 / H 2 ') resonances, which in turn provide the % DOT-DOT dyad and the % St-DOT dyad. Fortunately, in benzene-d6 solvent, these resonances do not overlap (in contrast to chloroform-d and dichloromethane-d2).

[0642] The content of DOT-terminated dyads in dPS (11) was calculated as follows (note: the other two dyads St-St and DOT-St were not derived here):

[0643] %DOT-DOT=(5.11 / 2) / (5.11 / 2+4.90)=34%

[0644] %St-DOT=4.90 / (5.11 / 2+4.90)=66%

[0645] Similarly, using benzene-d6 1 Arbitrary unit of H NMR spectrum:

[0646] Relative molar number of DOT = 4.90 + 5.11 / 2 = 7.46

[0647] Next, we used the aromatic region to determine the St content. Due to the chemical shift overlap of solvent residues in benzene-d6, for the highest accuracy we used dichloromethane-d2 1 The integral of the 367 aromatic region is obtained indirectly from the H NMR spectrum and is determined by normalizing the spectrum so that the integral of the 3.4-4.4 ppm region is 4.90 + 5.11 = 10.01. Therefore, after subtracting the integral of the DOT-derived resonance (which is obtained indirectly from the relative molar number of DOT obtained above), we obtain:

[0648] Relative molar number of St = (367-7.46*7) / 5 = 63.0

[0649] at last,

[0650] F DOT =(mol DOT unit) / (mol DOT unit+mol St unit)=1 / (1+(mol St unit / mol

[0651] DOT units)) = 1 / (1 + (63.0 / 7.46) = 0.0106 or 10.6%.

[0652] Thiolate-mediated deconstruction conditions: initial screening

[0653] The optimal conditions reported in the main text were based on the use of pure EtSH as the cleavage reagent, but preliminary studies were performed using PrSH as the nucleophile at a 0.1 M thioester concentration in DMF solvent (Tables 2 and Figure 11 Remarkably, only 2 equivalents of PrSH were required to cleave >95% of the thioester bonds, and equilibrium was reached within 1 h at room temperature in the presence of DBU as a catalyst.

[0654]

[0655]

[0656]

[0657] Table 2. Preliminary study of thioester-mediated deconstruction of dPS(11). Data are from crude oligomers separated under vacuum and volatiles evaporated. a The reaction was carried out under N2 with a thioester concentration of 0.1 M; b The consumption of thioester units is determined by1 H NMR spectroscopy; c No change after 22 hours; d M n,SEC = number average molar mass; = molar mass dispersion. dPS(F DOT ) and self-decomposition in the deconstruction of DOT homopolymer (pDOT)

[0658] The observation that the amount of thiolactone DTO equals the percentage of DOT-DOT dyads in dPS(11) after treatment with thiolates prompted us to investigate the role of this dyad in catalysis (i.e., self-decomposition) 1 ) process, such as the possibility of deconstruction Figure 12 shown.

[0659] Preliminary Study on te-OS(11) Polycondensation for PS Recovery

[0660] like Figure 15A As shown, the polycondensation of the thioester-thiol terminated oligomers produced here could, in principle, serve as a means to provide the original dPS (note: in practice, since the yield of DTO is equal to the percentage of DOT-DOT dyads and they may not be reactive, such dyads may not be present in the recovered version). Given that only 2 equivalents of 1-propanethiol are required to achieve 95% cleavage of the intrachain thioester groups (Table 2, entry 4), we anticipated that thermodynamics might require the removal of the byproduct thiol to make the reverse process feasible. Therefore, since ethanethiol is more easily removed due to its small size and low boiling point (35°C vs. 68°C for 1-propanethiol), we switched the nucleophile in the deconstruction step to ethanethiol (this gave the fully characterized oligomer te-OS (11) used herein).

[0661] Two experiments were performed in parallel, with the only difference being the method of EtSH removal. In each case, M n They increased by 1.8 times. 1 The presence of a resonance at 4.5 ppm in the H NMR spectrum (benzene-d6) strongly supports that the desired thioester formation is occurring.

[0662] Inspection of the 3.0-3.5 ppm region of these spectra suggests that oxidation to the disulfide (te-OS(11)-dim) is a significant side reaction, likely due to adventitious O2 that is difficult to completely remove in small-scale experiments (100 mg oligomer, ∼0.05 mmol thiol end group concentration). This was confirmed by comparison with an independently synthesized sample of te-OS(11)-dim. As expected, these resonances are less pronounced in the 5A MS reaction because it was performed in a sealed tube. Another possible limitation of the M nA further contributing factor was the use of a relatively large amount of DBU (0.2 equivalents), which may have hindered efforts to push the equilibrium toward the polymer because it could have hampered the ability to remove the thiol. These challenges with small-scale experiments prompted us to quickly shelve these studies in favor of the dithiol multioxidation presented in the main text. However, we note that these challenges are expected to be more easily alleviated at larger scales.

[0663] Optimization of disulfide formation on model systems

[0664] Since efficient stepwise polymerization requires near-quantitative disulfide bond formation, a series of common thiol oxidants were first screened in a model small molecule system (Table 3) that was chosen to mimic the α-terminal thiol in thiol-OS (11). The most promising reagents were then applied to dimerize te-OS (11), which serves as a model for the ω-terminal SH group ( Figure 16 ).

[0665]

[0666]

[0667]

[0668] Table 3. Small molecule model systems for disulfide formation. All experiments were performed at an RSH concentration of 0.3 M. (pyrS)2 = 2,2′-bipyridine disulfide. a use 1 H NMR spectroscopy was used, using mesitylene as the internal standard. Theoretical basis for the "molecular weight memory" of OS fragment repolymerization.

[0669] Consider a single polymer chain of a given molecular weight, M, with N cleavable units dispersed throughout the chain. If all cleavable units in this chain are cleaved, then N-2 difunctional fragments and 2 monofunctional fragments remain (assuming the number of cleavable comonomer dyads, triads, etc. is negligible). The number average molecular weight of each fragment will be equal to M / N. Assuming no deleterious side reactions occur during the cleavage event, for a step-growth polymerization of this mixture of difunctional and monofunctional fragments, the average fragment functionality f n，avg =(2N-2) / N. For step-growth polymerization with functional group conversion degree p, the number average degree of polymerization is:

[0670]

[0671] f n,avg Substituting the values ​​into this expression, we get the following result:

[0672]

[0673] When we consider the limit of complete functional group conversion we find that we recover the same number average degree of polymerization as the degraded fragments (N-2 bifunctional fragments plus 2 monofunctional fragments).

[0674]

[0675] This result can also be explained intuitively, since we do not change the number of chains during repolymerization (the number of chain ends remains the same, and each chain must have 2 ends).

[0676] To calculate the weight-average molecular weight of the repolymerized chains, we need information about the overall molecular weight distribution. If we consider the repolymerization of OS segments, the distribution of OS segments per polymer chain is described by a Flory-Schultz distribution, just as in the case of general step-growth polymerization. For the repolymerization of OS segments, we know that in the limit of complete end group conversion, the average number of OS segments per chain is close to N. Given this, the fractions of bifunctional and monofunctional OS segments are (N-2) / N and 2 / N, respectively. At the fraction of components reacting at complete conversion, the number of chains containing i OS segments, n, is i and weight fraction w i for:

[0677]

[0678] The dispersity of the repolymerized chain can then be calculated by summing these functions for all values ​​of i and taking their ratio:

[0679] X n =∑ i n i =N

[0680]

[0681] Figure 17 The dispersity values ​​for different values ​​of N are shown. We emphasize here that the above calculations are for the dispersity of the number of OS fragments per chain and not for the molecular weight dispersity of the repolymerized polymer. Now, to determine the molecular weight dispersity of the repolymerized polymer, we can consider the dispersity of the polymers in the sample containing a given number of OS fragments. The average molecular weight and dispersity of each repolymerized polymer containing m OS fragments depends on the population of OS fragments. To illustrate this, we first consider the molecular weight and dispersity of a repolymerized chain with 2 OS fragments. If the original OS fragment population has a number average molecular weight and M n，OS Dispersion D OS , then the number average molecular weight of the repolymer chain containing 2 fragments is 2*M n，OS and the dispersion is given by:

[0682]

[0683] Similarly, the population of repolymerized chains containing KOS segments will have a number average molecular weight of K*M n，OS And its dispersion can be calculated by iteratively applying the above formula:

[0684] etc...

[0685] As N increases, the dispersion of the repolymerized chain population with a specific N value rapidly approaches unity, e.g. Figure 18 As shown (assuming the dispersion of OS fragments is 2):

[0686] From this calculation, we find that for repolymerized chains with a given number of OS segments, the molecular weight dispersity will be very narrow, and thus the dispersity of the entire repolymerized chain population depends primarily on the dispersity of the number of OS segments per chain (e.g. Figure 17 In general, repolymerization of OS segments will produce chains with the same number average molecular weight as the original polymer, and the dispersity depends on the number of OS segments produced from a single original polymer:

[0687] M n，再聚合 =M n，原始

[0688] For large N

[0689] On the existence of cyclic oligomers

[0690] We observe a small fraction (~5-10% by mass) of low molecular weight species originating from the repolymerization of OS segments. Since these cyclic oligomers do not contain any monofunctional segments, they reduce the molecular weight of the linear repolymerized chains. In this way, we can estimate their impact on the number average molecular weight. If we consider a polymer sample containing an average of N OS segments, each with an average molecular weight of M n，OS , then the ratio of single-function to dual-function OS fragments will be equal to If a certain ratio (x) of bifunctional OS segments is present in the cyclic oligomer, the ratio of monofunctional to bifunctional OS segments constituting the linear chain will be modified to:

[0691]

[0692] This new ratio can be used to calculate f n,avg Modified value:

[0693]

[0694] From this we can calculate how much the number average molecular weight of the linear repolymerized chains will decrease as x increases. Figure 19 This effect is shown graphically for an initial N value of 10:

[0695] We note from our calculations above that the cyclic oligomers do not significantly change the dispersity of the repolymerized linear polymers, as the distribution of these linear polymers still follows the Flory-Schultz distribution.

[0696] Develop bulk polymerization conditions to obtain high M w Deconstructible PS

[0697] High concentrations achievable only in bulk, suspension, or emulsion polymerization are generally preferred to obtain high M due to faster kinetics and less chain transfer. w Therefore, we explored copolymerization under a range of conditions (Table 4). Notably, with one exception (see below), for all screened conditions f DOT ≈F DOT .

[0698]

[0699] Table 4. Development of scalable and reproducible bulk polymerization conditions. DOT = molar equivalent of DOT in the monomer feed, calculated by measuring the amount of DOT in the aliquot before heating. 1 H NMR spectrum was integrated and calculated; the conversion was performed by 1 H NMR analysis was performed using 1,3,5-trimethoxybenzene as an internal standard. DOT = molar equivalents of ring-opening DOT-derived units in the isolated polymer; M n 、M w = number-average molar mass and weight-average molar mass of the isolated polymer; = molar mass dispersity of the separated polymers.

[0700] First, the standard conditions were repeated using ACHN as initiator without solvent (Table 4, entry 1). As expected, the overall conversion, M n and The bulk styrene polymerization using azo initiators usually has relatively high This is believed to be due to the fact that the primary termination mechanism in high viscosity, high conversion media switches from PS-PS combinations to chain transfer (e.g., to initiator). The reaction was stopped at a lower conversion (74%, entry 2). These conditions were then applied at a lower ACHN concentration (0.2 mol%, entry 3) to give Mw values ​​comparable to commercially relevant PS; however, the molecular weight distribution of the polymer proved difficult to reproduce, likely due to the occurrence of the Trommsdorff effect.

[0701] When benzoyl peroxide (BPO) was used as the initiator at 75 °C (entry 4), the rate of copolymerization slowed down (total conversion was 17%) and the isolated polymer had a bimodal distribution. Higher, at 4.9, while M w The reaction was relatively low. Control experiments suggested that this was due to an oxidation / reduction reaction between BPO and DOT to form DTO. This has been previously observed with thiocarbonyl compounds in the context of RAFT. Peroxide initiators were not further investigated.

[0702] The best overall results (in terms of conversion, M w and Interestingly, although thermal isomerization of DOT in DMSO-d6 solvent was previously observed, temperatures of at least 150°C can be employed without observable isomerization byproducts (DTO). DOT = 0, 2.5, 5.2 and 10.1%, and such polymerizations were carried out at 150°C on a 1 g scale for 3 hours (entries 5-8). Next, the polymerization scale was scaled up to 5 g each (entries 9-12). The samples containing DOT used a lower oil bath temperature of 125°C. Based on the precedent of PS, it can be predicted that M W Finally, these reactions were scaled up as shown in entries 13–15, and these samples were used for the recovery studies discussed in the main text.

[0703] To evaluate whether the shoulder in the SEC traces of rPS(2.5)-hMW and rPS(5.0)-hMW might be derived from cyclic polymers, we performed the polymerization under the standard conditions described herein, but at a 50-fold dilution ( Figure 20 The sharp increase in the intensity of the low molecular weight peak supports this hypothesis. These data are consistent with previous observations on the cyclization of thiol-terminated PS.

