Polymers derived from vinyl ethers and methods of making polymers

Abstract

Disclosed herein are methods for the synthesis of a poly(vinyl ether) polymer that include one or more of: obtaining one or more phenolic compounds from a source; synthesizing one or more vinyl ether-functionalized monomers from the obtained one or more phenolic compounds; and polymerizing the one or more vinyl ether-functionalized monomers to form the poly(vinyl ether). Poly(vinyl ether) polymers produced from these methods, in addition to compositions and products containing the poly(vinyl ether) polymers, are also disclosed herein.

Description

[0001] 2101715-001297

[0002] -1 -

[0003] POLYMERS DERIVED FROM VINYL ETHERS AND METHODS OF MAKING POLYMERS

[0004] CROSS-REFERENCE TO RELATED APPLICATION

[0005] This application claims priority to U.S. Provisional Patent Application No. 63 / 637,006 filed on April 22, 2024, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0006] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0007] This invention was made with government support under Grant No. CMMI 1934887 awarded by the National Science Foundation and Grant No. W91 I NF-22- 2-0257 awarded by the Army Research Office. The government has certain rights in the invention.

[0008] FIELD

[0009] The present disclosure relates to polymers derived from vinyl ether compounds and methods for making said polymers. Articles created from polymers are also disclosed herein.

[0010] BACKGROUND

[0011] Current plastic production processes that rely on petrochemicals consume about 5 to 7% of the global oil supply and contribute to about 2% of the total global CO2 output annually. Indeed, in 2019, plastic production processes relying on petrochemicals released about 850 million tons of CO2 into the atmosphere, and it is currently projected that petrochemical-based plastic production processes will release around 2.5 billion tons of CO2 by 2050. Given the effect that CO2 emissions have had on the rise of global temperatures, petrochemical-based plastic production processes can contribute to long-term damage of the global ecosystem. In addition to their contribution to CO2 emissions, petrochemical-based plastic production processes are also not sustainable given the limited quantity of fossil fuels globally available. Another drawback of petrochemical-based plastic production processes is that polymerization of the petroleum-based vinyl ethers isolated from petrochemicals needs to be performed at low temperatures, i.e., temperatures of -78 °C, for the resulting polymer to achieve semi-crystallinity. 2101715-001297

[0012] -2-

[0013] To address the sustainability and environmental challenges associated with petrochemicals, researchers have exploited a plethora of renewable chemicals to generate bio-based, cost-effective, and thermomechanically useful macromolecules. Lignin is one renewable resource that shows promise as a desirable alternative to petroleum feedstocks due to its abundance as a byproduct of pulp and paper processing and biorefining, among other sources. Corresponding lignin-based bio-oils (e.g., the volatile fraction of pyrolyzed lignin or the soluble fraction of depolymerized lignin) contain numerous aromatic compounds that structurally resemble common monomers (e.g., bisphenol A and styrene) for various polymer applications.

[0014] Thus, to address the foregoing issues with petrochemical-based plastic production processes, the present disclosure provides novel approaches to vinyl ether-functionalized monomers that can be polymerized to poly(vinyl ethers) that are capable of achieving semi-crystallinity at or near ambient temperatures. SUMMARY

[0015] An aspect of the present disclosure is a method for the synthesis of a poly(vinyl ether) polymer, the method including ( / .e., comprising) one or more of the following: obtaining one or more phenolic compounds from a source; synthesizing one or more vinyl ether-functionalized monomers from the obtained one or more phenolic compounds; and / or polymerizing the one or more vinyl ether- functionalized monomers to form the poly(vinyl ether) polymer.

[0016] Another aspect of the present disclosure is a poly(vinyl ether) polymer of Formula I:

[0017] (Formula I) 2101715-001297

[0018] -3- wherein:

[0019] R1is selected from -H or -OCH3;

[0020] R2is selected from -H or -OCH3;

[0021] R3is selected from -H or -OCH3;

[0022] R4is selected from -H or -OCH3;

[0023] R5is selected from H, OH, COOH, CHO, NH2, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups; and n is an integer that is at least 10 or more, wherein the poly(vinyl ether) polymer possesses a crystallinity of 0% to about 50%.

