Biodegradable polymers and methods of making same

Abstract

The disclosure provides, in part, a polymer composition comprising a random copolymer of at least one cleavable monomer and at least one cyclic monomer, and methods of preparing the same. In certain embodiments, the method comprises subjecting at least one cleavable monomer to acyclic diene metathesis (ADMET) polymerization to prepare a cleavable oligomer, and further comprises subjecting the cleavable oligomer to ring opening metathesis polymerization (ROMP) in the presence of a cyclic monomer. In certain embodiments, the polymer compositions of the disclosure are degradable and / or prepared from plastic waste feedstock.

Description

[0001] Attorney Docket No. 047162-7531W01(02753)

[0002] TITLE OF THE INVENTION

[0003] Biodegradable Polymers and Methods of Making Same

[0004] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U. S. C. § 119(e) to U. S. Provisional Patent Application No. 63 / 721,745. filed November 18, 2024, which is incorporated herein by reference in its entirety.

[0005] BACKGROUND

[0006] One of the most pressing challenges facing the rapidly developing world is plastic management. For example, ethylene, a bulk chemical, and the key monomer of polyethylene (PE) plastic and other commodity chemicals, is mainly produced from crude oil in cracker units. Regrettably, its synthesis from renewable resources is rare. Moreover, PE plastics, which are produced in the largest quantities worldwide, cannot be considered neither chemically recyclable nor biodegradable. As a result, they are causing serious environmental issues and raising concerns about microplastic pollution. It is clear, that neither their production nor their waste management can be considered sustainable. Consequently, the development of sustainable, chemically recyclable and environmentally friendly plastics is one the greatest scientific challenges today.

[0007] Polypropylene (PP) and PE are the most common non-biodegradable thermoplastic polymers. Between 1990 and 2017 the annual growth of PE production was 3.7 %. It has been reported that 110 Mt of polyethylene was produced in 2022. Their most common field of use is short-lived materials, such as packaging. Practically, the plastic produced ends up in landfills or incinerators within a year. Additionally, PE shows only partial degradation in soil or oil over 32 years. The efforts to decrease their environmental impact includes incineration for energy recovery or recycling. Burning these plastics causes carbon dioxide emissions, and the existing mechanical recycling usually results in a loss of quality. Although alternative, biodegradable (compostable) polymers are known and are commercially available (e.g., polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), and polybutylene carbonate (PBC), their use is limited.

[0008] PBS and PBAT render similar physical properties to PP and low-density PE (LDPE). These polyesters are synthesized via the reaction of the appropriate di carboxylic acid and 1,4-butanediol at elevated temperature and reduced pressure in the presence of an organometallic catalyst (e.g., Zn, Zr, Sn, Hf, Bi, Sn and Ti). PBC is an emerging material, Attorney Docket No. 047162-7531W01(02753)

[0009] and it is among the most studied aliphatic polycarbonates today. It is a rubber-like, highly flexible polymer with beneficial properties in tape casting and other applications. However, since it is a new product, its complete range of benefits has not yet been fully identified. Nevertheless, it exhibits excellent impact resistance and good tensile strength, albeit PBC still has some drawbacks including poor barrier properties, low melting temperature and thermal instability. Although these biodegradable polymers may be considered environmentally friendly, they cannot be considered as sustainable choice due to their fossil origin.

[0010] Thus, there is a need in the art for biodegradable polymer materials and methods of preparing the same from renewable sources and / or municipal and industrial waste materials. The present disclosure addresses this unmet need.

[0011] BRIEF SUMMARY OF THE INVENTION

[0012] In one aspect, the disclosure provides a polymer composition comprising a random copolymer of at least one cleavable monomer and at least one cyclic monomer. In certain embodiments, each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer (i.e., -CH-CH2). In certain embodiments, each cyclic monomer independently comprises an optionally substituted C3-C10 cycloalkene or optionally substituted C2-C10 heterocycloalkene, wherein the C3-C10 cycloalkene or C2-C10 heterocycloalkene comprises an unsubstituted internal alkenylene moiety (i.e., -CH=CH-). In certain embodiments, each cleavable monomer is covalently linked to at least one adjacent cyclic monomer or cleavable monomer, and each cyclic monomer is covalently linked to at least one adjacent cleavable monomer or cyclic monomer, wherein each covalent linkage comprises a bond formed by an olefin metathesis reaction.

[0013] In another aspect, the disclosure provides a method for preparing a polymer composition. In certain embodiments, the method comprises subjecting at least one cleavable monomer to acyclic diene metathesis (ADMET) polymerization to prepare a cleavable oligomer. In certain embodiments, the method comprises subjecting the cleavable oligomer to ring opening metathesis polymerization (ROMP) in the presence of a cyclic monomer.

[0014] BRIEF DESCRIPTION OF THE FIGURES

[0015] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present application. Attorney Docket No. 047162-7531W01(02753)

[0016] FIG. 1: chemical structures of polybutylene succinate (PBS), polybutylene carbonate (PBC), and polybutylene adipate terephthalate (PBAT).

[0017] FIG. 2: Acyclic diene metathesis (ADMET) polymerization of diallyl succinate (DAS), diallyl adipate (DAA), diallyl terephthalate (DAT) and diallyl carbonate (DAC). Conditions: 0.1 mol% catalyst, RT, 3 h, toluene ([substrate]=2.5 M).

[0018] FIG. 3: Exemplary catalysts evaluated in ADMET reactions depicted in FIG. 2 (i.e., G2, HG2, G3, UNC, 1, and 2)

[0019] FIG. 4: A non-limiting, exemplary tandem ROMP-ADMET polymerization using diallyl esters (e.g., DAS) and cyclopentene (CP). Conditions: 0.1 mol% catalyst, RT, 3 h, toluene (20 vol% of CP).

[0020] FIG. 5: Scheme depicting insertion polymerization of cyclopentene into poly-DAS and the synthesis of polyethylene containing functional groups susceptible to hydrolysis.

[0021] FIGs. 6A-6C: Stacked1H NMR spectra of poly-DAS oligomer (FIG. 6A), CEMP-po / y-(DAS-co-CP)-10, (FIG. 6B) and poly pentenemer (FIG. 6C) (CDCl3).

[0022] FIG. 7: Hydrolysis of ester group containing polypentenamers leading to telechelic hydroxyl end group functionalized polypentenamer oligomers. Exemplary condition: 50 mg polymer in THF (25 mg / mL), 2 mL 2 M NaOH, refluxed, tr= 16 h.

[0023] FIGs. 8A-8B: Stacked1H NMR spectra of CEMP-po / y-(DAS-co-CP)-100 before (FIG. 8A) and after hydrolysis (CDCl3) (FIG. 8B).

[0024] FIGs. 9A-9C: APC investigation of CEMP-po / y-(DAS-co-CP)-100 (FIG. 9A). CEMP-po / y-(DAA-co-CP)-100 (FIG. 9B) and CEMP-po / y-(DAC-co-CP)-100 (FIG. 9C) polymers: before (left peak) and after hydrolysis (right peak). Peak label: Mw[kDa], retention time [min],

[0025] FIGs. 10A-10C: Stacked1H NMR spectra of CEMP-po / y-(DAS-co-CP)-10 before (FIG. 10A) and after (FIG. 10B) hydrogenation in CDCl3.1H-13C HMBC spectra of the hydrogenated product, showing correlation between carbonyl groups and the -O-CH2- moiety (FIG. 10C). For Hiand Hkassignation see FIGs. 6A-6C; Exemplary conditions: 50 mg polymer in THF (25 mg / mL), Wilkinson catalyst (1 mg, 1 µmol), 20 bar H2, 50 °C, tr= 16 h.

[0026] FIGs. 11A-11B: Representative example of DSC (FIG. HA) and TGA (FIG. I IB) data for CEMP- o / j’-(DAA-co-CP)-100 and CEMP-poZ)-(DAA-co-CP)-100-H2

[0027] FIG. 12: Expansion of the1H-1H COSY spectra of copolymer poly(DAS-co-CP), illustrating the1H-1H connectivities in the detected DAS-(E)-CP moiety.

[0028] FIG. 13:1H (middle panel) and13C (lower panel) NMR spectra of copolymer poly(DAS-co-CP), illustrating the various detected moieties (upper panel). Attorney Docket No. 047162-7531W01(02753)

[0029] FIG. 14:

[0030]

[0031] (middle panel) and13C (lower panel) NMR spectra of copolymer poly(DAA-co-CP), illustrating the various detected moieties (upper panel).

[0032] FIG. 15:1H (middle panel) and13C (lower panel) NMR spectra of copolymer poly(DAC-co-CP), illustrating the various detected moieties (upper panel).

[0033] FIG. 16:

[0034]

[0035] (middle panel) and13C (lower panel) NMR spectra of copoly mer poly(DAT-ctf-CP), illustrating the various detected moieties (upper panel).

[0036] FIG. 17:1H NMR spectra of poly-DAS in CDCl3. The chain-ending groups are marked with an asterisk.

[0037] FIG. 18: ’H NMR spectra of poly-DAA in CDCh. The chain-ending groups are marked with an asterisk.

[0038] FIG. 19:1H NMR spectra of poly-DAC in CDCl3. The chain-ending groups are marked with an asterisk.

[0039] FIG. 20:

[0040]

[0041] NMR spectra of poly-DAT in CDCH. The chain-ending groups are marked with an asterisk.

[0042] FIG. 21: Stacked1H NMR spectra of poly-DAS and copolymer CEMP-poly(DAS-co-CP), illustrating the various detected moieties (upper panel).

[0043] FIG. 22: Stacked1H NMR spectra of poly-DAA and copolymer CEMP-poly(DAA-co-CP), illustrating the various detected moieties (upper panel).

[0044] FIG. 23: Stacked

[0045]

[0046] NMR spectra of poly-DAC and copolymer CEMP-poly(DAC-co-CP), illustrating the various detected moieties (upper panel).

[0047] FIG. 24: Stacked

[0048]

[0049] NMR spectra of poly-DAT and copolymer CEMP-poly(DAT-co-CP), illustrating the various detected moieties (upper panel).

[0050] FIG. 25:

[0051]

[0052] NMR spectra of hydrogenated poly(DAS) in CDCh. The -CH2- moiety of the newly formed polyethylene chain is marked with an asterisk.

[0053] FIG. 26:1H NMR spectra of hydrogenated poly(DAA) in CDCl3. The -CH2- moiety of the newly formed polyethylene chain is marked with an asterisk.

[0054] FIG. 27:

[0055]

[0056] NMR spectra of hydrogenated poly(DAC) in CDCh. The -CH2- moiety7of the newly formed polyethylene chain is marked with an asterisk.

[0057] FIG. 28:

[0058]

[0059] NMR spectra of hydrogenated CEMP-poly(DAS-co-CP) in CDCh. The -CH2- moiety7of the new ly formed polyethylene chain is marked with an asterisk.

[0060] FIG. 29:

[0061]

[0062] NMR spectra of hydrogenated CEMP-poly(DAA-co-CP) in CDCh. The -CH2- moiety7of the newly formed polyethylene chain is marked with an asterisk.

[0063] FIG. 30:1H NMR spectra of hydrogenated CEMP-poly(DAC-co-CP) in CDCl3. The -CH2- moiety of the newly formed polyethylene chain is marked with an asterisk. Attorney Docket No. 047162-7531W01(02753)

[0064] FIGs. 31A-31D: FIG. 31A: FTIR-ATR spectra of ROIMP-po / y-(DAS-co-CP)-200), ROIMP-po / y-(DAS-co-CP)-200-H2and the reference HDPE samples. FIG. 31B: DSC traces of different polypentenamer samples. FIG. 31C: Stress-strain curves of the synthesized materials and the reference HDPE sample. FIG. 31D: Magnification of the initial part of the stress-strain curve.

[0065] FIG. 32:

[0066]

[0067] NMR spectra of scaled up ROIMP-po / v-(DAC-c<9-CP)-100 in CDCh. Indicating the ratio of the connected CP-CP and CP-DAS moieties.

[0068] FIG. 33:1H NMR spectra of the second scaled up ROIMP-po / y-(DAS-co-CP)-200 in CDCl3. Indicating the ratio of the connected CP-CP and CP-DAS moieties.

[0069] FIG. 34: ’H NMR spectra of the hydrogenated ROIMP-po / -(DAS-co-CP)-200 in CDCh. The ester -O-CH2- group is expanded for clarity at 4.08 ppm. Asterisk indicates water.

[0070] FIGs. 35A-35B: Stress-strain curves of ROIMP-poly-(DAS-co-CP)-200-H2(FIG. 35A) and magnification of the initial part (FIG. 35B).