[0704] Synthesis details and basic structural characterization

[0705] Naming conventions

[0706] The nomenclature of the monomers, oligomers, and polymers synthesized in this paper is shown in the figure below. X-Y-DOTrepresents the mol% of XY-DOT comonomer incorporated into a copolymer (e.g., a copolymer of styrene and XY-DOT) When X or Y = H, it is omitted from the name. For example, a DOT derivative with X = F and Y = H would be referred to as F-DOT, while a copolymer incorporating 9.1% of this comonomer would be referred to as F-dPS (9.1). The deconstruction product obtained after treatment of this polymer with cysteamine produces a thiol at the α-terminus and is therefore referred to as thiol-F-OS (9.1). Finally, the recycled polymer obtained by oxidative polymerization of thiol-F-OS (9.1) will be referred to as F-rPS (9.1). Finally, for simplicity, the molecular weight is divided into two categories: low M w (Manuscript Part I) and Gao M w (Manuscript Part II). For the latter, the name is appended with "-hMW", e.g., high M of F-rPS (9.1) w This version will be referred to as F-rPS(9.1)-hMW.

[0707]

[0708] DOT

[0709]

[0710] IUPAC name: Dibenzo[c,e]oxepin-5(7H)-thione

[0711] Procedure: To improve scalability, the following modifications were made to the published procedure: 1) increasing the concentration; and 2) adding a workup step to decompose the Lawesson's reagent byproduct. A 200 mL, oven-dried, two-necked round-bottom flask was equipped with a magnetic stir bar, a reflux condenser, and an N2 inlet. DOO (9.00 g, 42.8 mmol, 1.0 equiv) and Lawesson's reagent (10.4 g, 25.7 mmol, 0.60 equiv) were added to the flask. The system was evacuated and backfilled with N2, followed by the addition of anhydrous toluene (43 mL). Under a slight N2 flow, the stirred mixture was heated at 115°C for 5 hours, after which volatiles were removed by rotary evaporation at 60°C. The residue was dissolved in CHCl2 (50 mL), and the mixture was diluted with MeOH (150 mL) and stirred vigorously for 12 hours. The suspension was concentrated to a total mass of approximately 20 g, diluted with MeOH (50 mL), filtered, and the solid washed with MeOH (2 x 30 mL). The solid was chromatographed (5-30% CH2Cl2 in hexanes) to afford DOT (5.6 g, 58%) as a bright yellow crystalline solid.***

[0712] Note: *This step is used to decompose the Lawesson's reagent byproduct into an easily removable, MeOH-soluble material. **Due to the low solubility of DOT in this eluent, dry loading is necessary. Here, we used 25-30 g of silica gel for this purpose, for a total of approximately 300 g of silica gel in the column. ***While not required, we found it convenient to isolate the solid as follows (this also serves as a rapid, high-recovery recrystallization). Concentrate the product-containing fractions to dryness, then dissolve the solid in CH2Cl2 (50 mL). Dilute the solution with hexane (300 mL), then concentrate the suspension to a total mass of approximately 100 g and filter. Wash the solid with hexane (2 x 30 mL) and dry under high vacuum. Recovery: 5.3 g of bright yellow crystalline solid.

[0713] Characterization: Basic characterization data ( 1 H and 13 C NMR and IR spectra) were consistent with those in the literature (M. Bingham, N.; J. Roth, P. Degradable Vinyl Copolymers through Thiocarbonyl Addition-Ring-Opening (TARO) Polymerization. Chem. Commun. 2019, 55(1), 55-58. https: / / doi.org / 10.1039 / C8CC08287A).

[0714] SPr-F-DOT

[0715]

[0716] IUPAC name: 10-Fluoro-2-(propylthio)dibenzo[c,e]oxepin-5(7H)-thione

[0717]

[0146] Procedure: The following is a modified version of the procedure reported by Roth et al. for similar compounds. The main differences are in the concentration, reaction time, and equivalents of Lawesson's reagent. SPr-F-DOO (0.700 g, 2.31 mmol, 1.0 equiv), Lawesson's reagent (0.562 g, 1.39 mmol, 0.60 equiv), and anhydrous toluene (2.3 mL) were charged into a 15 mL flask with a Teflon stopper. The flask was sealed, and the stirred mixture was heated at 110°C for 3 hours. The mixture was transferred to a round-bottom flask with the help of CHCl, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (5-25% EtOAc in hexanes) to give SPr-F-DOT (0.426 g, 58%) as a bright yellow / orange solid, and the starting SPr-F-DOO (0.145 g, 21%) as a light yellow solid. The adjusted yield of the recovered starting material was 73%.

[0718] Characterization: 1 H NMR (chloroform-d, 400 MHz): δ = 8.10 (d, J = 8.4 Hz, 1H), 7.43 (dd, J = 8.4, 5.5 Hz, 1H), 7.36-7.27 (m, 3H), 7.14 (td, J = 8.3, 2.6 Hz, 1H), 5.24-5.04 (m, 2H), 3.02 (t, J = 7.2 Hz, 2H), 1.77 (h, J = 7.3 Hz, 2H), 1.08 (t, J = 7.4 Hz, 3H); 19 F{ 1 H} NMR (chloroform-d, 376 MHz): δ = -110.2; 13 C{ 1 H} NMR (chloroform-d, 101MHz): δ = 214.92, 163.78 (d, J = 249Hz), 144.55, 141.04 (d, J = 8.3Hz), 135.58, 134.88, 133.95 (d, J = 2.0Hz), 130.85 (d, J = 3.1Hz) ),130.55(d,J=8.8Hz),126.42,125.97,115.92(d,J=21.7Hz),115.38(d,J=23.1Hz),72.87,34.12,22.27,13.60; HRMS-DART-TOF(m / z):[M+H] + Calculated value C 17 H 16 OFS2, 319.0621; measured value 319.0645.

[0719] SPr-DOT

[0720]

[0721] IUPAC name: 2-(propylthio)dibenzo[c,e]oxepin-5(7H)-thione

[0722] Procedure: This compound was prepared according to the procedure for SPr-F-DOT. The solid obtained from column chromatography was further purified as follows. The solid was dissolved in CH2Cl2 (1.0 mL) and hexanes (10 mL) were added, resulting in a crystalline precipitate. The suspension was cooled to -20°C for 1 hour and then filtered. The solid was washed with hexanes (2 x 3 mL) to afford SPr-DOT (635 mg, 60%) as a yellow / orange crystalline solid.

[0723] Characterization: 1 H NMR (chloroform-d, 400MHz): δ = 8.10 (d, J = 8.4Hz, 1H), 7.63 (d, J = 7.7Hz, 1H), 7.58-7.50 (m, 1H), 7.48-7.42 (m, 2H), 7.33 (d, J = 1.9H) z,1H),7.30(dd,J=8.4,1.9Hz,1H),5.25-5.12(m,2H),3.01(t,J=7.2Hz,2H),1.77(h,J=7.3Hz,2H),1.08(t,J=7.4Hz,3H); 13 C{ 1 H} NMR (chloroform-d, 101 MHz:) δ = 215.47, 144.20, 138.83, 135.64, 135.11, 134.79, 134.74, 130.42, 129.09, 128.54, 128.44, 126.21, 125.98, 73.81, 34.13, 22.31, 13.61; HRMS-DART-TOF (m / z): [M+H] + Calculated value C 17 H 17 OS2,301.0715; measured value 301.0731.

[0724] F-DOT

[0725]

[0726] IUPAC name: 2-Fluorodibenzo[c,e]oxepin-5(7H)-thione

[0727] Procedure: This compound was prepared according to the procedure for SPr-F-DOT. The solid obtained from column chromatography was further purified as follows. The solid was dissolved in CH2Cl2 (1.0 mL) and hexane (10 mL) was added, resulting in an immediate crystalline precipitate. The suspension was cooled to -20°C for 1 hour and then filtered. The solid was washed with hexane (2 x 3 mL) to afford F-DOT (220 mg, 41%) as a bright yellow crystalline solid.

[0728] Characterization: 1 H NMR (chloroform-d, 400 MHz): δ = 8.22 (dd, J = 8.8, 5.8 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H), 7.60-7.52 (m, 1H), 7.52-7.44 (m, 2H), 7.21 (dd, J = 9.5, 2.6 Hz, 1H), 7.15 (ddd, J = 8.7, 7.7, 2.6 Hz, 1H), 5.44-4.92 (m, 2H); 19 F{ 1 H} NMR (chloroform-d, 376 MHz): δ = -106.68; 13 C{ 1 H}NMR: see spectrum below; HRMS-DART-TOF(m / z):[M+H] + Calculated value C 14 H 10 FOS, 245.0431; measured value 245.0423.F2-DOT

[0729]

[0730] IUPAC name: 2,10-difluorodibenzo[c,e]oxepin-5(7H)-thione

[0731] Procedure: This compound was prepared according to the procedure for SPr-F-DOT. The yellow solid obtained from column chromatography (224 mg) contained ~2% impurities and was further purified as follows. The solid was dissolved in CH2Cl2 (1.0 mL) and hexane (10 mL) was added, resulting in an immediate crystalline precipitate. The suspension was cooled to -20°C and held for 1 hour, then filtered. The solid was washed with cold hexane (2 x 3 mL) to give F 2- DOT (203 mg, 38%), as a bright yellow powder.

[0732] Characterization: 1H NMR (chloroform-d, 400 MHz): δ = 8.22 (dd, J = 9.6, 5.7 Hz, 1H), 7.46 (dd, J = 8.4, 5.4 Hz, 1H), 7.34 (dd, J = 9.2, 2.6 Hz, 1H), 7.23-7.12 (m, 3H), 5.30-5.02 (m, 2H); 19 F NMR (chloroform-d, 376 MHz): δ = -106.28 (td, J = 8.4, 5.6 Hz), -109.74 (td, J = 8.8, 5.5 Hz); 13 C{ 1 H} NMR (chloroform-d, 101 MHz): δ = 214.05, 164.67 (d, J = 255.4 Hz), 163.83 (d, J = 249.8 Hz), 140.34 (dd, J = 8.4, 1.7 Hz), 137.34 (d, J = 9.1 Hz), 136.10 (dd, J = 8.4, 2.1 Hz), 135.65 (d, J = 3.2 Hz), 130.77 (d, J = 8.9 Hz), 130.68 (d, J = 3.0 Hz), 116.45 (d, J = 11.0 Hz), 116.24 (d, J = 10. 9Hz), 115.51 (d, J = 23.2Hz), 115.02 (d, J = 23.0Hz), 72.90; HRMS-DART-TOF (m / z): [M+H] + Calculated value C 14 H9F2OS, 263.0337; measured value 263.0321.

[0733] OMe2-DOT

[0734]

[0735] IUPAC name: 2,10-dimethoxydibenzo[c,e]oxepin-5(7H)-thione

[0736] Procedure: This compound was prepared according to the procedure of SPr-F-DOT. The crude mixture was purified by column chromatography (35-65% CH2Cl2 in hexanes) and then the desired product was precipitated from a concentrated CH2Cl2 solution (~1 mL) using hexanes (5 mL). The isolated OMe 2- DOT was obtained as a bright yellow solid with a yield of 75 mg (14%).

[0737] Characterization: 1H NMR (chloroform-d, 400 MHz): δ = 8.22-8.15 (m, 1H), 7.36 (d, J = 8.3 Hz, 1H), 7.14 (d, J = 2.6 Hz, 1H), 7.01-6.93 (m, 3H), 5.19-5.06 (m, 2H), 3.92 (s, 3H), 3.88 (s, 3H); 13 CNMR (chloroform-d, 101 MHz): δ = 215.89, 162.58, 161.03, 140.54, 136.99, 136.85, 132.33, 129.91, 127.41, 114.21, 114.14, 114.03, 113.24, 73.35, 55.81, 55.69; HRMS-DART-TOF (m / z): [M+H] + Calculated value C 16 H 15 O3S, 287.0736; measured value 287.0753.

[0738] DOO

[0739]

[0740] IUPAC name: Dibenzo[c,e]oxepin-5(7H)-one

[0741] Procedure: This compound was prepared by a slightly modified literature procedure (Brandmeier, V.; Feigel, M. A Macrocycle Containing Two Biphenyl and Two Alanine Subunits, Synthesis and Conformation in Solution. Tetrahedron 1989, 45(5), 1365-1376).

[0742] Yield: 21 g (86%).

[0743] Characterization: 1 H and 13 The C NMR data are consistent with those in the literature (M. Bingham, N.; J. Roth, P. Degradable Vinyl Copolymers through Thiocarbonyl Addition-Ring-Opening (TARO) Polymerization. Chem. Commun. 2019, 55(1), 55-58. https: / / doi.org / 10.1039 / C8CC08287A).

