Cationic polymerization methods, polymerizable compositions, and products thereof

Abstract

Polymers, polymerizable compositions, methods of making polymers, and uses of the polymers and compositions. In various examples, a polymer comprises a desirable ratio of cis groups to trans groups. In various examples, a method is an acid-catalyzed cationic polymerization using hydrogen bond donor(s) (HBD(s)), where one or more or all of the hydrogen bond donor(s) is / are chiral HBD(s). In various examples, an acid is formed in-situ (e.g., by irradiation of a polymerization agent (such as, for example, a photoacid generator or the like)). In various examples, an irradiation is carried out in a pre-determined pattern. In various examples, a polymer or a cationic polymerization product(s) formed by a method of the present disclosure is a sealant, an adhesive, a consumer product, a photoresist, a thermoplastic elastomer, or a component thereof, or the like.

Description

Attorney Docket No.: 018617.01816 CATIONIC POLYMERIZATION METHODS, POLYMERIZABLE COMPOSITIONS, AND PRODUCTS THEREOF CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 581,264, filed September 7, 2023; the contents of the above-identified application are hereby fully incorporated herein by reference in their entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under 2108598 awarded by the National Science Foundation. The government has certain rights in the invention. BACKGROUND

[0003] Photoacid generators (PAGs) have facilitated a number of technology breakthroughs in the electronic, coating, and additive manufacturing industries. Traditionally, PAGs that contain weakly coordinating anions, such as PF6^, generate Brønsted superacids under UV irradiation for rapid cationic polymerizations. However, PAGs with strongly coordinating anions remain under-utilized as they form weak acids that are inefficient or even incapable of initiating polymerization.

[0004] Photoacid generators (PAGs) are a class of light-sensitive molecules that generate acids upon light exposure, inducing photoinitiated cationic polymerizations. The development of PAGs has enabled advances in numerous applications such as photolithography, photocurable coatings and adhesives, and 3D printing. To achieve efficient polymerizations on time scales for manufacturing, most ionic PAGs contain non-coordinating anions that form Brønsted superacids. Specifically, Crivello and Lam were the first to employ diphenyliodonium salts with weakly coordinating anions (SbF6–, PF6–, etc) for such applications. Under ultraviolet (UV) irradiation, strong acids (HSbF6, HPF6, etc) are formed from the photolysis of the diphenyliodonium, initiating cationic polymerization. While superacids facilitate rapid polymerization, the utilization of fluorine-containing PAGs poses potential health hazards that can limit their applications. PAGs with coordinating anions (e.g., Cl–) are often more benign but not commonly used, as they generate weak acids (e.g., HCl) that form monomer ^acid adducts with equilibria that lie primarily towards the covalent dormant state. With a lack of ionization at the chain end, propagation is infrequent, leading to polymerizations too slow for practical applications.

[0005] In response to this challenge, research has examined the use of diphenyliodonium halides to initiate cationic polymerization from the acids formed by UV irradiation. Zinc halides have previously been employes to impart livingness to the polymerization of isobutyl vinyl ether when initiated by diphenyliodonium halides. Leveraging the reversible cleavage of carbon ^iodine bonds, hydroiodic acid generated from UV irradiation of diphenyliodonium salts was previously used to control the polymerization of isopropyl vinyl ether. While these systems contain diphenyliodonium PAGs with non-fluorinated anions, the polymerizations require low temperatures, inert atmospheres, volatile solvents, and lengthy reaction times— conditions that can hinder application.

[0006] Hydrogen bond donors (HBDs) have been extensively studied for small molecule synthesis. Applying this chemistry to polymer science, HBDs have recently been utilized in the catalysis of cationic polymerizations under mild conditions, such as with thiophosphoramides and selenocyclodiphosph(V)azanes.

[0007] Cationic polymerizations of styrene monomers have limited applications because of the difficulty of controlling the reactive cationic intermediates. Reversible chain-end ionization via Lewis acid complexation is commonly employed to realize such polymerizations, but these methods require low temperatures and typically deliver materials contaminated by metal impurities.

[0008] The polymerization of styrene derivatives has long been studied with a variety of methods emerging including radical, anionic, cationic, and living polymerization. Living polymerizations are desirable because they offer desirable degree of control over molecular weights and narrow dispersities, which allows tuning of the resulting polymer’s properties. While many living anionic and radical polymerizations of styrene derivatives have been developed, living cationic polymerization of styrenes faces a number of challenges arising from the poor stability of the carbocation chain end leading to chain terminating elimination and Friedel-Crafts reactions. Mitigating these reactions typically is accomplished by performing the polymerization at low temperature. To expand the scope of conditions tolerated, new methods of chain end stabilization are required.

[0009] Reversible bond formation at the growing chain end to limit the concentration of reactive species contributes to controlling the polymerization process and as such favors weaker carbon-heteroatom bonds that can undergo heterolysis. For example, TiCl4can abstract a halide anion from an alkyl halide to form a carbocation that can serve as the propagating chain end. Another method of promoting bond ionization is the introduction of ahydrogen bond donor (HBD) co-catalyst which stabilizes the anionic fragment. While this technique has seen wide application to small molecule reactions, its use in cationic polymerizations has been limited with the most common example in polymerization is activation of neutral monomers such as lactones rather than interaction with anionic species. Similar methods utilizing halogen and chalcogen bond donors for anion abstraction in vinyl monomer polymerizations have begun to gain interest. A selenocyclodiphosph(V)azanes HBD chloride abstraction strategy for living cationic polymerization of vinyl ethers and N- vinylcarbazole was previously demonstrated and a halogen bond donor enhanced thiourea HBD abstraction method for vinyl ethers and styrene derivatives was also previously demonstrated.

[0010] Poly(2,3-dihydrofuran) (PDHF) made from 2,3-dihydrofuran (DHF), which can be produced by bioalcohol, has been demonstrated as a potential thermoplastic as it has strong, tough, and degradable properties. However, current methods are limited in their ability to produce more trans-selective PDHF through a thermo-dynamic control mechanism.

[0011] As the global plastic production increases, interest grows in developing sustainable materials with commercially competitive properties. High glass transition temperature (Tg), high melting temperature (Tm) and high decomposition temperature (Td) are desirable properties because they drive a material’s heat resistance, mechanical strength, and processing behaviors. Driven by the wide application of high temperature polymers, chemists have recently been challenged to design new techniques to improve thermal properties. Despite the advances realized, strategies used to improve a polymer’s thermal properties remain currently confined to: 1) the incorporation of bulky pendant groups in the side chain or the introduction of cyclic structures in the main chain to improve the rigidity of the backbone; 2) the insertion of heteroatoms (N, O, S, etc.) into the polymer backbone; 3) the improvement of the tacticity of polymer chains. However, the synthesis of bulky or rigid cyclic group-containing monomers or polymer backbone post-modification not only require multiple steps and specific reactions but also affect the polymers’ molecular weights and dispersity. While controlling the stereochemistry of polymers transforms an atactic amorphous polymer into an isotactic semicrystalline plastic with high melting temperature (Tm), for many applications amorphous polymers are preferred since the lack of crystallites generally permits superior optical transparency and impact resistance. Therefore, the development of a new strategy to synthesize high glass transition temperature (Tg) polymers using sustainable and biorenewable resources is desirable.

[0012] 2,3-dihydrofuran (DHF), a cyclic vinyl ether, produced from 1,4-butanediol has been demonstrated as a sustainable monomer to produce poly(2,3-dihydrofuran) (PDHF) under cationic polymerization since the 1950s. This cyclic vinyl ether results in a polymer with a rigid and oxygen atom-containing backbone, leading to a material with a high glass transition temperature (Tg). A Lewis acid initiate uncontrolled cationic polymerization of DHF at room temperature that led to a Tg of ∼112 °C for the 68% trans-PDHF was previously reported. They found that lower reaction temperatures favored cis-PDHF with a higher Tg, while higher temperatures favored trans-isomer with a lower Tg. Despite PDHF’s many attractive properties, its reported glass transition temperature (Tg) of 135 °C is not high enough for many industrial applications. SUMMARY OF THE DISCLOSURE

[0013] The present disclosure provides, inter alia, functionalized multiblock copolymer films and methods of making functionalized multblock copolymer films. The present disclosure also provides uses of the functionalized multiblock copolymer films.

[0014] In an aspect, the present disclosure provides polymers. In various examples, a polymer is produced by a method of the present disclosure. A polymer can be a homopolymer or a copolymer. In various examples, a polymer is (or comprises a plurality of repeat units) formed from one or more monomer(s) disclosed herein. In various examples, a polymer comprises the following structure. a structural analog thereof. In variousare as described herein. In various examples, a polymer comprises the following structure. a structural analog thereof. In variousthereof are as described herein. In various examples, a polymer comprises the following structure.a structural analog thereof. In various examples, eof is / are as described herein. In various examples, in any of these examples, n is at least 60%, at least 65%, or at least 70%.

[0015] In an aspect, the present disclosure provides polymerizable compositions. In various examples, a polymerizable composition is suitable for use in a method for the present disclosure. In various examples, polymerizable composition is used in a cationic polymerization method of the present disclosure. In various examples, a polymerizable composition a polymerizable composition comprises (consists essentially of or consists of) one or more monomer(s), and one or more chiral hydrogen bond donors (HBDs). In various examples, the polymerizable composition further comprises one or more acid(s) and / or one or more polymerization agent(s) and / or one or more solvent(s). In various examples, the polymerization agent or polymerization agents is / are a photoacid generator or photoacid generators, an acid or acids, or any combination thereof. In various examples, one or more or all of the HBD(s) is / are chiral HBDs. The polymerization composition may also further comprise one or more cross-linking monomer(s), one or more solvent(s), one or more chain transfer agent(s), or the like, or any combination thereof.

[0016] In an aspect, the present disclosure provides polymerization methods. In various examples, a polymerization method (which may be referred to a cationic polymerization method) forms one or more cationic polymerization product(s) (one or more or all of which may be a polymer or polymers of the present disclosure). In various examples, the polymerization method comprises reacting one or more acid(s) (which may be cationic polymerization initiator(s) (that may be referred to as initiator(s)) or form cationic polymerization initiator(s), respectively), one or more or all of which may be formed (e.g., in situ) from a polymerization agent or polymerization agents, with a polymerizable composition (e.g., a polymerizable composition comprising one or more monomer(s) and one or more hydrogen bond donor(s) (HBDs)). In various examples, a polymerizable composition further comprises one or more cross-linking monomer(s), one or more solvent(s), one or more chain transfer agent(s), or the like, or any combination thereof. In the method, at least a portion of, substantially all, or all of the monomer(s) is / are polymerized (such as, for example, to form a polymer or the like). In various examples, a polymerization method formsone or more cationic polymerization product(s). In various examples, a cationic polymerization product (which may be a polymer of the present disclosure or the like) comprises a desirable number of cis groups (e.g., the number of cis groups is greater than the number of trans groups (e.g., 51 to 100% of the cis groups and trans groups is cis groups).

[0017] In various examples, at least a portion or all of the acids is / are formed from a polymerization agent or polymerization agents. In the case where one or more acid(s) is / are formed form a polymerization agent or polymerization agents, a method (e.g., a reacting) further comprises irradiating (such as, for example, light or the like) a polymerization agent(s), such that an acid or acids are generated. In various examples, where a method comprises irradiating a polymer composition comprising one or more PAGs, the method is a lithography method, a photolithography method (e.g., positive photoresist or negative photoresist), an additive manufacturing method, a 3D printing method or the like.

[0018] In an aspect, the present disclosure provides articles of manufacture. In various examples, an article of manufacture comprises one or more polymer(s) and / or one or more cationic polymerization product(s) of the present disclosure. In various examples, one or more or all of the polymer(s) and / or cationic polymerization product(s) is / are formed by a method of the present disclosure. In various examples, an article of manufacture comprises one or more polymer(s) and / or cationic polymerization product(s) of the present disclosure, where at least a portion or all of the polymer(s) and / or cationic polymerization product(s) is / are formed by irradiation, crosslinked, or the like, or any combination thereof. BRIEF DESCRIPTION OF THE FIGURES

[0019] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0020] FIG.1 shows demonstration of the ability of a thiophosphoramide hydrogen bond donor (HBD) to catalyze polymerization from PAGs with a range of weakly to strongly coordinating anions under tolerant conditions with competitive rates.

[0021] FIG.2 shows (A) The photopolymerization kinetics with and without HBD for PAGs containing a range of anions were investigated (200 equiv isobutyl vinyl ether (IBVE), 1 equiv PAG ^A, 0 or 1 equiv HBD). These anions include: acetate (OAc^), chloride (Cl^), nitrate (NO3^), tosylate (TsO^), bromide (Br^), triflate (OTf^), and hexafluorophosphate (PF6^), with their structures and pKas in acetonitrile (MeCN) given. (B) Without HBD, the more strongly coordinating anions (OAc^, Cl^, NO3^, TsO^, Br^) did not polymerize (blackopen circles). Upon the addition of HBD, all of the anions experienced initiation within 60 minutes. (C) Only PAG ^OTf and PAG ^PF6resulted in polymerization without HBD. Even so, these weakly coordinating anions still saw accelerated rates with the addition of HBD.

[0022] FIG.3 shows (A) The titration of HBD (1 equiv) with tetrabutylammonium (TBA) ^Cl, ^NO3, ^TsO, ^Br, and ^PF6 (0 ^7 equiv) was tracked by1H-NMR. The N ^H protons on the HBD shifted downfield with increased TBA salt concentration. The data collected for TBA ^Cl, ^NO3, ^TsO, and ^Br fit the model for 1:1 binding with HBD, while TBA ^PF6 continued to shift the N ^H signal downfield even at large excess. (B) Geometry optimizations with density functional theory for the HBD ^TsO complex resulted in three H ^bonds, while the HBD ^NO3complex was predicted to contain only two H ^bonds.

[0023] FIG.4 shows (A) With HBD, the photopolymerizations still occur in air. PAG ^TsO demonstrated a small reduction in rate and thus a high tolerance to ambient conditions. With slower kinetics to begin with, the polymerization of PAG ^Cl under air experienced a more significant reduction in rate. (B) Both alkyl and cyclic vinyl ethers were polymerized with PAG ^Cl and HBD, reaching high conversions in 2 h. These include n-butyl vinyl ether (NBVE), ethyl vinyl ether (EVE), and 2,3-dihydrofuran (DHF).