[0071] FIG. 36: DSC traces of the ROIMP-po / y-(DAS-co-CP)-200 sample.

[0072] FIG. 37: DSC traces of the hydrogenated ROIMP-po / y-(DAS-co-CP)-200-H2.

[0073] DETAILED DESCRIPTION OF THE INVENTION

[0074] Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0075] Throughout this document, values expressed in a range format 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. For example, a range of "‘about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g, 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0076] In this document, the terms “a,” “an,” or “the” are used to include one or more than Attorney Docket No. 047162-7531W01(02753)

[0077] one unless the context clearly dictates otherwise. The term “or"’ is used to refer to a nonexclusive “of’ unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. All publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference.

[0078] In the methods described herein, the acts can be carried out in any order, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0079] Description

[0080] The replacement of persistent polymers with chemically recyclable and environmentally benign alternatives has become an urgent issue for society. Although an increasing number of degradable polymers are available, most of them are facing common challenges, including economic and physical property issues making them unsuitable for persistent plastic such as polyethylene replacement. In one aspect, the disclosure provides methods of synthesizing polyethylene containing degradable elements via chain expansion metathesis polymerization (CEMP). In the first step, diallyl ester oligomers were synthesized through acyclic diene metathesis (ADMET) polymerization using UltraNitroCat (UNC) olefin metathesis catalyst. Cyclopentene was then co-polymerized with the oligomers via CEMP giving long-chain hydrocarbon diads separated by easily cleavable ester or carbonate moieties. NMR measurements confirmed the presence of random co-polymer units and indicated a reduced ratio of the ester-ester block-oligomer signal. Hydrolysis experiments of the degradable unit containing polyolefins showed a decrease in molecular weight of more than 60%, which was accompanied by an increase in relative molecular weight dispersion. Hydrogenation of the synthesized co-polymers with Wilkinson's catalyst resulted in a randomly distributed degradable unit containing polyethylene with similar properties to commercial HDPE. Attorney Docket No. 047162-7531W01(02753)

[0081] Definitions

[0082] The term '‘about’’ as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0083] The term “alkenyl” as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms.

[0084] Examples include, but are not limited to vinyl, -CH=C=CCH2, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3). -C(CH2CH3)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among others.

[0085] The term “alkoxy” as used herein refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined herein. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy. isohexyloxy, and the like. Examples of cyclic alkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy. cyclopenty loxy, cyclohexyloxy, and the like. An alkoxy group can include about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms. For example, an allyloxy group or a methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structure are substituted therewith.

[0086] The term “alkyl” as used herein refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl. Representative substituted alky l groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0087] The term '‘alkylene” or “alkylenyl” as used herein refers to a bivalent saturated Attorney Docket No. 047162-7531W01(02753)

[0088] aliphatic radical (e.g., -CH2-, -CH2CH2-, and -CH2CH2CH2-, inter alia). In certain embodiments, the term may be regarded as a moiety derived from an alkene by opening of the double bond or from an alkane by removal of two hydrogen atoms from the same (e.g, -CH2-) different (e.g., -CH2CH2-) carbon atoms.

[0089] The term “alkynyl” as used herein refers to straight and branched chain alky l groups, except that at least one triple bond exists between two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to -C≡CH, -C≡C(CH3), -C≡C(CH2CH3), -CH2C≡CH, -CH2C≡C(CH3), and -CH2C≡C(CH2CH3) among others.

[0090] The term “aryl” as used herein refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl. biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups. Aryl groups can be unsubstituted or substituted, as defined herein. Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8-positions thereof.

[0091] The term “biodegradable” or “degradable” as used herein refers to a material that can be broken down by either chemical or physical process (e.g., hydrolysis), which may be natural or artificial, upon interaction with the physiological environment at an implantation site or a treatment facility, and erodes or dissolves within a period of time, typically within days, weeks or months. A biodegradable or degradable material serves a temporary function, such as packaging materials, and may be subsequently broken down into monomeric or oligomeric components.

[0092] The term “cleavable” as used herein refers to a group or bond within a molecule, or a fragment thereof, which can be broken by a chemical reaction. In certain embodiments, the cleavable moiety is cleaved by hydrolysis (e.g, reaction with water). In certain embodiments, the cleavage may be facilitated and / or accelerated by the addition of one or more agents (e.g, acid or base). In certain embodiments, the cleavable moiety is cleaved by a substance that is naturally present or artificially introduced. Attorney Docket No. 047162-7531W01(02753)

[0093] The term “contacting” as used herein refers to bringing two or more materials into close enough proximity such that the two materials can physically interact.

[0094] The term “copolymer” as used herein refers to a polymer resulting from the polymerization reaction of at least two different monomers.

[0095] The term “covalent linkage” as used herein refers to the feature of two or more molecules being linked together by at least one covalent bond.

[0096] The term “cycloalkyl” as used herein refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group can have 3 to about 8-12 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or 7. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to. norbomyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined herein. Representative substituted cycloalkyl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups or mono-, di- or tri-substituted norbomyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0097] The term “cycloalkylene” or “cycloalkylenyl” as used herein refers to a bivalent saturated cycloalkyl radical (e.g,

[0098]

[0099] A,.<C>. U, and "" O'", inter alia). In certain embodiments, the term may be regarded as a product of removal of two hydrogen atoms from the corresponding cycloalkane (e.g., cyclobutyl) by removal of two hydrogen atoms from the same (e.g,<^>) different (e.g., U and "" '") carbon atoms.

[0100] The term “diene” as used herein refers to a hydrocarbon compound that has two unsaturation sites (z.e., a compound having two double bonds connecting carbon atoms). Depending on the context, the term “diene” as used herein refers broadly to either a diene monomer prior to polymerization (e.g, forming part of the polymerization medium), or a diene monomer after polymerization has begun.

[0101] The terms “halo,” “halogen,” or “halide” group, as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0102] The term “haloalkyl” group, as used herein, includes mono-halo alkyl groups, poly- Attorney Docket No. 047162-7531W01(02753)

[0103] halo alkyl groups wherein all halo atoms can be the same or different, and per-halo alkyl groups, wherein all hydrogen atoms are replaced by halogen atoms, such as fluoro. Examples of haloalky 1 include trifluoromethyl, 1,1 -di chloroethyl, 1,2-dichloroethyL l,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

[0104] The term “heteroaryl” as used herein refers to aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S; for instance, heteroaryl rings can have 5 to about 8-12 ring members. A heteroaryl group is a variety of a heterocyclyl group that possesses an aromatic electronic structure. A heteroary l group designated as a C2-heteroaryl can be a 5-ring with two carbon atoms and three heteroatoms, a 6-ring with two carbon atoms and four heteroatoms and so forth.

[0105] Likewise a C4-heteroaryl can be a 5-ring with one heteroatom, a 6-ring with two heteroatoms, and so forth. The number of carbon atoms plus the number of heteroatoms sums up to equal the total number of ring atoms. Heteroaryl groups include, but are not limited to, groups such as py rrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, indolyl. azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups can be unsubstituted, or can be substituted with groups as is discussed herein.

[0106] Representative substituted heteroaryl groups can be substituted one or more times with groups such as those listed herein.

[0107] Additional examples of ary 1 and heteroary l groups include but are not limited to phenyl, biphenyl, indenyl, naphthyl (1-naphthyl, 2-naphthyl), N-hydroxytetrazolyl, N-hydroxytriazolyl, N-hydroxyimidazolyL anthracenyl (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophenyl (2 -thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), indolyl, oxadiazolyl, isoxazolyl, quinazolinyl, fluorenyl, xanthenyl, isoindanyl, benzhydryl, acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), pyrazolyl (3-pyrazolyl), imidazolyl (1-imidazolyl, 2 -imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2,3-triazol-l-yl, l,2,3-triazol-2-yl l,2,3-triazol-4-yl, l,2,4-triazol-3-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), thiazolyl (2 -thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5 -pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3- pyridazinyl, 4-pyridazinyl, 5 -pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl. 7-quinolyl. 8-quinolyl), isoquinolyl (1 -isoquinolyl, 3-isoquinolyl. 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7 -isoquinolyl, 8-isoquinolyl), benzo[b]furanyl (2-benzo[b]furanyl, Attorney Docket No. 047162-7531W01(02753)

[0108] 3-benzo[b]furanyl, 4-benzo[b] furanyl, 5-benzo[b]furanyl, 6-benzo[b] furanyl, 7-benzo[b] furanyl), 2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl), 3-(2.3-dihydro-benzo[b] furanyl), 4-(2,3-dihydro-benzo[b]furanyl), 5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl), 7-(2,3-dihydro-benzo[b]furanyl), benzo[b]thiophenyl (2-benzo[b]thiophenyl, 3-benzo[b]thiophenyl, 4-benzo[b]thiophenyl, 5-benzo[b]thiophenyl, 6-benzo[b]thiophenyl, 7-benzo[b]thiophenyl), 2,3-dihydro-benzo[b]thiophenyl, (2-(2,3-dihydro-benzo[b]thiophenyl), 3-(2,3-dihydro-benzo[b]thiophenyl), 4-(2,3-dihydro-benzo[b]thiophenyl), 5-(2,3-dihydro-benzo[b]thiophenyl), 6-(2,3-dihydro-benzo[b]thiophenyl), 7-(2,3-dihydro-benzo[b]thiophenyl), indolyl (1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl. 6-indazolyl, 7-indazolyl), benzimidazolyl (1 -benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 8-benzimidazolyl), benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl), benzothiazolyl (1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5 -benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl ( 1 -carbazolyl, 2-carbazolyl. 3-carbazolyl. 4-carbazolyl), 5H-dibenz|b,f]azepine (5H-dibenz|b,f| azepin- 1-yl, 5H-dibenz|b,f|azepine-2-yl,

[0109] 5H-dibenz[b,f]azepine-3-yl, 5H-dibenz[b,f]azepine-4-yl, 5H-dibenz[b,f]azepine-5-yl), 10.1 l-dihydro-5H-dibenz[b,f] azepine (10,1 l-dihydro-5H-dibenz[b,f]azepine-l-yl, 10,ll-dihydro-5H-dibenz[b,f]azepine-2-yl, 10,ll-dihydro-5H-dibenz[b,f|azepine-3-yl.

[0110] 10.1 l-dihydro-5H-dibenz[b.f]azepine-4-yl, 10,1 l-dihydro-5H-dibenz[b,f|azepine-5-yl), and the like.

[0111] The term “heteroarylalkyl” as used herein refers to alkyl groups as defined herein in which a hydrogen or carbon bond of an alkyl group is replaced with a bond to a heteroaryl group as defined herein.

[0112] The term '‘heteroarylene” or '‘heteroarylenyl” as used herein refers to a bivalent heteroaryl radical (e.g., 2,4-pyridylene). In certain embodiments, the term may be regarded as a divalent radical formed by the removal of two hydrogen atoms from one or more rings of a heteroaryl moiety, wherein the hydrogen atoms may be removed from the same or different rings, preferably the same nng.

[0113] The term “heterocycloalkyl” as used herein refers to an aliphatic, partially unsaturated or fully saturated, 3- to 14-membered ring system, including single rings of 3 to 8 atoms and bi- and tricyclic ring systems where at least one of the carbon atoms of the ring is replaced with a heteroatom such as. but not limited to, nitrogen, oxygen, sulfur, or phosphorus. A heterocycloalkyl can include one to four heteroatoms independently selected from oxygen, Attorney Docket No. 047162-7531W01(02753)

[0114] nitrogen, and sulfur, wherein a nitrogen and sulfur heteroatom optionally can be oxidized and a nitrogen heteroatom can be optionally substituted. Representative heterocycloalkyl groups include, but are not limited, to the following exemplary groups: pyrrolidinyl, pyrazolinyL pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, and tetrahydrofuryl. The term heterocycloalkyl group can also be a C2 heterocycloalkyl, C2-C3 heterocycloalkyl, C2-C4 heterocycloalkyl, C2-C5 heterocycloalkyl, C2-C6 heterocycloalkyl, C2-C7 heterocycloalky l, C2-C8 heterocycloalkyl, C2-C9 heterocycloalkyl, C2-C10 heterocycloalkyl, C2-C11 heterocycloalkyd, and the like, up to and including a C2-I45 heterocycloalkyd. For example, a C2 heterocycloalkyl comprises a group which has two carbon atoms and at least one heteroatom, including, but not limited to, aziridinyl. diazetidinyl, oxiranyl, thiiranyl, and the like. Alternatively, for example, a Cs heterocycloalkyl comprises a group which has five carbon atoms and at least one heteroatom, including, but not limited to, piperidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, diazepanyl, and the like. It is understood that a heterocycloalkyl group may be bound either through a heteroatom in the ring, where chemically possible, or one of carbons comprising the heterocycloalkyl ring. The heterocycloalkyl group can be substituted or unsubstituted.