[0744] F2-DOO

[0745]

[0746] IUPAC name: 2,10-difluorodibenzo[c,e]oxepin-5(7H)-one

[0747] Procedure: The following is an adaptation of the method developed by Miyagawa and Akiyama. The major modifications involve concentration, workup, and purification. 2-Bromo-4-fluorobenzaldehyde (10.0 g, 49.3 mmol, 1.0 equiv), activated Zn powder (5.16 g, 78.9 mmol, 1.6 equiv), tetrabutylammonium iodide (36.4 g, 98.6 mmol, 2.0 equiv), and Ni(PPh3)2Cl2 (1.62 g, 2.47 mmol, 0.05 equiv) were charged to an oven-dried 500 mL Schlenk flask. The flask was then sealed with a rubber septum and deoxygenated by three vacuum / N2 cycles. Anhydrous, N2-purged o-xylene (150 mL) was added via cannula, and the stirred mixture was then heated to 135°C (internal temperature). The rubber septum was replaced with a ground glass stopper, and the stirred mixture was heated at 135°C for 18 hours. The hot biphasic mixture was then transferred to a separatory funnel, and the top clear layer (o-xylene) was set aside. The dark brown, viscous bottom layer (primarily tetrabutylammonium iodide) was extracted with toluene (50 mL). The combined o-xylene / toluene layers were filtered through a plug of silica gel (~20 g), the plug was rinsed with CHCl (250 mL), and the filtrate was concentrated by rotary evaporation at room temperature and then at 70-80°C. The residue was dissolved in a small amount of boiling CHCl (15-20 mL), the solution was diluted with MeOH (150 mL), and the volume of the resulting mixture was reduced to approximately 50 mL by rotary evaporation. The precipitate was collected on a sintered funnel, washed with MeOH (3 x 20 mL), and dried under high vacuum to afford F2-DOO (2.80 g, 46%) as an off-white solid.

[0748] Characterization: 1 H NMR (chloroform-d, 400MHz): δ = 8.04 (dd, J = 8.6, 5.8Hz, 1H), 7.47 (dd, J = 8.4, 5.5Hz, 1H), 7.33 (dd, J=9.3,2.6Hz,1H),7.30-7.22(m,2H),7.16(td,J=8.3,2.6Hz,1H),5.00(d,J=4.5Hz,2H); 19 F{ 1 H} NMR (chloroform-d, 376 MHz): δ = -105.3, -110.1; 13 C{1 H}NMR: see spectrum below; HRMS-DART-TOF(m / z):[M+H] + Calculated value C 14 H9O2F2, 247.0565; measured value 247.0584.

[0749] F-DOO

[0750]

[0751] IUPAC name: 2-Fluorodibenzo[c,e]oxepin-5(7H)-one

[0752] Procedure: Methyl 2-bromo-4-fluorobenzoate (10.0 g, 42.9 mmol, 1.0 equiv), 2-formylphenylboronic acid (8.36 g, 55.8 mmol, 1.3 equiv), anhydrous K 3 PO 4 powder (11.8 g, 55.8 mmol, 1.3 equiv), and Pd(PPh 3 ) 4 (0.50 g, 0.43 mmol, 0.01 equiv) were placed in a 100 mL Schlenk flask. The flask was sealed with a rubber septum and deoxygenated using three vacuum / N 2 cycles. Anhydrous, N 2 -purged DMF (43 mL) was added via syringe, and the stirred mixture was heated at 120° C. (oil bath temperature) under a light N 2 flow for 24 h. *The mixture was partitioned between EtOAc (200 mL) and water (200 mL), and the organic layer was then washed with water (200 mL) and saturated aqueous NaCl solution (200 mL), dried over MgSO4, filtered into a 500 mL round-bottom flask, and concentrated by rotary evaporation. Remaining volatiles were removed under high vacuum (~1 hour) to yield 11.4 g of a golden oil. A magnetic stirrer and anhydrous EtOH (200 mL) were then added to the flask. The resulting homogeneous solution was cooled to approximately 2°C using an ice / water bath, and NaBH4 (3.16 g, 83.6 mmol, 2 equiv) was then added portionwise over 5-10 minutes, ensuring that the temperature did not exceed 10°C. At the end of the addition, the cooling bath was removed, and the mixture was allowed to warm to room temperature and stirred for an additional 2 hours. The reaction was quenched by the careful addition of water (300 mL), and the precipitate was then collected by filtration and washed with water (3 x 50 mL). The resulting brown solid was dissolved in CH2Cl2 (125 mL), the solution was treated with MgSO4, and the mixture was then filtered through a silica gel plug (20 g). The plug was eluted with CH2Cl2 until TLC indicated complete elution of the desired compound. The solvent was removed by rotary evaporation, and the resulting solid was further purified as follows. The crude solid was suspended in MeOH (75 mL), and the stirred suspension was boiled for about 3 minutes. The mixture was allowed to cool to room temperature, then filtered to collect the solid, washed with MeOH (2 x 30 mL), and dried under high vacuum. This gave F-DOO (5.20 g, 53%) as a white crystalline solid.

[0753] Notes: *Passed after 1 hour, 3 hours and 24 hours 1 H NMR spectrum analysis showed that the raw material conversions were 76%, 85% and 100%, respectively.

[0754] Characterization: 1H NMR (chloroform-d, 400 MHz): δ = 8.05 (dd, J = 8.7, 5.9 Hz, 1H), 7.65 (d, J = 7.7 Hz, 1H), 7.61-7.55 (m, 1H), 7.53-7.46 (m, 2H), 7.33 (dd, J = 9.7, 2.6 Hz, 1H), 7.27-7.21 (m, 1H), 5.20-4.88 (m, 2H); 19 F{ 1 H} NMR (chloroform-d, 376 MHz): δ = -105.85; 13 C{ 1 H} NMR: See spectrum below. 1 H NMR data are consistent with literature reports (Zhang, X.-S.; Zhang, Y.-F.; Li, Z.-W.; Luo, F.-X.; Shi, Z.-J. Groups. Angew. Chem. Int. Ed. 2015, 54(18), 5478-5482).

[0755] SPr-F-DOO

[0756]

[0757] IUPAC name: 10-fluoro-2-(propylthio)dibenzo[c,e]oxepin-5(7H)-one

[0758] Procedure: F 2-DOO (1.40 g, 5.69 mmol, 1.0 equiv), K2CO3 (2.36 g, 17.1 mmol, 3.0 equiv), and anhydrous DMF (21 mL) were placed in a 100 mL Teflon-stoppered flask. The flask was briefly deoxygenated using three rapid vacuum / N2 cycles (approximately 15 seconds each), followed by the addition of 1-propanethiol (0.477 g, 6.26 mmol, 1.10 equiv) via syringe. The flask was sealed, and the vigorously stirred mixture was heated at 90°C for 1 hour. The mixture was cooled to room temperature, diluted with EtOAc (100 mL), washed with water (2 x 100 mL) and saturated aqueous NaCl solution (100 mL), dried over MgSO4, and filtered. The solvent was removed from the filtrate by rotary evaporation, and the residue was purified by column chromatography (50-100% CH2Cl2 in hexanes) to provide SPr-F-DOO (1.41 g, 82%) as a white solid.

[0759] Characterization: 1 H NMR (chloroform-d, 400MHz): δ = 7.93-7.88 (m, 1H), 7.44 (dd, J = 8.4, 5.5Hz, 1H), 7.42-7.37 (m, 2H), 7.33 (dd, J = 9.5, 2.6Hz, 1H), 7.13(td,J=8.3,2.6Hz,1H),5.09-4.89(m,2H),3.03(t,J=7.3Hz,2H),1.78(sext,J=7.3Hz,2H),1.09(t,J=7.3Hz,3H); 19 F{ 1 H} NMR (chloroform-d, 376 MHz): δ = -110.6; 13 C{ 1 H} NMR (chloroform-d, 101MHz): δ = 169.76, 163.72 (d, J = 249Hz), 144.83, 140.98 (d, J = 8.1Hz), 136.71 (d, J = 2.2Hz), 132.75, 131.19 (d, J = 3.1Hz), 130.7 0(d,J=8.8Hz),127.03,126.86,126.39,115.78(d,J=22.3Hz),115.54(d,J=23.0Hz),68.35,34.18,22.26,13.61; HRMS-DART-TOF(m / z):[M+H] + Calculated value C 17 H 16 O2FS, 303.0850; measured value 303.0867.

[0760] SPr-DOO

[0761]

[0762] IUPAC name: 2-(propylthio)dibenzo[c,e]oxepin-5(7H)-one

[0763] Procedure: This compound was prepared in the same manner as SPr-F-DOO, but using 1.2 equivalents of 1-propanethiol and column chromatography using 100% CH2Cl2. SPr-DOO was obtained as a white solid in a yield of 2.02 g (81%).

[0764] Characterization: 1 H NMR (chloroform-d, 400 MHz): δ = 7.92 (d, J = 8.3 Hz, 1H), 7.68-7.62 (m, 1H), 7.56 (ddd, J = 7.8, 6.3, 2.5 Hz, 1H), 7.52-7.41 (m, 3H), 7.39 (dd, J = 8.3, 1.9 Hz, 1H), 5.18-4.88 (m, 2H), 3.04 (t, J = 7.2 Hz, 2H), 1.79 (sext, J = 7.3 Hz, 2H), 1.10 (t, J = 7.4 Hz, 3H); 13 CNMR (chloroform-d, 101 MHz): δ = 170.11, 144.39, 138.76, 137.81, 135.08, 132.59, 130.27, 129.00, 128.72, 128.59, 127.06, 126.60, 126.41, 69.23, 34.20, 22.31, 13.61; HRMS-DART-TOF (m / z): [M+H] + Calculated value C 17 H 17 O2S, 285.0944; measured value 285.0951.

[0765] OMe2-DOO

[0766]

[0767] IUPAC name: 2,10-dimethoxydibenzo[c,e]oxepin-5(7H)-one

[0768] Procedure: The compound was prepared according to F 2- DOO was prepared as per the procedure except that the combined o-xylene / toluene extracts were concentrated by rotary evaporation at 70-80° C. and purified by column chromatography (50-100% CH 2 Cl 2 in hexanes) to afford OMe 2 -DOO as a white solid (0.77 g, 25%).

[0769] Characterization: 1 The H NMR spectrum was consistent with that shown in the literature (Dana, S.; Chowdhury, D.; Mandal, A.; Chipem, FAS; Baidya, M. Ruthenium (II) Catalysis / Noncovalent Interaction Synergy for Cross-Dehydrogenative Coupling of Arene Carboxylic Acids. ACS Catal. 2018, 8(11), 10173-10179).

[0770] Deconstructible polystyrene (dPS)

[0771] Evaluation of solvents for dPS synthesis

[0772] Solvent screening procedure (Table 1, entries 1-6): To a 4 mL vial containing DOT (0.150 mmol) was added stock solutions of styrene (1.50 mmol), AIBN (0.015 mmol), and TMB (0.045 mmol, internal standard) (added by mass). To this mixture was then added the relevant solvent (0.75 mL). The vial was capped and the mixture was vortexed until homogeneous and transferred to a J-Young NMR tube. The contents of the tube were deoxygenated by three free pump thaw cycles and then backfilled with N2. A baseline was acquired 1 H NMR spectrum (d1 = 10s), and then the mixture was placed in an oil bath preset at 70 ° C for 18 hours. Then the second 1 H NMR spectroscopy was used to determine the conversion values. For MeCN and DMSO-d6, precipitates formed, so these mixtures were homogenized by adding CDCl3 before analysis. The polymer was isolated by precipitation into MeOH (2-3x using CH2Cl2 as solvent) to give a pale yellow to white powder. 1 H NMR spectrum and SEC analysis, and as Figure 22 Degradation shown.

[0773] Evaluation of the DOT Substituent (XY-DOT): Synthesis of XY-dPS

[0774] DOT derivative (XY-DOT) screening program (Table 1, entries 7-11), including kinetic analysis: These studies were performed in parallel. First, stock solutions of styrene (703 mg), TMB (37.8 mg), and AIBN (12.3 mg) were prepared. Next, a vial was charged with XY-DOT (0.075 mmol), followed by 75 mg of the above stock solution (representing 0.675 mmol styrene, 0.0075 AIBN, and 0.0225 mmol TMB) and toluene-d8 (0.65 mL). The vial was capped and the mixture was vortexed until homogeneous and transferred to a J-Young NMR tube. The contents of the tube were deoxygenated by three free pump thaw cycles and then backfilled with N2. A baseline was acquired 1 H NMR spectrum (d1 = 10s), and then the mixture was placed in an oil bath preset at 70 ° C for 1 h. 1 The conversion value was determined by H NMR spectroscopy. This process was repeated and the results were acquired at 70 °C after 3, 5.5 and 30 h. 1 H NMR spectrum. The copolymer (XY-dPS) was isolated by precipitation into MeOH (2-3x, using CH2Cl2 as solvent) to give a pale yellow to white powder. 1 H NMR spectroscopy and SEC analysis were performed and degradation was performed as described below. Kinetic analysis results are shown in Figures 8A to 8B As shown, they present in more detail the data provided in Table 1 of the main text. Preparation of low M nanostructured carbon nanotubes with variable composition by ACHN-initiated solution polymerization W dPS

[0775] Procedure: A 150 mL Teflon-stoppered flask was charged with DOT (1.30 g, 5.74 mmol, 10 equiv), styrene (5.39 g, 51.7 mmol, 90 equiv), 1,1′-azobis(cyanocyclohexane) (0.140 g, 0.574 mmol, 1.00 equiv), 1,3,5-trimethoxybenzene (0.0965 g, 0.574 mmol, 1.00 equiv, internal standard) and toluene (52 mL). The mixture was deoxygenated by three free pump thaw cycles and backfilled with N2. The stirred homogeneous mixture was heated at 100 °C for 24 h (Note: Before sealing the flask, the contents were allowed to equilibrate under a light N2 flow for 15 min to avoid pressure buildup). Aliquots were taken before and after heating and the mixture was filtered by 1H NMR spectroscopy quantified the consumption of DOT and styrene (88% and 80%, respectively). The polymer was isolated as follows. The reaction mixture was added dropwise over 5-10 minutes to rapidly stirred MeOH (600 mL) in a 1000 mL Erlenmeyer flask. The residue was transferred using CH2Cl2 (2 x 5 mL). The precipitate was collected in a 60 mL medium porosity sintered funnel. Two more 50 mL portions of MeOH were used to quantitatively transfer the solid from the flask to the sintered funnel. Three additional precipitations were performed using the same amount of solvent, replacing toluene with CH2Cl2. A pale yellow color indicated the presence of DOT. The solid was dried under high vacuum for approximately 24 hours to give dPS (11) (5.05 g, 74%) as a free-flowing white powder. F DOT =11%,M n,SEC =12.5 kDa, M w,SEC =20.8 kDa,

[0776] Similar polymers PS-L (0.57 g, 67%), dPS (2.6) (0.73 g, 68%), dPS (5.8) (0.33 g, 66%), dPS (22) (0.18 g, 61%), dPS (55) (0.22 g, 74%), and pDOT (0.53 g, 87%) were prepared as white powders (except for pDOT, which was initially a flocculent white solid and could be made into a powder by grinding). The preparation procedures were the same as above except where noted. The reaction times were 32, 24, 36, 36, 40, and 20 h, respectively (note that the conversion essentially ceased after 24 h due to exhaustion of the initiator, so these time differences were not significant). The amount of ACHN initiator was 1.0 mol% based on the total amount of monomers. For dPS (22) and dPS (55), due to the heterogeneity of the initial reaction mixture, the first sample had to be removed after a brief (<1 min) gentle heating to provide a representative sample for analysis. Several controls were performed without the 1,3,5-trimethoxybenzene internal standard and gave the same results.