[0024] FIG.5 shows (A) (1) No polymerization was observed with IBVE and HCl, at room temperature under nitrogen. (2) Upon the addition of HBD to these conditions, the resulting polymer had a bimodal distribution, indicating initiation but not control. (3) A chain transfer agent (CTA) was added to impart control through a reversible addition ^fragmentation chain transfer (RAFT) mechanism. Due to the addition of HBD, HCl- initiated cationic RAFT was performed at room temperature, without monomer purification, and under air. (B) The resulting polymer from this HBD catalyzed RAFT had matching theoretical and experimental molecular weights and a relatively low dispersity, as confirmed by gel permeation chromatography.

[0025] FIG.6 shows conversion versus time plot for PAG ^SbF6without HBD (open circles) and with 1 equiv HBD (closed circles).

[0026] FIG.7 shows the fitting for plotted titration data of HBD and PAG ^Cl. Coefficients (with 95% confidence bounds): [B]0= 1.176 (1.052, 1.3); Keq= 31.8 (6.268, 57.32); δb = 5.74 (fixed at bound); δc = 8.86 (fixed at bound). Goodness of fit: SSE: 0.09743; R-square: 0.9916; Adjusted R-square: 0.9909; RMSE: 0.09011.

[0027] FIG.8 shows the fitting for plotted titration data of HBD and PAG ^NO3. Coefficients (with 95% confidence bounds): [B]0= 0.001258 (0.00122, 0.001297); Keq=5.578e+04 (3.699e+04, 7.458e+04); δb= 5.74 (fixed at bound); δc= 8.4 (fixed at bound). Goodness of fit: SSE: 0.004502; R-square: 0.9994; Adjusted R-square: 0.9994; RMSE: 0.02122.

[0028] FIG.9 shows the fitting for plotted titration data of HBD and PAG ^TsO. Coefficients (with 95% confidence bounds): [B]0= 0.9041 (0.8302, 0.978); Keq= 55.69 (19.89, 91.49); δb = 5.74 (fixed at bound); δc = 8.31 (fixed at bound). Goodness of fit: SSE: 0.03676; R-square: 0.9952; Adjusted R-square: 0.9948; RMSE: 0.05535.

[0029] FIG.10 shows the fitting for plotted titration data of HBD and PAG ^Br. Coefficients (with 95% confidence bounds): [B]0= 1.257 (1.156, 1.358); Keq= 29.57 (7.893, 51.25); δb = 5.74 (fixed at bound); δc = 8.47 (fixed at bound). Goodness of fit: SSE: 0.04668; R-square: 0.9947; Adjusted R-square: 0.9942; RMSE: 0.06515.

[0030] FIG.11 shows the fitting for plotted titration data of HBD and PAG ^PF6. Coefficients (with 95% confidence bounds): [B]0= 0.7103 (-0.01317, 1.434); Keq= 1.362 (0.78, 1.945); δb = 5.74 (fixed at bound); δc = 6.43 (fixed at bound). Goodness of fit: SSE: 0.007672; R-square: 0.983; Adjusted R-square: 0.9814; RMSE: 0.02641.

[0031] FIG.12 shows predicted hydrogen bonds between HBD and OTs^, shown as yellow lines.

[0032] FIG.13 shows predicted hydrogen bonds between HBD and NO3-, shown as yellow lines.

[0033] FIG.14 shows conversion versus time plot for the polymerization of IBVE with HBD, run under air. PAG ^TsO and ^Cl.

[0034] FIG.15 shows conversion versus time plot for the polymerization of IBVE with PAG ^Cl and HBD for NBVE, EVE, and DHF.

[0035] FIG.16 shows GPC traces of IBVE polymerization with PAG ^Cl and HBD. For 2 hours, Mn,exp = 7.4 kg / mol, Đ = 1.75.

[0036] FIG.17 shows GPC traces of EVE polymerization with PAG ^Cl and HBD. For 2 hours, Mn,exp= 4.0 kg / mol, Đ = 1.73.

[0037] FIG.18 shows GPC traces of NBVE polymerization with PAG ^Cl and HBD. For 2 hours, Mn,exp= 5.6 kg / mol, Đ = 1.87.

[0038] FIG.19 shows GPC traces of DHF polymerization with PAG ^Cl and HBD. For 30 minutes, Mn,exp= 8.8 kg / mol, Đ = 3.61.

[0039] FIG.20 shows a proposed mechanism of HBD- assisted cationic polymerization of pMS with PCCP.

[0040] FIG.21 shows structures of PCCP 1-3 and HBD.

[0041] FIG.22 shows GPC traces of selected entries from Table 5.

[0042] FIG.23 shows the kinetics plot of pMS polymerization with 250 ppm TEMPO. Top: natural log of conversion over time. Bottom: Mn vs conversion.

[0043] FIG.24 shows GPC traces for entries in Table 3.

[0044] FIG.25 shows strategies for reaching high thermal property polymers.

[0045] FIG.26 shows hydrogen bond donors (HBDs) controlled cis-selective polymerization of DHF. A - Evaluation of hydrogen bond donors (HBDs) for cis-selective cationic polymerization of DHF; B First order relationship between the cis-contents and Tg of PDHF.

[0046] FIG.27 shows stress−strain curves for PDHF samples at a strain rate of 2 mm min−1to failure, indicated by x. A - Stress−strain curve for 60% trans-content PDHF; B - Stress−strain curves for cis-favored PDHF.

[0047] FIG.28 shows thermal and viscoelastic properties of cis-favored PDHF. A - DSC date of PDHF-81; B - TGA date of PDHF-81; C - Melt stability of PDHF evaluated through complex viscosity(η*) D - Frequency sweeps of PDHF-64, PDHF-76, and PDHF-81 showing the effect of Mnon complex viscosity (η*). DETAILED DESCRIPTION OF THE DISCLOSURE

[0048] Although subject matter of the present disclosure is described in terms of certain embodiments and examples, other embodiments and examples, including embodiments and examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. For example, various structural, logical, and process step changes may be made without departing from the scope of the disclosure.

[0049] As used herein, unless otherwise indicated, “about”, “substantially”, or “the like”, when used in connection with a measurable variable (such as, for example, a parameter, an amount, a temporal duration, or the like) or a list of alternatives, is meant to encompass variations of and from the specified value including, but not limited to, those within experimental error (which can be determined by, e.g., a given data set, an art accepted standard, etc. and / or with, e.g., a given confidence interval (e.g., 90%, 95%, or more confidence interval from the mean), such as, for example, variations of + / -10% or less, + / -5% or less, + / -1% or less, and + / -0.1% or less of and from the specified value), insofar such variations in a variable and / or variations in the alternatives are appropriate to perform in the instant disclosure. As used herein, the term “about” may mean that the amount or value inquestion is the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, compositions, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, or the like, or other factors known to those of skill in the art such that equivalent results or effects are obtained. In general, an amount, size, composition, parameter, or other quantity or characteristic, or alternative is “about” or “the like,” whether or not expressly stated to be such. It is understood that where “about,” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0050] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “0.1% to 5%” should be interpreted to include not only the explicitly recited values of 0.1% to 5%, but also, unless otherwise stated, include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 0.5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range. It is also understood (as presented above) that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0051] As used herein, unless otherwise stated, the term “group” refers to a chemical entity that is monovalent (i.e., has one terminus that can be (is) covalently bonded to other chemical species), divalent, or polyvalent (i.e., has two or more termini that can be (are) covalently bonded to other chemical species). The term “group” also includes radicals (e.g.,monovalent radicals and multivalent radicals, such as, for example, divalent radicals, trivalent radicals, and the like). Illustrative examples of groups include: the like. term “aliphatic” or “aliphaticthat, optionally, contain one or more degree(s) of unsaturation. Degrees of unsaturation can arise from, but are not limited to, carbon-carbon double bond group(s), carbon-carbon triple bond group(s), cyclic aliphatic group(s), or the like, or any combination thereof. In various examples, an aliphatic group is a C1to C40aliphatic group, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, or C40). Aliphatic groups include, but are not limited to, alkyl groups, alkene groups, and alkyne groups, and the like. In various examples, an aliphatic group is unsubstituted or substituted with one or more substituent(s). Examples of substituents include, but are not limited to, various substituents such as, for example, halogen groups (-F, -Cl, -Br, and -I), aliphatic groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, and the like), halogenated aliphatic groups (e.g., trifluoromethyl group and the like), aryl groups, halogenated aryl groups, hydroxyl group, amine groups, nitro group, cyano groups, isocyano groups, azide group, silane groups (e.g., alkyl silane groups, aryl silane groups, alkyl / aryl silane groups, or the like), alkoxide groups, alcohol groups, ether groups, ketone groups, carboxylate groups, carboxylic acid groups, ester groups, amide groups, thioether groups, thioester groups, and the like, and any combination thereof.

[0053] As used herein, unless otherwise indicated, the term “alkyl” or “alkyl group” refers to branched or unbranched hydrocarbon groups that include only single bonds between carbon atoms. In various examples, an alkyl group is a C1to C40alkyl group, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, and C40). In various examples, an alkyl group is a saturated group. In various examples, an alkyl group is a cyclic alkyl group, e.g., a monocyclic alkyl group or a polycyclic alkyl group. Examples of alkyl groups include, but are not limited to, methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, benzyl groups, cyclohexyl groups, adamantylgroups, and the like. In various examples, an alkyl group is unsubstituted or substituted with one or more substituent(s). Examples of substituents include, but are not limited to, various substituents such as, for example, halide groups (-F, -Cl, -Br, and -I), aliphatic groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, and the like), halogenated aliphatic groups (e.g., trifluoromethyl group and the like), aryl groups, halogenated aryl groups, hydroxyl groups, amine groups, nitro groups, cyano groups, isocyano groups, silyl groups, alkoxide groups, alcohol groups, ether groups, ketone groups, carboxylate groups, carboxylic acid groups, ester groups, amide groups, thioether groups, and the like, and any combination thereof.

[0054] As used herein, unless otherwise indicated, the term “aryl” or “aryl group” refers to C5 to C30 aromatic or partially aromatic carbocyclic groups, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, and C30). Aryl groups may comprise polyaryl groups such as, for example, fused ring groups, biaryl groups, or the like, or any combination thereof. The aryl group may be unsubstituted or substituted with one or more substituent(s). Examples of substituents include, but are not limited to, substituents such as, for example, halide groups (-F, -Cl, -Br, and -I), aliphatic groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, and the like), halogenated aliphatic groups (e.g., trifluoromethyl group and the like), aryl groups, halogenated aryl groups, hydroxyl groups, amine groups, nitro groups, cyano groups, isocyano groups, silyl groups, alkoxide groups, alcohol groups, ether groups, ketone groups, carboxylate groups, carboxylic acid groups, ester groups, amide groups, thioether groups, and the like, and any combination thereof. Aryl groups may contain hetero atoms, such as, for example, oxygen, nitrogen (e.g., pyridinyl groups and the like), sulfur, and the like, and any combination thereof. Examples of aryl groups include, but are not limited to, phenyl groups, biaryl groups (e.g., biphenyl groups and the like), fused ring groups (e.g., naphthyl groups and the like), hydroxybenzyl groups, tolyl groups, xylyl groups, furanyl groups, benzofuranyl groups, indolyl groups, imidazolyl groups, benzimidazolyl groups, pyridinyl groups, and the like.

[0055] As used herein, the term "structural analog" refers to a compound, a polymer, or group that can be envisioned by one of ordinary skill in the art to arise from another compound or group, respectively, if one atom or group of atoms, functional groups, or substructures is replaced with another atom or group of atoms, functional groups, substructures, or the like. In various examples, the term “structural analog” refers to any compound, monomer, polymer, polymerization product, or the like, or any portion thereof(such as, for example, one or more group(s) thereof or the like) or group if one atom or group of atoms, functional group or functional groups, or substructure or substructures is / are replaced with another atom or group of atoms, functional group or functional groups, substructure or substructures, or the like. In various examples, the term “structural analog” refers to any group that is derived from an original compound, monomer, polymerization product, or the like or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like by a chemical reaction, where the compound, monomer, polymerization product, or the like or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like is modified or partially substituted such that at least one structural feature of the compound, monomer, polymerization product, or the like or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like is retained.

[0056] The present disclosure describes, inter alia, polymers, polymerizable compositions, and methods of making polymers. The present disclosure also provides uses of the polymers and compositions.

[0057] In an aspect, the present disclosure provides polymers. In various examples, a polymer is produced by a method of the present disclosure. Non-limiting examples of polymers are disclosed herein.

[0058] A polymer can be a homopolymer or a copolymer. In various examples, a polymer is (or comprises a plurality of repeat units) formed from one or more monomer(s). Non- limiting examples of monomers are disclosed herein.

[0059] In various examples, a polymer comprises the following structure. a structural analog thereof. In variousO, C, S, or the like; and / or z is independently at each occurrence 0, 1, 2, 3, or 4; and / or n and m are independently 1 to 1,000,000, including all integer values and ranges therebetween (e.g., 1 to 2,000, 1 to 10,000, 2 to 2,000, 2 to 10,000, 5 to 2,000, 5 to 10,000, 10 to 2,000, or 10 to 10,000); and / or n (cis groups) is greater than m (trans groups) (e.g., n is 51 to 100% of the n and m groups). In various examples, a polymer comprises the following structure.a structural analog thereof. In various percentage of n groups (relative to the total number of n and m groups) is as set out in the previous example and / or R, R1, R2, R3are independently at each occurrence an aliphatic group, an aryl group, or the like. In various examples, R, R1, R2, R3are independently at each occurrence an aliphatic group, an aromatic group, or a heteroatom-containing group (such as, for example, a heteroatom-containing aliphatic group (e.g., a heteroatom-containing alkyl group or the like), a heteroatom- containing aryl group (e.g., a heteroatom-containing aromatic group or the like), or the like), or the like. In various examples, n is at least 60%, at least 65%, or at least 70%.

[0060] In various examples, a polymer comprises the following structure. a structural analog thereof. In various examples,N, S, or the like; and / or R, R1, and R2are independently at each occurrence an aliphatic group, an aryl group, or the like; and / or n and m are independently 1 to 1,000,000, including all integer values and ranges therebetween (e.g., g., 1 to 2,000, 1 to 10,000, 2 to 2,000, 2 to 10,000, 5 to 2,000, 5 to 10,000, 10 to 2,000, or 10 to 10,000); and / or n (trans groups) is greater than m (cis groups) (e.g., n is 51 to 100% of the n and m groups). In various examples, R, R1, R2, R3are independently at each occurrence an aliphatic group, an aromatic group, or a heteroatom-containing group (such as, for example, a heteroatom-containing aliphatic group (e.g., a heteroatom-containing alkyl group or the like), a heteroatom-containing aryl group (e.g., a heteroatom-containing aromatic group or the like), or the like), or the like. In various examples, n is at least 60%, at least 65%, or at least 70%.