[0115] The term “heterocycloalkydene” or “heterocycloalkylenyd” as used herein refers to a H I

[0116] .. N,HN—\ / — \ \ bivalent saturated cycloalkyl radical (e.g.,

[0117]

[0118] 7, \ — / N, andN\ — / N, inter alia). In certain embodiments, the term may be regarded as a product of removal of two hydrogen atoms from the corresponding heterocycloalkane (e.g., piperidine) by removal of two hydrogen atoms from the same (e.g.,

[0119]

[0120] different (e.g,

[0121]

[0122] and ) carbon atom(s) and / or heteroatom(s).

[0123] The term “hydrolytic cleavage” as used herein refers to the cleavage of a bond in a moiety, molecule, or fragment thereof, by the addition of a water molecule across the bond (e.g, hydrolytic cleavage of an ester provides a carboxylic acid and an alcohol).

[0124] The term “independently selected from” as used herein refers to referenced groups being the same, different, or a mixture thereof, unless the context clearly indicates otherwise. Thus, under this definition, the phrase “X1, X2, and X3are independently selected from noble gases” would include the scenario where, for example, X1, X2, and X3are all the same, where X1, X2, and X3are all different, where X1and X2are the same but X3is different, and other analogous permutations. Attorney Docket No. 047162-7531W01(02753)

[0125] The term “linker’ as used herein refers to an organic moiety that connects two parts of a compound (e.g, a small molecule drug and an antibody). The linker can be, in non-limiting examples, a direct bond, a single atom (e.g, -O-), or a substituted or unsubstituted alkylene or heteroalkylene moiety (e.g, polyethylene glycol).

[0126] The term “moiety” as used herein means a designated region, fragment or functional group of a molecule or compound. A chemical moiety is sometimes expressed as a chemical entity (e.g. a substituent or variable) embedded or appended to a molecule, compound, or chemical formula.

[0127] The term “monomer” as used herein refers to a small molecule of low molecular weight that can be chemically bonded to other monomers to form a polymer. The term “monomer” is used throughout the specification to describe chemical compounds containing at least one polymerizable double bond (e.g, cyclic and / or acyclic double bonds).

[0128] The term “olefin metathesis” is used herein in accordance with its art-recognized meaning to refer to reactions in which the carbons of two reactant alkenes swap bonding partners, dissolving the initial reactant bonds and forming two new alkene bonds (e.g, C1=C2 + C3=C4 > C1=C3 + C2=C4). The term “ring-opening metathesis polymerization” (“ROMP”) refers specifically to an olefin metathesis reaction in which one of the two reactant alkenes is a cyclic alkene (z'.e., a ring). In some embodiments, the cyclic alkene is destabilized relative to the corresponding linear alkene due to bonding strain (e.g, because the bonds in the cyclic alkene are constrained by the ring, and therefore cannot relax to the lowest energy conformation), such that the metathesis reaction is energetically driven by the release of ring strain when the cyclic alkene bond is broken. In olefin metathesis polymerization and ROMP, the reaction occurs between a first alkene in the substrate (e.g., monomer) and a second M=L “alkene” in the catalyst (e.g, at the double bond between the metal and a intermediate carbene ligand, where the ligand L may be part of a polymer chain).

[0129] The term “oligomer” as used herein refers to a molecule of intermediate relative molecular mass, the structure of which essentially comprises a small plurality of one or more distinct monomeric units of lower molecular mass.

[0130] The term “phenylene” or “phenylenyl” as used herein refers to a bivalent phenyl radical (e g, 1,4-phenylene). In certain embodiments, the term may be regarded as a divalent radical formed by the removal of two hydrogen atoms from a benzene moiety.

[0131] The term “random copolymer” as used herein refers to a polymer having two or more different types of monomers joined together in the same polymer chain wherein the different monomers may be arranged in any order. Attorney Docket No. 047162-7531W01(02753)

[0132] The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%. 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of’ as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that the composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less. The term “substantially free of’ can mean having a trivial amount of, such that a composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4. 3.5, 3, 2.5. 2, 1.5, 1, 0.9. 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0133] The term “substituted” as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The term “functional group” or “substituent” as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R)2, CN, NO, NO2, ONO2, azido, CFs, OCF3, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R. C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)O-2N(R)C(O)R, (CH2)O-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, and C(=NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (Ci-C100) hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen Attorney Docket No. 047162-7531W01(02753)

[0134] atoms can together with the nitrogen atom or atoms form a heterocyclyl.

[0135] The term “susceptible” as used herein refers to having a likelihood of being undergoing at least one process, such as cleavage of a bond by a chemical reaction (e.g., hydrolysis).

[0136] The term “terminus” as used herein refers to the last carbon atom or heteroatom of a linear or branched chain of carbon atoms and / or heteroatom.

[0137] Polymer Compositions

[0138] In one aspect, the disclosure provides a polymer composition comprising a random copolymer of at least one cleavable monomer and at least one cyclic monomer.

[0139] A person of ordinary skill in the art appreciates that, in certain aspects, the polymer of the disclosure is described in terms of its monomeric components e.g., one or more “cleavable monomerfs]” and one or more “cyclic monomerfs]”) before polymerization. Additionally, one of ordinary' skill in the art of polymer synthesis can at once envisage the connectivity of a polymer and the chemical or structural changes to the monomeric precursor(s) thereof, once the monomer(s) used to prepare the polymer are identified. For example, one of ordinary skill in the art appreciates that a polymer prepared by an olefin metathesis reaction (e.g., ring opening metathesis reaction) which is prepared using a “cyclic monomer” comprising a cyclic alkene moiety (e.g., cyclopentene) comprises a number of acyclic moieties derived from the “cyclic monomer” (e.g., “ring opened” cyclic monomers). Exemplary incorporation of a “ring opened” cyclic monomer into a polymer composition is depicted in FIGs. 4-5, inter alia (e.g., “CP” to “poly-CP” in FIG. 4).

[0140] In certain embodiments, each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer (i.e., -CH=CH2).

[0141] In certain embodiments, each cyclic monomer independently comprises an optionally substituted C3-C10 cycloalkene or optionally substituted C2-C10 heterocycloalkene, wherein the C3-C10 cycloalkene or C2-C10 heterocycloalkene comprises an unsubstituted internal alkenylene moiety (i.e., -CH=CH-).

[0142] In certain embodiments, each cleavable monomer is covalently linked to at least one adjacent cyclic monomer or cleavable monomer, and each cyclic monomer is covalently linked to at least one adjacent cleavable monomer or cyclic monomer, wherein each covalent linkage comprises a bond formed by an olefin metathesis reaction.

[0143] In certain embodiments, the moiety susceptible to hydrolytic cleavage is an ester. In Attorney Docket No. 047162-7531W01(02753)

[0144] certain embodiments, the moiety susceptible to hydrolytic cleavage is a carbonic ester. In certain embodiments, the moiety susceptible to hydrolytic cleavage is an amide. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a carbamate. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a thioester. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a thiocarbamate. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a dithiocarbamate.

[0145] In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Ci-Ce alkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Ci-Ce heteroalkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Cs-Cs cycloalkydenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by optionally substituted C2-C8 heterocycloalkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Ce-Cio arylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by optionally substituted C2-C8 heteroaryl enyl.

[0146] In certain embodiments, the cleavable monomer comprises two independently selected moieties susceptible to hydrolytic cleavage.

[0147] In certain embodiments, the two moieties susceptible to hydrolytic cleavage are covalently linked by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkyl enyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-C10 arylenyl, and optionally substituted C2-C8 heteroarylenyl.

[0148] In certain embodiments, the cleavable monomer is a compound of Formula (la):

[0149] £la £lb

[0150]

[0151] wherein:

[0152] Lla, Llh, and L2are each independently selected from the group consisting of optionally Attorney Docket No. 047162-7531W01(02753)

[0153] substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalk lenyl, optionally- substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl;

[0154] X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA;

[0155] Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; and

[0156] RAand RBare each independently selected from the group consisting of H, optionally substituted Ci-Ce alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted Ce-Cio aryl.

[0157] In certain embodiments, L1ais -(CH2)-. In certain embodiments, L1bis -(CH2)-.

[0158] In certain embodiments, L2is -(CH2)2- In certain embodiments, L2is -(CH2)4-. In certain embodiments, L2is phenylene.

[0159] In certain embodiments, X1ais -O-. In certain embodiments, X1bis -O-.

[0160] In certain embodiments, Zlais O. In certain embodiments, Zlbis O.

[0161] O

[0162]

[0163] In certain embodiments, the cleavable monomer is 0 In

[0164] O

[0165]

[0166] certain embodiments, the cleavable monomer is0. In certain O

[0167] embodiments, the cleavable monomer is

[0168]

[0169] in certain embodiments, the

[0170]

[0171] In certain embodiments, each cyclic monomer independently comprises a compound of formula (lb):

[0172] L3

[0173]

[0174] (lb),

[0175] wherein L3is selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, and optionally substituted C2-C8 heterocyloalkylenyl.

[0176] In certain embodiments, L3is -(CH2)3- In certain embodiments, L3is -(CH2)6-. In Attorney Docket No. 047162-7531W01(02753)

[0177] certain embodiments, L ’ is

[0178]

[0179] '. In certain embodiments, L3is

[0180]

[0181] ' ”

[0182] In certain embodiments, the cyclic monomer is

[0183]

[0184] . In certain embodiments, the

[0185] cyclic monomer is

[0186]

[0187] In certain embodiments, the cyclic monomer is

[0188]

[0189] certain embodiments, the cyclic monomer is

[0190]

[0191] In certain embodiments, the poly mer has a ratio of cleavable monomer to cyclic monomer of about 1:1000, 1:900, 1:800, 1:700, 1:600, 1:500, 1:400, 1:300. 1:200, 1:100, or about 1: 1. In certain embodiments, the polymer has a ratio of cleavable monomer to cyclic monomer of about 1: 100, 1:99, 1:98, 1:97, 1:96, 1:95, 1:94, 1:93, 1:92, 1:91, 1:90, 1:89, 1:88, 1:87, 1:86, 1:85, 1:84, 1:83, 1:82, 1:81, 1:80, 1:79, 1:78, 1:77, 1:76, 1:75, 1:74, 1:73, 1:72, 1:71, 1:70, 1:69, 1:68, 1:67, 1:66, 1:65, 1:64, 1:63, 1:62, 1:61, 1:60, 1:59, 1:58. 1:57, 1:56, 1:55, 1:54, 1:53, 1:52, 1:51, 1:50, 1:49, 1:48, 1:47, 1:46, 1:45, 1:44, 1:43, 1:42. 1:41. 1:40.

[0192] 1:39, 1:38, 1:37, 1:36, 1:35, 1:34, 1:33, 1:32, 1:31, 1:30, 1:29, 1:28, 1:27, 1:26, 1:25, 1:24, 1:23, 1:22, 1:21, 1:20, 1:19, 1:18, 1:17, 1:16, 1:15, 1:14, 1:13, 1:12, 1:11, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or about 1:1.

[0193] In certain embodiments, the polymer has a molecular weight of about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98. 99. or 100 kDa or more.

[0194] In certain embodiments, each covalent linkage between monomers comprises a double bond. In certain embodiments, each covalent linkage between monomers comprises a single bond. In certain embodiments, the single bond was obtained by reduction of the double bond.

[0195] In certain embodiments, the disclosure provides a polymer composition of Formula (III):

[0196] T1a— A^T1b(III).

[0197] wherein: Attorney Docket No. 047162-7531W01(02753)

[0198] Z"1a

[0199] .> [_1a U U Tlaand Tlbare each independently

[0200]

[0201] " 'X1aL2X1bOr '' L3

[0202] A comprises m units of A1and n units of A2;

[0203] £la £lb

[0204] I 1a H 1J 1 1b

[0205] A1IS '^L'X1a'VL2^X1b'L^';

[0206]

[0207] A2IS

[0208] each occurrence of L1a, L1b, and L2is independently selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl;

[0209] each occurrence of L3is independently selected from the group consisting of optionally substituted C1-C6alkylenyl, optionally substituted Ci-Cs heteroalkylenyl, optionally substituted Ch-C's cycloalkylenyl, and optionally substituted C2-C8 heterocyloalkylenyl;

[0210] X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA;

[0211] Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; each bond independently indicates a single or double bond;

[0212] each bond - - - independently indicates a single or double bond between: (i) Tlaand A1, (ii) Tlaand A2, (iii) Tlband A1, (iv) Tlband A2, (v) A1and A1, (vi) A1and A2, and (vii) A2and A2;

[0213] m is an integer ranging from 1 to 10.000;

[0214] n is an integer ranging from 1 to about 100,000; and

[0215] each occurrence of RAand RBis independently selected from the group consisting of H, optionally substituted Ci-Ce alkyl, optionally substituted Ci-Cs cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted Ce-Cio aryl.