[0777] Characterization: Specific values ​​are given in Table 2 of the text, and the corresponding spectra are given in the figures.

[0778] Preparation of high M by bulk polymerization without adding initiator W dPS

[0779] Procedure 1 (1-5 g scale): This procedure corresponds to that of Table 4, entry 10. * A mixture of DOT (0.278 g, 1.23 mmol, 2.5 eq.) and styrene (5.00 g, 48.0 mmol, 97.5 eq.) (pre-mixed in a vial to ensure homogeneity) was added to a 100 mL round-bottom flask with a Teflon stopper, and an aliquot was taken and passed through 1H NMR spectroscopy was performed to determine the DOT The exact value (2.46%) was obtained and oxygen was released from the contents of the flask by three freeze-pump-thaw cycles. The flask was sealed** and immersed in an oil bath preset to 125°C to the midpoint***. The mixture was gently stirred to ensure homogeneity****. The mixture was allowed to stand at this temperature for 12 hours, after which the mixture solidified. The solid was dissolved in CH2Cl2 (50 mL) and the mixture was stirred by 1 A sample was analyzed by HNMR spectroscopy, and DOT and styrene conversion values ​​were obtained (77% and 75%, respectively). The polymer was then subjected to the same precipitation procedure as dPS (11) to obtain dPS (2.4)-hMW (3.4 g, 64%) as a fibrous flocculent white solid. DOT =2.43%,M n,SEC =145 kDa, M w,SEC =278kDa,

[0780] Procedure 2 (>20 g scale): This procedure corresponds to that of Table 4, entry 14. *The main difference here (compared to Procedure 1) is the equipment, which was modified for safety reasons (an open system was used due to the larger scale). A mixture of DOT (1.11 g, 4.92 mmol, 2.5 eq) and styrene (20.0 g, 192 mmol, 97.5 eq) (pre-mixed in a vial to ensure homogeneity) was charged to a 200 mL pear-shaped flask, an aliquot was taken and passed through 1 H NMR spectroscopy was performed to determine the DOT The flask was prepared by adding a Vigreux column and a N2 inlet (both with lightly greased ground glass joints) to the reaction mixture. The oxygen in the apparatus was removed by three freeze-pump-thaw cycles, and the apparatus was then placed under a gentle N2 flow to complete the remaining reaction. The flask was immersed in an oil bath preset to 130°C to the midpoint** and the mixture was gently stirred to ensure homogeneity***. The mixture was allowed to stand at this temperature for 15 hours, after which the mixture was solidified. The solid material was dissolved in CH2Cl2 (150 mL) and filtered through 1 A sample was analyzed by H NMR spectroscopy to obtain DOT and styrene conversion values ​​(89% and 88%, respectively). The polymer was then subjected to the same precipitation procedure as dPS (11), but using different relative solvent amounts (275 mL CH2Cl2 and 1500 mL MeOH for each precipitation), to obtain dPS (2.5) -hMW (16.7 g, 64%) as a fibrous flocculent white solid. DOT =2.45%,M n,SEC =159 kDa, M w,SEC=312 kDa,

[0781] Note: *All other dPS (F DOT )-hMW samples were prepared using either of these two procedures. **We recommend the use of a blast shield; ***Because temperature is the primary determinant of molecular weight parameters in thermally initiated styrene polymerization, any factors that affect heat transfer will affect the results; ****DOT may precipitate during the freeze-pump-thaw process.

[0782] Deconstruction Research

[0783] Degradation of XY-dPS with n-propylamine in air (Table 1, entries 1-11)

[0784] In air, a 4 mL vial containing the relevant XY-dPS (6 mg) and n-propylamine (0.5 mL) was capped, and the resulting homogeneous mixture was allowed to stand at room temperature. After 3 days, a 0.25 mL aliquot was concentrated to dryness by rotary evaporation. In order to remove residual n-propylamine, the residue was dissolved in CHCl (0.5 mL), and the solution was concentrated to dryness by rotary evaporation. After 7 days at room temperature, this separation process was repeated for the remaining mixture, and each sample was then analyzed by SEC. In all cases, the SEC traces after 3 and 7 days were almost indistinguishable (Figure 27), indicating that each reaction was complete.

[0785] From dPS(F DOT ) deconstructed Pr-OS(F DOT )

[0786]

[0787] Procedure: dPS (11) (305 mg, 0.267 mmol thioester units, 1.0 equiv) was charged to a 10 mL flask with a Teflon stopper. The flask was deoxygenated with 3 vacuum / N2 cycles*, and then deoxygenated n-propylamine (2.0 mL) was added via syringe. The resulting homogeneous stirred mixture was immersed in an oil bath preset at 50°C for 6 h. The mixture was allowed to cool to room temperature and concentrated to dryness under high vacuum. The residue was dissolved in deoxygenated CHCl (2 mL) and the volatiles were again removed under vacuum. **Repeat 1x. Finally, the residue was quantitatively transferred to a 20 mL vial containing CHCl (~1 mL) and cyclohexane*** (~6 mL), and the mixture was concentrated to dryness by rotary evaporation and dried under high vacuum for approximately 1 h, after which the foam was broken up with a spatula. The contents of the vial were placed under high vacuum overnight to afford Pr-OS (11) (329 mg, >98%****) as a free-flowing colorless solid. M n,SEC =1.1 kDa, M w,SEC=2.1 kDa,

[0788] Similar fragments Pr-OS(2.6), Pr-OS(5.8), Pr-OS(22), Pr-OS(55), and oDOT were prepared in the same manner as colorless solids in similarly high yields. The only difference was the reaction time for Pr-OS(2.6) and Pr-OS(5.8) (36 h each).

[0789] NOTE: *Performing this reaction in air will produce a complex mixture of end groups resulting from the initial oxidation of the thiol to the disulfide followed by further unidentified degradation reactions. It is best to exclude air until all n-propylamine is removed. **The purpose of this dissolution / evaporation step is to ensure complete evaporation of the n-propylamine prior to exposure to air. ***This transfer solvent was chosen for the following reasons: 1) Its relatively high boiling point (81°C) ensures removal of other volatile species whose resonances may mask the 1 The following are the key regions of the H NMR spectrum (cyclohexane produces a single peak in the less important region); 2) We found complete solvent removal from these oligomers to be very difficult, and the residual cyclohexane is expected to be inert in almost any subsequent transformation; 3) The physical properties of the solid produced by evaporation of cyclohexane are that of a voluminous, easily weighable powder. ****Contains ~10 mg of cyclohexane.

[0790] Allyl-OS(11)

[0791]

[0792] Procedure: The procedure was the same as for Pr-OS(11) to give allyl-OS(11) (333 mg, >98%) as a free-flowing colorless solid. n,SEC =1.1 kDa, M w,SEC =2.0 kDa,

[0793] te-OS(11)

[0794]

[0795] Procedure: dPS (11) (503 mg, 0.440 mmol thioester units, 1.0 eq) and EtSH (1.00 mL, 862 mg, 13.9 mmol, 31 eq) were charged into a 20 mL Teflon stoppered flask. The solution was deoxygenated by three free pump-thaw cycles, and then deoxygenated DBU (7.9 mg, 0.052 mmol, 0.12 eq) was added via syringe, resulting in an immediate color change from colorless to light yellow. The flask was sealed and the mixture was stirred at room temperature for 22 hours. The reaction was terminated by the addition of deoxygenated AcOH (30 uL, 0.53 mmol, 1.2 eq) under a stream of N2. The mixture turned from light yellow to colorless within 15 minutes and was then diluted with EtOAc (30 mL), washed with water (3 x 30 mL) and saturated aqueous NaCl solution (30 mL), dried over Na2SO4 and filtered. The solvent was removed from the filtrate by rotary evaporation and the residue was transferred to a 20 mL vial as described for Pr-OS (11) (volume adjusted linearly) to give 537 mg of a free-flowing colorless solid. 1 H NMR spectroscopy determined that it was 90% by mass of te-OS (11). The remaining mass was DTO (6%) and cyclohexane (4%). Adjusting these known components, the isolated yield of te-OS (11) was 483 mg (93%). n,SEC =1.3 kDa, M w,SEC =2.1 kDa,

[0796] DTO self-decomposed from pDOT

[0797] Procedure: A solution of pDOT (50 mg, 0.22 mmol repeat unit, 1.0 eq) and mesitylene (18 mg, 0.15 mmol, 0.7 eq, internal standard) in DMF (0.7 mL) was charged into a J-Young NMR tube and a baseline was obtained. 1 H NMR. The solution was subjected to two freeze-pump-thaw cycles, and then 1-propanethiol (6.2 uL, 5.1 mg, 0.66 mmol, 0.30 equiv) and triethylamine (9.2 uL, 6.7 mg, 0.66 mmol, 0.30 equiv) were quickly added to the frozen solution under tapered N2. The mixture was subjected to two more free pump thaw cycles, backfilled with N2, and allowed to stand at room temperature. After 20 minutes and 13 hours, 1 H NMR indicated that the yields of DTO were 50% and >98%, respectively. The mixture was poured into a vial, the tube was rinsed with CH2Cl2, and the volatiles were removed by rotary evaporation at room temperature and then at 70°C. The residue was subjected to preparative thin layer chromatography (1:1 hexanes:CH2Cl2) to afford DTO (47 mg, 94%) as a colorless oil. 1H NMR (benzene-d6, 400MHz): δ = 7.74 (dd, J = 7.7, 1.5Hz, 1H), 7.06 (td, J = 7.5, 1.5Hz, 1H), 7. 02-6.92(m,5H),6.74-6.68(m,1H),3.75(d,J=14.0Hz,1H),2.71(d,J=14.1Hz,1H).

[0798] 13 C NMR (chloroform-d, 101 MHz): δ = 199.03, 139.22, 138.27, 138.10, 137.53, 132.21, 130.84, 130.47, 128.78, 128.63, 128.56, 128.34, 126.50, 34.16.