[0024] Another aspect of the present disclosure is a composition including any one or more of the poly(vinyl ether) polymers disclosed herein and one or more additives.

[0025] Another aspect of the present disclosure is an article formed from any one or more of the poly(vinyl ether) polymers disclosed herein.

[0026] BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Other features and advantages of the compositions, devices and methods disclosed herein will be apparent to those skilled in the art reading the following detailed description in conjugation with the exemplary embodiments illustrated in the drawings, wherein:

[0028] FIG. 1 depicts a scheme for an exemplary synthesis of polymers derived from vinyl ether compounds.

[0029] FIG. 2 depicts a13C NMR spectrum of an exemplary poly(vinyl ether) polymer pMeSyrVE in deuterated toluene. Lorentzian peak fits of the13C NMR profile of pMeSyrVE enable estimations of percent racemic (r-curves) and meso (m-curves) diads within the sample to evaluate tacticity.

[0030] FIG. 3 depicts the differential scanning calorimetry (DSC) profile of an exemplary poly(vinyl ether) polymer pMeSyrVE. 2101715-001297

[0031] -4-

[0032] FIG. 4 depicts the thermogravimetric analysis (TGA) profile of an exemplary poly(vinyl ether) polymer pMeSyrVE upon heating in N2. Td,s% and Ta, 50% are identified with arrows.

[0033] FIG. 5 depicts the thermogravimetric analysis (TGA) profile of an exemplary poly(vinyl ether) polymer pMeSyrVE upon heating in air. 7d,s% and Ta, 50% are identified with arrows.

[0034] FIG. 6 depicts an X-ray diffraction (XRD) of an exemplary poly(vinyl ether) polymer pMeSyrVE. Integrations of the area below the three largest, left-most peaks compared to the background were used to estimate crystallinity.

[0035] FIG. 7 depicts DSC heating curves of an exemplary poly(vinyl ether) pMeSyrVE over several thermal cycles with annealing at 150 °C. ACPthrough the Tgof each heating curve is shown and was used to estimate crystallinity via a mobile-bead approximation.

[0036] FIG. 8 depicts DSC heating curves of exemplary pMeSyrVE polymers over various thermal cycles.

[0037] FIG. 9 depicts TGA profiles for exemplary pMeSyrVE polymers upon heating in N2.

[0038] FIG. 10 depicts XRD profiles for exemplary pMeSyrVE polymers of differing molecular weights.

[0039] DETAILED DESCRIPTION

[0040] All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

[0041] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise 2101715-001297

[0042] -5- stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

[0043] As used herein, the term “exemplary embodiments” refers to specific examples or embodiments of any of the aspects disclosed herein that serve as illustrations to demonstrate the various ways in which the various aspects can be implemented, constructed or practiced.

[0044] As used herein, the term "about" refers to a value that is ± 5% of the stated value. In addition, it is understood that reference to a range of a first value to a second value includes the range of the stated values, e.g., a range of about 1 to about 5 also includes the more precise range of 1 to 5. It is also understood that the ranges disclosed herein include any selected subrange within the stated range, e.g., a subrange of about 50 to about 60 is contemplated in a disclosed range of about 1 to about 100.

[0045] An aspect of the present disclosure is a method for the synthesis of a poly(vinyl ether) polymer, the method including one or more of the following: obtaining one or more phenolic compounds from a source; synthesizing one or more vinyl ether-functionalized monomers from the obtained one or more phenolic compounds; and / or polymerizing the one or more vinyl ether-functionalized monomers to form the poly(vinyl ether) polymer.

[0046] The source of the one or more phenolic compounds can be selected from, but is not limited to, renewable sources {e.g., herbaceous plants, softwood, hardwood, agriculture residues, food waste, pulp, paper wastes, and other lignincontaining sources known by those of ordinary skill in the art) and non-renewable sources e.g., fossil fuels, oil refineries, coking plants, and other petrochemicals). The source of the one or more phenolic compounds can also be a synthetic source, i.e., the one or more phenolic compounds can be synthetically derivable from the chemical transformation of other compounds.