[0061] The values of n and m can be determined by methods known in the art. In various examples, n and m (or the relative amounts of each) is determined by nuclear magnetic resonance spectroscopy (such as, for example,13C NMR or the like) or the like, or any combination thereof.

[0062] In various examples, polymer comprises (or has) an Mn and / or Mw of from about 5 g / mol to about 750 kg / mol, including all 0.1 g / mol values and ranges therebetween (e.g., about 5 kg / mol to about 500 kg / mol, about 10 kg / mol to about 200 kg / mol, or about 15 kg / mol to about 188 kg / mol), and / or a polydispersity index (PDI) of about 1.05 g / mol to about 10, including all 0.01 values and ranges therebetween (e.g., about 1.5 to about 5, about 1.7 to about 3, about 1.71 to about 2.32). Molecular weight (Mn and / or Mw) and / or PDI can be determined by methods known in the art. In various examples, molecular weight (Mn and / or Mw) and / or PDI is determined by gel permeation chromatography (GPC) or the like.

[0063] A polymer can comprise various end groups. In various examples, a polymer comprises (or has) one or more end group(s). In various examples, one or more or all of the end groups results from formation of the polymer (e.g., from a method of the present disclosure or the like, such as, for example, a quenching reaction or the like). Non-limiting examples of end groups include H, alkoxy groups (-OR groups, where R is an alkyl group), dithiocarbamate groups (-S2CNR2, where R is an alkyl group), groups formed from a nucleophile, groups formed by a quenching reaction, structural analogs thereof, and any combination thereof.

[0064] A polymer can have various forms. In various examples, a polymer is a monolith, a powder, a fiber or fibers, a film, a sheet, particulate, or the like.

[0065] In an aspect, the present disclosure provides polymerizable compositions. In various examples, a polymerizable composition is suitable for use in a method for the present disclosure. In various examples, polymerizable composition is configured for use in a polymerization method of the present disclosure. Non-limiting examples of compositions are provided herein.

[0066] In various examples, a polymerizable composition a polymerizable composition comprises (consists essentially of or consists of) one or more monomer(s), and one or more chiral hydrogen bond donors (HBDs). In various examples, a polymerizable composition further comprises one or more acid(s) and / or one or more polymerization agent(s) (which may be cationic polymerization initiator(s) (that may be referred to as initiator(s)) or form cationic polymerization initiator(s), respectively) and / or one or more solvent(s). In various examples, a polymerization agent or polymerization agents is / are a photoacid generator or photoacid generators, an acid or acids, or any combination thereof.

[0067] A polymerization composition can comprise various monomers. Combinations of monomers may be used. In various examples, a monomer or monomers is / are chosen from cationic polymerization monomers (e.g., monomers suitable for cationic polymerization orthe like) and the like, and any combination thereof. Non-limiting examples of cationic polymerization monomers include epoxides, lactones, cyclic acetals (e.g., heterocyclic acetals, such as, for example, dioxolane and the like), vinyl ethers, isoprenes (such as, for example, 1,2-isoprene and 1,4-isoprene and the like), butadiene, vinyl sulfides, vinyl-aryl monomers (such, as for example, aryl monomers comprising one or more vinyl group(s) (e.g., styrene, alkyl substituted styrenes, and the like), structural analogs thereof, and the like, and any combination thereof. In various examples, a monomer is a multifunctional monomer comprising two or more vinyl groups (e.g., vinyl groups suitable for cationic polymerization).

[0068] Various amounts of monomer(s) can be used. In various examples, a polymerization composition comprises about 1 weight percent (wt.%) to about 100 wt.% monomer(s) (based on the total weight of the polymerization composition), including all 0.1 wt.% values and ranges therebetween (e.g., about 1 wt. % to about 90 wt. % or about 1 wt. % to about 99 wt. %). In various examples, a polymerization composition does not comprise a solvent and the monomer(s) is / are the remainder of the composition.

[0069] A polymerization composition can comprise various hydrogen bond donors (HBDs). Combinations of hydrogen bond donors may be used. Without intending to be bound by any particular theory, it is considered a HBD donates electron density to (e.g., such that it forms a hydrogen bond with) an anion (e.g., a coordinating or a non-coordinating anion). It is considered this decreases the anion basicity and may facilitate cationic polymerizations. In various example, hydrogen bond donor(s) is / are chosen from thiophosphoramides, sulfamides, structural analogs thereof, and the like, or any combination thereof.

[0070] In various examples, a thiophosphoramide is a N-aryl substituted thiophosphoramide (such as, for example, a tri-N-aryl substituted thiophosphoramide or the like) or the like. In various examples, an HBD is a substituted thiophosphoramide or sulfamide comprising one or more aryl and / or alkyl group(s). In various examples, a thiophosphoramide comprises the following structure: isgroups) and the like. In various examples, a sulfamide comprises the following structure:is independently at each occurrence chosen from aryl groups) and the like. In various examples, an HBD is a structural analog thereof, or any combination thereof. an HBD comprises the following structure (or is):where Ar is an aryl group (such as,for example, a structural analog thereof or the like), Ph is a phenyl group, structurallike, and any combination thereof. In various other examples of the above examples, an Ar group or groups is / are independently replaced with an alkyl group. In various other examples of the above examples, a Ph group or groups is / are independently replaced with an aryl group or an alkyl group.

[0072] In various examples, one or more or all of the HBD(s) is / are chiral HBDs. In various examples, a chiral HBD comprises one or more chiral alkyl group(s). In various examples, an HBD comprises one or more stereocenters. In various examples, an HBD is a chiral compound. In various examples, an HBD a single stereoisomer (such as, for example, a single enantiomer). In various examples, an HBD comprises a chiral alkyl group comprising 1–40 carbons, including all integer numbers of carbons and ranges therebetween. In various examples an alkyl group comprises one or more stereocenters. In various examples, an alkyl group is a chiral alkyl group. In various examples, an alkyl is a chiral compound. In various examples, an HBD a single stereoisomer (such as, for example, a single enantiomer). Invarious examples, an alkyl group is derived from a natural product. Without intending to be bound by any particular theory, it is considered a chiral alkyl group may control tacticity of a polymer produced by the method.

[0073] Various amounts of hydrogen bond donor(s) can be used. In various examples, where a polymerization composition comprises polymerization agent(s), a polymerization composition comprises about 0.1 times to about 10 times the amount of the polymerization agent(s), including all 0.05 times values and ranges therebetween. In various examples, a polymerization composition comprises about 0.5 weight percent (wt.%) to about 10 wt.% (based on the total weight of the polymerization composition) of hydrogen bond donor(s), including all 0.1 wt.% values and ranges therebetween.

[0074] A polymerization composition may comprise various acids. Various acids can be used. Combinations of acids can be used. Non-limiting examples of acids include Lewis acids, Brønsted acids, and the like. Non-limiting examples of Lewis acids include AlCl3, BF3, TiCl4, and other metal-based acids with a formula of MXn, where M is a metal and X is an anion, or the like, and any combination thereof. Non-limiting examples of Brønsted acids include HOAc, HCl, HBr, H2SO4, HNO3, p-toluenesulfonic acid (TsOH), or the like, and any combination thereof. Without intending to be bound by any particular theory, it is considered an acid or acid formed from a polymerization agent initiates cationic polymerization of the monomer(s). In various examples, an acid or acid formed from a polymerization agent initiates cationic polymerization of the monomer(s) is an initiator or the like.

[0075] In various examples, an acid comprises an anion. In various examples, the anion is a coordinating anion (e.g. an anion having a pKa from 0 to 25, including every integer number and ranges therebetween). In various examples, the anion is a weakly coordinating or non-coordinating anion (e.g. an anion having a pKa from -15 to 0, including every integer number and ranges therebetween). Without intending to be bound by any particular theory, it is considered a HBD may interact with a coordinating anion such that it exhibits properties of a non-coordinating anion (such as, for example, catalytic properties or the like). In various examples, the acid or the anion (e.g., the coordinating anion) does not contain fluorine. In various examples, the acid is or is not 1,2,3,4,5-pentacarbo-methoxycyclopentadiene (PCCP- H), and the anion is or is not PCCP-. PCCP-H and PCCP- are shown below..

[0076] Without intending to be bound by any particular theory, it is considered that coordinating anion(s) in a polymerizable composition (which in this case may be referred to a photobuffer) buffers the number of protons present in the polymerizable composition after an irradiation. In various examples, a polymerizable composition comprises a photobuffer comprising (or formed from) one or more photoacid generator(s) comprising a non- coordinating anion and one or more coordinating anion(s).

[0077] A polymerization composition can comprise various polymerization agents. Combinations of polymerization agents may be used. In various examples, a polymerizable composition comprises one or more acid(s) and one or more polymerization agent(s). In various examples, a polymerizable composition does not comprises an acid and / or comprises one or more polymerization agent(s). In various examples, polymerization agent(s) is / are chosen from photoacid generators (which, independently, may comprise one or more non- coordinating anion(s)), or the like, or any combination thereof. In the case where a polymerization agent is a photoacid generator, a polymerizable composition may further comprise one or more coordinating anion(s). In various examples, a polymerization agent does not comprise fluorine.

[0078] In various examples, a photoacid generator (PAG) comprises (or the anion(s) of the PAG salt(s) is / are) a non-coordinating anion / non-coordinating anions. Non-limiting examples of non-coordinating anions include PF6-, SbF6-, ClO4-, CF3SO3-, structural analogs thereof, and the like, and any combination thereof.

[0079] Various amounts of polymerization agent(s) can be used. In various examples, a polymerization composition comprises about 0.5 weight percent (wt.%) to about 10 wt.% (based on the total weight of the polymerization composition) of polymerization agent(s), including all 0.1 wt.% values and ranges therebetween (e.g., 1 weight percent (wt.%) to about 10 wt.%).

[0080] In the case where a polymerization agent is a photoacid generator (e.g., a photoacid generator comprising one or more non-coordinating anion(s)), a polymerizablecomposition may further comprise one or more salt(s), each salt comprising one or more coordinating anion(s) (e.g., in about a stoichiometric amount relative to the photoacid generator(s)).

[0081] Non-limiting examples of salts comprising one or more coordinating anion(s) include organic salts comprising coordinating anion(s), inorganic soluble salts comprising coordinating anion(s), and the like, and any combination thereof. Non-limiting examples of coordinating anions include halides (such as, as for example, Cl-, Br-, I-, NO2, sulfonate, sulfate, phosphate, acetate, and the like), pentacarbomethoxycyclopentadienes (PCCP-s), carboxylates (such as, for example, acetate OAc-, and the like), and the like, and any combination thereof. In various examples, a polymerizable composition comprises a tetraalkylammonium salt comprising one or more coordinating anion(s) (such as, for example, tetrabutylammonium (TBA) salt and the like), or the like, or any combination thereof. In various examples, the cation of a coordinating anion is a tetraalkylammonium cation (such as, for example, tetrabutylammonium cation and the like), or the like, or any combination thereof.

[0082] In various examples, a polymerizable composition comprises about a stoichiometric amount or less of coordinating anion(s) (which may be relative to the amount of photoacid generator(s) (e.g., photoacid generator(s) comprising non-coordinating anion(s)). In various examples, the mole ratio of coordinating anion(s) to photoacid generator(s) comprising a non-coordinating anion / non-coordinating anions is about 1:1 or less (e.g., about 1:1 to about 0.01:1). In various examples, the mole ratio of coordinating anion(s) to non-coordinating anion(s) is about 1:1 or less (e.g., about 1:1 to about 0.01:1).

[0083] A polymerization composition may comprise various cross-linking monomers. In various examples, a polymerizable composition further comprises one or more cross-linking monomer(s). Non-limiting examples of crosslinking monomers include acrylate crosslinkers (such as, for example, tetraethylene glycol diacrylate (TEDGA), 1,4-butanediol diacrylate (BDA), and the like), methacrylate crosslinkers, structural analogs thereof, and the like, and any combination thereof.

[0084] A polymerization composition may comprise various solvents. In various examples, a polymerizable composition further comprises one or more solvent(s). Combinations of solvents may be used. Non-limiting examples of solvents include chlorinated hydrocarbons (e.g., dichloromethane (DCM), dichloroethane (DCE), and the like), alkanes (e.g., hexanes, cyclohexane, and the like), ethers (diethyl ether, cyclopentylmethyl ether (CPME), and the like), aromatic hydrocarbons (toluene and the like), and the like, and any combination thereof.

[0085] A polymerization composition may comprise chain transfer agents. In various examples, a polymerizable composition further comprises one or more chain transfer agent(s) (such as, for example, cationic RAFT polymerization agent(s) or the like, or any combination thereof). Non-limiting examples, of cationic RAFT polymerization chain transfer agents include trithiocarbonates, dithiocarbamates, structural analogs thereof, and the like, and any combination thereof. In various examples, chain transfer agent(s) independently comprise the following structure: or a structural analog thereof. In various examples, Z is O, S, or -N(R), wherean alkyl group, a heterocarbocyclic group, or the like. In various examples, chain transfer groups are chosen , S, structural analogs thereof, and

[0086] A polymerizable composition can have different forms. In various examples, a polymerizable composition is a liquid (such as, for example, a solution or the like), a film, a sheet, or the like.

[0087] Polymerization compositions can have various uses. In various examples, a composition is suitable for use in a photolithography method, a 3-D printing method, an additive manufacturing method, or the like, or any combination thereof. In various examples, a polymerizable composition is a photoresist or the like or a photoresist comprises a polymerizable composition. In various examples, a polymerization composition is used to make an article of manufacture.

[0088] In an aspect, the present disclosure provides polymerization methods. In various examples, a polymerization method is a cationic polymerization method. In various examples, a polymerization method forms one or more cationic polymerization product(s) (one or more or all of which may be a polymer or polymers of the present disclosure). Non- limiting examples of methods are disclosed herein.