[0799] Thiol-OS(11)

[0800]

[0801] Procedure: dPS (11) (520 mg, 0.455 mmol thioester unit, 1.0 eq), cysteamine hydrochloride (78 mg, 0.68 mmol, 1.5 eq) and DMF (1.5 mL) were charged into a 20 mL Teflon stoppered flask. The solution was deoxygenated by 3 free pump-thaw cycles, and then deoxygenated DBU (125 mg, 0.82 mmol, 1.8 eq) was added dropwise via syringe under a stream of N2. The flask was sealed and the mixture was stirred at room temperature for 18 hours. AcOH (94 uL, 1.64 mmol, 3.6 eq) was added under a stream of N2 to quench the reaction. After 15 minutes, the colorless mixture was diluted with EtOAc (30 mL), washed with water (3×30 mL) and saturated aqueous NaCl solution (30 mL), dried over Na2SO4 and filtered. The solvent was removed from the filtrate by rotary evaporation and the residue was transferred to a 20 mL vial as described for Pr-OS (11) (volume adjusted linearly) to give 580 mg of a free-flowing colorless solid. 1 H NMR spectrum showed 94% by mass of thiol-OS (11) (the remainder being cyclohexane). Therefore, the isolated yield of thiol-OS (11) was 544 mg (98%). n,SEC =1.1 kDa, M w,SEC =2.0 kDa,

[0802] Thiol-OS(2.5)-hMW and Thiol-OS(5.0)-hMW

[0803]

[0804] Procedure 1 (Purification by Precipitation): dPS(2.5)-hMW (8.00 g, 1.83 mmol thioester units, 1.0 equiv) and a magnetic stir bar were placed in a 250 mL round-bottom Schlenk flask, sealed with a rubber septum, and placed under a N2 atmosphere, with three vacuum / N2 cycles. A separate 100 mL round-bottom Schlenk flask was also charged with cysteamine hydrochloride (0.416 g, 3.66 mmol, 2.0 equiv) and deoxygenated DMF (37 mL), followed by the dropwise addition of DBU (0.836 g, 5.49 mmol, 3.0 equiv) via syringe. The contents of this flask were transferred via cannula to the flask containing dPS(2.5)-hMW, and the resulting mixture was stirred at room temperature under N2 for 24 h. The reaction was quenched by the addition of deoxygenated AcOH (0.66 mL, 11.5 mmol, 6.3 equiv). After 15 minutes, the mixture was transferred to a 1 L separatory funnel with the aid of EtOAc (350 mL), washed with water (3x 350 mL) and saturated aqueous NaCl solution (350 mL), dried over Na2SO4 and filtered. The solvent was removed from the filtrate by rotary evaporation, and the oligomer was purified as follows. The residue was dissolved in CH2Cl2 (40 mL), and the solution was added dropwise to stirred MeOH (400 mL). The precipitate was collected by filtration and washed with MeOH (30 mL). The precipitation procedure was repeated 1x, and the solid was then placed under high vacuum at room temperature until a constant mass was obtained. Thiol-OS(2.5)-hMW (7.06 g, 88%) was obtained as a white powder. M n,SEC =5.49 kDa, M w,SEC =9.59 kDa,

[0805] The precipitated thiol-OS(5.0)-hMW was prepared in the same manner with a yield of 83% (5.71 g). n,SEC =3.29 kDa, M w,SEC =5.18 kDa,

[0806] Procedure 2 (crude isolation): Same as procedure 1 with the following differences. 3.03 g of dPS(2.5)-hMW was used, and the other amounts were scaled linearly. After rotary evaporation, the residue was isolated by solvent transfer as described for Pr-OS(11) (volumes adjusted linearly) to give 3.38 g of a free-flowing colorless solid. 1 H NMR spectrum showed 89% by mass of thiol-OS(2.5)-hMW (the remainder being cyclohexane). Therefore, the isolated yield of thiol-OS(2.5)-hMW was 3.02 g (98%). n,SEC =4.40 kDa, Mw,SEC =9.06kDa,

[0807] Crude thiol-OS(5.0)-hMW was prepared in the same manner with a yield >98% (0.73 g). n,SEC =2.11 kDa, M w,SEC =4.49 kDa,

[0808] Note: * Manual stirring immediately after addition is preferred to obtain a homogeneous solution.

[0809] Recycled polystyrene (rPS)

[0810]

[0811] I2 / pyr stock solution (representative procedure).

[0812] To a 5.00 mL volumetric flask, charge a small magnetic stir bar, powdered I2 (877 mg, 3.46 mmol, 1.0 equiv), pyridine (545 mg, 6.89 mmol, 2.0 equiv), and CHCl (3 mL). Stir the mixture until homogeneous, then carefully add CHCl to bring the volume to 5.00 mL. The final I2 concentration is 325 mg / mL (1.28 mmol / mL). Use this solution within 30 minutes of preparation.

[0813] rPS(11)

[0814] Procedure 1 (isolation by direct precipitation): A 4 mL vial was charged with a magnetic stir bar, thiol-OS (11) (300 mg, 0.00168 mmol R-SH*, 0.504 mmol R-SH per mg polymer) and CHCl (600 uL). 236 uL of the above I / pyr stock solution (0.302 mmol or 0.60 equivalents of I) was then added dropwise to the stirred solution over 2-3 minutes. The mixture remained colorless until 70-75% of the addition was complete, after which the color changed significantly to yellow / brown. The mixture was stirred at room temperature for an additional hour, diluted with CHCl to a total volume of 4 mL, and then added dropwise to rapidly stirring MeOH (50 mL). The solid was collected using a 15 mL sintered funnel and washed with MeOH (2 x 5 mL). This precipitation procedure was repeated until a white solid was obtained (typically 3-4x in total). To avoid excessive mechanical losses, all products were quantitatively mixed with CHCl before subsequent precipitation. The final product was dried in a vacuum oven at 50°C for 3 hours to obtain 250 mg (89%) of white powder. n,SEC =12.3 kDa, M w,SEC =22.3 kDa,

[0815] Note: *Since excess I2 was found not to affect the outcome of this reaction, for simplicity, the R-SH concentration was assumed to be twice the thioester concentration in the precursor dPS. The actual value is lower due to the presence of cyclohexane (this is taken into account in the yield calculation).

[0816] Procedure 2 (Isolation by aqueous workup): The first part of the procedure was the same as Procedure 1. After the reaction was complete, the mixture was quantitatively transferred to a separatory funnel containing EtOAc (50 mL), then washed with 3% aqueous sodium thiosulfate (50 mL), aqueous HCl (1 M, 50 mL), water (50 mL), and brine (50 mL), dried over Na2SO4, filtered, and the filtrate was concentrated by rotary evaporation and then subjected to high vacuum. The residue was then analyzed by SEC. M n,SEC =11.4 kDa, M w,SEC =22.6 kDa,

[0817] rPS(2.5)-hMW and rPS(5.0)-hMW

[0818] Oligomer from Precipitation: A 40 mL vial was charged with a magnetic stir bar, precipitated thiol-OS(2.5)-hMW (3.00 g, 0.000458 mmol R-SH*, 1.37 mmol R-SH per mg polymer), and CHCl (6.00 mL). An I / pyr / CHCl solution (2.36 mL total volume, 0.822 mmol I and 1.64 mmol pyr), prepared similarly to the above method, was then added dropwise to the stirred solution over 2-3 minutes. The mixture remained colorless until 59% of the addition was complete, after which the color changed significantly to yellow / brown. At this point, the viscosity increased dramatically, the magnitude of which correlated with the molecular weight of the polymer product. At this point, the mixture was stopped and the remaining addition required mixing using a vortexer. The mixture was allowed to stand at room temperature for another hour and quantitatively transferred to a separatory funnel with the aid of EtOAc (final volume 250 mL), then washed with 3% aqueous sodium thiosulfate (250 mL), aqueous HCl (1 M, 250 mL), water (250 mL), and brine (250 mL), dried over Na2SO4, filtered, and the filtrate concentrated by rotary evaporation. The residue was then dissolved in CHCl (50 mL), and the solution was added dropwise to rapidly stirred MeOH (500 mL). The solid was collected in a 60 mL sintered funnel, washed with MeOH (2 x 20 mL), and dried under high vacuum at room temperature to afford rPS(2.5)-hMW (2.87 g, 96%) as a flocculent white solid. A 0.1x scale experiment (300 mg) yielded a polymer with the same molecular weight distribution, as determined by SEC. From SEC (main peak ***), M n =165kDa, M w =322 kDa and

[0819] The same procedure was used for rPS(5.0)-hMW. The concentrations of I2 / pyr / CH2Cl2 were adjusted to make the total volume the same. The mixture remained colorless until 47% of the addition was complete. The isolated yield of rPS(5.0)-hMW was 2.84 g (95%). From SEC (main peak ***), it can be seen that M n =163 kDa, M w =312 kDa, and

[0820] From crude oligomer: The procedure was identical to that using the precipitated oligomer, with the following exceptions: The mixture was very viscous, but stirred easily throughout the reaction. The mixture remained colorless until 69% of the addition was complete. The isolated yield of rPS(2.5)-hMW was 95%. From SEC (main peak ***), M n=125 kDa, M w =241kDa and

[0821] The same method was used for rPS(5.0)-hMW, and the same observations were made, except that the mixture remained colorless until 69% of the addition was complete. The isolated yield of rPS(5.0)-hMW was 93%. From SEC (main peak ***), it can be seen that M n =100 kDa, M w =184 kDa,

[0822] Notes: *Because excess I2 was found not to affect the outcome of this reaction, for simplicity, the R-SH concentration was assumed to be twice the thioester concentration in the precursor dPS. The actual value is lower. **Due to the high viscosity of the final reaction mixture, extreme care was taken to avoid splashing the solution down the side of the vial. ***As described in the main text, each recovered PS sample has a shoulder peak in the SEC trace. The spectra were deconvoluted, and the data shown here are for the main peak, which accounts for 90-95% of the mass. For M w The calculation of the values ​​includes this shoulder, and the values ​​are comparable.

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[0866] Example 2.

[0867] Synthesis, deconstruction and reconstruction of copolymers

[0868] General pathways for replacing DOT

[0869] Three different substitution strategies for DOT were developed, all ultimately undergoing thiolation using Lawesson's reagent to generate the desired DOT derivatives (Figure 48). These strategies differ only in the synthetic details of the dibenzo[c,e]oxepin-5(7H)-one (DOO) precursor of the DOT derivatives.

[0870] Determination of the solubility of DOT in styrene

[0871] As described in this paper, by quantitative 1 The solubility of DOT in styrene at 22°C was determined by H NMR spectroscopy to be 1.0 molar equivalent of DOT per 35 molar equivalents of styrene. First, a saturated solution of DOT in styrene was prepared. To a vial containing 20 mg (0.088 mmol) of freshly recrystallized DOT was added 145 mg (16 equivalents) of styrene. The mixture was vortexed for approximately 5 minutes and then allowed to stand for 10 minutes. A large amount of solid DOT remained. The mixture was passed through a 0.2 μm filter into an NMR tube (the temperature during filtration was 22°C). The mixture was then diluted with chloroform-d and quantitatively analyzed by 1 H NMR spectroscopy was used for analysis ( Figure 50 ).

[0872] Deconstruction of cross-linked styrene copolymers

[0873] The results presented here should be applicable to any styrene copolymer. As cross-linked variants are of great commercial importance and are particularly difficult to deconstruct, a styrene / divinylbenzene resin system was chosen as a proof of concept ( Figure 48A Notably, this is perhaps one of the most challenging targets due to the lack of naturally cleavable bonds (unlike other networks such as styrene-butadiene rubber and “vinyl ester” resins, which contain polysulfide and ester bonds, respectively).

[0874] For our proof-of-concept network deconstruction study ( Figure 48A ), the more soluble SPr-DOT was used instead of DOT because it can prepare homogeneous resins in a wider range of comonomer loading. The resin containing DVB and ACHN (1 mol% each) was doped with SPr-DOT (f SPr-DOT = 1, 3 and 5 mol%) and oven cured at 100°C for 18 h, far exceeding the time required to ensure maximum crosslinking. In all cases, >95% of the SPr-DOT was incorporated into the network, which was determined by exhaustive extraction with CH2Cl2 followed by quantitative 1 The extracts were determined by H NMR spectroscopy. The extracts were treated with 3% DBU in EtSH (chosen for its fast decomposition kinetics) to give SPr-DOT >1% of the sample was completely dissolved within 1 hour. SPr-DOT =1%), partial dissolution (~50%) was observed. 1 H NMR and SEC characterization ( Figure 48C ). The former looks almost identical to te-OS(11). As expected, M n The value increases with f SPr-DOT and is higher than expected and M n The values ​​may be attributed to the heterogeneity of the vinyl network generated by bulk free radical polymerization.

[0875] Equivalents and scope

[0876] In the claims, words such as "a," "an," and "the" may refer to one or more than one, unless the context indicates otherwise or is otherwise clear. For claims or specifications that include "or" between one or more members of a group, the claim is considered satisfied if one, more than one, or all of the members of the group are present, employed, or otherwise related to a given product or process, unless otherwise indicated or obvious from the context. The invention includes embodiments in which only one member of the group is present, employed, or otherwise related to a given product or process. The invention includes embodiments in which more than one or all of the members of the group are present, employed, or otherwise related to a given product or process, unless otherwise indicated or obvious from the context.

[0877] In addition, the present invention includes all variations, combinations and arrangements, wherein one or more limitations, elements, words and descriptive terms in one or more listed claims are introduced into another claim. For example, any claim that is subordinate to another claim can be modified to include one or more limitations in any other claim that is subordinate to the same basic claim. When an element is presented in a list, for example, in the form of a Markush group, each subset of the element is also disclosed, and any element can be removed from the group. It should be understood that, in general, when the present invention or various aspects of the present invention are specified to include specific elements and / or features, some embodiments of the present invention or various aspects of the present invention are composed of such elements and / or features, or are substantially composed of such elements and / or features. For the purpose of simplicity, those embodiments are not specifically described in this article. It should also be noted that the terms "including" and "containing" are intended to be open and allow the inclusion of other elements or steps. When a range is given, the endpoints are included. Furthermore, unless otherwise noted or clearly indicated otherwise by the context and understanding of those skilled in the art, values ​​expressed in ranges may take any specific value or sub-range within the range recited in the various embodiments of the invention, to the tenth of the lower limit of the range, unless the context clearly indicates otherwise.