[0047] In exemplary embodiments, the source is a lignin-containing source selected from, but not limited to, herbaceous plants, softwood, hardwood, agriculture residues, food waste, pulp, and paper wastes. Those of ordinary skill in the art will appreciate that weight amount of lignin and the relative number of methoxy groups 2101715-001297

[0048] -6- in the one or more phenolic compounds will depend on the source of the lignin material. Accordingly, those of ordinary skill in the art are readily capable of selecting the appropriate lignin source to obtain phenolic compounds possessing a select number of methoxy groups. In exemplary embodiments, the one or more phenolic compounds include zero or more methoxy substitutions, and are derivable from a lignin deconstruction process. Lignin deconstruction processes are well known in the art {e.g., see US 2022 / 0324779 A1 , US 10,723,859, and US 10,669,598) and those of ordinary skill in the art would be readily capable of performing these processes to obtain one or more phenolic compounds.

[0049] In exemplary embodiments, the one or more phenolic compounds are selected from: wherein R is selected from H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional 2101715-001297

[0050] -7- groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups.

[0051] As used herein, the term “alkyl” refers to any straight chain or branched, non-cyclic or cyclic, saturated aliphatic hydrocarbon. An alkyl group can be a "lower alkyl" group, i.e., an alkyl group containing from 1 to 3 carbon atoms. An alkyl group can be a "higher alkyl", e.g., an alkyl group containing 4 or more carbon atoms. Representative saturated straight chain alkyls include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and the like, while saturated branched alkyls include, but are not limited to, isopropyl, secbutyl, isobutyl, tert-butyl, isopentyl, and the like. As used herein, a methyl substituent may be depicted as “CH3” or “Me” or as a terminal bond with no indication of specific atoms.

[0052] As used herein, the term "alkene" refers to an unbranched or branched hydrocarbon chain having one or more carbon-carbon double bonds therein. The double bond of an alkene group can be unconjugated or conjugated to another unsaturated group. Suitable alkene groups include, but are not limited to, vinyl, allyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, 2- ethylhexenyl, 2-propyl-2-butenyl, and 4-(2-methyl-3-butene)-pentenyl. An alkenyl group can be unsubstituted or substituted with one or more functional groups.

[0053] As used herein, the term "alkyne" refers to a straight or branched chain of hydrocarbon groups containing at least one carbon-carbon triple bond. An alkyne can be a substituted alkyne, such as an alkyne substituted with at least one alkyl, hydroxyalkyl, or dihydroxy group, as well as at least one oxygen-containing, nitrogen-containing or sulfur-containing group.

[0054] As used herein, the term "substituted" refers to at least one hydrogen atom of a molecular arrangement that is replaced with a substituent or a functional group. The number of substituents or functional groups present depends on the number of hydrogen atoms available for replacement and includes replacement of more than one hydrogen atom bound to a single atom (such as in the case of a carbon atom which may be available for di- or tri-substitution). Possible substituents and function groups include, but are not limited to, halogen (e.g., F, Cl, Br, I), hydroxy (OH), oxo, cyano (CN), nitro (NO2), amino, a carboxylic acid (COOH), alkylamino, 2101715-001297