[0089] In various examples, a polymerization method comprises reacting one or more acid(s), one or more or all of which may be formed (e.g., in situ) from a polymerization agent or polymerization agents, with a polymerizable composition comprising one or more monomer(s) and one or more hydrogen bond donor(s). In various examples, a polymerization method comprises: reacting an acid and a polymerizable composition comprising: one or more monomer(s), and one or more hydrogen bond donor(s) (HBDs). In the method, at least a portion of, substantially all, or all of the monomer(s) is / are polymerized (such as, for example, to form a polymer or the like). In various examples, a polymerization method comprises a stereoselective cationic polymerization (such as, for example, a HBD controlled stereoselective cationic polymerization or the like) or the like. In various examples, a polymerization method is a cationic reversible addition polymerization, a cationic reversible addition ^fragmentation chain transfer (RAFT) polymerization, or the like.

[0090] In various examples, a polymerization exhibits a desired polymerization (e.g., conversion percentage or the like) of one or more or all monomer(s). In various examples, a polymerization results in about 0.1 % conversion to about 100 % conversion of one or more, substantially all, or all monomer(s). In various examples, conversion percentage is observed by spectroscopy (e.g., nuclear magnetic resonance spectroscopy, such as, for example,1H NMR,13C NMR, or the like, infrared spectroscopy, or the like), thermal analysis (e.g., differential scanning calorimetry (DSC) or the like), or the like, or any combination thereof. In various examples, a polymerization exhibits a desired polymerization (e.g., conversion percentage or the like) of one or more or all monomer(s) and moisture tolerance (e.g., the polymerization is carried out in the presence of water).

[0091] Various monomers can be used. Combinations of monomers may be used. Non- limiting examples of monomers are disclosed herein (e.g., in the polymerizable composition description).

[0092] Various hydrogen bond donors (HBDs) can used. Combinations of hydrogen bond donors may be used. Non-limiting examples of HBDs are disclosed herein (e.g., in the polymerizable composition description). In various examples, an HBD is independently achiral, a stereoisomer (e.g., is chiral), a racemic mixture of stereoisomers, or the like, or any combination thereof.

[0093] In various examples, a cationic polymerization product (which may be a polymer of the present disclosure or the like) comprises a desirable number of cis groups (e.g., the number of cis groups is greater than the number of trans groups (e.g., 51 to 100% of the cisgroups and trans groups is cis groups. In various examples, the number of cis groups is at least 60%, at least 65%, or at least 70%. The number of cis groups and / or trans groups can be determined by methods known in the art. In various examples, the number of cis groups and / or trans groups is determined by nuclear magnetic resonance spectroscopy (such as, for example,13C NMR or the like) or the like, or any combination thereof.

[0094] Various acids may be used. Combinations of acids may be used. Non-limiting examples of acids are disclosed herein (e.g., in the polymerizable composition description). In various examples, an acid or acids is / are formed from a polymerization agent or polymerization agents. In various examples, a reaction mixture comprises a polymerization agent and may not comprise an acid.

[0095] In various examples, an acid comprises a coordinating anion and a polymerization exhibits a faster polymerization rate when compared to a polymerization of the same coordinating anion and the same polymerizable composition without one or more HBD(s). In various examples, substantially no or no cationic polymerization is observable for the same coordinating anion and the same polymerizable composition without one or more HBD(s). Polymerization can be observed by methods known in the arts. In various examples, polymerization is observed by spectroscopy (e.g., nuclear magnetic resonance spectroscopy, such as, for example,1H NMR,13C NMR, or the like, infrared spectroscopy, or the like), thermal analysis (e.g., differential scanning calorimetry (DSC) or the like), or the like, or any combination thereof.

[0096] In various examples, at least a portion or all of the acids is / are formed from a polymerization agent or polymerization agents. Non-limiting examples of polymerization agent(s) include photoacid generators and any combination thereof. Non-limiting examples of polymerization agents are disclosed herein (e.g., in the polymerizable composition description).

[0097] In the case where one or more acid(s) is / are formed form a polymerization agent or polymerization agents, a method (e.g., a reacting) further comprises irradiating (such as, for example, light or the like) a polymerization agent(s), such that an acid or acids are generated. In various examples, where a method comprises irradiating a polymer composition comprising one or more PAGs, the method is a lithography method, a photolithography method (e.g., positive photoresist or negative photoresist), an additive manufacturing method, a 3D printing method or the like.

[0098] Irradiation (e.g., light or the like) can provided by various sources. Suitable light sources are commercially available. In various examples, the irradiation comprises use of (orlight comprising a wavelength (which may be about a single wavelength) of about 365 nm, about 405 nm, about 530 nm, about 470 nm, about 615 nm, or the like. In various examples, the polymerization agent(s) each absorb at least a portion of the light (e.g., the wavelength of light).

[0099] In various examples, an irradiating (such as, for example, a first irradiating) results in a desired polymerization (e.g., conversion percentage or the like) of one or more or all monomer(s). In various examples, the irradiating results in about 0.1 % conversion to about 100 % conversion of one or more, substantially all, or all monomer(s). In various examples, conversion percentage is observed by spectroscopy (e.g., nuclear magnetic resonance spectroscopy, such as, for example,1H NMR,13C NMR, or the like, infrared spectroscopy, or the like), thermal analysis (e.g., differential scanning calorimetry (DSC) or the like), or the like, or any combination thereof.

[0100] In various examples, an irradiating comprises two or more discrete irradiations (e.g., in terms of wavelength, duration, intensity, or the like, or any combination thereof). In various examples, an irradiating comprises or is patterned irradiating. In various examples, an irradiating is carried out in a selected of pre-determined pattern. In various examples, an irradiating is independently (or comprises) photopatterning (such as, for example, photolithography or the like). In various examples, an irradiating is independently carried out using a photomask, a direct-write system, or the like. In various examples, a polymer comprising a desired shape is formed. In various examples, a polymer comprises two or more domains, where at least two or more of the domains comprise one or more different structural features, one or more different physical properties (e.g., Young’s modulus, stiffness, crosslink density, storage modulus, or the like), or any combination thereof.

[0101] Various amounts of polymerization agent(s) can be used. In various examples, a polymerization composition comprises about 0.5 weight percent (wt.%) to about 10 wt.% (based on the total weight of the polymerization composition) of first polymerization agent(s), including all 0.1 wt.% values and ranges therebetween (e.g., about 1 wt.% to about 10 wt.%).

[0102] A crosslinked polymer may be formed. In various examples, a polymerizable composition further comprises one or more cross-linking monomer(s). Non-limiting examples of crosslinking monomers include acrylate crosslinkers (such as, for example, tetraethylene glycol diacrylate (TEDGA), 1,4-butanediol diacrylate (BDA), and the like), methacrylate crosslinkers, structural analogs thereof, and the like, and any combination thereof.

[0103] In various examples, cationic polymerization product(s) (which may independently be polymer(s) of the present disclosure) is / are formed by a method of the present disclosure. In various examples, a cationic polymerization product is a sealant, an adhesive, consumer products, a photoresist, a thermoplastic elastomer, or a component thereof, or the like.

[0104] In various examples, a polymerization is run neat (e.g., the polymerizable composition does not comprise a solvent). In various examples, the polymerizable composition comprises one or more solvent(s). Non-limiting examples of solvents are disclosed herein (e.g., in the polymerizable composition description).

[0105] A method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) can be performed under various reaction conditions. A method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) can comprise one or more step(s) and each step can be performed under the same or different reaction conditions as other steps.

[0106] A method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) can be carried out at various temperatures. In various examples, a polymerization reaction, an irradiation, or the like, or any combination thereof is carried out at about room temperature (e.g., from about 20 °C to about 30 °C, including all 0.1 °C values and ranges therebetween), below room temperature (e.g., below about room temperature, such as for example, from about -78 °C to about room temperature, including all 0.1 °C values and ranges therebetween), or above room temperature (e.g., above room temperature up to or about a boiling point of the solvent(s), if present) (e.g., room temperature to about 100 °C or above, or any combination thereof (e.g., where each polymerization reaction, an irradiation, or the like, or any combination thereof is performed at a different temperature as other steps). In various examples, a method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) is carried out at about -78 °C to about 100 °C, including all 0.1 °C values and ranges therebetween.

[0107] A method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) can be carried out at various pressures. In various examples, a method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) is carried out at atmospheric pressure (e.g., 1 standard atmosphere (atm) at sea level), at greater than atmospheric pressure (e.g. heating in a sealed pressurized reaction vessel and the like), at below atmospheric pressure (e.g., under vacuum (e.g., from about 1 mTorr or less to about 100 mTorr or less, including all 0.1 mTorr values and ranges therebetween) (e.g., about 100mTorr or less, about 50 mTorr or less, about 10 mTorr or less, or about 1 mTorr or less) and the like), or any combination thereof (e.g., where each step is performed at a different pressure as other steps).

[0108] A method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) can be carried out for various times. The reaction time can depend on factors such as, for example, temperature, pressure, irradiation time(s), efficiency of the polymerization agent(s), mixing (e.g., stirring or the like), or the like, or any combination thereof. In various examples, reaction times range from about seconds (e.g., about 10 seconds) to greater than about 24 hours, including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at the same time or a different time as other steps).

[0109] In various examples, a method (e.g., a polymerization reaction, an irradiation, or the like, or any combination thereof) is carried out in air or an inert atmosphere. In various examples, a method is carried out in an inert atmosphere comprising one or more inert gas(es). Non-limiting examples of inert gases include nitrogen, argon, and the like, and any combination thereof.

[0110] In various examples, a polymerizable composition and / or a cationic polymerization product is a film, a sheet, or the like. In various examples, a polymerizable composition and / or a cationic polymerization product is bulk material, which may be confined in container, reactor, or the like.

[0111] In an aspect, the present disclosure provides articles of manufacture. In various examples, an article of manufacture comprises one or more polymer(s) and / or one or more cationic polymerization product(s) of the present disclosure. In various examples, one or more or all of the polymer(s) and / or cationic polymerization product(s) is / are formed by a method of the present disclosure. In various examples, an article of manufacture comprises one or more polymer(s) and / or cationic polymerization product(s) of the present disclosure, where at least a portion or all of the polymer(s) and / or cationic polymerization product(s) is / are formed by irradiation, crosslinked, or the like, or any combination thereof. Non- limiting examples of articles of manufacture are disclosed herein.

[0112] Non-limiting examples of articles of manufacture include containers (such as, for example, food storage containers, consumer product containers, water bottles (e.g., reusable water bottles and the like), and the like), plastic grocery bags, packaging, pipes, insulating panels, bathtubs, window panel doors, floors, tiles, syringes, petri dishes, specimen bottles, safety helmets, tendon prostheses, tracheal tubes, automobile components, electroniccomponents, clothing (such as, for example, waterproof clothing, fiber form for clothing, and the like), carpets, non-stick pots and pans, eye-wear, CDs and DVDs, furniture, outdoor play equipment, toys, and the like. Methods of making articles of manufacture using cationic polymerization product(s) and / or polymer(s) of the present disclosure are known in the art.

[0113] The following Statements describe various examples of functionalized multiblock copolymer films, methods of making functionalized multiblock copolymer films, and uses of the functionalized multiblock copolymer films of the present disclosure and are not intended to be in any way limiting: Statement 1. A cationic polymerization method, comprising reacting one or more acid(s) and a polymerizable composition, wherein the polymerizable composition comprises one or more monomer(s), and one or more hydrogen bond donor(s) (HBDs), where at least a portion of, substantially all, or all of the monomer(s) is / are polymerized (e.g., to form one or more cationic polymerization product(s) and / or polymer(s)). Statement 2. A cationic polymerization method according to Statement 1, where the HBD(s) is / are a thiophosphoramide, sulfamide, structural analog thereof, and the like, or any combination thereof. Statement 3. A cationic polymerization method according to Statement 1 or 2, where the HBD(s) is / are chosen from:as,Statement 4. A cationic polymerization method according to any one of Statements 1–3, where the HBD(s) is / are independently a substituted thiophosphoramide, sulfamide, or thelike comprising one or more alkyl group(s), one or more aryl groups, or the like, or any combination thereof. Statement 5. A cationic polymerization method according to Statement 4, where the HBD(s) comprise(s) one or more chiral alkyl group(s), one or more chiral aryl group(s), or the like, or any combination thereof. Statement 6. A cationic polymerization method according to any one of the preceding Statements, where one or more or all of the HBD(s) is / are a chiral HBD or chiral HBDs. Statement 7. A cationic polymerization method according to Statement 6, where the chiral HBD(s) is / are chosen from: ,, structural analogs thereof (such as, in variousgroup) or CF3 group is independently an alkyl group), and the like, and any combination thereof. Statement 8. A cationic polymerization method according to any one of the preceding Statements, where the acid(s) is / are independently a Lewis acid or a Brønsted acid or the like. Statement 9. A cationic polymerization method according to Statement 8, where the Lewis acid is chosen from metal-based acids comprising formula of MXn or the like, where M is a metal and X is an anion and any combination thereof.Statement 10. A cationic polymerization method according to Statement 8, where the Brønsted acid is chosen from HOAc, HCl, HBr, H2SO4, HNO3, p-toluenesulfonic acid (TsOH), structural analogs thereof, and the like, and any combination thereof. Statement 11. A cationic polymerization method according to any one of the preceding Statements, where the acid or one or more or all of the acid(s) comprise(s) a coordinating anion. Statement 12. A cationic polymerization method according to Statement 11, where the acid or the coordinating anion, or both, do(es) not contain fluorine. Statement 13. A cationic polymerization method according to any one of the preceding Statements, where the polymerizable composition further comprises one or more polymerization agent(s). Statement 14. A cationic polymerization method according to Statement 13, where the polymerization agent(s) is / are independently a photoacid generator, or a combination thereof. Statement 15. A cationic polymerization method according to Statement 13 or 14, where the reacting further comprises irradiating the photoacid generator(s) such that the acid is generated. Statement 16. A cationic polymerization method according to any one of the preceding Statements, where the monomer(s) is / are independently chosen from vinyl ethers, epoxides, lactones, acetals, cyclic acetals, vinyl ethers, isoprenes, butadiene, vinyl sulfides, styrene, structural analogs thereof, and the like, and any combination thereof. Statement 17. A cationic polymerization method according to any one of the preceding Statements, where the polymerizable composition further comprises one or more crosslinker(s) or the like. Statement 18. A cationic polymerization method according to any one of the preceding Statements, where a lithography method, a photolithography method (e.g., positive photoresist or negative photoresist or the like), an additive manufacturing method, a 3D printing method or the like comprises the cationic polymerization method. Statement 19. A polymerizable composition, comprising: one or more monomer(s), and one or more chiral hydrogen bond donors (HBDs), and optionally, one or more acid(s) and / or polymerization agent(s).Statement 20. A polymerizable composition according to Statement 19, where the HBD(s) is / are a thiophosphoramide, a sulfamide, a structural analog thereof, and the like, or any combination thereof. Statement 21. A polymerizable composition according to Statement 19 or 20, where the HBD(s) is / are chosen from: where Ar is an aryl group (such as,for example, a structural analog thereof or the like), Ph is a phenyl group, structurallike, and any combination thereof. Statement 22. A polymerizable composition according to any one of Statements 19 to 21, where the HBD(s) is / are independently a substituted thiophosphoramide, sulfamide, or the like comprising one or more chiral alkyl group(s), one or more chiral aryl group(s), or the like, or any combination thereof. Statement 23. A polymerizable composition according to any one of Statements 19 to 22, where the HBD(s) comprise(s) one or more chiral alkyl group(s), one or more chiral aryl group(s), or the like, or any combination thereof. Statement 24. A polymerizable composition according to any one of Statements 19 to 23, where one or more or all of the HBD(s) is / are a chiral HBD or chiral HBDs. Statement 25. A polymerizable composition according to Statement 24, where the chiral HBD(s) is / are chosen from:, , structural analogs thereof, and the like, and anyStatement 26. A polymerizable composition according to any one of Statements 19 to 25, where the acid(s) is / are independently a Lewis acid or a Brønsted acid or the like. Statement 27. A polymerizable composition according to Statement 26, where the Lewis acid is chosen from metal-based acids with a formula of MXn or the like, where M is a metal and X is an anion, and any combination thereof and / or the Brønsted acid is chosen from HOAc, HCl, HBr, H2SO4, HNO3, p-toluenesulfonic acid (TsOH), structural analogs thereof, and the like and any combination thereof. Statement 28. A polymerizable composition according to any one of Statements 19 to 27, where the acid comprises a coordinating anion or the like. Statement 29. A polymerizable composition according to any one of Statements 19 to 28, where the acid or the coordinating anion, or both, do(es) not contain fluorine or the like. Statement 30. A polymerizable composition according to any one of Statements 19 to 29, where the polymerizable composition further comprises one or more polymerization agent(s). Statement 31. A polymerizable composition according to Statement30, where the polymerization agent(s) is / are independently a photoacid generator or the like, or a combination thereof.Statement 32. A polymerizable composition according to Statement19, where the monomer(s) is / are independently chosen from vinyl ethers, epoxides, lactones, acetals, cyclic acetals, vinyl ethers, isoprenes, butadiene, vinyl sulfides, styrene, structural analogs thereof, and the like, and any combination thereof. Statement 33. A polymerizable composition according to Statement19, where the polymerizable composition further comprises one or more crosslinker(s) or the like. Statement 34. A polymer comprising the following structure: is 0,or n m are to and ranges therebetween (e.g., 1 to 2,000, 1 to 10,000, 2 to 2,000, 2 to 10,000, 5 to 2,000, 5 to 10,000, 10 to 2,000, or 10 to 10,000); and n is greater than m (e.g., n is 51 to 100% of the n and m groups), or a structural analog thereof, where X isS, or the like; R, R1, and R2are independently at each occurrence an aliphatic group, an aryl group, or the like; n and m are independently 1 to 1,000,000, including all integer values and ranges therebetween (e.g., 1 to 2,000, 1 to 10,000, 2 to 2,000, 2 to 10,000, 5 to 2,000, 5 to 10,000, 10 to 2,000, or 10 to 10,000); and n is greater than m (e.g., n is 51 to 100% of the n and m groups). Statement 35. A polymer according to Statement 34, where the polymer comprises the following structure:a structural analog thereof, where R, R1, phatic group, an aryl group, or the like.