[0216] O

[0217]

[0218] In certain embodiments, A1is O In certain embodiments, O O O

[0219] A

[0220]

[0221] 1is O. In certain embodiments, A1is O O' Attorney Docket No. 047162-7531W01(02753)

[0222] . In certain embodiments,

[0223]

[0224] A1is

[0225] In certain embodiments, A2is

[0226]

[0227] In certain embodiments, A2is

[0228] In certain embodiments, A2is

[0229] O

[0230]

[0231] In certain embodiments, Tlais ° In certain embodiments,

[0232]

[0233] In certain embodiments, Tlais In certain embodiments,

[0234]

[0235] Tlais

[0236] O

[0237]

[0238] In certain embodiments, Tlbis O. In certain embodiments,

[0239] O

[0240] T

[0241]

[0242] lbis O. In certain embodiments, Tlbis > jncertain embodiments,

[0243]

[0244] Tlbis

[0245] In certain embodiments, has a ratio ofm to n of about 1:1000, 1:900, 1:800, 1:700, 1:600, 1:500, 1:400, 1:300, 1:200, 1:100, or about 1:1. In certain embodiments, has a ratio of m to n of about 1:100, 1:99, 1:98, 1:97, 1:96, 1:95, 1:94, 1:93, 1:92, 1:91, 1:90, 1:89, 1:88, 1:87, 1:86, 1:85, 1:84, 1:83, 1:82, 1:81, 1:80, 1:79, 1:78, 1:77, 1:76, 1:75, 1:74. 1:73. 1:72, 1:71. 1:70. 1:69. 1:68, 1:67, 1:66, 1:65, 1:64, 1:63, 1:62, 1:61, 1:60, 1:59, 1:58. 1:57. 1:56.

[0246] 1:55, 1:54, 1:53, 1:52, 1:51, 1:50, 1:49, 1:48, 1:47, 1:46, 1:45, 1:44, 1:43, 1:42, 1:41, 1:40, 1:39, 1:38, 1:37, 1:36, 1:35, 1:34, 1:33, 1:32, 1:31, 1:30, 1:29, 1:28, 1:27, 1:26, 1:25, 1:24, 1:23, 1:22, 1:21, 1:20, 1:19, 1:18, 1:17, 1:16, 1:15, 1:14, 1:13, 1:12, 1:11, 1:10. 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3. 1:2, or about 1:1.

[0247] Methods

[0248] In another aspect, the disclosure provides a method for preparing a polymer composition. In certain embodiments, the method comprises subjecting at least one cleavable monomer to acyclic diene metathesis (ADMET) polymerization to prepare a cleavable oligomer. In certain embodiments, the method further comprises subjecting the cleavable Attorney Docket No. 047162-7531W01(02753)

[0249] oligomer to ring opening metathesis polymerization (ROMP) in the presence of a cyclic monomer.

[0250] In certain embodiments, each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer (i.e., -CH=CH2).

[0251] In certain embodiments, the moiety susceptible to hydrolytic cleavage is an ester. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a carbonic ester. In certain embodiments, the moiety' susceptible to hydrolytic cleavage is an amide. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a carbamate. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a thioester. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a thiocarbamate. In certain embodiments, the moiety susceptible to hydrolytic cleavage is a dithiocarbamate.

[0252] In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Ci-Ce alkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Ci-Ce heteroalkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted C3-C8cycloalkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by optionally substituted C2-C8 heterocycloalkylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by an optionally substituted Ce-Cio arylenyl. In certain embodiments, the unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by optionally substituted C2-C8 heteroarylenyl.

[0253] In certain embodiments, the cleavable monomer comprises two independently selected moieties susceptible to hydrolytic cleavage.

[0254] In certain embodiments, the two moieties susceptible to hydrolytic cleavage are covalently linked by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-C10 arylenyl, and optionally substituted C2-C8 heteroarylenyl. Attorney Docket No. 047162-7531W01(02753)

[0255] In certain embodiments, the cleavable monomer is obtained from a plastic waste feedstock.

[0256] In certain embodiments, the cleavable monomer is a compound of Formula (la):

[0257]

[0258] (la),

[0259] wherein:

[0260] L1a, L1b, and L2are each independently selected from the group consisting of optionally substituted C1-C6alkylenyl, optionally substituted C1-C6 heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroaryl enyl;

[0261] X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA:

[0262] Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; and

[0263] RAand RBare each independently selected from the group consisting of H, optionally substituted Ci-Ce alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted Ce-Cio aryl.

[0264] In certain embodiments, L1ais -(CH2)-. In certain embodiments, L1bis -(CH2)-.

[0265] In certain embodiments, L2is -(CH2)2- In certain embodiments, L2is -(CH2)4-. In certain embodiments, L2is phenylene.

[0266] In certain embodiments, X1ais -O-. In certain embodiments, X1bis -O-.

[0267] In certain embodiments, Z1aand Z1bare each independently O.

[0268] O

[0269]

[0270] In certain embodiments, the cleavable monomer is O. In

[0271] O

[0272]

[0273] certain embodiments, the cleavable monomer is0. In certain

[0274] embodiments, the cleavable monomer is

[0275]

[0276] 'O O' In certain embodiments, the

[0277]

[0278] Attorney Docket No. 047162-7531W01(02753)

[0279] In certain embodiments, ADMET polymerization comprises contacting the cleavable monomer with a ruthenium metathesis catalyst. In certain embodiments, the ruthenium metathesis catalyst comprises a N-heterocyclic carbene ruthenium catalyst. In certain

[0280] embodiments, the ruthenium catalyst

[0281]

[0282] is In certain embodiments, the

[0283] In certain embodiments, the ruthenium catalyst

[0284] In certain embodiments, the ruthenium catalyst is

[0285]

[0286] In certain embodiments, the cleavable monomer and catalyst have a molar ratio of about 1000:1, 900:1, 800:1, 700:1, 600:1, 500:1, 400:1, 500:1, 400:1, 300:1, 200:1, 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 5:1, or about 1:1. In certain embodiments, the cleavable monomer and catalyst have a molar ratio of about 100: 1 (i.e., about 1 mol% catalyst).

[0287] In certain embodiments, the contacting occurs with a concentration of cleavable monomer of about 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, or about 1.0 M. In certain embodiments, the contacting occurs with a concentration of cleavable monomer of about 2.5 M.

[0288] In certain embodiments, the contacting occurs in the presence of a solvent, optionally wherein the solvent is a non-polar, aromatic solvent. In certain embodiments, the solvent is toluene. Attorney Docket No. 047162-7531W01(02753)

[0289] In certain embodiments, the cleavable oligomer is a compound of Formula (II):

[0290] „JL 2-k

[0291]

[0292] L(II).

[0293] In certain embodiments, o is 2, 3, 4, 5, 6, 7, 8, or 9.

[0294] In certain embodiments, the ROMP comprises contacting the cleavable oligomer and at least one cyclic monomer in the presence of a second catalyst.

[0295] In certain embodiments, each cyclic monomer independently comprises a compound of Formula (lb):

[0296] L3

[0297]

[0298] wherein L3is selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, and optionally substituted C2-C8 heterocycloalkylenyl.

[0299] In certain embodiments, L3is -(CH2)3-. In certain embodiments, L3is -(CH2)6-. In

[0300] certain embodiments, L3is

[0301]

[0302] ''. In certain embodiments, L3is

[0303]

[0304] ''

[0305] In certain embodiments, the cyclic monomer is

[0306]

[0307] . In certain embodiments, the

[0308] cyclic monomer is

[0309]

[0310] . In certain embodiments, the cyclic monomer is

[0311]

[0312] . In

[0313] certain embodiments, the cyclic monomer is

[0314]

[0315] In certain embodiments, the second catalyst is a ruthenium metathesis catalyst. In certain embodiments, the ruthenium metathesis catalyst comprises a N-heterocyclic carbene

[0316] ruthenium catalyst. In certain embodiments, the second catalyst

[0317]

[0318] is. In Attorney Docket No. 047162-7531W01(02753)

[0319]

[0320] certain embodiments, the second catalyst is In certain embodiments,

[0321]

[0322] In certain embodiments, the cleavable oligomer and cyclic monomer have a molar ratio of about 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46. 1:47. 1:48.

[0323] 1:49, 1:50, 1:51, 1:52, 1:53, 1:54, 1:55, 1:56, 1:57, 1:58, 1:59, 1:60, 1:61, 1:62, 1:63, 1:64, 1:65, 1:66, 1:67, 1:68, 1:69, 1:70, 1:71, 1:72, 1:73, 1:74, 1:75, 1:76, 1:77, 1:78, 1:79, 1:80, 1:81, 1:82, 1:83, 1:84, 1:85, 1:86, 1:87, 1:88, 1:89, 1:90, 1:91, 1:92, 1:93, 1:94, 1:95, 1:96, 1:97, 1:98, 1:99, or about 1: 100 (oligomermonomer). In certain embodiments, the cleavable oligomer and cyclic monomer have a molar ratio of about 1:10 (oligomermonomer).

[0324] In certain embodiments, the cleavable oligomer and second catalyst have a molar ratio of about 10000:1, 9000:1, 8000:1, 7000:1, 6000:1, 5000:1, 4000:1, 3000:1, 2000:1, 1000:1, 900:1, 800:1, 700:1, 600:1, 500:1, 400:1, 500:1, 400:1, 300:1, 200:1, 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 5:1, or about 1:1. In certain embodiments, the cleavable monomer and catalyst have a molar ratio of about 1000:1 (z.e., about 1 mol% second catalyst).

[0325] In certain embodiments, the contacting occurs in the presence of a solvent. In certain embodiments, the solvent is a non-polar, aromatic solvent. In certain embodiments, the solvent is toluene.

[0326] In certain embodiments, the contacting occurs at a temperature ranging from about 0, Attorney Docket No. 047162-7531W01(02753)

[0327] 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or about 23 °C (room temperature).

[0328] In certain embodiments, the contacting occurs for about 3 hours.

[0329] In certain embodiments, the polymer composition is a biodegradable polymer.

[0330] In certain embodiments, the polymer composition is reduced.

[0331] In certain embodiments, the biodegradable polymer is the polymer of the disclosure.

[0332] EXAMPLES

[0333] Various embodiments of the present application can be better understood by reference to the following Examples which are offered by way of illustration. The scope of the present application is not limited to the Examples given herein.

[0334] General Information

[0335] All metathesis reactions were conducted under nitrogen atmosphere using Schlenk-technique or under argon using a glovebox. CDCh, reagents and solvents (Aldrich) were used as received. Solution-state NMR spectra were acquired using Varian NMR System spectrometers operating at 300, 400 and 600 MHz respectively. Notation for the1H NMR spectral splitting patterns includes singlet (s), doublet (d), triplet (t), broad (br) and multiplet / overlapping peaks (m). Chemical shifts (5 values) are given in ppm, coupling constants (J) are expressed in Hertz. 'H and13C NMR assignment of the diester-cyclopentene copolymers were obtained using the combination of two-dimensional homonuclear (¹H-¹H TOCSY, ¹H-¹H COSY) and heteronuclear (¹H-¹³C HSQC and ¹H-¹³C HMBC) measurements.

[0336] APC measurements were carried out using Acquity Advanced Polymer Chromatography System and Waters 2414 Refractive Index detector at 45 °C and columns at 30 °C. The sample manager was used at 25 °C. Column manager contained three columns in series, (4.6x150 mm): ACQUITY APCTM XT 200 A 1.7 pm, ACQUITY APCTM XT 125 A 2.5 pm, ACQUITY APCTM XT 45 A 1.7 pm. The third order calibration curve was used, and polystyrenes standards (66000 Da, 21500 Da, 4920 Da, 2280 Da) were used for calibration. HPLC grade THF was used as eluent (VWR). The flow rate was 0.5 mL / min. For the calculations of the molecular weights, Empower Chromatography Data System was used. The concentration of the sample was 1 mg / mL, and the volumes of injections were 50 μL Thermal measurements were performed on a Setaram LabsysEvo (Lyon, France) TG-DSC system, in flowing high purity nitrogen (99.999%, flow rate 90 mL / min) atmosphere. Samples were weighed into 100 pL alumina crucibles (the reference cell was empty) and Attorney Docket No. 047162-7531W01(02753)

[0337] were heated from 25 °C to 600 °C with a heating rate of 10 °C / min. The obtained data was blank corrected and further processed with the thermoanalyzer’s processing software (Calisto Processing v2.15, AKTS, Switzerland). The thermal analyzer (both the temperature scale and calorimetric sensitivity) was calibrated by a multipoint calibration method, in which seven different certified reference materials were used to cover the thermal analyzer’s entire operating temperature range.