[0055] -8- dialkylamino, branched or unbranched alkyl (e.g., methyl, ethyl, propyl, isopropyl, sec-butyl, etc.), fluoroalkyl (e.g., CF3, CF2H, CH2F, CH2CF3, CHFCHF2, CF2CH2F, CF2CF3, CF2CH3, CF(CH3)2, CH2CH2CF3, CF2CH2CF3, CF2CF2CF3, etc.) or more generally, haloalkyl (e.g., CH2CI, CH(CH3)Br, etc.), O-alkyl (alkoxy) (e.g., OCH3, OCH2CH3, OCH(CH3)2, etc.), O-haloalkyl (e.g., OCF2H, OCFH2, OCF3or OCH2CI), thioalkyl (e.g., S-CH3), hydroxyalkyl (e.g., CH2OH), alkyl ether (e.g., CH2OCH3), alkynyl (e.g., -C=CRf), alkenyl (e.g., -CRf=CRfRg), aryl (e.g., phenyl), arylalkyl (e.g., CH2Ph), heteroaryl, heteroarylalkyl (e.g., CH2-pyridine), heterocyclyl and heterocycloalkyl, as well as, -NRfRg, -NRfC(=O)Rg, -NRfC(=O)NRfNRg, - NRf-C(=O)ORfSO2Rg, -C(=O)Rf, -C(=O)ORf, -ORf, -C(=O)NRfRg, -OC(=O)NRfRg, - SRf, -SORf, -S(=O)2Rf, -OS(=O)2Rf and -S(=O)ORf, where each Rf and Rgmay be the same or different and are independently, hydrogen, alkyl (e.g., CH3), substituted alkyl, haloalkyl, aryl, substituted aryl, arylalkyl, substituted arylalkyl, heterocyclyl, substituted heterocyclyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl or substituted heteroaryl. In addition, the above substituents can be further substituted with one or more of the above substituents, such that the substituent can constitute, for example, a substituted alkyl, a substituted aryl, a substituted arylalkyl, a substituted heterocyclyl, or a substituted heterocycloalkyl.

[0056] In exemplary embodiments, R is a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups. In exemplary embodiments, R is an optionally substituted methyl group, an optionally substituted ethyl group, an optionally substituted propyl group, an optionally substituted butyl group, an optionally substituted hexyl group, an optionally substituted heptyl group, an optionally substituted octyl group, an optionally substituted nonyl group, or an optionally substituted decyl group.

[0057] In exemplary embodiments, R is a C2to C10 linear or branched alkene optionally substituted with one or more functional groups. In exemplary embodiments, R is an optionally substituted propylene group, an optionally substituted butylene group, an optionally substituted pentylene group or an optionally substituted hexylene group.

[0058] In exemplary embodiments, R is a C2to C10 linear or branched alkyne optionally substituted with one or more functional groups. In exemplary 2101715-001297

[0059] -9- embodiments, R is an optionally substituted ethynyl group, an optionally substituted prop-1 -yne group, an optionally substituted but-1-yne group, an optionally substituted pent-1-yne group, an optionally substituted hex-1-yne group, an optionally substituted hept- 1 -yne group, an optionally substituted oct-1 -yne group, an optionally substituted non-1-yne group, or an optionally substituted dec-1-yne group.

[0060] In exemplary embodiments, the polymerization is performed in an anhydrous solvent and in a presence of polymerization initiator. The anhydrous solvent can be selected from, but is not limited to, chloroform, toluene, dichloromethane, tetrahydrofuran, acetone, anisole, dimethyl sulfoxide, N,N-dimethylformamide, diethyl ether, hexane and methanol. The polymerization initiator can be selected from, but is not limited to, protic acids, Lewis acids {e.g., AlCh, TiCL, BF3, SnC BFsOEt2, AIF3, SiB , SiF4, FeCh, and CuSC>4), carbonium ion salts (e.g., triphenylmethyl antimony hexachloride, triphenylmethyl aluminum tetrachloride, triphenylmethyl tin pentachloride, triphenylmethyl boron tetrachloride, triphenylmethyl dimethyl aluminum dichloride, triphenylmethyl-chloro-boron trifluoride, triphenylrnethyl-bromo-antimony pentachloride, and diphenylmethyl antimony hexachloride), ionizing radiation, and other polymerization initiators known by those of ordinary skill in the art.

[0061] In exemplary embodiments, the polymerization is performed at a temperature ranging from about -78 °C to about 200 °C, about -20 °C to about 150 °C, about -10 °C to about 120 °C, or about 0 °C to 50 °C. In exemplary embodiments, the polymerization is performed at an ambient temperature (i.e. , at an average temperature of a specific environment, such as a room or the area surrounding a piece of equipment). Those of ordinary skill in the art are aware that the temperature ranges the polymerization can be performed at depends on the boiling point of the solvent used to carry out the reaction. Accordingly, those of ordinary skill in the art are readily capable of determining appropriate temperature ranges to perform the polymerization reaction.