[0114] The steps of the methods described in the various embodiments and examples disclosed herein are sufficient to produce one or more polymer(s) and / or one or more cationic polymerization product(s), or the like, or any combination thereof or to carry out a method of the present disclosure. Thus, in various examples, a method consists essentially of a combination of the steps of the methods disclosed herein. In various other examples, a method consists of such steps.

[0115] The following Examples are presented to illustrate the present disclosure. The Examples are not intended to be limiting in any manner. EXAMPLE 1

[0116] This example describes polymerizable compositions and polymerization methods of the present disclosure, and uses thereof.

[0117] Described is a catalyst that accelerated photoinitiated cationic polymerizations using non-fluorinated diphenyliodonium salts under mild reaction conditions.

[0118] A bench-stable organic acid 1,2,3,4,5-pentacarbomethoxycyclopentadiene (PCCP) afforded controlled polymerization of vinyl ethers under ambient conditions. The addition of HBDs lowered the basicity and thus nucleophilicity of the PCCP anion, reducing its affinity for the cationic chain end and accelerating polymerization. As depicted in FIG.1, the thiophosphoramide HBD afforded both rapid kinetics as well as controlled polymerization. When this was adapted to a cationic reversible addition ^fragmentation chain transfer (RAFT) polymerization, the addition of HBD contributed to achieving high conversions while retaining moisture tolerance. This HBD has also been shown to coordinate to a variety of other anions and improve systems ranging from ion recognition for transport to ionic Diels- Alder reactions.

[0119] It was considered that the addition of HBD to cationic polymerizations with coordinating anions would diminish the ion affinity to the propagating chain ends, accelerating the polymerization rate. This was shown by accelerating not only photopolymerizations initiated by PAGs containing both weakly and strongly coordinatinganions, but also Brønsted acid-initiated RAFT polymerizations under ambient conditions. The stability of the ^CF3groups on the HBD reduces the likelihood of hazardous byproducts in the polymerization. Thus, it was demonstrated that HBD catalysis is broadly applicable to a variety of cationic polymerization methods, with potential applications from fluorine-free photoinitiation to user friendly controlled polymerizations.

[0120] Results and discussion. To test the HBD catalysis, a diphenyliodonium PAG with a chloride counteranion (PAG ^Cl) was utilized, as the HCl generated has a similar pKa but very different structure to PCCP. As a control, 200 equiv of isobutyl vinyl ether (IBVE) was added to 1 equiv of PAG ^Cl in the absence of solvent and irradiated with 300 nm UV light. No polymerization was observed after 120 minutes of light irradiation, indicating that the HCl generated by PAG ^Cl was insufficient to polymerize IBVE. However, adding 1 equiv of the thiophosphoramide HBD relative to the PAG led to a 91% IBVE monomer conversion after 120 min of light irradiation (FIG.2B). It was considered that this catalysis was a result of HBD coordination to the chloride anion, which facilitated ionization to form a cationic chain end for propagation.

[0121] To test the anion versatility of the HBD, commercially available diphenyliodonium PAGs were used that result in conjugate acids with a breadth of pKasincluding: hexafluorophosphate (PF6^), triflate (OTf^), bromide (Br^), tosylate (TsO^), nitrate (NO3^), and acetate (OAc^) (FIG.2A). After exposure to UV light without HBD, neat IBVE reached full conversion in under 30 minutes for PAG ^PF6and PAG ^OTf, while the other PAGs were unable to initiate polymerization after 120 minutes (FIG.2B-C, open circles). For the anions unable to initiate, the effects were probed of 1 equiv of HBD relative to PAG on the polymerization kinetics. The addition of HBD enabled initiation in under 60 minutes, with the polymerization rates trending as TsO^^ Br^^ Cl^^ NO3^^ OAc^(FIG.2B, closed circles). HBD also led to faster rates of polymerization for PAG ^PF6and PAG ^OTf, which are known for their rapid photoinitiation (FIG.2C, closed circles). The hexafluoroantimonate anion (SbF6^) was also tested in the form of a p-(octyloxyphenyl)phenyliodonium salt, which also demonstrated faster kinetics upon the addition of 1 equiv HBD (FIG.6). Interestingly, the polymerization using PAG ^TsO and HBD achieved similar kinetics as the polymerizations of PAG ^OTf and PAG ^PF6without HBD, demonstrating the ability of HBD catalysis to achieve competitive rates with current photoinitiation standards.

[0122] In general, the polymerization kinetics with HBD correlate with the acidity of the Brønsted acids generated from the PAGs. Acids with lower pKa values in acetonitrile(MeCN) resulted in faster polymerization rates. However, based solely on pKa, both PAG ^Br and PAG ^NO3 saw less rate acceleration from HBD than predicted. To investigate the reasons behind these trends,1H ^NMR titrations were performed with HBD as the host and increasing amounts of anion in the form of their tetrabutylammonium (TBA) salts (FIG.3A). The amine protons on the HBD were tracked as the signal moved downfield with increasing anion concentration. The more strongly coordinating anions reached saturation with approximately 1 equiv of TBA salt with respect to HBD, indicating that there is 1:1 binding of the anion to the hydrogen bond donor (FIG.3A). Titrations with OAc−were unsuccessful as the N ^H signal broadened into the baseline, which has previously been reported as being due to deprotonation instead of binding. The relatively large induction period for the polymerization of PAG−OAc and HBD may be due to similar unproductive pathways that stall polymerization until sufficient acid is produced. In contrast, the weakly coordinating anion PF6^continued to shift downfield even after the addition of 7 equivalents of TBA salt relative to HBD, indicating that the system was still not fully saturated at large excess.

[0123] Utilizing the titration experiments for TsO−, Br^, Cl^, and NO3^, the binding constants (Keq) were approximated by fitting the data to the equation for 1:1 binding (Equation 1 and FIG.7–10). The resulting fits gave Keqs in the order of TsO^^ NO3^^ Br^^ Cl^. From these approximations, TsO^binds more strongly to the HBD than Br^and Cl^, likely increasing ionization at the chain end and allowing for higher rates of propagation. As Br^and Cl^have similar binding constants for HBD, the similar reaction kinetics also align with the titration data, despite the differences in their pKas.

[0124] However, the titration data alone is unable to explain the experimental differences between PAG ^OTs and PAG ^NO3. Despite nitric acid and tosic acid having similar pKasand their anions having similar Keqswith HBD, the PAG ^NO3polymerization was significantly slower. The PAG ^NO3 polymerization reached only 80% conversion after 2 hours, whereas the PAG ^OTs achieved 85% conversion after 5 minutes of light irradiation. One alternative explanation for the disparity in kinetics could arise from the differences in their geometries. The pseudo-tetrahedral geometry of the sulfate group on TsO^may allow for more favorable coordination to the tetrahedral shape of the HBD, compared to the trigonal planar geometry of NO3^.

[0125] Density functional theory (DFT) was utilized to generate optimized geometries for binding between the HBD and the anions. The optimized geometry for TsO^corresponded tothe oxygens of the sulfate group on TsO^hydrogen bonding to all three of the hydrogens of the amines on the HBD. However, the optimized geometry between the nitrate anion and HBD resulted in only two hydrogen bonds between the oxygens on NO3^and the hydrogens of the N ^Hs on the HBD (FIG.3B). It was considered that the ability to coordinate to all three sites on the HBD increases the rate of polymerization compared to binding to just two sites. From these optimizations, it was considered that the geometry mismatch between NO3^and HBD is likely the cause of its reduced polymerizations rates. From these binding studies, it was found that HBD is broadly applicable to a variety of counteranions, with the degree of rate acceleration impacted by acidity and geometry.

[0126] To further demonstrate the feasibility of HBD catalysis, the polymerizations were performed neat with exposure to air (FIG.4A). Once again, PAG ^TsO with 1 equiv of HBD displayed the fastest kinetics, achieving 90% conversion after 30 min (min = minute(s)). Despite reacting under ambient conditions, the polymerization still reached full conversion within 2 hours. However, when PAG ^Cl was polymerized with 1 equiv of HBD under air, a major reduction in polymerization rate was observed, reaching only 14% conversion after 2 hours. The dramatic decrease in kinetics for PAG ^Cl is likely due to the slower kinetics originally observed under nitrogen, enabling chain-end quenching due to moisture. As PAG ^TsO with HBD still provides reasonable kinetics under air, these results exemplify the ability of HBD to catalyze cationic polymerizations that were previously difficult to access.

[0127] Examining the tolerance of the photoinitiated polymerizations further, the storage stability of the resins was investigated under air over 3 days. Amber vials of uninhibited IBVE, PAG ^TsO, and HBD were stored at 20 °C (room temperature), 4 °C (in the fridge), and ^18 °C (in the freezer) under air. After 3 days, no polymerization was observed by1H ^NMR for any of the conditions, demonstrating the stability of the resins over multiple days, even at room temperature. To ensure polymerization was still possible, the resins were transferred to quartz tubes with dichloromethane and irradiated with 300 nm lights under ambient conditions. In all cases, high conversions (>97%) of IBVE to polymer were achieved within 1 hour, indicating that the resins were still viable after storage in a range of conditions.

[0128] A variety of vinyl ethers were studied to show the monomer scope of HBD- catalyzed cationic polymerizations in the absence of solvent: n-butyl vinyl ether (NBVE), ethyl vinyl ether (EVE), and 2,3-dihydrofuran (DHF). PAG ^Cl was utilized to explore the boundaries of the weaker acids generated in this system. Without HBD, no polymerization was observed for these vinyl ethers using PAG ^Cl. EVE did undergo monomerdecomposition as a result of acid-catalyzed hydrolysis to form acetaldehyde and acetals. Upon the addition of 1 equiv of HBD, all monomers achieved high conversions after 120 minutes. Importantly, for EVE in the presence of HBD, most of the monomer conversion was to polymer, with very little degradation products observed by1H ^NMR. DHF exhibited the greatest rate increase, achieving almost full conversion after 30 minutes (88% conversion). These additional monomers expand the range of achievable physical properties of the resulting polymers with reported glass transition temperature ranging from ^50 °C to 135 °C.

[0129] As the HBD was adapted to PAGs that generated acids of various pKas, it was considered that the HBD could catalyze Brønsted acid-initiated polymerizations outside of PCCP, such as those initiated by hydrochloric acid (HCl). Very few examples of HCl- initiated cationic polymerizations are reported in literature. Sugihara and co-workers demonstrated HCl ^Et2O is capable of initiating controlled cationic polymerization at 0 °C, under nitrogen with rigorously dried reagents. They adapted this system to initiate cationic RAFT polymerization, requiring similarly dry and cold conditions.