[0338] Flash column chromatography was performed on a CombiFlash Rf 150 apparatus using gradient elution in normal (silica hexane-ethyl acetate) phase mode. Sample loadings were performed in the case of silica flash chromatography by coating the sample onto a silica cartridge.

[0339] Monomer Synthesis

[0340] The synthesis of DAA and DAS followed the same procedure as reported by Yang for the formation of DAT. The NMR spectra of DAA and DAS were identical to those in the literature.

[0341] Representative example of the synthesis of diallilyc esters

[0342] SOCl2

[0343]

[0344] Terephthalic acid (1.0 g, 6 mmol, 1 eq) was placed in a Schlenk-tube and suspended in SOCl2(2.2 mL, 30 mmol), followed by the addition of one drop of DMF. The mixture was refluxed for 16 hours. After cooling down the mixture, the excess SOCl2was evaporated under vacuum and the crude product w as used in the next step without further purification.

[0345] TEA DCM

[0346]

[0347] Terephthalic chloride (1.22 g, 6 mmol, leq) was placed in a Schlenk-tube and was dissolved in DCM (10 mL) and DCM (10 mL) solution of triethylamine (1.68 mL, 12 mmol, 2 eq.) and ally alcohol (0.82 mL, 12 mmol, 2 eq.) was added dropwise to the solution at 0°C. The mixture was allowed to warm up to room temperature and was stirred overnight. After that water was added to the suspension, the layers were separated. The aqueous layer was extracted with DCM (3x10ml). The combined organic phases were dried over Na2SO4. and the solvent was evaporated in vacuum. The crude product was purified by flash Attorney Docket No. 047162-7531W01(02753)

[0348] chromatography on silica using Hex: EtOAc = 4: 1 as eluent to obtain DAT as a colourless oil (1.3 g, 87%).XH NMR (300 MHz. Chloroform-d) δ 8.12 (s, 1H), 6.04 (ddt, J = 17.1, 10.3, 5.7 Hz, 1H), 5.42 (dq, J = 17.2, 1.5 Hz, 1H), 5.31 (dq, J = 10.4, 1.3 Hz, 1H), 4.85 (dt, J = 5.7, 1.4 Hz, 2H).13C NMR (75 MHz, Chloroform-d) δ 165.56, 134.14, 132.04, 129.75, 118.79, 66.10.

[0349] Representative example ofADMET copolymerization

[0350]

[0351] Diallyl succinate (100 mg, 0.5 mmol, 1 eq.) and cyclopentene (462 pL, 5.0 mmol, 10 eq.) was placed in a vial and was dissolved in toluene (1.9 mL) with stirring bar and toluene solution of UNC (3.8 mg, 5.5 μmol, 0.1 mol% in 380 μL toluene) was added. The mixture was stirred at RT for 3 hours. After that the formed precipitation was dissolved in THF, followed by the addition of ethyl vinyl ether (0.1 mL). The mixture was stirred for 10 minutes, and MeOH was added to precipitate the polymer (310 mg, 70%).

[0352] To confirm the random copolymerization between the diesters and cyclopentene, two-dimensional NMR experiments were conducted in CDCh. This involved a combination of homonuclear (¹H-¹H TOCSY,

[0353]

[0354] COSY) and heteronuclear ('H-13C HSQC and 'H-13C HMBC) measurements to obtain assignments for the different linked moieties.

[0355] Representative example ofADMET homopolymerization

[0356]

[0357] DAS poly-DAS Diallyl succinate (500 mg, 2.5 mmol, 1 eq.) was placed in a vial and dissolved in 330 pL of toluene with stirring bar and toluene solution of UNC (3.7 mg, 2.5 μmol, 0.1 mol% in 170 μL toluene) was added. The mixture was stirred at RT for 3 hours. After that, the resulting precipitate was dissolved in THF, and ethyl vinyl ether (0.1 mL) was added. The mixture was stirred for 10 minutes, and MeOH was added to precipitate the polymer (350 mg, 82%).

[0358] Representative example ofCEMP polymerization Attomey Docket No. 047162-7531W01(02753)

[0359]

[0360] 0CP O°c ° poly-DAS cemp-poly-(DAS-co-CP) Cyclopentene (690 μL, 7.5 mmol) and poly-DAS (20 mg) was placed in a vial with stirring bar and were dissolved in toluene (2.2 mL), The solution was cooled down to 0 °C and toluene solution of UNC (5.2 mg, 7.5 μmol, 0.1 mol% in 520 μL toluene) was added. The mixture was stirred at 0 °C for 3 hours. After that, the resulting precipitate was dissolved in THF, and ethyl vinyl ether (0.1 mL) was added. The mixture was stirred for 10 minutes, and MeOH was added to precipitate the polymer (380 mg, 71%).

[0361] NMR analysis ofCEMP copolymerization

[0362] An example analysis of CEMP-poly-(DAS-co-CP). The starting material poly-DAS has an approximate 6.4 degree of polymerization, based on amount of free chain ending groups. After the CEMP reaction with 10 equivalent of cyclopentene, the formed polymer contain DAS-DAS and DAS-CP connectivity in an approximate ration of 1:5, while the poly-DAS chain endings are fully converted to DAS-CP connectivity. This suggests that not only did the chain-ending terminal olefin groups reacted, but also the insertion of cyclopentene into the DAS-DAS chain occurred. If only the chain ending double bonds were reacting, then the ratio would be approximately 6: 1 instead of 1:5.

[0363] NaOH THF / H2O 2M hydrolysis product

[0364]

[0365] Cemp-(DAS-co-CP)-100 (100 mg) polymer was dissolved in toluene (1 mL) and 2 M NaOH aqua solution (2 mL) was added to the solution. The mixture was refluxed for 16 hours. After that the mixture was acidify with 5 M HC1. And the layers were separated. The aquas layer was extracted with toluene (3 x 10 mL). The organic layers were combined, and the solvent was evaporated. The crude product was analyzed with APC.

[0366] Representative example of hydrogen of oligomers and cemp-polymers Attorney Docket No. 047162-7531W01(02753)

[0367]

[0368] Oligomer (50 mg), and Wilkinson catalyst (5 mg, 5 μmol) were dissolved in THF in a 20 mL autoclave. The autoclave was sealed, purged with hydrogen gas. and pressurized to 20 bar. The reaction mixture was stirred at 100 °C for 16 hours. Subsequently, the pressure was released, and the insoluble product was filtered out (45 mg, 90%).

[0369] Scaled-up ADMET homopolymerization

[0370] UNC

[0371] toluene

[0372] O

[0373]

[0374] DAS poly-DAS

[0375] Diallyl succinate (3.1 g, 15.6 mmol, 1 eq.) was placed in a vial and dissolved in 3.1 mL of toluene with stirring bar and toluene solution of UNC (23.1 mg, 15.6 pmol, 0.1 mol%) was added. The mixture was stirred at RT for 3 hours. After that, the resulting precipitate was dissolved in THF, and ethyl vinyl ether (1.0 mL) was added. The mixture was stirred for 10 minutes, and MeOH was added to precipitate the polymer (1.5 g, 56 %).

[0376] Scaled-up ROIMP copolymerization of poly-DAS in 100:1 ratio

[0377] HG2

[0378] toluene.

[0379]

[0380] CP DAS poly-(DAS-co-CP) Cyclopentene (40 mL, 435 mmol) and poly-DAS (0.73 g, 4.35 mmol diester unit) were placed in a vial with stirring bar and were dissolved in toluene (160 mL), The solution was cooled to 0°C and toluene solution of HG2 (325.8 mg, 0.52 mmol, 0.1 mol%) was added. The mixture was stirred at 0°C for 24 hours. After that, the resulting precipitate was dissolved in THF, and ethyl vinyl ether (1.0 mL) was added. The mixture was stirred for 10 minutes, and MeOH was added to precipitate the polymer (16.0 g, 64%).

[0381] NMR analysis of the polymer indicated a CP-CP to CP-DAS moiety ratio of 40: 1. APC measurements showed a Mwof 22.5 kDa, and thus a second ROIMP reaction was carried out as follows.

[0382] Scaled-up ROIMP copolymerization of ROIMP-poly-(DAS-co-CP)-100 Attorney Docket No. 047162-7531W01(02753)

[0383] HG2 O

[0384]

[0385] poZy-(DAS-co-CP) po / y-(DAS-co-CP) Cyclopentene (40 mL, 435 mmol) and ROIMP-po / y-(DAS-co-CP)-100 (16.0 g) were placed in a vial with stirring bar and were dissolved in toluene (150 mL), The solution was cooled to 0°C HG2 (281 mg, 0.45 mmol, 0.1 mol%) was added. The mixture was stirred at 0°C for 24 hours. After that, the resulting precipitate was dissolved in THF. and ethyl vinyl ether (1.0 mL) was added. The mixture was stirred for 10 minutes, and MeOH was added to precipitate the polymer. The product was washed with additional MeOH (2x100 mL) to yield the chain-extended polymer (34.6 g, 56%). NMR analysis of the polymer indicated a CP-CP to CP-DAS moiety ratio of 100: 1. APC measurements showed a Mwof 27.3 kDa for the polymer.

[0386] Scaled-up hydrogenation of ROIMP-poly-(DAS-co-CP)-200

[0387] 20 bar H2

[0388] Wilkinson's

[0389] catalyst THF

[0390]

[0391] poZy-(DAS-co-CP) hydrogenated po / y-(DAS-co-CP) ROIMP-po / y-(DAS-co-CP)-200 (8.0 g) and Wilkinson’s catalyst (160 mg,

[0392] 0.173 mmol) were dissolved in THF (300 mL). The autoclave was sealed, purged with hydrogen gas, and pressurized to 20 bar. The reaction mixture was stirred at 50 °C for

[0393] 48 hours, and occasionally repressurized. 250 mL MeOH was added to the suspension, and after 15 minutes of stirring, it was filtered and washed fresh MeOH (3 x 250 mL) to yield the polymer as a white solid (6.2 g, 78%).

[0394] Physical properties

[0395] Standard specimens for mechanical characterization (ISO 527 / 25A) were produced by compression molding (Fontijne SRA100) at 150 °C mold temperature, 150 kN pressing force, and a 5 -minute holding time. All specimens were kept in a room with controlled temperature and humidity' (23 °C and 50%) for at least one week prior to further testing.

[0396] Mechanical properties were characterized by tensile testing on standard 4 mm thick ISO 527 / 25A specimens using an Instron 5566 apparatus (Instron, Norwood, MA, USA).

[0397] Stiffness (E) w as determined at 0.5 mm / min cross-head speed and 50 mm gauge length. Attorney Docket No. 047162-7531W01(02753)

[0398] Tensile strength (u) and elongation-at-break (E) were calculated from force vs. deformation traces measured on the same specimens at 10 mm / min cross-head speed.

[0399] Thermal properties were determined by differential scanning calorimetry using a Perkin Elmer DSC 7 (PerkinElmer, Inc., CT, USA) apparatus. Two heating and one cooling run were done on 5 mg samples with a heating rate of 10 °C / min between room temperature and 160 °C. The purge gas was pure nitrogen.

[0400] Example 1: ADMET polymerization of diallyl esters

[0401] Diallyl esters have been reported to exhibit low activity in ADMET polymerization with both Grubbs and Schrock type catalysts, resulting in predominantly oligomer formation. No ADMET reactions of DAT and DAC monomers were reported.

[0402] The ADMET activity of catalyst depicted in FIG. 3 has been investigated on the reaction of DAS. While catalysts 2 and G2 were inactive in ADMET reaction (FIG. 2, top; Table 1, entries 1-4) 1 and G3 have already shown some monomer conversion. Surprisingly, UNC and HG2 showed reasonable activity, high monomer conversion and molecular mass dispersity (DM) was observed meanwhile the molecular eight (Mw) of the formed oligomers remained low (Table 1, entry 5 and 6).

[0403] Table 1. G2, HG2, G3, 1, and 2 catalyst activities on ADMET poly merization of diallyl succinate (DAS)[a]

[0404] Entry Catalyst Conversion (NMR %) Mw(kDA) DM 1 G2 0 NA NA 2 2 0 NA NA 3 G3 17 NA NA 4 1 46 NA NA 5 HG2 72 1.0 2.25

[0405]

[0406] 6 UNC 74 1.6 2.16

[0407] [aI[DAS] = 2.5 M, 0.1 mol% catalyst loading, RT, toluene. 3h.