[0062] In exemplary embodiments, the polymerization is performed for at most 24 hours, about 1 minute to about 1 hour, about 0.5 hours to about 1 week, about 3 hours to about 24 hours, about 6 hours to about 24 hours, about 12 hours to about 2101715-001297

[0063] -IQ-

[0064] 24 hours, about 24 hours to about 96 hours, about 1 hour to about 96 hours, or about 96 hours to about 1 week. In exemplary embodiments, the polymerization reaction is performed for more than 1 week. Those of ordinary skill in the art are readily aware that the amount of time the polymerization reaction is performed depends on the monomer(s) used to create the polymer and the length of the desired polymer product. Accordingly, those of ordinary skill in the art are readily capable of determining appropriate amount of time to perform the polymerization reaction.

[0065] In exemplary embodiments, the polymerization is performed in the presence of a Reversible Addition-Fragmentation Chain Transfer (RAFT) agent. Possible RAFT agents that can be used in the polymerization reaction include, but are not limited to, thiocarbonyl-thio groups {e.g., dithioesters, dithiocarbamates, trithiocarbonates, and xanthates). Examples of other RAFT agents that can be used in the polymerization reaction include those described in “The Chemistry of Radical Polymerization”, Graeme Moad & David H. Solomon, 2ndrev. ed., 2006, Elsevier, p. 508-514, and Mineto Uchiyama, Kotaro Satoh, Masami Kamigaito, “Cationic RAFT and DT polymerization”, Prog. Polym. Sci., 2022, 124, 101485, the contents of which are incorporated herein in their entireties by reference.

[0066] In exemplary embodiments, the polymerization is controlled by a radical polymerization methodology such as, but not limited to, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), free-radical polymerization, and stable free radical polymerization (SFRP).

[0067] In exemplary embodiments, the polymerization is a cationic polymerization ( / .e., a chain-growth polymerization where a carbocation is used to initiate the polymerization process). Those of ordinary skill in the art are aware of conditions and reagent required to perform a cationic polymerization (see Singha S. et al. “Recent Developments on Cationic Polymerization of Vinyl Ethers”, Acs Polym. Au., 2024, 4, 3, 189-207; Ouchi, M. et al. “Stereoregulation in Cationic Polymerization by Designed Lewis Acids. 1. Highly Isotactic Poly(isobutyl vinyl ether) with Titanium-Based Lewis Acids”, Macromolecules 1999, 32, 20, 6407-6411 ; Teator, A. J., & Leibfarth, F. A. “Catalyst-controlled stereoselective cationic polymerization of vinyl ethers”, Science, 2019, 363(6434), 1439-1443; and George Odian, 2004, 2101715-001297

[0068] -11-

[0069] “Principles of Polymerization”, 4thEdition, Wiley-lnterscience). Accordingly, those of ordinary skill in the art would be readily capable of performing a cationic polymerization reaction to produce any one of the poly(vinyl ether) polymers disclosed herein.

[0070] In exemplary embodiments, the polymerization is a radical polymerization (i.e., a chain-growth polymerization process where radicals are used to initiate the polymerization process). Those of ordinary skill in the art are aware of conditions and reagent required to perform a radical polymerization (see Goto, A., Fukuda, T. “Kinetics of living radical polymerization”, Prog. Polym. Sci., 2004, 29(4), 329-385; Sugihara, S. et al. “Direct Radical Polymerization of Vinyl Ethers: Reversible Addition-Fragmentation Chain Transfer Polymerization of Hydroxy-Functional Vinyl Ethers”, Macromolecules 2016, 49, 5, 1563-1574; and George Odian, 2004, “Principles of Polymerization”, 4thEdition, Wiley-lnterscience). Accordingly, those of ordinary skill in the art would be readily capable of performing a radical polymerization reaction to produce any one of the poly(vinyl ether) polymers disclosed herein.