[0130] Initiation of cationic RAFT polymerizations with HCl under ambient conditions through HBD catalysis was investigated. To test this hypothesis, 1 equiv of HCl in ether was added to 150 equiv of distilled IBVE in a nitrogen glove box but at room temperature. No polymerization was observed by1H-NMR, although there was decomposition of IBVE to acetal side products. Upon the addition of 0.5 equiv of HBD under the same conditions, the reaction reached full conversion after 3.5 hours, yielding polymers with a bimodal distribution (FIG.5B). To impart control, 1 equiv of a dithiocarbamate RAFT chain transfer agent (CTA) was added, and the amount of HCl was dropped to 0.5 equiv to match that of the HBD. To test the tolerance, this polymerization was performed under air, neat without monomer purification, and at room temperature. After 4 hours, 72% conversion of IBVE was observed, resulting in polymer with a dispersity of 1.34 and an experimental Mn = 7.2 kg / mol, matching the theoretical Mn = 7.5 kg / mol (FIG.5B). When no HBD was added under the same reaction conditions, no polymerization was seen after 2 days, with 12% conversion to degradation products. These results suggest that HBD will catalyze various methods of solvent-free cationic polymerizations, accessing counteranions and conditions that were previously difficult to achieve.

[0131] It was demonstrated that HBD can be used as a general catalyst for various cationic polymerization methods with a wide range of counteranions. Described is HBD- catalyzed photopolymerizations of vinyl ethers using PAG counteranions that werepreviously unable to initiate vinyl ethers in reasonable time scales. The accelerated polymerization rates were enabled by the formation of hydrogen bonding between the HBD and PAG anion, thus reducing the anion’s affinity to the growing cationic polymer chain end. The acceleration was primarily dictated by the pKa of the resulting conjugate acid, with exceptions investigated by1H ^NMR titrations and DFT geometry optimizations. By expanding these reaction conditions to different monomers and atmospheres, it is expected to increase the feasibility of this method for the fabrication of polymeric materials with tunable physical properties. Furthermore, through HBD catalysis, HCl-initiated cationic RAFT polymerization was performed without monomer purification, under air, and at room temperature. Therefore, it is expected that HBD catalysis is able to accelerate a variety of cationic polymerizations, improving the feasibility of current initiation methods, as well as expanding the scope of possible initiators.

[0132] General Reagent Information. Diphenyliodonium chloride (PAG ^Cl, 98%, TCI), diphenyliodonium nitrate (PAG ^NO3, TCI), diphenyliodonium p-toluenesulfonate (PAG ^TsO, >99%, electronic grade, Millipore Sigma), diphenyliodonium bromide (PAG ^Br, 95%, Astatech), diphenyliodonium trifluoromethanesulfonate (PAG ^OTf, 98%, TCI), diphenyliodonium hexafluorophosphate (PAG ^PF6, >98%, Millipore Sigma), tetrabutylammonium acetate (TBA ^OAc, >99%, Sigma), tetrabutylammonium chloride (TBA ^Cl, 97%, Sigma Aldrich), tetrabutylammonium nitrate (TBA ^NO3, 97%, Alfa Aesar), tetrabutylammonium p-toluenesulfonate (TBA ^TsO, >98%, TCI), tetrabutylammonium bromide (TBA ^Br, 98%, Sigma Aldrich), tetrabutylammonium hexafluorophosphate (TBA ^PF6, 98%, Strem Chemicals), silver acetate (AgOAc, 99.99%, Sigma Aldrich), aluminum oxide (activated, basic, Brockmann I, Sigma), calcium hydride (CaH2, 93% extra pure, 0-2 mm grain size, ACROS organics), deuterated chloroform (CDCl3, 99.8%, Cambridge Isotope), and hydrogen chloride in ether (HCl in Et2O, 2 M, Millipore Sigma) were used as received. Unless noted otherwise, isobutyl vinyl ether (IBVE, 99%, TCI), ethyl vinyl ether (EVE, 98%, TCI), butyl vinyl ether (NBVE, 98%, Sigma Aldrich), and 2,3- dihydrofuran (DHF, 99%, TCI) were dried over calcium hydride overnight, distilled under nitrogen followed by 3 freeze-pump thaw cycles and then stored in the glove box freezer (−35 ˚C). Tris(3,5-bis(trifluoromethyl)phenyl) thiophosphotriamide (HBD) and S-1- isobutoxyethyl N,N-diethyl dithiocarbamate (CTA) were synthesized according to reported literature procedures. Diphenyliodonium acetate (PAG ^OAc) was synthesized as described below.

[0133] General Analytical Information. All polymer analysis was performed using a Tosoh EcoSEC HLC 8320 GPC system with two SuperHM-M columns in series at a flow rate of 0.350 mL / min with tetrahydrofuran (THF) as the eluent. For the cationic RAFT polymerization initiated by HCl, number-average molecular weights (Mn), weight-average molecular weights (Mw), and dispersities (Đ) were determined by light scattering using a Wyatt miniDawn Treos multi-angle light scattering detector and 0.0381 mL / g for the dn / dc of PIBVE. Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker 400 MHz or a Bruker 500 MHz instrument at room temperature using CDCl3as a solvent unless otherwise noted.

[0134] Synthesis. Synthesis of PAG ^OAc. A 25 mL round bottom flask was equipped with a magnetic stir bar, flame dried, and charged with PAG ^Cl (101.3 mg, 0.32 mmol, 1 equiv). The flask was evacuated and backfilled with N2 three times. The solid was dissolved in 1 mL anhydrous MeOH. AgOAc (52.7 mg, 0.32 mmol, 1 equiv) was dissolved in a minimum amount of MeOH before being added to PAG ^Cl. The reaction was stirred for 24 hours while wrapped with aluminum foil. The reaction was filtered, and the solution was concentrated in vacuo to yield PAG ^OAc (97.6 mg, 90% yield).1H-NMR (CD3OD, 500 MHz): 1.89 ppm (s, 3 H), 7.54 ppm (t, J = 7.7 Hz, 4 H), 7.70 ppm (t, J = 7.7 Hz, 2 H), 8.17 ppm (d, J = 7.7 Hz, 4 H).13C-NMR (CD3OD, 500 MHz): 24.26 ppm, 116.44 ppm, 133.09 ppm, 133.54 ppm, 136.40 ppm, 180.22 ppm.

[0135] General Procedures for IBVE Polymerizations Using PAGs Without HBD. In an oven-dried quartz tube, 1 equiv of PAG salt was added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at desired light irradiation time points and quenched with 5% NEt3 in MeOH.

[0136] PAG ^OAc: In an oven-dried quartz tube, PAG ^OAc (6.8 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 15 min, 1 h (h = hour(s)), 2 h.

[0137] PAG ^Cl: In an oven-dried quartz tube, PAG ^Cl (6.3 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 15 min, 30 min, 1 h, 2 h.

[0138] PAG ^NO3: In an oven-dried quartz tube, PAG ^NO3 (6.8 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 15 min, 30 min, 1 h, 2 h.

[0139] PAG ^TsO: In an oven-dried quartz tube, PAG ^TsO (9 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 2 h.

[0140] PAG ^Br: In an oven-dried quartz tube, PAG ^Br (7.2 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 1 h, 2 h.

[0141] PAG ^OTf: In an oven-dried quartz tube, PAG ^OTf (8.6 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 10 min, 15 min, 30 min, 1 h, 2 h.

[0142] PAG ^PF6: In an oven-dried quartz tube, PAG ^PF6(8.5 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 10 min, 15 min, 30 min, 1 h, 2 h.

[0143] PAG ^SbF6: In an oven-dried quartz tube, p-(octyloxyphenyl)phenyliodonium hexafluoroantimonate (PAG ^SbF6) (12.9 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 2, 5, 10, 15, 30, and 60 minutes.

[0144] Procedure for IBVE Polymerizations Using PAGs with HBD. In an oven- dried quartz tube, PAG salt (0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at desired light irradiation time points and quenched with 5% NEt3 in MeOH.

[0145] PAG ^OAc: In an oven-dried quartz tube, PAG ^OAc (6.8 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 1 h, 2 h.

[0146] PAG ^Cl: In an oven-dried quartz tube, PAG ^Cl (6.3 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 1 h, 2 h.

[0147] PAG ^NO3: In an oven-dried quartz tube, PAG ^NO3(6.8 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 1 h, 2 h.

[0148] PAG ^TsO: In an oven-dried quartz tube, PAG ^TsO (9 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 1 h, 2 h.

[0149] PAG ^Br: In an oven-dried quartz tube, PAG ^Br (7.2 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2 three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 15 min, 30 min, 1 h, 2 h.

[0150] PAG ^OTf: In an oven-dried quartz tube, PAG ^OTf (8.6 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 10 min, 15 min, 30 min, 1 h, 2 h.

[0151] PAG ^PF6: In an oven-dried quartz tube, PAG ^PF6 (8.5 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 5 min, 10 min, 15 min, 30 min, 1 h, 2 h.

[0152] PAG ^SbF6: In an oven-dried quartz tube, p-(octyloxyphenyl)phenyliodonium hexafluoroantimonate (PAG ^SbF6) (12.9 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2three times. Then IBVE (0.52 mL, 4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at 2, 5, 10, 15, 30, and 60 minutes.

[0153] General Sample Prep for NMR Titrations. All CDCl3 used was filtered through basic alumina. The HBD stock solution was made by combining HBD and CDCl3to give an expected molarity of 2.5 mM. The solution was vortexed until the HBD was visibly dissolved. This solution was passed through a 0.45 ^m PTFE filter. To the filtered solution, dioxane was added as an internal standard. A new stock solution of HBD was made for every new anion. The tetrabutylammonium anion salts (TBA ^A) were made into stock solutions by adding TBA ^A (10 mg) to CDCl3(1 mL). The salts readily dissolved so they were not passed through filters.

[0154] In a one dram vial, HBD solution (0.5 mL) was added. The below amounts of TBA ^A stock solution were added. The total NMR sample volume was brought up to 0.6 mL by adding the corresponding CDCl3amount. For higher TBA ^A equiv, the TBA ^A salt was added as a solid and an additional 0.1 mL of CDCl3was added. This solution was then transferred into an NMR tube. Final concentrations for the HBD and TBA ^A salt in the tube were calculated from NMR, based off of the dioxane internal standard. The HBD concentration was checked to ensure consistency between NMR samples, as its concentration stayed relatively constant. The TBA ^A concentration was used in the binding fit calculations later.

[0155] TBA ^OAc: HBD stock solution: HBD (0.018 mmol, 13.1 mg) in CDCl3(7 mL) with dioxane (0.035 mmol, 3.0 ^L). TBA ^OAc stock solution: salt (0.033 mmol, 10 mg) in CDCl3 (1 mL).

[0156] TBA ^Cl: HBD stock solution: HBD (0.018 mmol, 13.1 mg) in CDCl3 (7 mL) with dioxane (0.035 mmol, 3.0 ^L). TBA ^Cl stock solution: salt (0.036 mmol, 10 mg) in CDCl3 (1 mL).

[0157] TBA ^NO3: HBD stock solution: HBD (0.015 mmol, 11.2 mg) in CDCl3 (6 mL) with dioxane (0.030 mmol, 2.6 ^L). TBA ^NO3 stock solution: salt (0.033 mmol, 10 mg) in CDCl3 (1 mL).

[0158] Table 1. Titration of HBD (1 equiv) with TBA ^NO3.. , . g with dioxane (0.035 mmol, 3.0 ^L). TBA ^TsO stock solution: salt (0.024 mmol, 10 mg) in CDCl3 (1 mL).

[0160] Table 2. Titration of HBD (1 equiv) with TBA ^TsO.with dioxane (0.035 mmol, 3.0 ^L). TBA ^Br stock solution: salt (0.031 mmol, 10 mg) in CDCl3 (1 mL).

[0162] Table 3. Titration of HBD (1 equiv) with TBA ^Br.

[0163] TBA ^PF6: HBD stock solution: HBD (0.018 mmol, 13.1 mg) in CDCl3 (7 mL) with dioxane (0.035 mmol, 3.0 ^L). TBA ^Br stock solution: salt (0.026 mmol, 10 mg) in CDCl3 (1 mL).

[0164] Table 4. Titration of HBD (1 equiv) with TBA ^PF6.

[0166] Derivation of Equation for 1:1 Binding. Anion = A; HBD = B Anion ^HBD = C [A]eq = concentration of A at equilibrium [A]0= initial concentration of A δb = NMR shift of N ^H of HBD without anion δc = NMR shift of N ^H of HBD when saturated with anion δ = observed NMR shift of N ^H of HBD at given [A] [^^]^^ ^^ ^^^^ ^^ =⋅ ^^[[ ^^]^^ ^^[ ^^]0= [ ^^]^^ ^^+ [ ^^]^^ ^^[ ^^]^^ ^^= [ ^^]0− [ ^^]^^ ^^[ ^^]^^ ^^= ^^^^ ^^⋅ [ ^^]^^ ^^⋅ ([ ^^]0− [ ^^]^^ ^^) [ ^^]0= [ ^^]^^ ^^+ [ ^^]^^ ^^[ ^^]^^ ^^= [ ^^]0− [ ^^]^^ ^^[ ^^]^^ ^^= ^^^^ ^^⋅ ([ ^^]0− [ ^^]^^ ^^) ⋅ ([ ^^]0− [ ^^]^^ ^^) 1+ ^^ ^^ ^^ + ^^ ^^ ^^ ± √ − ^^ ^^ ^^ − ^^ ^^ ^^ 2 − 4 ^^ ^^ ^^20^^ =^^ ^^ ⋅ [ ^^] ^^ ^^ + ^^ ^^ ⋅ [ ^^] ^^ ^^[^^]0) Equation 11+ ^^ [ ^^] + ^^ [ ^^] −√(−1− ^^ [ ^^] − ^^ [ ^^] ) −4 ^^ [ ^^] [ ^^]^^ ^^[ ^^] ^^ + ( ^^ ^^ − ^^ ^^) ⋅ ( )^^ =2 ^^

[0167] Matlab R2021a Curve Fitting Toolbox Extension using a non-linear least squares model. δb was fixed at 5.74 ppm, and δcwas fixed at the corresponding shift of the N ^H bonds when saturated with anion.

[0168] Geometric Optimizations. Density Functional Theory for Geometry Optimizations. All DFT calculations were performed with the Gaussian 09 program package. The geometry optimization of all the minima involved was carried out at the B3LYP-D3 level of theory with the 6-31G(d) basis set. The vibrational frequencies were computed at the same level to check whether each optimized structure is an energy minimum to evaluate its zero- point vibrational energy (ZPVE) and thermal corrections at 298 K.