[0408] According to these preliminary results, the UNC catalyst was used for all further reactions. Then ADMET reactions of DAS, DAA, DAT and DAC were carried out using relatively low, 0.1 mol% UNC catalyst loading in toluene solution at room temperature (Table 2). Interestingly, high yield but low Mw was observed for DAT (Table 2, entry 3), which could be explained by the immediate precipitation of the oligomers from the reaction mixture even at diluted condition (0.05 M). In the other cases (Table 2, entries 1, 2 and 4), the reaction mixture became a highly viscous liquid, which did not hinder the propagation of the Attorney Docket No. 047162-7531W01(02753)

[0409] oligomerization.

[0410] Table 2. ADMET polymerization of diallyl esters using UNC[aI

[0411] Entry Polymer Yield [%] Mw[kDa] DM Dplbl DpM 1 o / zgo-DAS 82 1.6 2.16 4.2 6.4 2 o / zgo-DAA 65 2.2 1.94 5.6 6.7 3 o / zgo-DAT 98 1.0 1.92 2.2 3.0 4 o / zgo-DAC 75 1.8 2.01 7.4 8.3 5[d] o / zgo-DAT 93 1.0 1.25 4.0 4.0

[0412]

[0413] 6[d]o / zgo-DAA 94 8.3 6.38 7.0 6.0[aI[diaIlyl ester] = 2.5 M, 0.1 mol% catalyst loading, RT, toluene, 3h;[bIDegree of polymerization according to PC results;[c]Degree of polymerization according to NMR results;[dIData reported in the literature.

[0414] Example 2: Random ADMET / ROMP co-polymerization of cyclopentene (CP) with diallyl esters

[0415] CP has been co-polymerized with allylic esters using UNC catalyst at 1: 10 ratio using UNC catalyst in toluene at room temperature. The formed co-polymers have been precipitated out by adding MeOH to the reaction mixture giving the white polymers in reasonable yield (70%. based onXH NMR). These conversions are slightly higher than those of homopolymers of CP could be obtained via equilibria polymerization at similar condition (ca. 50% at the reported condition in the absence of diallylic esters). This indicates that CP is less prone to equilibrium polymerization during co-polymerization. The random monomer distribution has been indicated by homonuclear (’H-1!! TOCSY, ’H-1!! COSY) and heteronuclear ^H-^C HSQC and ^-^C HMBC) measurements (FIGs. 12-15). In all cases, the expected block and alternating dyads were identified showing random distribution of the monomers in the polymer chain.

[0416] Table 3. Co-polymerization of diallyl esters and CP (1: 10 ratio) using UNC catalyst[a]Entry Polymer Isolated yield [%] Mw[kDa] DM 1 po / y-(DAS-co-CP)-10 41 1.6 2.16 2 po / y-(DAA-co-CP)- 10 45 2.2 1.94 3 po / v-(DAT-co-CP)-10 97 0.5 1.92

[0417]

[0418] 4 po / y-(DAC-co-CP)- 10 46 1.8 2.01[aIConditions: 0.1 mol% catalyst, RT, 3 h, toluene (20 vol% of CP)

[0419] The molecular weights and dispersity indices of the formed polymers were investigated by APC indicating some molecular weight improvement comparing to the Attorney Docket No. 047162-7531W01(02753)

[0420] ADMET homopolymers of allylic esters, however these values were still far below the polypentenamer Mw could be obtained at similar condition in the absence of diallyl esters. The DM in each case were relatively high, above two (Table 3). Tentatively it is presumed that upon the metathesis of allylic esters ethylene forms which can take part in post crossmetathesis and shreds the longer polymer chains resulting in significant drop of molecular weight and high dispersity.

[0421] Example 3: Chain expansion metathesis polymerization (CEMP), synthesis of degradable unit containing polyethylene

[0422] Following the random co-polymerization investigation of CP and diallyl esters the reaction of diallyl ester oligomers with CP was investigated at 0 °C in toluene solution according to literature procedure. First the ratio of diallylester units and applied CP monomers was 1:10. After three-hour reaction time the polymers were precipitated as a white solid by adding MeOH to the reaction mixture. As it was expected insertion of CP ring into the olefinic double bonds of the oligomers of diallyl ester oligomers was observed (FIG. 5). In contrast to the random ADMET / ROMP co-polymerization of CP with diallyl esters the molecular weight of the co-polymers significantly improved (approximately from 4 kDato 10 kDa). Based on 'H NMR measurements, the formed polymers contained relatively small amounts of ester-ester / carbonate-carbonate dyads compared to the starting oligomers (FIGs.

[0423] 11-11B, Hesignal; FIGs. 20-23). This indicates that during the CEMP reaction, not block polymers containing polyester and polypentenamer dyads are formed, but polypentenamer containing randomly distributed ester monomers. Interestingly, it was also found that not only the internal but also the terminal double bonds of the oligoesters and oligocarbonate can participate in CEMP reaction which could be clearly seen by the upshift of the multiplet proton signals from 5.2 to 4.9 ppm (FIG. 5. H"1signal). The assignation of H6and Hcprotons were confirmed by 2D NMR correlation spectroscopy (COSY).

[0424] In general, the CEMP reaction leads to a significant increase in the molecular weight of the polymers compared to the ADMET reactions (Table 4). while the ester / carbonate units are randomly distributed in the polypentenamer chain. In the next experiment the ratio of the added CP to the allyl esters and carbonate has been increased by one magnitude resulting in polymers with even higher molecular weight (26-32 Mw) (Table 5).

[0425] Thermal measurements revealed, that comparing samples CEMP-po / y-(DAC-co-CP)-10 and CEMP- / ?o / y-(DAC-co-CP)-100, the former is less stable thermally. Its degradation starts above 225 °C, while the latter starts to decompose at considerably higher Attorney Docket No. 047162-7531W01(02753)

[0426] temperatures (325 °C) Table 4 and 5). Both samples are showing a two-step decomposition pathway, where in both cases, the first step (approximately between 250 and 400 °C) is exothermic, while the second, larger step is endothermic. Despite of the inert (pyrolytic) conditions used in the measurements, both sample’s decomposition ends at the same temperature (492 °C) and is almost quantitative (residue at the end of the measurement for sample CEMP-po / y-(DAC-co-CP)-10 is 1%, while for the CEMP-w / y-(DAC-co-CP)-100 is 2.5%).

[0427] Table 4. Co-polymerization of poly-diallyl esters with cyclopentene|a|

[0428] CP / Ester Entry Polymer Yield [%] MwDM Td[°C]

[0429] ratio CEMP-jUo / y-(DAS- 1 75 4.1 2.56 206 6 (94%)

[0430] co-CP)-10

[0431] CEMP-po / y- 2 81 3.1 2.04 225 3 (89%) (DAA-co-CP)-lO

[0432] CEMP-po / y-(DAT- 3 97 4.2 2.13 - 4 (95%)

[0433] co-CP)-10

[0434] CEMP-jUo / y- 4 84 3.2 2.09 200 5 (94%) (DAC-co-CP)-lO

[0435] ROIMP-po / v- 5™ 67 9.2 1.94 206 6 (72%) (DAS-co-CP)-lO

[0436] ROIMP-po / v- 6™ 61 11 1.88 225 5 (85%) (DAA-co-CP)-lO

[0437] 7[b] ROIMP-po / y- 81 8.8 4.22 - 4 (65%) (DAT-co-CP)-lO

[0438] ROIMP-po / y- 8[b]63 14 2.01 200 5 (61%)

[0439]

[0440] (DAC-co-CP)-lO

[0441] [aICyclopentene / diallyl ester ratio = 10 / 1; 20 Vol% in toluene. UNC = 0.1 mol%, 25 °C, tr = 3 h;[b]0 °C.

[0442] Table 5. Co-polymerization of poly-diallyl esters with cyclopentene[a]

[0443] T CP / Este Entry Polymer Yield [ Mw dr %] DM

[0444] [°C] ratio 1 CEMP-j»o / y-(DAS- 93 27 1.71 312 48 (74%) co-CP)-100

[0445] 2 CEMP-jOo / y-(DAA- 87 32 1.37 325 36 (96%) co-CP)-100

[0446] 3 CEMP-po / y-(DAT- 95 11 3.12 ND 73 (83%) co-CP)-100

[0447] 4 CEMP-jOo / y-(DAC- 89 26 1.42 291 39 (82%)

[0448]

[0449] co-CP)-100

[0450] [aICyclopentene / diallyl ester ratio = 100 / 1; Toluene, UNC = 0.1 mol%, 0 °C, tr = 3 h. Attorney Docket No. 047162-7531W01(02753)

[0451] Example 4: Hydrolysis of co-polymers

[0452] Polymer degradation studies of CEMP co-polymers (Table 6) were performed at alkaline conditions. The co-polymers (Table 6) were dissolved in THF then aqueous solution of sodium hydroxide (2 M) was added. The mixture was refluxed overnight. Then the solution was neutralized by addition of hydrochloride acid resulting in telechelic. hydroxyl group end functionalized polypentenamer chains in high yield (61-99%). APC analysis of the formed mixture revealed significant drop of the Mww hile the D increased remarkably comparing to the starting polymers.

[0453] In a E pical example based on the ’H NMR and 'H-nC HMBC measurements the CEMP-po / y-(DAS-co-CP)-100 polymer could be completely hydrolyzed to telechelic polypentenamer diols (Table 6; Entry 3; FIGs. 8A-8B) while the Mw of the starting polymer dropped from 26.7 kDa to 12.0 kDa and the D increased from 1.37 to 2.26 (FIG. 9A). The HMBC analysis has shown that there is no correlation between the a-position protons and carbonyl carbon indicating that at the end of the reaction, the products do not contain ester groups.

[0454] Table 6. Hydrolysis of CEMP co-polymers1"1

[0455] Conversion Mw[blMw[clDM[blDM Entry Polymer|C|

[0456] [%] [kDa] [kDa] 1-1 1-1 1 CEMP-po / y-(DAS-co-CP)-100 99 26.7 12.0 1.71 4.25 2 CEMP-po / y-(DAA-co-CP)-100 61 31.6 12.2 1.37 2.26

[0457]

[0458] 3 CEMP-po / y-(DAC-co-CP)-100 76 26.1 14.1 1.42 2.04|a|50 mg polymer in THF (25 mg / mL), 2 mL 2 M NaOH, refluxed, tr = 16 h; [^before hydrolysis;[cIafter hydrolysis.

[0459] Example 5: Hydrogenation of CEMP co-polymers

[0460] The synthesized CEMP co-polymers were hydrogenated using Wilkinson catalyst in THF solution at 50 °C and 20 bar hydrogen atmosphere. During the reaction, the hydrogenated polymer gradually precipitated from the solution. The obtained polymers contained polyethylene-like carbon chains, which made the 1: 100 copolymers insoluble, while the 1:10 copolymers w ere poorly soluble in chloroform and dichloromethane (FIG. 5).

[0461] The T1 NMR analysis of the hydrogenated 1:10 co-polymer indicated that the polymer chain was fully hydrogenated, only traces of double bonds were detected (FIG. 10B). Furthermore, theJH-1?C HMBC measurement showed that the methylene group next to the oxygen still correlates with the carbonyl group of the polymer chain after hydrogenation, Attorney Docket No. 047162-7531W01(02753)

[0462] which confirms the presence of ester groups in the polymer chain. (FIG. 10C). The formed polymers could not be detected by the RI and PDA detectors, making the APC analysis unfeasible.

[0463] To demonstrate that the ester and carbonate groups remain intact during hydrogenation, we performed the reduction of ADMET polyester and polycarbonate oligomers.

[0464]

[0465] NMR measurements did not show a significant change in the degree of polymerization of the oligomers compared to the unsaturated starting oligomers (Table 7), which indicates that the ester or carbonate functional groups in the polymer chain are less affected during the hydrogenation.

[0466] Table 7. Polymerization degree of ADMET oligomers before and after hydrogenation Entry Polymer Degree of Polymerization Degree of Polymerization 1 / Jo / y-DAS 6.4 5.8

[0467] 2 po / y-DAA 6.7 5.4

[0468]

[0469] 3 poly-DAC 8.3 8.0

[0470] 50 mg polymer in THF (25 mg / mL), Wilkinson catalyst (1 mg, 1 pmol), 20 bar H2, t = 16 h.