[0071] In exemplary embodiments, the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds includes a Williamson Ether synthesis. A Williamson Ether synthesis includes the formation of an ether through the reaction of a phenoxide formed from one of the phenolic compounds (via deprotonation with a non-nucleophilic base) and an alkyl halide. In exemplary embodiments, the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds includes reacting the one or more phenolic compounds with a 1 ,2-halogenated ethane {e.g., 1 ,2-dichloroethane, 1 ,2-dibromoethane, and 1 ,2-diiodethane) to create an intermediate possessing one of the following structures: 2101715-001297

[0072] -12- wherein: R is selected from H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups; and 2101715-001297

[0073] -13-

[0074] X is a halogen; and using an elimination mechanism to obtain the one or more vinyl ether- functionalized monomers. In exemplary embodiments, the elimination mechanism includes reacting the intermediate possessing with a non-nucleophilic base.

[0075] In exemplary embodiments, the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds includes reacting the obtained one or more phenolic compounds with a base or metal catalyst in acetylene. Possible metal catalysts that can be used include, but are not limited to, those based on mercury, gold, palladium, and iridium (e.g., bis(1 ,5-cyclooctadiene)diiridium(l)dichloride), catalysts containing the chemical formula MCln where M is Iron (Fe), Gallium (Ga), Tin (Sn), Indium (In), Zinc (Zn), Bismuth (Bi), Titanium (Ti), Silicon (Si), Germanium (Ge), or Antimony (Sb), and those disclosed in B. Spiegelberg et al., Adv. Synth. Catal. 2022, 364, 1251 ; Winternheimer, D.J. et al, “Methods for Vinyl Ether Synthesis”, Synthesis, 2010(15): 2497-2511 ; and Kanazawa, A. et al. “Major Progress in Catalysts for Living Cationic Polymerization of Isobutyl Vinyl Ether: Effectiveness of a Variety of Conventional Metal Halides”, Macromolecules 2009, 42, 12, 3965-3972, the contents of which are hereby incorporated in their entireties by reference.

[0076] In exemplary embodiments, the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds includes reacting the obtained one or more phenolic compounds with vinyl acetate in the presence of a catalyst and / or a base. Possible catalysts and bases that can be used in these embodiments can be found in David J. Winternheimer, Ryan E. Shade, Craig A. Merlic, “Methods for Vinyl Ether Synthesis”, Synthesis 2010(15): 2497-2511 ; and Teong, S.P et al. “Direct vinylation of natural alcohols and derivatives with calcium carbide”, Green Chemistry, 2017, 19(7), 1659-1662, the contents of which are hereby incorporated in their entireties by reference.

[0077] In exemplary embodiments, the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds includes reacting the obtained one or more phenolic compounds with a metal carbide, optionally in a presence of a catalyst. Possible carbides that can be used include, but are not limited to, calcium carbide, silicon carbide (SiC), and boron 2101715-001297

[0078] -14- carbide (B4C). Possible carbides and catalysts that can be used also include those disclosed in Ryosuke Matake, Yusuke Adachia, and Hiroshi Matsubara, “Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH / DMSO)”, Green Chemistry, 2016, 9, the content of which is hereby incorporated in its entirety by reference.

[0079] In exemplary embodiments, the one or more vinyl ether-functionalized monomers have one of the following structures: wherein:

[0080] R is selected from H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups.

[0081] Another aspect of the present disclosure is a poly(vinyl ether) polymer of Formula I: 2101715-001297

[0082] (Formula I) wherein:

[0083] R1is selected from -H or -OCH3;

[0084] R2is selected from -H or -OCH3;

[0085] R3is selected from -H or -OCH3;

[0086] R4is selected from -H or -OCH3;

[0087] R5is selected from H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups; and n is an integer that is at least 10 or more, wherein the poly(vinyl ether) polymer possesses a crystallinity of about 0% to about 50%.

[0088] In exemplary embodiments, the poly(vinyl ether) polymer is lignin-derivable. As used herein, a “lignin-derivable” poly(vinyl ether) polymer is a polymer that has been formed from one or more vinyl ether-functionalized compounds that can originate from a lignin source.