[0878] The present application refers to various published patents, disclosed patent applications, periodicals and other publications, all of which are incorporated herein by reference. If there is a conflict between any reference cited and the present application, this specification shall prevail. In addition, any specific embodiment of the present invention that falls within the prior art may be clearly excluded from any one or more claims. Because such embodiments are considered to be known to those skilled in the art, even if the exclusion is not clearly mentioned in this article, they may also be excluded. Any specific embodiment of the present invention may be excluded from any claim for any reason, regardless of whether it relates to the existence of the prior art.

[0879] Those skilled in the art will appreciate or be able to ascertain, by use of no more than routine experimentation, many equivalents to the specific embodiments described herein. The scope of the specific embodiments described herein is not intended to be limited by the foregoing description, but rather by reference to the appended claims. Those skilled in the art will appreciate that various changes and modifications may be made to this description without departing from the spirit or scope of the present invention as defined by the claims.

Claims

1. A copolymer comprising: Examples of m1 first repeating units of formula i: Examples of m2 second repeating units of formula ii-A or ii-B: optionally one or more types of additional repeating units; in: The copolymer is substantially free of crosslinks; m1 is an integer between 10 and 1,000,000 (inclusive); m2 is an integer between 2 and 1,000,000 (inclusive); R 1 , R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl; Ring A is an aryl group; R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a 、-SCN、-SR a 、-SSR a 、-N3、-NO、-N(R a )2, -NO2, -C(=O)R a 、-C(=O)OR a 、-C(=O)SR a 、-C(=O)N(R a )2, -C(=NR a )R a 、-C(=NR a )OR a 、-C(=NR a )SR a 、-C(=NR a )N(R a )2, -S(=O)R a 、-S(=O)OR a 、-S(=O)SR a 、-S(=O)N(R a )2, -S(=O)2R a 、-S(=O)2OR a 、-S(=O)2SR a 、-S(=O)2N(R a )2, -OC(=O)R a 、-OC(=O)OR a 、-OC(=O)SR a 、-OC(=O)N(R a )2, -OC(=NR a )R a 、-OC(=NR a )OR a 、-OC(=NR a )SR a 、-OC(=NR a )N(R a )2. -OS(=O)R a 、-OS(=O)OR a 、-OS(=O)SR a 、-OS(=O)N(R a )2, -OS(=O)2R a 、-OS(=O)2OR a 、-OS(=O)2SR a 、-OS(=O)2N(R a )2、-ON(R a )2、-SC(=O)R a 、-SC(=O)OR a 、-SC(=O)SR a 、-SC(=O)N(R a )2、-SC(=NR a )R a 、-SC(=NR a )OR a 、-SC(=NR a )SR a 、-SC(=NR a )N(R a )2、-NR a C(=O)R a 、-NR a C(=O)OR a 、-NR a C(=O)SR a 、-NR a C(=O)N(R a )2、-NR a C(=NR a )R a 、-NR a C(=NR a )OR a 、-NR a C(=NR a )SR a 、-NR a C(=NR a )N(R a )2、-NR a S(=O)R a 、-NR a S(=O)OR a 、-NR a S(=O)SR a 、-NR a S(=O)N(R a )2、-NR a S(=O)2R a 、-NR a S(=O)2OR a 、-NR a S(=O)2SR a 、-NR a S(=O)2N(R a )2、-Si(R a )3、-Si(R a )2OR a , -Si(R a )(OR a )2, -Si(OR a )3, -OSi(R a )3, -OSi(R a )2OR a , -OSi(R a )(OR a )2 or -OSi(OR a )3; R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; n1 is 0, 1, 2, 3, 4 or 5, as long as the valence permits; R 7 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2, -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2, -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2, -S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2, -S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2, -OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2. -OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2, -OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、 -NR b S(=O)2N(R b )2, -Si(R b )3, -Si(R b )2OR b , -Si(R b )(OR b )2, -Si(OR b )3, -OSi(R b )3, -OSi(R b )2OR b , -OSi(R b )(OR b )2 or -OSi(OR b )3; is alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene; n2 is an integer between 0 and 14 (including the endpoint values), as long as the valence allows; each Examples of are independently a single bond or a double bond; R 8 Each instance of is independently: When attached to a carbon atom: halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2, -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2, -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2, -S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2, -S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2, -OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2. -OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2, -OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b 、-Si(R b )(OR b )2, -Si(OR b )3, -OSi(R b )3, -OSi(R b )2OR b , -OSi(R b )(OR b )2, -OSi(OR b )3, =O, =S or =NR b ; When attached to a nitrogen atom: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -OR b 、-N(R b )2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2, -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2, -S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2, -S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, or a nitrogen protecting group; or When attached to a sulfur atom: =O; And / or: R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and / or R 8 Two examples of and their middle atom together form a substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; and R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; The conditions are: R 1 , R 2 , R 3 , R 4 , Ring A, R 7 and R 8 None of them contain one or more non-aromatic unsaturated CC bonds; any additional monomer does not contain two or more non-aromatic unsaturated CC bonds; The second repeating unit does not have the formula: and If the first repeating unit has the following formula: Then the second repeating unit does not have the formula:

2. The copolymer of claim 1, prepared by a process comprising polymerizing a first monomer, a second monomer, and optionally one or more types of additional monomers, wherein: The first monomer has formula I: or a tautomer or a salt thereof; and The second monomer has formula II-A or II-B: or a tautomer or salt thereof, wherein is ring B, and ring B is a heterocycle; The conditions are: Ring B does not contain one or more non-aromatic unsaturated CC bonds; The second monomer does not have the formula: or a tautomer thereof; and If the first monomer is unsubstituted styrene, then the second monomer does not have the formula: or a tautomer thereof.

3. A method of preparing the copolymer of claim 2, comprising polymerizing the first monomer, the second monomer, and optionally one or more types of the additional monomers.

4. Homopolymers having the formula: or a salt thereof, wherein: m1 is an integer between 10 and 1,000,000, inclusive; R 1 , R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl; Ring A is an aryl group; R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a , –SCN, –SR a , –SSR a , –N3, –NO, –N(R a )2, –NO2, –C(=O)R a 、–C(=O)OR a 、–C(=O)SR a 、–C(=O)N(R a )2, –C(=NR a )R a , –C(=NR a )OR a , –C(=NR a )SR a , –C(=NR a )N(R a )2. –S(=O)R a 、–S(=O)OR a 、–S(=O)SR a , –S(=O)N(R a )2, –S(=O)2R a 、–S(=O)2OR a 、–S(=O)2SR a 、–S(=O)2N(R a )2. –OC(=O)R a 、–OC(=O)OR a 、–OC(=O)SR a 、–OC(=O)N(R a )2. –OC(=NR a )R a 、–OC(=NR a )OR a 、–OC(=NR a )SR a 、–OC(=NR a )N(R a )2. –OS(=O)R a 、–OS(=O)OR a 、–OS(=O)SR a 、–OS(=O)N(R a )2, –OS(=O)2R a 、–OS(=O)2OR a 、–OS(=O)2SR a 、–OS(=O)2N(R a )2、–ON(R a )2、–SC(=O)R a 、–SC(=O)OR a 、–SC(=O)SR a 、–SC(=O)N(R a )2、–SC(=NR a )R a 、–SC(=NR a )OR a 、–SC(=NR a )SR a 、–SC(=NR a )N(R a )2、–NR a C(=O)R a 、–NR a C(=O)OR a 、–NR a C(=O)SR a 、–NR a C(=O)N(R a )2、–NR a C(=NR a )R a 、–NR a C(=NR a )OR a 、–NR a C(=NR a )SR a 、–NR a C(=NR a )N(R a )2、–NR a S(=O)R a 、–NR a S(=O)OR a 、–NR a S(=O)SR a 、–NR a S(=O)N(R a )2、–NR a S(=O)2R a 、–NR a S(=O)2OR a 、–NR a S(=O)2SR a 、–NR a S(=O)2N(R a )2、–Si(R a )3、–Si(R a )2OR a , –Si(R a )(OR a )2, –Si(OR a )3, –OSi(R a )3, –OSi(R a )2OR a , –OSi(R a )(OR a )2 or –OSi(OR a )3; R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; n1 is 0, 1, 2, 3, 4 or 5, as long as the valence permits; R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b , –N3, –NO, –N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b 、–N3、–NO、–N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b , –C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b , –S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; and L 1 is substituted or unsubstituted alkylene or substituted or unsubstituted heteroalkylene; The conditions are: The condition is R 1 , R 2 , R 3 , R 4 , Ring A, R 10 , R 11 and L 1 The aromatic hydrocarbons do not contain one or more non-aromatic unsaturated CC bonds.

5. A process for preparing a homopolymer as claimed in claim 4, which comprises reacting a copolymer as claimed in any one of the preceding claims with a compound of the formula: HS-L 1 -NH2, or a salt thereof.

6. The homopolymer of claim 4 having the formula: or a salt thereof.

7. The homopolymer of claim 4 having the formula: or a salt thereof.

8. A copolymer comprising m3 examples of repeating units of formula III: in: m3 is an integer between 10 and 10,000, inclusive; Each instance of m1 is independently an integer between 10 and 1,000,000, inclusive; R 1 , R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl; Ring A is an aryl group; R 4 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR a 、-SCN、-SR a 、-SSR a 、-N3、-NO、-N(R a )2, -NO2, -C(=O)R a 、-C(=O)OR a 、-C(=O)SR a 、-C(=O)N(R a )2, -C(=NR a )R a 、-C(=NR a )OR a 、-C(=NR a )SR a 、-C(=NR a )N(R a )2, -S(=O)R a 、-S(=O)OR a 、-S(=O)SR a 、-S(=O)N(R a )2, -S(=O)2R a 、-S(=O)2OR a 、-S(=O)2SR a 、-S(=O)2N(R a )2, -OC(=O)R a 、-OC(=O)OR a 、-OC(=O)SR a 、-OC(=O)N(R a )2, -OC(=NR a )R a 、-OC(=NR a )OR a 、-OC(=NR a )SR a 、-OC(=NR a )N(R a )2. -OS(=O)R a 、-OS(=O)OR a 、-OS(=O)SR a 、-OS(=O)N(R a )2, -OS(=O)2R a 、-OS(=O)2OR a 、-OS(=O)2SR a 、-OS(=O)2N(R a )2、-ON(R a )2、-SC(=O)R a 、-SC(=O)OR a 、-SC(=O)SR a 、-SC(=O)N(R a )2、-SC(=NR a )R a 、-SC(=NR a )OR a 、-SC(=NR a )SR a 、-SC(=NR a )N(R a )2、-NR a C(=O)R a 、-NR a C(=O)OR a 、-NR a C(=O)SR a 、-NR a C(=O)N(R a )2、-NR a C(=NR a )R a 、-NR a C(=NR a )OR a 、-NR a C(=NR a )SR a 、-NR a C(=NR a )N(R a )2、-NR a S(=O)R a 、-NR a S(=O)OR a 、-NR a S(=O)SR a 、-NR a S(=O)N(R a )2、-NR a S(=O)2R a 、-NR a S(=O)2OR a 、-NR a S(=O)2SR a 、-NR a S(=O)2N(R a )2、-Si(R a )3、-Si(R a )2OR a , -Si(R a )(OR a )2, -Si(OR a )3, -OSi(R a )3, -OSi(R a )2OR a , -OSi(R a )(OR a )2 or -OSi(OR a )3; R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; n1 is 0, 1, 2, 3, 4 or 5, as long as the valence permits; R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b 、–N3、–NO、–N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b , –C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b , –S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b 、–N3、–NO、–N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b , –C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b , –S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b , -Si(R b )(OR b )2, -Si(OR b )3, -OSi(R b )3, -OSi(R b )2OR b , -OSi(R b )(OR b )2 or -OSi(OR b )3; R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; and L 1 is substituted or unsubstituted alkylene or substituted or unsubstituted heteroalkylene; The condition is R 1 , R 2 , R 3 , R 4 , Ring A, R 10 , R 11 and L 1 The aromatic hydrocarbons do not contain one or more non-aromatic unsaturated CC bonds.

9. A process for preparing the copolymer of claim 8 which comprises polymerizing the homopolymer of any one of the preceding claims in the presence of I2 and a HI scavenger.

10. The method of claim 9, wherein the HI scavenger is a base.

11. A process according to any one of the preceding claims, wherein the base is an aromatic amine, preferably pyridine.

12. The process of any one of the preceding claims, wherein the base is 1,5,7-triazabicyclo(4.4.0)dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo(4.4.0)dec-5-ene (MTBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,1,3,3-tetramethylguanidine (TMG), quinuclidine, 2,2,6,6-tetramethylpiperidine (TMP), pentamethylpiperidine (PMP), tributylamine, triethylamine, 1,4-diazabicyclo[2.2.2]octane (TED), collidine or 2,6-lutidine (2,6-dimethylpyridine).

13. The copolymer of any one of the preceding claims, wherein formula iii is:

14. The copolymer of claim 13, wherein formula iii is:

15. The homopolymer, copolymer or method of any one of the preceding claims, wherein L 1 is a substituted or unsubstituted alkylene group.

16. The homopolymer, copolymer or method of any one of the preceding claims, wherein L 1 For unsubstituted C 2-6 Alkylene.