[0471] Table 8. Thermoanalysis of hydrogenated CEMP co-poly mers

[0472] Entry Polymer Conversion [%] Tm[°C] Td[°C] CEMP-po / y-(DAS-co-CP)-100- 1 99 110 347 H2

[0473] CEMP -po / y-(DAA-co-CP)- 100- 2

[0474] H261 111 366 CEMP -po / y-(DAC-co-CP)- 100- 3 76 107 369

[0475]

[0476] H2

[0477] The effect of the hydrogenation of the sample CEMP-po / -(DAA-co-CP)-100 is clearly visible on both comparative graphs (mass loss / TG / and heat flow / DSC / ). As expected, the well visible difference is the further increase of the thermal stability of the hydrogenated sample. Its thermal decomposition starts at 400 °C, more than 50 °C higher, comparing to the corresponding non-hydrogenated sample (325 °C). Additionally, the hydrogenated sample shows a clear and well visible melting endotherm (onset temperature 99.47 °C, peak maximum temperature 106.88 °C and melting enthalpy of 119 J / g) (FIGs. 11A-11B). The decomposition of the sample ends at 500 °C, and in this case, too, is also almost quantitative (residue at the end of the measurement for sample CEMP- »o / y-(DAC-co-CP)-100-H2 is 1.5%). These data are similar to the thermoanalytical data reported in the literature for commercial polyethylene. The melting temperatures of commercial PE (without Attorney Docket No. 047162-7531W01(02753)

[0478] additives) with different density are between 100 °C and 140 °C, and the thermal decomposition start above 400 °C. In summary, it can be concluded that the introduction of degradable units (ester or carbonate) into the polyethylene chain under the above-mentioned conditions does not result in a significant change in the thermoanalytical properties of the polymer.

[0479] Example 6: Polymerization on multigram scale and polymer physical properties investigation

[0480] The synthesis of ROIMP copolymers was successfully performed on a multigram scale using UNC as the ADMET catalyst and HG2 as the ROIMP catalyst. The ADMET reaction afforded o / zgo-DAS with molecular weight and yield comparable to those obtained in small-scale experiments (Mw = 5 kDa; 56%). Subsequent ROIMP of o / zgo-DAS with CP at a CP-to-succinate ratio of 100 resulted in a substantial increase in molecular weight (Mw = 22 kDa; ROIMP -po / y-(DAS-co-CP)-100) with good yield (64%) and maintained a reasonable dispersity (DM = 1.40). These values are slightly lower than those observed in the small-scale synthesis (Mw= 27 kDa; M = 1.71).

[0481] XH NMR analysis indicated that the ratio of cyclopentene to ester units in the resulting ROIMP copolymer was approximately 80 per succinate unit (40 per ester dyad), consistent with the theoretically calculated CP incorporation per succinate assuming ROMP of CP reached equilibrium (82% at 20 vol% CP in toluene at 0 °C). Repeating the ROIMP reaction with an additional 100-fold portion of CP and HG2 catalyst led to a modest increase in molecular weight (Mw = 27 kDa; ROIMP- / 7o / i-(DAS-co-CP)-200). while dispersity remained essentially unchanged (DM = 1.40). The isolated copolymers were obtained in reasonable yield (56%), and as it was expected, the

[0482]

[0483] NMR confirmed that the CP-to-succinate ratio approximately doubled to 180 (90 per ester dyad).

[0484] The ROIMP copolymer was subsequently hydrogenated in a 700 mL stainless steel autoclave using Wilkinson’s catalyst in THF (see Physical Properties elsewhere herein), yielding the saturated polymer in high yield (78%). It is presumed, based on previous 'H NMR analysis of ROIMP- o / v-(DAS-co-CP)-10-H2 (Figure S19b) that approximately 95% of the olefinic double bonds are hydrogenated.

[0485] Infrared spectra recorded in ATR mode are shown in FIGs. 31A-31D. A commercial grade HDPE (Melt Index > 10.5, Mw= 72.4 kDa) w as used as a reference. Based on the ATR-FTIR spectra, it can be concluded that the non-hydrogenated elastomer exhibits the characteristic vibrations associated with carbon-carbon double bonds, as expected: the Attorney Docket No. 047162-7531W01(02753)

[0486] absorptions observed between 3050 and 3000 cm’1correspond to the symmetric stretch of =CH- structural units, while the intense peak at 965 cm’1is likewise attributed to the =CH-bending vibration of olefinic unit. The figure clearly shows that the intensity of these bands decreases markedly upon hydrogenation; however, they do not completely vanish, indicating the presence of residual unsaturation consistent with the earlierJH NMR analysis.

[0487] Enumerated Embodiments

[0488] The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

[0489] Embodiment 1 provides a polymer composition comprising a random copolymer of at least one cleavable monomer and at least one cyclic monomer, wherein:

[0490] (a) each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer ( / . e., -CH=CH2);

[0491] (b) each cyclic monomer independently comprises an optionally substituted C3-C10 cycloalkene or optionally substituted C2-C10 heterocycloalkene, wherein the C3-C10 cycloalkene or C2-C10 heterocycloalkene comprises an unsubstituted internal alkenylene moiety (z.e., -CH=CH-);

[0492] (c) each cleavable monomer is covalently linked to at least one adjacent cyclic monomer or cleavable monomer, and each cyclic monomer is covalently linked to at least one adjacent cleavable monomer or cyclic monomer, wherein each covalent linkage comprises a bond formed by an olefin metathesis reaction.

[0493] Embodiment 2 provides the polymer composition of Embodiment 1, wherein each moiety susceptible to hydrolytic cleavage is independently selected from the group consisting of an ester, carbonic ester, amide, carbamate, thioester, thiocarbamate, and dithiocarbamate.

[0494] Embodiment 3 provides the polymer composition of Embodiment 1 or 2, wherein each unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Cs heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl.

[0495] Embodiment 4 provides the polymer composition of any one of Embodiments 1-3. wherein the cleavable monomer comprises two independently selected moieties susceptible to Attorney Docket No. 047162-7531W01(02753)

[0496] hydrolytic cleavage.

[0497] Embodiment 5 provides the polymer composition of Embodiment 4, wherein the two moieties susceptible to hydrolytic cleavage are covalently linked by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl.

[0498] Embodiment 6 provides the polymer composition of any one of Embodiments 1-5, wherein the cleavable monomer is a compound of Formula (la):

[0499] ^1a

[0500]

[0501] 'X1aL2X1b

[0502] wherein:

[0503] Lla. Llb, and L2are each independently selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl;

[0504] X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA;

[0505] Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; and

[0506] RAand RBare each independently selected from the group consisting of H, optionally substituted Ci-Ce alkyl, optionally substituted Cb-Cs cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted Ce-Cio aryl.

[0507] Embodiment 7 provides the polymer composition of Embodiment 6, wherein at least one of the following applies:

[0508] (a) Llaand Llbare each independently -(CH2)-;

[0509] (b) L2is selected from the group consisting of -(CH2)2-, -(CH2)4-, and phenylene;

[0510] (c) X1aand X1bare each independently -O-; and

[0511] (d) Z1aand Z1bare each independently O.

[0512] Embodiment 8 provides the polymer composition of any one of Embodiments 1-7, wherein each cleavable monomer is independently selected from the group consisting of Attorney Docket No. 047162-7531W01(02753)

[0513] o o

[0514]

[0515] Embodiment 9 provides the polymer composition of any one of Embodiments 1-8. wherein each cyclic monomer independently comprises a compound of formula (lb):

[0516] L3

[0517]

[0518] (lb),

[0519] wherein L3is selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, and optionally substituted C2-C8 heterocyloalkylenyl.

[0520] Embodiment 10 provides the polymer composition of Embodiment 9, wherein L3is

[0521] selected from the group consisting of -(CH2)3-, -(CH2)6-,

[0522]

[0523] and Embodiment 11 provides the polymer composition of any one of Embodiments 1-10, wherein each cyclic monomer is independently selected from the group consisting of

[0524] o. © tro... O

[0525] Embodiment 12 provides the polymer composition of any one of Embodiments 1-11, wherein the polymer has a ratio of cleavable monomer to cyclic monomer ranging from about 1: 1000 to about 1:1, optionally wherein the polymer has a ratio of cleavable monomer to cyclic monomer of about 1:100, and optionally wherein the polymer has a ratio of cleavable monomer to cyclic monomer of about 1:3.

[0526] Embodiment 13 provides the polymer composition of any one of Embodiments 1-12, wherein the polymer has a molecular weight ranging from about 1 kDa to about 100 kDa or more, optionally wherein the polymer has a molecular weight ranging from about 5 kDa to about 50 kDa, and optionally wherein the polymer has a molecular weight ranging from about 11 kDa to about 32 kDa.

[0527] Embodiment 14 provides the polymer composition of any one of Embodiments 1-13, wherein each covalent linkage between monomers comprises a double bond or single bond, w herein the single bond was obtained by reduction of the double bond. Attorney Docket No. 047162-7531W01(02753)

[0528] Embodiment 15 provides a method for preparing a polymer composition, the method comprising:

[0529] (a) subjecting at least one cleavable monomer to acyclic diene metathesis (ADMET) polymerization to prepare a cleavable oligomer; and

[0530] (b) subjecting the cleavable oligomer to ring opening metathesis polymerization (ROMP) in the presence of a cyclic monomer.

[0531] Embodiment 16 provides the method of Embodiment 15, wherein each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer (i.e., -CH=CH2).

[0532] Embodiment 17 provides the method of Embodiment 15 or 16. wherein each moiety susceptible to hydrolytic cleavage is independently selected from the group consisting of an ester, carbonic ester, amide, carbamate, thioester, thiocarbamate, and dithiocarbamate.

[0533] Embodiment 18 provides the method of Embodiment 16 or 17, wherein each unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl.

[0534] Embodiment 19 provides the method of any one of Embodiments 16-18, wherein the cleavable monomer comprises two independently selected moieties susceptible to hydrolytic cleavage.

[0535] Embodiment 20 provides the method of Embodiment 19, wherein the two moieties susceptible to hydrolytic cleavage are covalently linked by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl.

[0536] Embodiment 21 provides the method of any one of Embodiments 15-20, w herein the cleavable monomer is obtained from a plastic waste feedstock.

[0537] Embodiment 22 provides the method of any one of Embodiments 15-21, wherein the cleavable monomer is a compound of Formula (la): Attorney Docket No. 047162-7531W01(02753)

[0538] ^1a 21 b

[0539] I1aJI JI I 1b VL'x1AL2^x1b' (ia),

[0540]

[0541] wherein:

[0542] Lla. Llb, and L2are each independently selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl;

[0543] X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA;

[0544] Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; and

[0545] RAand RBare each independently selected from the group consisting of H, optionally substituted Ci-Ce alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted Ce-Cio aryl.

[0546] Embodiment 23 provides the method of Embodiment 22, at least one of the following applies:

[0547] (a) Llaand Llbare each independently -(CH2)-;

[0548] (b) L2is selected from the group consisting of -(CH2)2-, -(CH2)4-, and phenylene;

[0549] (c) X1aand X1bare each independently -O-; and

[0550] (d) Z1aand Z1bare each independently O.

[0551] Embodiment 24 provides the method of any one of Embodiments 15-23, wherein each cleavable monomer is independently selected from the group consisting of:

[0552]

[0553] Embodiment 25 provides the method of Embodiment 17-22, wherein the ADMET polymerization comprises contacting the cleavable monomer with a ruthenium metathesis catalyst.

[0554] Embodiment 26 provides the method of Embodiment 25, wherein the ruthenium Attorney Docket No. 047162-7531W01(02753)

[0555] metathesis catalyst comprises a N-heterocyclic carbene ruthenium catalyst.

[0556] Embodiment 27 provides the method of Embodiment 25 or 26, wherein the catalyst selected from the group consisting of:

[0557]

[0558] Embodiment 28 provides the method of any one of Embodiments 23-27, wherein at least one of the following applies:

[0559] (a) the cleavable monomer and catalyst have a molar ratio of about 100: 1 (i.e., about 1 mol% catalyst);

[0560] (b) the contacting occurs with a concentration of cleavable monomer of about 2.5 M; and (c) the contacting occurs in the presence of a solvent, optionally wherein the solvent is a non-polar, aromatic solvent, and optionally wherein the solvent is toluene.

[0561] Embodiment 29 provides the method of any one of Embodiments 22-28. wherein the cleavable oligomer is a compound of Formula (II):

[0562] £la £lb

[0563]

[0564] wherein o is 2, 3, 4, 5, 6, 7, 8, or 9.

[0565] Embodiment 30 provides the method of Embodiment 29, wherein o is an integer ranging from about 5 to about 100.

[0566] Embodiment 31 provides the method of any one of Embodiments 15-30, wherein the ROMP comprises contacting the cleavable oligomer and at least one cyclic monomer in the presence of a second catalyst.