[0089] In exemplary embodiments, the poly(vinyl ether) polymer possesses a crystallinity of about 0% to about 50%, of about 20% to 50%, of about 30% to about 50%, or of about 40% to 50%. Those of ordinary skill in the art will appreciate that the polymer’s crystallinity is affected by the temperature and the processing history and will appreciate that the polymer’s crystallinity is present at temperatures below the polymer’s melting temperature or degradation temperature, whichever is lower. 2101715-001297

[0090] -16-

[0091] Those of ordinary skill are readily capable of determining the degradation temperature of a polymer with, for example, well-known thermogravimetric techniques.

[0092] In exemplary embodiments, the poly(vinyl ether) polymer possesses a glass transition temperature ranging from about 0 °C to about 200 °C, about 50 °C to about 200 °C, about 80 °C to about 150 °C, or about 100 °C to 150 °C.

[0093] In exemplary embodiments, the poly(vinyl ether) polymer possesses a degradation temperature ranging from about 250 °C to about 350 °C, about 250 °C to about 300 °C, about 270 °C to about 320 °C, or about 290 °C to 310 °C.

[0094] In exemplary embodiments, the poly(vinyl ether) polymer possesses a dispersity ranging from about 1.2 to about 15.0, about 1.2 to about 10.0, about 1.2 to about 3.0, about 1.5 to about 12.0, about 2.0 to about 10.0, about 3.0 to about 8.0, about 4.0 to about 6.0, or at least 15.0. Those of ordinary skill in the art are readily aware that the dispersity of the poly(vinyl ether) polymer can be found be dividing the weight-average molecular weight of a polymer sample by the numberaverage molecular weight of a polymer sample.

[0095] In exemplary embodiments, the poly(vinyl ether) polymer possesses a number-average molecular weight ranging from about 1 kg / mol to about 500 kg / mol, about 5 kg / mol to about 500 kg / mol, about 100 kg / mol to 400 kg / mol, about 200 kg / mol to about 300 kg / mol, or at least 500 kg / mol.

[0096] In exemplary embodiments, the poly(vinyl ether) polymer possesses a weight-average molecular weight ranging from about 1 kg / mol to about 7500 kg / mol, about 6 kg / mol to about 7500 kg / mol, about 50 kg / mol to about 7000 kg / mol, about 100 kg / mol to 7000 kg / mol, about 1000 kg / mol to about 6000 kg / mol, about 2000 kg / mol to 4000 kg / mol, or at least 7500 kg / mol.

[0097] In exemplary embodiments, the poly(vinyl ether) polymer possesses a Hansen distance (Ra) in a solvent that ranges from about 10.0 to about 40.0, about 13.0 to about 25.0, or about 15.0 to about 20.0. The solvent can be selected from, but is not limited to, anisole, chloroform, toluene, dichloromethane, tetrahydrofuran, dimethylsulfoxide, N-N-dimethylformamide, acetone, diethyl ether, hexane, methanol and water. 2101715-001297

[0098] -17-

[0099] In exemplary embodiments, the poly(vinyl ether) polymer possesses a solvent dispersive contribution (6d) of about 10.0 to about 20.0 MPa1 / 2, or about 13.0 to about 19.0 MPa1 / 2in a solvent. The solvent can be selected from, but is not limited to, anisole, chloroform, toluene, dichloromethane, tetrahydrofuran, dimethylsulfoxide, N-N-dimethylformamide, acetone, diethyl ether, hexane, methanol and water.

[0100] In exemplary embodiments, the poly(vinyl ether) polymer possesses a solvent dipolar contribution (<5P) of 0.0 to about 20.0 MPa1 / 2, about 1.0 to about 16.0 MPa1 / 2, or about 3.0 to about 13.0 MPa1 / 2in a solvent. The solvent can be selected from, but is not limited to, anisole, chloroform, toluene, dichloromethane, tetrahydrofuran, dimethylsulfoxide, N-N-dimethylformamide, acetone, diethyl ether, hexane, methanol and water.