[0169] General Procedure for IBVE Polymerizations under Air. PAG ^A (1 equiv, 0.02 mmol) and HBD (1 equiv, 0.02 mmol, 14.9 mg) were weighed out and added to a quartz reaction tube equipped with a stir bar. IBVE (200 equiv, 4 mmol, 0.52 mL, distilled) was added to the tube. The reaction was irradiated with 300 nm UV light for the indicated amount of time. Aliquots were taken by opening the cap and quenched in a separate vial with a drop of 5% NEt3 in MeOH in CDCl3.

[0170] Storage Stability of Resins. In amber 1-dram vials, IBVE monomer (inhibitor removed with basic alumina plug, 0.26 mL, 2 mmol, 200 equiv), PAG ^TsO (4.5 mg, 0.01 mmol, 1 equiv), and HBD (7.5 mg, 0.01 mmol, 1 equiv) were combined. The amber vials were placed in different conditions for 3 days: at room temperature, at 4 °C in the fridge, andat ^18 °C in the freezer. Aliquots for NMR were taken at 0 minutes and 3 days and quenched with 5% NEt3 in MeOH.

[0171] After 3 days, the resins in the vials were transferred into oven-dried quartz tubes. An additional 0.2 mL of uninhibited IBVE were added to account for aliquots and evaporation. Once the resin was transferred, the vials were rinsed with 0.2 mL of dry DCM, which was then added to the quartz tube as well. The polymerizations were run under air and irradiated with 300 nm light. After 1 hour of light irradiation, the polymerizations were quenched with 50 ^L of 5% NEt3 in MeOH, and aliquots were taken for NMR analysis.

[0172] General Procedures for Polymerizations of Vinyl Ethers with PAG ^Cl Without HBD. In an oven-dried quartz tube, PAG–Cl (6.3 mg, 0.02 mmol, 1 equiv) was added, and the tube was evacuated and backfilled with N2 three times. Then the respective vinyl ether monomer (4 mmol, 200 equiv) was added to the reaction tube under N2 atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at desired irradiation time.

[0173] General Procedure for Polymerizations of Vinyl Ethers with PAG-Cl and HBD. In an oven-dried quartz tube, PAG ^Cl (6.3 mg, 0.02 mmol, 1 equiv) and HBD (15 mg, 0.02 mmol, 1 equiv) were added, and the tube was evacuated and backfilled with N2three times. Then the respective vinyl ether monomer (4 mmol, 200 equiv) was added to the reaction tube under N2atmosphere and irradiated with 300 nm light. Aliquots for1H NMR analysis were taken at desired irradiation time.

[0174] Procedure for HCl initiated polymerizations. Procedure for HCl initiated polymerization of IBVE without HBD. A one dram vial with a septum cap and stir bar were pumped into a nitrogen glove box overnight. IBVE (distilled, 150 equiv, 3.75 mmol, 0.49 mL) was added, followed by 2 M HCl in ether (1 equiv, 0.025 mmol, 13 ^L). The reaction was stirred on a magnetic stir plate at room temperature in the glove box for 24 hours. The vial was pulled out of the box and quenched with 50 ^L of 5% NEt3 in MeOH. The crude polymerization was analyzed by1H-NMR and GPC.

[0175] Procedure for HCl initiated polymerization of IBVE with HBD: HBD (0.5 equiv, 0.013 mmol, 9.3 mg) was weighed into a one dram vial with a septum cap and stir bar. The vial was pumped into a nitrogen glove box overnight. IBVE (distilled, 150 equiv, 3.75 mmol, 0.49 mL) was added, followed by 2 M HCl in ether (1 equiv, 0.025 mmol, 13 ^L). The reaction was stirred on a magnetic stir plate at room temperature in the glove box for 3.5hours. The vial was pulled out of the box and quenched with 50 ^L of 5% NEt3 in MeOH. The crude polymerization was analyzed by1H-NMR and GPC.

[0176] Procedure for HCl initiated RAFT polymerization of IBVE without HBD, under air: The dithiocarbamate CTA (1 equiv, 0.040 mmol, 10.0 mg) was weighed out in a one dram vial and equipped with a stir bar. IBVE (filtered through basic alumina plug, 150 equiv, 6 mmol, 0.78 mL) was added, followed by 2 M HCl in ether (0.5 equiv, 0.020 mmol, 10 ^L). The reaction was stirred on a magnetic stir plate at room temperature for 2 days and then was quenched with 40 ^L of 5% NEt3 in MeOH. The crude polymerization was analyzed by1H- NMR and GPC.

[0177] Procedure for HCl initiated RAFT polymerization of IBVE with HBD, under air: The dithiocarbamate CTA (1 equiv, 0.040 mmol, 10.0 mg) and HBD (0.5 equiv, 0.020 mmol, 15.0 mg) were weighed out in a one dram vial and equipped with a stir bar. IBVE (filtered through basic alumina plug, 150 equiv, 6 mmol, 0.78 mL) was added, followed by 2 M HCl in ether (0.5 equiv, 0.020 mmol, 10 ^L). The reaction was stirred on a magnetic stir plate at room temperature for 4 hours and then was quenched with 40 ^L of 5% NEt3in MeOH. The crude polymerization was analyzed by1H-NMR and GPC. EXAMPLE 2

[0178] This example describes polymerizable compositions and polymerization methods of the present disclosure, and uses thereof.

[0179] Described is use of a reversibly cleavable carbon-carbon bond to mediate the cationic polymerization of p-methylstyrene. The active chain end is comprised of an alkylated pentacarboxycyclopentadiene (PCCP), which undergoes ionization with the assistance of a hydrogen-bond donor (HBD) co-catalyst. Because the ionization requires heat, the active chain end can be retained upon cooling, thus realizing a telechelic polymer. This work represents a rare example of polymerization mediated by a reversibly ionizable carbon- carbon bond.

[0180] To further expand this method’s application to the less activated monomer p- methylstyrene (pMS), it was considered that a more stable C-C bond capped chain end would be desirable.

[0181] It was demonstrated that the pentacarboxycyclopentadiene (PCCP) Brønsted acid is capable of living cationic polymerization of vinyl ethers through a tight ion-pair interaction and is enhanced by a thiophosphoramide HBD (hereafter referred to as HBD) co-catalyst. Toutilize this approach with pMS, ionization between the benzylic carbon of the chain end and PCCP is necessary. It was considered to use an HBD to promote the heterolysis of a carbon- carbon bond between the PCCP cyclopentadienyl ring and a poly(p-methylstyrene) chain end to form the propagating carbocationic species. Recombination of the PCCP anion with the propagating species would return the chain to a dormant state, thereby providing reaction control. Reintroduction of the HBD could then reactivate the polymerization, allowing for post-synthetic chain extension or block copolymer production. Described is the controlled cationic polymerization of p-methylstyrene mediated by reversible carbon-carbon bond cleavage.

[0182] Results and Discussion: The reactivity of PCCP 1 towards pMS was investigated by subjecting it to the optimal conditions previously used for isobutylvinyl ether. No polymerization was observed at room temperature in the presence of the HBD co-catalyst (Table 5, entry 1). Heating the reaction to 50 ºC with PCCP 1 alone showed no reaction (Table 5, entry 2). Addition of HBD and heating resulted in low conversion to oligomeric material (Table 5, entry 3). Despite PCCP 1 having a pKa comparable to that of HCl, it proved to be inefficient at initiation of pMS by protonation.

[0183] Under the proposed polymerization mechanism, protonation of pMS by PCCP 1 would be followed by recombination with the PCCP anion, which results in the formation of PCCP 2. Subsequent propagation requires ionization of this structure and resulting chain ends that closely resemble it. To circumvent the inefficient protonation, PCCP 2 was directly synthesized as a source of a more competent carbocation initiator species that mirrors the desired propagation. Alkylated PCCPs can be synthesized in a straightforward manner from the silver salt of PCCP 1 and an alkyl halide. This method provides a simple strategy for both varying the initiating species and studying the propagation step. To gain insight into the ionization step, PCCP 3 was synthesized, where the desired C-C bond ionization occurs between tertiary carbons.

[0184] PCCPs 2 and 3 were isolated in moderate yields as bench-stable white solids. Confirmation of the covalent C-C bond between the alkyl fragment and cyclopentadienyl ring carbon was obtained via the X-ray crystal structures of PCCPs 2 and 3. This sharply contrasts the nature of the propagating species produced during polymerization of vinyl ethers with PCCP 1. In that case, a tight ion pair between the oxocarbenium chain end and PCCP anion is hypothesized to be in equilibrium with a covalent complex, but the species have proven too reactive to directly isolate. The comparatively lower stability of the (p-methylphenyl)ethyland adamantyl carbocations push the equilibrium to the covalent complex, which was found to be stable under ambient conditions.

[0185] Table 5: Optimization of pMS polymerization. 2 7 1 6 1 3 8 9 6 9 4

[0186] Reaction conditions were then screened for the cationic polymerization of pMS with PCCP 2 (Table 5). No reaction was observed with PCCP 2 and HBD at room temperature (Table 5, entry 4). Heating the reaction to 50oC in the absence of HBD was also insufficient to initate the reaction (Table 5, entry 5), demonstrating the high stability of the covalent complex. The combination of PCCP 2, HBD, and heating to 40 °C resulted in slow polymerization (Table 5, entry 6). Increasing the temperature to 50°C slightly improved conversion and Mn (Table 5, entry 7). Increasing the equivalents of HBD to 1.5 achieved higher conversion, a higher Mnin good agreement with the theoretical weight, and a narrower dispersity (Table 5, entry 8). Further increasing the equivalents of HBD to 3 resulted in even higher conversion and Mn, but introduced a widening gap between the theoretical and experimental Mn (Table 5, entry 9). These results demonstrate that the HBD is critical for promoting ionization of the covalent complex. Increasing the temperature of the reaction to60°C with 1.5 HBD equivalents showed a similar effect to increasing HBD equivalents with increased conversion and Mnwhile trailing theoretical weights (Table 5, entry 10). Both heat and HBD equivalents favor ionization, which suggests that the equilibrium lies heavily on the side of the dormant covalent chain end during polymerization.

[0187] Increasing the monomer equivalents caused a sharp decline in conversion (Table 5, entries 11 and 12). The lower reaction concentration presumably disfavors ionization. When both monomer and HBD equivalents are doubled to maintain the same HBD concentration as entry 7, conversion is dramatically improved (Table 5, entry 13). However, the increase in Mn falls far short of the theoretical weight expected from the higher monomer equivalents, which suggests that chain transfer is prevalent. Comparison of the GPC traces for entries 8, 9, and 13 (FIG.22) shows the higher HBD concentration increased Mn without noticeable change in the distributions. Diluting the reaction with benzene to reduce the HBD concentration without increasing the monomer equivalents led to similar results as reducing HBD concentration with monomer, supporting the importance of HBD concentration (Table 5, entry 15). Use of more polar dichloroethane (DCE) instead of benzene resulted in high conversion and broad dispersity characteristic of uncontrolled polymerization. The low polarity of benzene and pMS makes complete solvation of the ion pair unfavorable, while the higher polarity of DCE likely results in complete solvation and dissociation.

[0188] To prove that PCCP ionization precedes pMS addition, adamantyl PCCP 3 was used as an initiator. The polymerization produced similar results to PCCP 2 (Table 5, entries 8 and 14). The tertiary centers involved in the ionization of the PCCP and adamantyl fragments exclude the possibility of nucleophilic attack by monomer as the initiating step. The following chain growth would proceed in an identical manner for both catalysts, reflected in the comparable Mn and dispersities that result.

[0189] The kinetics of the polymerization follows a first-order relationship in monomer conversion over time. The initial linear increase in the Mn with conversion is consistent with a chain growth mechanism, but the plateau in Mn at higher conversion is further evidence that chain transfer to monomer is significant. The constant reaction rate reflects that quenching of the carbocation is not occurring and the concentration of propagating species is constant. The most likely termination reactions are ^-proton elimination at the chain end producing an olefin and intramolecular Fridel-Crafts alkylation to an indanyl derivative. Both reactions involve the loss of a proton, which can transfer to monomer, initiating a new chain.

[0190] Investigation of the nature of the PCCP chain end post-polymerization was then performed to identify if these chain termination reactions were occurring. Examining the1H NMR spectra of the precipitated and washed polymer shows the presence of several chain ends. The peak at 0.93 ppm is the terminal methyl group from either the PCCP 2 initiator or from protonation of the pMS monomer. The molecular weight of the polymer was calculated as 4.0 kg / mol, which is in excellent agreement with the weight found via GPC analysis (4.0 kg / mol). The region of 3.20-3.84 corresponds to the PCCP methyl esters and accounts for 45% of chain ends. An olefin peak resulting from elimination can be seen at 5.90 in 18% abundance. Lastly, the indanyl derivative formed by intramolecular alkylation at the chain end can be identified by the peak at 2.90 ppm and accounts for the remaining 37%. Undesired termination events resulting in the olefin or indanyl chain ends are promoted by the higher reaction temperature necessary for PCCP ionization. The competition between the propagating ionization reaction and chain transfer termination reactions is therefore the primary challenge of this method.

[0191] To demonstrate that the PCCP chain ends are still reactive, poly(p-methylstyrene) from polymerization with PCCP 2 was used as a macroinitiator (MI). Polymerization was once again only achieved in the presence of HBD (Table 6, entry 1). The increase in Mn trailed the theoretical weight calculated from monomer conversion with low molecular weight tailing observed in the GPC trace (FIG.24). Increasing the concentration of HBD resulted in a broader low molecular weight shoulder. The shoulder is likely the result of the incomplete incorporation of the PCCP chain end only allowing a portion of the chains to extend while continued chain transfer reactions broaden dispersity.

[0192] Table 6: Polymerization with poly(pMS) Macroinitator.EntryHBD MMIĐMICtheo exp(epqMuiSv)n onv. Mn Mn Đ (equiv) (kg / mol) (%) (kg / mol) (kg / mol) 1 100 1.5 3.5 1.53 25 6.5 5.0 1.54 2 250 1.5 3.9 1.43 20 6.6 5.7 1.603 250 3.0 3.9 1.43 23 7.1 5.8 1.63 4 100 - 3.9 1.43 - - 3.9 1.43 Cationic polymerization of pMS by HBD-assisted ionization of a covalently bound PCCP chain end was demonstrated. An alkylated PCCP initiator expands the monomer scope beyond that available to the Brønsted acid PCCP catalyst. Stabilization of the PCCP anion provided by the HBD is critical to the ionization process and provides control over the reaction. The PCCP chain end is incorporated into the polymer and allows its use as a macroinitiator when re-subjected to the polymerization conditions. The high reaction temperature required for the PCCP ionization causes competitive chain transfer reactions that limit Mn, but do not cause significant quenching of the reaction as evidenced by the kinetics. Tuning the equilibrium between the PCCP anion and covalent complex by modification of the PCCP, HBD, and reaction polarity are promising avenues for further development. EXAMPLE 3

[0194] This example describes polymers, polymerizable compositions, and polymerization methods of the present disclosure, and uses thereof.