17. A copolymer comprising: Examples of m1 first repeating units of formula i': Examples of m2 second repeating units of formula ii-A or ii-B: m3' examples of cross-linking groups, wherein the cross-linking groups are multivalent groups of small molecules, wherein the multivalent groups are at least tetravalent; and optionally one or more types of additional repeating units; in: The copolymer is substantially cross-linked; m1 is an integer between 10 and 1,000,000, inclusive; m2 is an integer between 2 and 1,000,000, inclusive; R 1 , R 2 and R 3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl; R 4 ' is halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, -CN, -OR a , –SCN, –SR a , –SSR a 、–N3、–NO、–N(R a )2, –NO2, –C(=O)R a 、–C(=O)OR a 、–C(=O)SR a , –C(=O)N(R a )2, –C(=NR a )R a , –C(=NR a )OR a , –C(=NR a )SR a , –C(=NR a )N(R a )2. –S(=O)R a 、–S(=O)OR a , –S(=O)SR a , –S(=O)N(R a )2, –S(=O)2R a 、–S(=O)2OR a 、–S(=O)2SR a 、–S(=O)2N(R a )2. –OC(=O)R a 、–OC(=O)OR a 、–OC(=O)SR a 、–OC(=O)N(R a )2. –OC(=NR a )R a 、–OC(=NR a )OR a 、–OC(=NR a )SR a 、–OC(=NR a )N(R a )2. –OS(=O)R a 、–OS(=O)OR a 、–OS(=O)SR a 、–OS(=O)N(R a )2, –OS(=O)2R a 、–OS(=O)2OR a 、–OS(=O)2SR a 、–OS(=O)2N(R a )2、–ON(R a )2、–SC(=O)R a 、–SC(=O)OR a 、–SC(=O)SR a 、–SC(=O)N(R a )2、–SC(=NR a )R a 、–SC(=NR a )OR a 、–SC(=NR a )SR a 、–SC(=NR a )N(R a )2、–NR a C(=O)R a 、–NR a C(=O)OR a 、–NR a C(=O)SR a 、–NR a C(=O)N(R a )2、–NR a C(=NR a )R a 、–NR a C(=NR a )OR a 、–NR a C(=NR a )SR a 、–NR a C(=NR a )N(R a )2、–NR a S(=O)R a 、–NR a S(=O)OR a 、–NR a S(=O)SR a 、–NR a S(=O)N(R a )2、–NR a S(=O)2R a 、–NR a S(=O)2OR a 、–NR a S(=O)2SR a 、–NR a S(=O)2N(R a )2、–Si(R a )3、–Si(R a )2OR a , –Si(R a )(OR a )2, –Si(OR a )3, –OSi(R a )3, –OSi(R a )2OR a , –OSi(R a )(OR a )2 or –OSi(OR a )3; R a each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; R 7 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b 、–N3、–NO、–N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b , –C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b , –S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2, -OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2. -OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2, -OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b , -Si(R b )(OR b )2, -Si(OR b )3, -OSi(R b )3, -OSi(R b )2OR b , -OSi(R b )(OR b )2 or -OSi(OR b )3; is alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene or heteroalkynylene; n2 is an integer between 0 and 14, inclusive, as long as the valence permits; Each Examples of are independently a single bond or a double bond; R 8 Each instance of is independently: When attached to a carbon atom: halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2, -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2. -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2、-S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2、-S(=O)2R b 、-S(=O)2OR b 、 -S(=O)2SR b 、-S(=O)2N(R b )2、-OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2、-OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、 -OC(=NR b )N(R b )2、-OS(=O)R b -OS(=O)OR b 、-OS(=O)SR b 、 -OS(=O)N(R b )2、-OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、 -OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、 -SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、 -SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、 -NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、 –NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、 –NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b 、 –Si(R b )(OR b )2、–Si(OR b )3、–OSi(R b )3、–OSi(R b )2OR b 、–OSi(R b )(OR b )2、 –OSi(OR b )3, =O, =S or =NR b ; When attached to a nitrogen atom: substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, –OR b , –N(R b )2. –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2、–C(=NR b )R b 、 –C(=NR b )OR b 、–C(=NR b )SR b 、–C(=NR b )N(R b )2、–S(=O)R b 、–S(=O)OR b 、–S(=O)SR b 、–S(=O)N(R b )2、–S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、 –S(=O)2N(R b )2, or a nitrogen protecting group; or When attached to a sulfur atom: =O; And / or: R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and / or R 8 Two examples of and their middle atom together form a substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; and R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; Provided that if the first repeating unit has the formula: And the cross-linking group has the following formula: Then the second repeating unit does not have the formula:

18. The copolymer of claim 17, prepared by a process comprising polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more of the additional monomers, wherein: The first monomer has formula I': or a tautomer or a salt thereof; The second monomer has formula II-A or II-B: or a tautomer or salt thereof, wherein is Ring B, and Ring B is a heterocycle; and The third monomer is a small molecule containing two or more non-aromatic unsaturated CC bonds; Provided that if the first monomer is unsubstituted styrene and the third monomer is unsubstituted 1,4-divinylbenzene, then the second monomer does not have the formula: or a tautomer thereof.

19. A method of making the copolymer of claim 18, comprising polymerizing the first monomer, the second monomer, the third monomer, and optionally one or more types of the additional monomers.

20. The copolymer or method of any of the preceding claims, wherein the crosslinking group or third monomer does not contain -C(=O)O- or -OC(=O)- in the backbone chain.

21. The copolymer or method of any preceding claim, wherein the crosslinking group or third monomer comprises only carbon atoms in the backbone chain.

22. The copolymer or method of any of the preceding claims, wherein the third monomer comprises (non-aromatic C=C or non-aromatic C≡C)-L 1 '-(non-aromatic C=C or non-aromatic C≡C), where L 1 ' is substituted or unsubstituted C 1-1000 Alkylene, substituted or unsubstituted C 2-1000 Alkenylene, substituted or unsubstituted C 2-1000 Alkyne, substituted or unsubstituted C 1-1000 Heteroalkylene, substituted or unsubstituted C 2-1000 Heteroalkenylene, substituted or unsubstituted C 2-1000 Heteroalkynylene, optionally wherein the C 1-1000 Alkylene, C 2-1000 Alkenylene, C 2-1000 Alkynylidene, C 1-1000 Heteroalkylene, C 2-1000 Heteroalkenylene, or C 2-1000 One or more backbone carbon atoms of the heteroalkynylene group is replaced with a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

23. The copolymer or method of any preceding claim, wherein: The crosslinking group has the formula: or The third monomer has the formula: or a tautomer or salt thereof, wherein R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Each is independently hydrogen, halogen, or substituted or unsubstituted alkyl.

24. The copolymer or method of any of the preceding claims, wherein R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Each is hydrogen.

25. The copolymer or method of any of the preceding claims, wherein L 1 ' is substituted or unsubstituted C 1-1000 Heteroalkylene, optionally wherein the C 1-1000 One or more backbone carbon atoms of the heteroalkylene group is replaced with a substituted or unsubstituted arylene group.

26. The copolymer or method of any of the preceding claims, wherein L 1 ' is substituted or unsubstituted C 10-100 Heteroalkylene, optionally wherein the C 10-100 One or more backbone carbon atoms of the heteroalkylene group is replaced with a substituted or unsubstituted arylene group.

27. The copolymer or method of any of the preceding claims, wherein L 1 ' is substituted or unsubstituted C 10-50 Heteroalkylene, optionally wherein the C 10-50 One or more backbone carbon atoms of the heteroalkylene group are replaced with a substituted or unsubstituted phenylene group.

28. The copolymer or method of any of the preceding claims, wherein L 1 'Has the following formula: wherein each instance of n is independently 1, 2, 3, 4 or 5.

29. The copolymer or method of any preceding claim, wherein: The crosslinking group has the formula: or The third monomer has the formula: or a salt thereof, wherein each instance of n is independently 1, 2, 3, 4 or 5.

30. The copolymer or method of any of the preceding claims, wherein L 1 ' is a substituted or unsubstituted arylene group.

31. The copolymer or method of any of the preceding claims, wherein L 1 ' is unsubstituted 1,4-phenylene.

32. The homopolymer, copolymer or process of any of the preceding claims, wherein ml is an integer between 30 and 3,000, inclusive.

33. The homopolymer, copolymer or process of any of the preceding claims, wherein m2 is an integer between 3 and 300, inclusive.

34. The homopolymer, copolymer or process of any of the preceding claims, wherein m3 is an integer between 30 and 3,000, inclusive.

35. The homopolymer, copolymer or method of any of the preceding claims, wherein R 1 For hydrogen.

36. The homopolymer, copolymer or method of any of the preceding claims, wherein R 2 For hydrogen.

37. The homopolymer, copolymer or method of any of the preceding claims, wherein R 3 For hydrogen.

38. The homopolymer, copolymer or method of any of the preceding claims, wherein R 3 is a substituted or unsubstituted alkyl group.

39. The homopolymer, copolymer or method of any of the preceding claims, wherein R 3 It is an unsubstituted C1-C6 alkyl group.

40. The copolymer or method of any of the preceding claims, wherein R 4 ' is –C(=O)OR a ; Where R a is a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

41. The copolymer or method of any of the preceding claims, wherein R 4 ' is –C(=O)N(R a )2; Each R a are independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; The condition is that at least one R a Not hydrogen.

42. The homopolymer, copolymer or method of any of the preceding claims, wherein at least one R a is a substituted or unsubstituted alkyl group.

43. The homopolymer, copolymer or method of any of the preceding claims, wherein at least one R a is a substituted or unsubstituted alkyl group.

44. The copolymer or method of any of the preceding claims, wherein R 4 ' is a substituted or unsubstituted phenyl group.

45. The copolymer or method of any of the preceding claims, wherein R 4 ' is an unsubstituted phenyl group.

46. ​​The homopolymer, copolymer or method of any of the preceding claims, wherein R 1 , R 2 , R 3 , R 4 '、R 7 , R 8 Neither R nor Ring B contains one or more non-aromatic unsaturated CC bonds.

47. The copolymer or method of any of the preceding claims, wherein Formula I' is 48. The copolymer or method of any of the preceding claims, wherein the molar ratio of the first repeating unit to the crosslinking group or the molar ratio of the first monomer to the third monomer is between 2:1 and 10:1, between 10:1 and 30:1, or between 30:1 and 100:1, inclusive.

49. The copolymer or method of any of the preceding claims, wherein the degree of crosslinking is between 0.1% and 0.3%, between 0.3% and 1%, between 1% and 3%, between 3% and 10%, between 10% and 20%, or between 20% and 50%, inclusive, on a mol:mol basis.

50. The copolymer or method of any preceding claim, wherein the degree of crosslinking is between 1% and 10%, inclusive, on a mol:mol basis.

51. The homopolymer, copolymer or process of any preceding claim, wherein Ring A is phenyl.

52. The homopolymer, copolymer or process of any preceding claim wherein n1 is 0.

53. The homopolymer, copolymer or method of any of the preceding claims, wherein: The first repeating unit has the formula: or The first monomer is unsubstituted styrene.

54. The homopolymer, copolymer or method of any of the preceding claims, wherein is an alkylene group, preferably, C 2-5 Alkylene.

55. The homopolymer, copolymer or process of any preceding claim wherein Ring B is a monocyclic heterocycle.

56. The homopolymer, copolymer or process of any of the preceding claims, wherein Ring B has the formula:

57. The homopolymer, copolymer or method of any of the preceding claims, wherein R 7 Each instance of is hydrogen.

58. The homopolymer, copolymer or method of any of the preceding claims, wherein n2 is 0.

59. The homopolymer, copolymer or method of any of the preceding claims, wherein R 9 or R 7 An example and R 8 An example of R together with its middle atom forms a substituted or unsubstituted carbocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and / or R 8 The two examples of and their middle atom together form a substituted or unsubstituted carbocyclyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

60. The homopolymer, copolymer or method of any of the preceding claims, wherein R 9 or R 7 An example and R 8 An example of R together with its intermediate atom forms a substituted or unsubstituted phenyl group, and / or R 8 The two examples of are taken together with their middle atoms to form a substituted or unsubstituted phenyl group.

61. The homopolymer, copolymer or method of any of the preceding claims, wherein: The second repeating unit has the formula: The second monomer has the formula: or a tautomer or a salt thereof; in: R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2, -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2, -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2, -S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2, -S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2, -OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2. -OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2, -OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、-SC(=NR b )N(R b )2、-NR b C(=O)R b 、-NR b C(=O)OR b 、-NR b C(=O)SR b 、-NR b C(=O)N(R b )2、-NR b C(=NR b )R b 、-NR b C(=NR b )OR b 、-NR b C(=NR b )SR b 、-NR b C(=NR b )N(R b )2、-NR b S(=O)R b 、-NR b S(=O)OR b 、-NR b S(=O)SR b 、-NR b S(=O)N(R b )2、-NR b S(=O)2R b 、-NR b S(=O)2OR b 、-NR b S(=O)2SR b 、-NR b S(=O)2N(R b )2、-Si(R b )3、-Si(R b )2OR b , -Si(R b )(OR b )2, -Si(OR b )3, -OSi(R b )3, -OSi(R b )2OR b , -OSi(R b )(OR b )2 or -OSi(OR b )3; R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and n3 is 0, 1, 2, 3, or 4; The condition is R 10 None of the examples contain one or more non-aromatic unsaturated CC bonds.