[0567] Embodiment 32 provides the method of Embodiment 31, wherein each cyclic monomer independently comprises a compound of Formula (lb):

[0568] L3

[0569]

[0570] (lb),

[0571] wherein L3is selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, and optionally substituted C2-C8 heterocycloalkylenyl.

[0572] Embodiment 33 provides the method of Embodiment 32, wherein L3is selected from Attorney Docket No. 047162-7531W01(02753)

[0573] the group consisting o

[0574]

[0575] f -(CH2)3-, -(CH2)e-. and

[0576] Embodiment 34 provides the method of Embodiment 32 or 33, wherein each cyclic monomer is independently selected from the group consisting of:

[0577] o © Co..dO

[0578] Embodiment 35 provides the method of any one of Embodiments 31-34, wherein the second catalyst is a ruthenium metathesis catalyst.

[0579] Embodiment 36 provides the method of Embodiment 35. wherein the ruthenium metathesis catalyst comprises a N-heterocyclic carbene ruthenium catalyst.

[0580] Embodiment 37 provides the method of Embodiment 35 or 36, wherein the catalyst selected from the group consisting of:

[0581]

[0582] Embodiment 38 provides the method of any one of Embodiments 32-37. wherein at least one of the following applies:

[0583] (a) the cleavable oligomer and cyclic monomer have a molar ratio ranging from about 1: 1 to about 1:100 (oligomer: monomer), optionally wherein the cleavable oligomer and cyclic monomer have a molar ratio of about 1:10 (oligomermonomer);

[0584] (b) the cleavable oligomer and second catalyst have a molar ratio of about 1000: 1 (z.e., about 0.1 mol% catalyst);

[0585] (c) the contacting occurs in the presence of a solvent, optionally wherein the solvent is a non-polar, aromatic solvent, and optionally wherein the solvent is toluene;

[0586] (d) the contacting occurs at a temperature ranging from about 0 °C to about 23 °C (room temperature); and

[0587] (e) the contacting occurs for about 3 hours.

[0588] Embodiment 39 provides the method of any one of Embodiments 15-38, wherein the polymer composition is a biodegradable polymer.

[0589] Embodiment 40 provides the method of any one of Embodiments 15-39, wherein the Attomey Docket No. 047162-7531W01(02753)

[0590] polymer composition is reduced.

[0591] Embodiment 41 provides the method of any one of Embodiments 15-40, wherein the biodegradable polymer is the polymer of any one of Embodiments 1-14.

[0592] The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present application. Thus, it should be understood that although the present application describes specific embodiments and optional features, modification and variation of the compositions, methods, and concepts herein disclosed may be resorted to by those of ordinary skill in the art. and that such modifications and variations are considered to be within the scope of embodiments of the present application.

Claims

1. Attorney Docket No. 047162-7531W01(02753)2.CLAIMS3.What is claimed is:

1. A polymer composition comprising a random copolymer of at least one cleavable monomer and at least one cyclic monomer, wherein:5.(a) each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer (i.e., -CH=CH2);6.(b) each cyclic monomer independently comprises an optionally substituted Cs- Cio cycloalkene or optionally substituted C2-C10 heterocycloalkene, wherein the C3-C10 cycloalkene or C2-C10 heterocycloalkene comprises an unsubstituted internal alkenylene moiety (z.e., -CH=CH-);7.(c) each cleavable monomer is covalently linked to at least one adjacent cyclic monomer or cleavable monomer, and each cyclic monomer is covalently linked to at least one adjacent cleavable monomer or cyclic monomer, wherein each covalent linkage comprises a bond formed by an olefin metathesis reaction.

2. The polymer composition of claim 1, wherein each moiety susceptible to hydrolytic cleavage is independently selected from the group consisting of an ester, carbonic ester, amide, carbamate, thioester, thiocarbamate, and dithiocarbamate.

3. The polymer composition of claim 1 or 2, wherein each unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C -C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-C10 arylenyl, and optionally substituted C2-C8 heteroarylenyl.

4. The polymer composition of any one of claims 1-3, wherein the cleavable monomer comprises two independently selected moieties susceptible to hydrolytic cleavage.

5. The polymer composition of claim 4, wherein the two moieties susceptible toAttorney Docket No. 047162-7531W01(02753)12.hydrolytic cleavage are covalently linked by a moiety selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl.

6. The polymer composition of any one of claims 1-5, wherein the cleavable monomer is a compound of Formula (la):14.£la £lb15.i 1a X U I1 b^5-16.

17. 'X1aX2^X1b' ^ (la)18.wherein:19.L1a, L1b, and L2are each independently selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl;20.X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA;21.Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; and22.RAand RBare each independently selected from the group consisting of H, optionally substituted Ci-Cs alkyl, optionally substituted Cb-Cs cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted C6-C10 aryl.

7. The polymer composition of claim 6, wherein at least one of the following applies:24.(a) Llaand Llbare each independently -(CH2)-;25.(b) L2is selected from the group consisting of -(CH2)2-, -(CFh)-!-, and phenylene; (c) X1aand X1bare each independently -O-; and26.(d) Z1aand Z1bare each independently O.

8. The polymer composition of any one of claims 1-7, wherein each cleavable monomerAttorney Docket No. 047162-7531W01(02753)28.o30.

31. is independently selected from the group consisting of032.O34.

9. The polymer composition of any one of claims 1-8, wherein each cyclic monomer independently comprises a compound of formula (lb):37.L339.

40. (lb),41.wherein L3is selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, and optionally substituted C2-Cs heterocyloalkylenyl.

10. The polymer composition of claim 9, wherein L3is selected from the group consisting43.of-(44.

45. CH2)3-, -(CH2)6-,11. The polymer composition of any one of claims 1-10, wherein each cyclic monomer is independently selected from the group consisting of48.

12. The polymer composition of any one of claims 1-11, wherein the polymer has a ratio of cleavable monomer to cyclic monomer ranging from about 1: 1000 to about 1:1, optionally wherein the polymer has a ratio of cleavable monomer to cyclic monomer of about 1:100, and optionally wherein the polymer has a ratio of cleavable monomer to cyclic monomer of about 1:3.

13. The polymer composition of any one of claims 1-12, wherein the polymer has a molecular weight ranging from about 1 kDa to about 100 kDa or more, optionally wherein the polymer has a molecular weight ranging from about 5 kDa to about 50 kDa, andAttomey Docket No. 047162-7531W01(02753)52.optionally wherein the polymer has a molecular weight ranging from about 11 kDa to about 32 kDa.

14. The polymer composition of any one of claims 1-13, wherein each covalent linkage between monomers comprises a double bond or single bond, wherein the single bond was obtained by reduction of the double bond.

15. A method for preparing a polymer composition, the method comprising:55.(a) subjecting at least one cleavable monomer to acyclic diene metathesis (ADMET) polymerization to prepare a cleavable oligomer; and (b) subjecting the cleavable oligomer to ring opening metathesis polymerization (ROMP) in the presence of a cyclic monomer.

16. The method of claim 15, wherein each cleavable monomer independently comprises at least one moiety susceptible to hydrolytic cleavage and further comprises an unsubstituted alkene at both termini of the cleavable monomer (z. e., -CH=CH2).

17. The method of claim 15 or 16, wherein each moiety' susceptible to hydrolytic cleavage is independently selected from the group consisting of an ester, carbonic ester, amide, carbamate, thioester, thiocarbamate, and dithiocarbamate.

18. The method of claim 16 or 17, wherein each unsubstituted alkene at the terminus of the cleavable monomer is covalently linked to the moiety susceptible to hydrolytic cleavage by a moiety’ selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl.

19. The method of any one of claims 16-18, wherein the cleavable monomer comprises two independently selected moieties susceptible to hydrolytic cleavage.

20. The method of claim 19, wherein the two moieties susceptible to hy drolytic cleavage are covalently linked by a moiety selected from the group consisting of optionally substituted C1-C6 alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8Attorney Docket No. 047162-7531W01(02753)61.cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-C10 arylenyl, and optionally substituted C2-C8 heteroarylenyl.

21. The method of any one of claims 15-20, wherein the cleavable monomer is obtained from a plastic waste feedstock.

22. The method of any one of claims 15-21, wherein the cleavable monomer is a compound of Formula (la):64.^L'x1a\2^x1b'L1^ (ia),65.wherein:66.L1a, L1b, and L2are each independently selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, optionally substituted C2-C8 heterocycloalkylenyl, optionally substituted Ce-Cio arylenyl, and optionally substituted C2-C8 heteroarylenyl;67.X1aand X1bare each independently selected from the group consisting of a bond (absent), O, S, and NRA;68.Z1aand Z1bare each independently selected from the group consisting of O, S, and NRB; and69.RAand RBare each independently selected from the group consisting of H, optionally substituted Ci-Ce alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C8 heterocycloalkyl, optionally substituted C2-C10 heterocyclyl, and optionally substituted Ce-Cio aryl.

23. The method of claim 22, at least one of the following applies:71.(a) Llaand Llbare each independently -(CH2)-;72.(b) L2is selected from the group consisting of -(CH2)2-, -(CH2)4-, and phenylene: (c) X1aand X1bare each independently -O-; and73.(d) Z1aand Z1bare each independently O.

24. The method of any one of claims 15-23, wherein each cleavable monomer is independently selected from the group consisting of:Attorney Docket No. 047162-7531W01(02753)75.o o77.

25. The method of claim 17-22, wherein the AD MET polymerization comprises contacting the cleavable monomer with a ruthenium metathesis catalyst.

26. The method of claim 25, wherein the ruthenium metathesis catalyst comprises a N-heterocyclic carbene ruthenium catalyst.

27. The method of claim 25 or 26, wherein the catalyst selected from the group consisting of:

83.

28. The method of any one of claims 23-27, wherein at least one of the following applies:86.(a) the cleavable monomer and catalyst have a molar ratio of about 100: 1 (i.e., about 1 mol% catalyst);87.(b) the contacting occurs with a concentration of cleavable monomer of about 2.5 M; and88.(c) the contacting occurs in the presence of a solvent, optionally wherein the solvent is a non-polar, aromatic solvent, and optionally wherein the solvent is toluene.

29. The method of any one of claims 22-28, wherein the cleavable oligomer is a compound of Formula (II):

91.

92. ° (II), Attorney Docket No. 047162-7531W01(02753)93.wherein o is 2, 3, 4, 5, 6, 7, 8, or 9.

30. The method of claim 29, wherein o is an integer ranging from about 5 to about 100.

31. The method of any one of claims 15-30, wherein the ROMP comprises contacting the cleavable oligomer and at least one cyclic monomer in the presence of a second catalyst.

32. The method of claim 31, wherein each cyclic monomer independently comprises a compound of Formula (lb):97.L399.

100. (lb),101.wherein L3is selected from the group consisting of optionally substituted Ci-Ce alkylenyl, optionally substituted Ci-Ce heteroalkylenyl, optionally substituted C3-C8 cycloalkylenyl, and optionally substituted C2-C8 heterocycloalkylenyl.

33. The method of claim 32, wherein L3is selected from the group consisting of -(CH2)3-,103.-104.

105. (CH2)6-, '''O''', and34. The method of claim 32 or 33, wherein each cyclic monomer is independently selected from the group consisting of:107.O 0 CO.. O35. The method of any one of claims 31-34, wherein the second catalyst is a ruthenium metathesis catalyst.

36. The method of claim 35, wherein the ruthenium metathesis catalyst comprises a N-heterocyclic carbene ruthenium catalyst.

37. The method of claim 35 or 36, wherein the catalyst selected from the group consisting of:Attorney Docket No. 047162-7531W01(02753)112.

38. The method of any one of claims 32-37, wherein at least one of the following applies:115.(a) the cleavable oligomer and cyclic monomer have a molar ratio ranging from about 1:1 to about 1:100 (oligomer: monomer), optionally wherein the cleavable oligomer and cyclic monomer have a molar ratio of about 1:10 (oligomer: monomer);116.(b) the cleavable oligomer and second catalyst have a molar ratio of about 1000: 1 (z.e., about 0.1 mol% catalyst);117.(c) the contacting occurs in the presence of a solvent, optionally wherein the solvent is a non-polar, aromatic solvent, and optionally wherein the solvent is toluene;118.(d) the contacting occurs at a temperature ranging from about 0 °C to about 23 °C (room temperature); and119.(e) the contacting occurs for about 3 hours.

39. The method of any one of claims 15-38, wherein the polymer composition is a biodegradable polymer.

40. The method of any one of claims 15-39, wherein the polymer composition is reduced.

41. The method of any one of claims 15-40, wherein the biodegradable polymer is the polymer of any one of claims 1-14.

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