[0195] Described is a PCCP initiated cis-selective cationic polymerization of DHF controlled by hydrogen bond donor (HBD) at room temperature.69% cis-selective PDHF were synthesized with a molecular wight (Mn) up to 81 kg / mol and a high glass transition temperature (Tg) up to 170 °C. The structure and thermal property study suggests that cis- selective PDHF featured high glass transition temperature (Tg), yet strong and toughness. The thermal, mechanical, and rheological experiments all demonstrate these cis-selective PDHF produced by this method could serve as a competitive sustainably sourced thermoplastic.

[0196] In developing new synthetic methods for controlled polymerization, it was considered to enable a stereoselective cationic polymerization of DHF to synthesize the cis- favored PDHF. It was considered that hydrogen bond donors (HBDs) could serve as an additive to help DHF monomer selectivity polymerization through interaction between HBDs, PCCP anion and the oxocarbenium ion chain end.

[0197] Described is a PCCP acid initiated, HBD controlled stereoselective cationic polymerization of DHF at room temperature (FIG.25, bottom). Structure and thermal property relationship study suggesting cis-PDHF featured high glass transition temperature (Tg). Satisfyingly, this PDHF resulted in an increased Tg of 170 °C through increase the cis- content to 69%. Excitingly, tensile characterization of these highly tactic PDHF materialsrevealed that cis-enriched PDHF displayed comparable strength to their less tactic counterparts at lower molecular weights. Comprehensive thermal, mechanical, and rheological characterization all demonstrate that these tactic PDHF materials could serve as a competitive, sustainably sourced thermoplastic.

[0198] The cis-selectivity polymerization of DHF at room temperature was investigated using PCCP as initiator in the presence of hydrogen-bond-donors (HBDs) 1-12 (FIG.26A). Mixing the PCCP, HBDs and DHF in a 1:1:400 ratio in toluene produced PDHF with a molecular weight (Mn) around 15 kg / mol after 40 hours at room temperature. Careful evaluation of the polymerization of DHF revealed the critical role exerted by the nature and substitution pattern of the HBDs backbone on the stereoselectivity. Specifically,13C NMR was used to determine the cis content of each polymer. Thiourea catalyst HBD-1 and thiophosphoramide HBD-2 yielding the PDHF with 40% cis-isomer. The cis-content was increased to 57% when using sulfamide HBD-3 as hydrogen bond donor. Importantly, the sulfamide HBD-4 and thiourea HBD-5 are containing cyclic diamine side chains could significantly increasing the cis-contents of PDHF to 66%. Gratifyingly, the peptide type HBD tethering a cyclic diamine group HBD-6 provides PDHF with 69% cis-isomer (Table 7). Moreover, no polymerization occurred when only using cyclic- or acyclic diamines (HBD- 11, HBD-12) as additive, suggesting the essential of HBD-6 for yielding high cis-selective PDHF. The glass transition temperature of these polymers was further evaluated using differential scanning calorimetry (DSC). A direct relationship was observed between the cis- content of PDHF and Tg; polymers with higher cis-contents displayed higher Tgvalues (Table 7). HBD-6 produced PDHF with a high Tg of 164 °C, 30 °C higher than other PDHF materials.

[0199] Table 7. HBD-6 controlled cationic polymerization of DHF for high molecular weights PDHF.aDHF (400−2000 equiv), PCCP (1 equiv, 0.01 mmol) and HBD-6 (1 equiv, 0.01 mmol) in toluene (0.4 mL) were stirred under N2 atmosphere at room temperature unless otherwise noted.bConversion determined by1H NMR by comparing the integrals of the resonances for the DHF vs PDHF; Mnand Đ are determined by GPC in THF, calibrated using polystyrene standards; Tg are measured by DSC from the second scan at a heating rate of 10 °C · min−1.cWithout toluene solvent.a,bDHF (400−2000 equiv), PCCP (1 equiv, 0.01 mmol) and HBD-6 (1 equiv, 0.01 mmol) in toluene (0.4 mL) were stirred under ambient atmosphere at room temperature unless otherwise noted.cConversion determined by1H NMR by comparing the integrals of the resonances for the DHF vs PDHF; Mnand Đ are determined by GPC in THF, calibrated using polystyrene standards; Tgare measured by DSC from the second scan at a heating rate of 10 °C min−1.

[0200] Having demonstrated the HBDs controlled stereoselective cationic polymerization of DHF, the molecular weights of PDHF were increased by varying the ratio of DHF to HBD- 6 and PCCP. As shown in Table 7, PDHF with Mnvalues up to 80 kg / mol were synthesized, and increased Tg’s were observed with increasing molecular weight, up to 170 °C. Importantly, no polymer was observed in the absence of PCCP (Table 7, entry 1), ensuring that molecular weight is solely controlled by PCCP:DHF ratio. Additionally, removing HBD- 6 resulted in polymers of similar Mnand Đ values, but with lower Tg’s (Table 7, entries 2 and 3), further emphasizing the HBD only affects the stereoselectivety of the polymerization.

[0201] The trans-favored PDHF was very brittle at low molar masses thus restricting their industrial applications. For instance, a 76 kg / mol PDHF with 60% trans-content was made using a known method. However, this polymer was very brittle, with a strain at break (εB) of 4.5% (FIG.27A). It was considered that the increase of the cis-content of PDHF may increase the toughness and thus gain access to a material with desirable properties. The tensile properties were measured of the cis-isomer favored polymers with Mns ranging from 49 to 81 kg / mol which were synthesized with this HBD-6 controlled polymerization method. All the cis-enriched polymers displayed yielding events, leading to high toughnesses (FIG. 27B). Surprisingly, the low molar masses PDHF-49 also present a tensile strength reaching 54 MPa and strain at break of 25.9 %. It was found that high molecular weight PDHF-81 exhibited a most ductile and tougher, with a strain-at-break up to 70% and the toughness to a maximum of 28.8 MJ / m3.

[0202] Encouraged by the good tensile properties displayed by these cis-favored PDHF materials, their thermal and viscoelastic properties were examined, since these will control the temperature ranges over which they can be processed and used. As shown in FIG.28, the 81 kg / mol PDHF was characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and oscillatory shear rheology. The sample showing a Tgof 170 °C, the highest glass transition temperatures of PDHF yet reported (FIG.28A). This value corroborated by variable temperature oscillatory shear rheology, where PDHF’s tan(δ) peak was observed at 175 °C. In addition, the sample also show the necessary high temperature stability, with a 5% mass loss temperature of 351 °C (FIG.28B). These results indicate a wide processing temperature range, where heat molding in polymer melt processing can take place.

[0203] The melt stability of PDHF was further evaluated through evaluating the complex viscosity (η*) in rheology. In these investigations, PDHF were stabilized with 0.5 wt % of commercial phenolic inhibitor (Irganox 1010) to prevent their thermo-oxidative degradation. As shown in FIG.28C, no variation was observed after 0.1% oscillatory strain was applied at a frequency of 0.1 rad s−1for 20 min at 200 °C, suggesting this cis-favored PDHF is thermal stable. The entanglement molecular weight (Me) of PDHF-81 was measured by time- temperature superposition. The generated master curve determined the Meto be ~8.5 kg · mol−1, similar to previous reports. The low Me value corresponds with the strength of the material, as lower Mevalues are typically indicative of stronger thermoplastics.

[0204] To further probe the influence of the Mn on the melt property, the samples were analyzed by variable frequency rheology (FIG.28D). Specifically, the complex viscosity ofthe PDHF materials was measured during frequency sweeps at 200 °C from 0.1 to 100 rad s-1. As expected, increasing the molecular weight increased the complex viscosity of the material.

[0205] A HBD controlled cis-selective cationic polymerization of DHF at room temperature using PCCP acid as initiator was demonstrated. The cis-selective PDHF materials produced through this method have high Tg values up to 170 °C. Careful evaluation of the thermal, mechanical, and rheological properties of these materials demonstrate that the cis-selective PDHF produced by this method could serve as an industrially competitive, sustainably sourced thermoplastic. This HBD controlled stereoselective polymerization method presents a novel strategy for polymer stereocontrol that is essential to developing next generation materials.

[0206] Although the present disclosure has been described with respect to one or more particular embodiment(s) and / or example(s), it will be understood that other embodiment(s) and / or example(s) of the present disclosure may be made without departing from the scope of the present disclosure.

Claims

CLAIMS:

1. A cationic polymerization method, comprising reacting one or more acid(s) and a polymerizable composition comprising: one or more monomer(s), and one or more hydrogen bond donor(s) (HBDs), wherein at least a portion of, substantially all, or all of the monomer(s) is / are polymerized.

2. The cationic polymerization method of claim 1, wherein the HBD(s) is / are a thiophosphoramide, sulfamide, structural analog thereof, or any combination thereof.

3. The cationic polymerization method of claim 1, wherein the HBD(s) is / are chosen from: wherein Ar is an aryl group, Ph is athereof.

4. The cationic polymerization method of claim 1, wherein the HBD(s) is / are independently a substituted thiophosphoramide or a sulfamide comprising one or more chiral alkyl group(s), one or more chiral aryl group(s), or any combination thereof.

5. The cationic polymerization method of claim 4, wherein the HBD(s) comprise(s) one or more chiral alkyl group(s), one or more chiral aryl group(s), or any combination thereof.

6. The cationic polymerization method of claim 1, wherein one or more or all of the HBD(s) is / are a chiral HBD or chiral HBDs.

7. The cationic polymerization method of claim 6, wherein the chiral HBD(s) is / are chosen from:, , structural analogs thereof, and any combination8. The cationic polymerization method of claim 1, wherein the acid(s) is / are independently a Lewis acid or a Brønsted acid.

9. The cationic polymerization method of claim 8, wherein the Lewis acid is chosen from metal-based acids with a formula of MXn, wherein M is a metal and X is an anion, and any combination thereof.

10. The cationic polymerization method of claim 8, wherein the Brønsted acid is chosen from HOAc, HCl, HBr, H2SO4, HNO3, p-Toluenesulfonic acid (TsOH), and any combination thereof.

11. The cationic polymerization method of claim 1, wherein the acid or one or more or all of the acid(s) comprise(s) a coordinating anion.

12. The cationic polymerization method of claim 11, wherein the acid or the coordinating anion, or both, do(es) not contain fluorine.

13. The cationic polymerization method of claim 1, wherein the polymerizable composition further comprises one or more polymerization agent(s).

14. The cationic polymerization method of claim 13, wherein the polymerization agent(s) is / are independently a photoacid generator, an acid, or a combination thereof.

15. The cationic polymerization method of claim 14, wherein the reacting further comprises irradiating the photoacid generator(s) such that the acid is generated.

16. The cationic polymerization method of claim 1, wherein the monomer(s) is / are independently chosen from vinyl ethers, epoxides, lactones, acetals, cyclic acetals, isoprenes, butadiene, vinyl sulfides, vinyl ethers, styrene, structural analogs thereof, and any combination thereof.

17. The cationic polymerization method of claim 1, wherein the polymerizable composition further comprises one or more crosslinker(s).

18. The cationic polymerization method of claim 1, wherein a lithography method, a photolithography method, an additive manufacturing method, or a 3D printing method comprises the cationic polymerization method.

19. A polymerizable composition, comprising: one or more monomer(s); one or more chiral hydrogen bond donors (HBDs); optionally, one or more acid(s) and / or one or more polymerization agent(s).

20. The polymerizable composition of claim 19, wherein the HBD(s) is / are a thiophosphoramide, sulfamide, structural analog thereof, or any combination thereof.

21. The polymerizable composition of claim 20, wherein the HBD(s) is / are chosen from:wherein Ar is an aryl group, Ph is a bination thereof.

22. The polymerizable composition of claim 19, wherein the HBD(s) is / are independently a substituted thiophosphoramide or sulfamide comprising one or more chiral alkyl group(s), one or more chiral aryl group(s), or any combination thereof.

23. The polymerizable composition of claim 22, wherein the HBD(s) comprise(s) one or more chiral alkyl group(s), one or more chiral aryl group(s), or any combination thereof.

24. The polymerizable composition of claim 19, wherein one or more or all of the HBD(s) is / are a chiral HBD or chiral HBDs.

25. The polymerizable composition of claim 25, wherein the chiral HBD(s) is / are chosen from: ,, structural analogs thereof, and any combination 26. The polymerizable composition of claim 19, wherein the acid(s) is / are independently a Lewis acid or a Brønsted acid.

27. The polymerizable composition of claim 26, wherein the Lewis acid is chosen from metal-based acids with a formula of MXn, wherein M is a metal and X is an anion, and any combination thereof and / or the Brønsted acid is chosen from HOAc, HCl, HBr, H2SO4, HNO3, p-toluenesulfonic acid (TsOH), and any combination thereof.

28. The polymerizable composition of claim 19, wherein the acid comprises a coordinating anion.

29. The polymerizable composition of claim 28, wherein the acid or the coordinating anion, or both, do(es) not contain fluorine.

30. The polymerizable composition of claim 19, wherein the polymerizable composition further comprises one or more polymerization agent(s).

31. The polymerizable composition of claim 30, wherein the polymerization agent(s) is / are independently a photoacid generator.

32. The polymerizable composition of claim 19, wherein the monomer(s) is / are independently chosen from vinyl ethers, epoxides, lactones, acetals, cyclic acetals, vinyl ethers, isoprenes, butadiene, vinyl sulfides, styrene, structural analogs thereof, and any combination thereof.

33. The polymerizable composition of claim 19, wherein the polymerizable composition further comprises one or more crosslinker(s).

34. A polymer comprising the following structure:a structural analog thereof, wherein S; z is independently at each occurrence 0, 1, 2, 3, or 4; n and m are independently 1 to 1,000,000; and n is greater than m, orR, and are independently at each occurrence an aliphatic group or an aryl group; n and m are independently 1 to 1,000,000; and n is greater than m.

35. The polymer of claim 34, wherein the polymer comprises the following structure: a structural analog thereof, whereinan aliphatic group or an aryl group.

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