62. The homopolymer, copolymer or method of any of the preceding claims, wherein: The second repeating unit has the formula: or The second monomer has the formula: or a tautomer or a salt thereof; in: R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2, -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2, -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2, -S(=O)R b 、-S(=O)OR b 、-S(=O)SR b 、-S(=O)N(R b )2, -S(=O)2R b 、-S(=O)2OR b 、-S(=O)2SR b 、-S(=O)2N(R b )2, -OC(=O)R b 、-OC(=O)OR b 、-OC(=O)SR b 、-OC(=O)N(R b )2, -OC(=NR b )R b 、-OC(=NR b )OR b 、-OC(=NR b )SR b 、-OC(=NR b )N(R b )2. -OS(=O)R b 、-OS(=O)OR b 、-OS(=O)SR b 、-OS(=O)N(R b )2, -OS(=O)2R b 、-OS(=O)2OR b 、-OS(=O)2SR b 、-OS(=O)2N(R b )2、-ON(R b )2、-SC(=O)R b 、-SC(=O)OR b 、-SC(=O)SR b 、-SC(=O)N(R b )2、-SC(=NR b )R b 、-SC(=NR b )OR b 、-SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b 、–N3、–NO、–N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b , –C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b , –S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; provided that R 10 and R 11 None contain one or more non-aromatic unsaturated CC bonds.

63. The homopolymer, copolymer or method of any of the preceding claims, wherein: The second repeating unit has the formula: The second monomer has the formula: or a tautomer or a salt thereof.

64. The homopolymer, copolymer or method of any preceding claim, wherein n3 is 1.

65. The homopolymer, copolymer or method of any preceding claim, wherein n4 is 1.

66. The homopolymer, copolymer or method of any of the preceding claims, wherein R 10 or R 11 At least one example of which is substituted or unsubstituted alkyl, -O(substituted or unsubstituted alkyl), or -S(substituted or unsubstituted alkyl).

67. The homopolymer, copolymer or method of any of the preceding claims, wherein R 10 or R 11 At least one example of which is a substituted or unsubstituted C 2-6 Alkyl, -O (substituted or unsubstituted C 2-6 Alkyl) or -S (substituted or unsubstituted C 2-6 alkyl).

68. The homopolymer, copolymer or method of any of the preceding claims, wherein R 10 or R 11 At least one instance of unsubstituted C 2-6 Alkyl, -O(unsubstituted C 1-6 Alkyl) or -S(unsubstituted C 1-6 alkyl).

69. The homopolymer, copolymer or method of any of the preceding claims, wherein: The second repeating unit has the formula: The second monomer has the formula: or a tautomer or a salt thereof.

70. The homopolymer, copolymer or method of any of the preceding claims, wherein: The second repeating unit has the formula: or The second monomer has the formula: or a tautomer thereof.

71. The copolymer or method of any of the preceding claims, wherein: The second repeating unit does not have the formula: or The second monomer does not have the formula: or a tautomer thereof.

72. The copolymer or method of any of the preceding claims, wherein: The second repeating unit does not have the formula: or The second monomer does not have the formula: or a tautomer thereof.

73. The copolymer or method of any of the preceding claims, wherein: The second repeating unit does not have the formula: Or the second monomer does not have the formula: or a tautomer thereof.

74. The copolymer or method of any of the preceding claims, wherein the second monomer has the formula: or a tautomer or a salt thereof.

75. The homopolymer, copolymer or process of any preceding claim, wherein the additional repeating unit or the additional monomer, if present, does not comprise -C(=O)O- or -OC(=O)- in the backbone.

76. The homopolymer, copolymer or process of any preceding claim, wherein the additional repeating unit or the additional monomer, if present, comprises only carbon atoms in the backbone chain.

77. The homopolymer, copolymer or method of any of the preceding claims, wherein the polymerizing step further comprises a free radical initiator.

78. The homopolymer, copolymer or process of any of the preceding claims wherein the free radical initiator is azobisisobutyronitrile.

79. The homopolymer, copolymer or method of any of the preceding claims, wherein the polymerizing step further comprises a solvent.

80. The homopolymer, copolymer or process of any of the preceding claims, wherein the polymerizing step is substantially free of solvent.

81. The homopolymer, copolymer or process of any of the preceding claims, wherein the temperature of the polymerization step is between 25 and 150°C, between 50 and 150°C, or between 70 and 120°C, inclusive.

82. The homopolymer, copolymer or process of any of the preceding claims, wherein the duration of the polymerization step is between 1 and 3 hours, between 3 and 8 hours, between 8 and 24 hours, between 1 and 3 days, or between 3 and 7 days, inclusive.

83. The homopolymer, copolymer or method of any of the preceding claims, wherein the molar ratio of the first repeating unit to the second repeating unit or the molar ratio of the first monomer to the second monomer is between 1:1 and 3:1, between 3:1 and 10:1, between 10:1 and 30:1, between 30:1 and 100:1, or between 100:1 and 300:1, inclusive.

84. The homopolymer, copolymer or method of any of the preceding claims, wherein the molar ratio of the first repeating unit to the second repeating unit or the molar ratio of the first monomer to the second monomer is between 3:1 and 30:1, inclusive.

85. The homopolymer, copolymer or method of any of the preceding claims, wherein the molar ratio of the first repeating unit to the second repeating unit or the molar ratio of the first monomer to the second monomer is between 30:1 and 100:1, inclusive.

86. The homopolymer, copolymer or process of any preceding claim wherein the degree of crosslinking is less than 0.1%, mol:mol.

87. The homopolymer, copolymer or method of any of the preceding claims, wherein the degree of crosslinking is determined by the consumption of monomers polymerized to form the copolymer.

88. The homopolymer, copolymer or method of any of the preceding claims, wherein the copolymer is a random copolymer.

89. The homopolymer, copolymer or method of any of the preceding claims, wherein the copolymer is a block copolymer.

90. A compound having the formula: or a tautomer or salt thereof, wherein: X 1 is S or O; R 10 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b 、-SCN、-SR b 、-SSR b 、-N3、-NO、-N(R b )2, -NO2, -C(=O)R b 、-C(=O)OR b 、-C(=O)SR b 、-C(=O)N(R b )2, -C(=NR b )R b 、-C(=NR b )OR b 、-C(=NR b )SR b 、-C(=NR b )N(R b )2, -S(=O)R b 、-S(=O)OR b 、-S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R 11 Each instance of is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -CN, -OR b , –SCN, –SR b , –SSR b , –N3, –NO, –N(R b )2, –NO2, –C(=O)R b 、–C(=O)OR b 、–C(=O)SR b 、–C(=O)N(R b )2, –C(=NR b )R b , –C(=NR b )OR b , –C(=NR b )SR b , –C(=NR b )N(R b )2. –S(=O)R b 、–S(=O)OR b 、–S(=O)SR b , –S(=O)N(R b )2, –S(=O)2R b 、–S(=O)2OR b 、–S(=O)2SR b 、–S(=O)2N(R b )2. –OC(=O)R b 、–OC(=O)OR b 、–OC(=O)SR b 、–OC(=O)N(R b )2. –OC(=NR b )R b 、–OC(=NR b )OR b 、–OC(=NR b )SR b 、–OC(=NR b )N(R b )2. –OS(=O)R b 、–OS(=O)OR b 、–OS(=O)SR b 、–OS(=O)N(R b )2, –OS(=O)2R b 、–OS(=O)2OR b 、–OS(=O)2SR b 、–OS(=O)2N(R b )2、–ON(R b )2、–SC(=O)R b 、–SC(=O)OR b 、–SC(=O)SR b 、–SC(=O)N(R b )2、–SC(=NR b )R b 、–SC(=NR b )OR b 、–SC(=NR b )SR b 、–SC(=NR b )N(R b )2、–NR b C(=O)R b 、–NR b C(=O)OR b 、–NR b C(=O)SR b 、–NR b C(=O)N(R b )2、–NR b C(=NR b )R b 、–NR b C(=NR b )OR b 、–NR b C(=NR b )SR b 、–NR b C(=NR b )N(R b )2、–NR b S(=O)R b 、–NR b S(=O)OR b 、–NR b S(=O)SR b 、–NR b S(=O)N(R b )2、–NR b S(=O)2R b 、–NR b S(=O)2OR b 、–NR b S(=O)2SR b 、–NR b S(=O)2N(R b )2、–Si(R b )3、–Si(R b )2OR b , –Si(R b )(OR b )2, –Si(OR b )3, –OSi(R b )3, –OSi(R b )2OR b , –OSi(R b )(OR b )2 or –OSi(OR b )3; R b each instance of is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; and n3 is 0, 1, 2, 3 or 4, n4 is 0, 1, 2, 3 or 4, and at least one of n3 and n4 is 1, 2, 3 or 4; provided that R 10 and R 11 None contain one or more non-aromatic unsaturated CC bonds.

91. The compound of any one of the preceding claims, or a tautomer or salt thereof, wherein the compound has the formula: or a tautomer or a salt thereof.

92. A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof, wherein X 1 For S.

93. The compound of any of the preceding claims, or a tautomer or salt thereof, wherein n3 is 1.

94. The compound of any of the preceding claims, or a tautomer or salt thereof, wherein n4 is 1.

95. A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof, wherein R 10 or R 11 At least one example of is halogen, preferably fluorine.

96. A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof, wherein R 10 or R 11 At least one example of which is substituted or unsubstituted alkyl, -O(substituted or unsubstituted alkyl), or -S(substituted or unsubstituted alkyl).

97. A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof, wherein R 10 or R 11 At least one example of which is a substituted or unsubstituted C 2-6 Alkyl, -O (substituted or unsubstituted C 1-6 Alkyl) or -S (substituted or unsubstituted C 1-6 alkyl).

98. A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof, wherein R 10 or R 11 At least one instance of unsubstituted C 2-6 Alkyl, -O(unsubstituted C 1-6 Alkyl) or -S(unsubstituted C 1-6 alkyl).

99. The compound of any of the preceding claims, wherein the compound has the formula: or a tautomer or a salt thereof.

100. The compound of any of the preceding claims, wherein the compound has the formula: or a tautomer or a salt thereof.

101. A homopolymer prepared by a process comprising polymerising a compound according to any preceding claim, or a tautomer or salt thereof.

102. The copolymer, homopolymer, or method of any of the preceding claims, wherein the copolymer or homopolymer has a number average molecular weight of between 20 kDa and 100 kDa, between 100 kDa and 300 kDa, between 300 kDa and 1,000 kDa, between 1,000 kDa and 3,000 kDa, or between 3,000 kDa and 10,000 kDa as determined by gel permeation chromatography.

103. The copolymer, homopolymer, or method of any of the preceding claims, wherein: The number average molecular weight of the copolymer or homopolymer determined by gel permeation chromatography is between 300 Da and 7 kDa, including end points.

104. The copolymer, homopolymer, or method of any of the preceding claims, wherein the copolymer or homopolymer has a number average molecular weight of 7 kDa to 100 kDa, inclusive, as determined by gel permeation chromatography.

105. The copolymer, homopolymer, or method of any of the preceding claims, wherein: The copolymer or homopolymer has a number average molecular weight of 100 kDa to 3,000 kDa, both inclusive, as determined by gel permeation chromatography.

106. The copolymer, homopolymer, or method of any of the preceding claims, wherein the copolymer or homopolymer is degradable.

107. The copolymer, homopolymer, or method of any of the preceding claims, wherein the copolymer or homopolymer is degradable after reacting the copolymer or homopolymer with a nucleophile.

108. A composition comprising: The copolymer of any one of the preceding claims; and Optionally, an excipient.

109. A composition comprising: A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof; and Optionally, an excipient.

110. A composition comprising: A homopolymer as claimed in any one of the preceding claims; and Optionally, an excipient.

111. A kit comprising: The copolymer of any of the preceding claims or the composition of claim 108; and Instructions for use of the copolymer or composition.

112. A kit comprising: A compound as claimed in any one of the preceding claims, or a tautomer or salt thereof, or a composition as claimed in claim 109; and Instructions for use of the compound, tautomer, salt or composition.

113. A kit comprising: The homopolymer of any of the preceding claims or the composition of claim 110; and Instructions for use of the homopolymer or composition.

114. A method of degrading a copolymer or homopolymer as claimed in any preceding claim comprising reacting the copolymer or homopolymer with a nucleophile.

115. The copolymer, homopolymer, or method of any of the preceding claims, wherein the nucleophile degrades the copolymer or homopolymer under ambient conditions.

116. The copolymer, homopolymer, or method of any of the preceding claims, wherein the nucleophile is an amine.

117. The copolymer, homopolymer or method of any of the preceding claims, wherein the nucleophile is (substituted or unsubstituted alkyl)-NH2, preferably (unsubstituted C 2-6 Alkyl) –NH2.

118. The copolymer, homopolymer or method of any of the preceding claims, wherein the nucleophile is (alkyl substituted with at least -SH)-NH2, preferably HS-(CH2) 2-6 -NH2.

119. The copolymer, homopolymer, or method of any of the preceding claims, wherein the nucleophile is a thiol.

120. The copolymer, homopolymer or method of any of the preceding claims, wherein the nucleophile is (substituted or unsubstituted alkyl)-SH, preferably (unsubstituted C 2-6 Alkyl)-SH.

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