[0101] In exemplary embodiments, the poly(vinyl ether) polymer possesses a solvent hydrogen-bonding contribution (6h) of 0.0 to about 45.0 MPa1 / 2, about 4.0 to about 25.0 MPa1 / 2, or about 6.0 to about 13.0 MPa1 / 2in a solvent. The solvent can be selected from, but is not limited to, anisole, chloroform, toluene, dichloromethane, tetrahydrofuran, dimethylsulfoxide, N-N-dimethylformamide, acetone, diethyl ether, hexane, methanol and water.

[0102] In exemplary embodiments, the poly(vinyl ether) polymer possesses greater than 50% racemic diads, greater than 60% racemic diads, greater than 70% racemic diads, greater than 80% racemic diads, greater than 90% racemic diads, about 50% to about 90% racemic diads, or about 50% to 99.99% racemic diads

[0103] The inventors have surprisingly discovered that the poly(vinyl ether) polymers disclosed herein could not only be produced from renewable sources {e.g., lignin), but they also are capable of possessing semi-crystalline properties when the polymerization is performed at temperatures well above -78 °C, for example temperatures ranging from about 0 °C to the degradation temperature of the polymer and ambient temperatures, which have not been observed with petroleum-derivable or derived poly(vinyl ether) polymers. Without being bound to any particular theory, the surprising semi-crystalline properties of the poly(vinyl ether) polymers disclosed herein could be linked to their high tacticty. Tacticity refers to the spatial arrangement of pendent groups (side groups) along the main 2101715-001297

[0104] -18- chain backbone and there are three main types of tacticty: isotactic (all pendent groups on the same side), syndiotactic (alternating pendent groups), and atactic (random arrangement). The poly(vinyl ether) polymers disclosed herein have been found to possess high syndiotactic profiles {e.g., high percentages of racemic diads). In view of these surprising discoveries, the poly(vinyl ether) polymers can behave similarly to syndiotactic polystyrene and thus be blended with other additives to produce mixtures or blends with improved physical properties.

[0105] Accordingly, another aspect of the present disclosure is a composition including one or more of the poly(vinyl ether) polymers disclosed herein and one or more additives. The additives can include, but are not limited to, polymer modifiers, performance enhancers and processing aids. Examples of these additives include, but are not limited to, glass fiber composites, clay nanocomposites, elastomerthermoplastic blends, and those disclosed in Andrews, S.M., 2010, Additives, “Encyclopedia of Polymer Science and Technology”; and Baur, E.; Osswald, T. A.; Rudolph, N., 2019, Additives, Fillers, and Fibers, “Plastics Handbook: The Resource for Plastics Engineers”. The additives can also include any additive that syndiotactic polystyrene and syndiotactic polymers have been blended or mixed with. Those of ordinary skill in the art are aware of other additives that are compatible with the disclosed compositions and thus are readily capable of creating the disclosed compositions.

[0106] Another aspect of the present disclosure is an article or product formed from any one or more of the poly(vinyl ether) polymers or compositions disclosed herein. The article or product can be, but is not limited to, electrical components or connectors, heating, ventilation, and air conditioning (HVAC) components, water handling components, household appliance components, lacquer resins, plasticizers, adhesives, paints, copolymer compositions such as those for fire retardants, marine coatings, anticorrosion agents, thickening agents, bio-inert interfaces, optical lenses, packaging products, clothing articles, electronics, medical devices, construction gear (e.g., safety helmets and roofing materials), and storage materials (e.g., plastic bags and bottles).

[0107] Examples 2101715-001297

[0108] -19-

[0109] The present disclosure will be described in more detail with reference to the following Examples, which shows exemplary embodiments in accordance with the present disclosure. The present disclosure is not limited to these exemplary embodiments.

[0110] Example 1

[0111] Materials

[0112] 2,6-dimethoxy-4-methylphenol (4-methylsyringol, 99%, Thermo Scientific), 1,2-dibromoethane (98%, Thermo Scientific), potassium tert-butoxide (pure, 1M in tetrahydrofuran, Thermo Scientific), hydrogen chloride solution (1.0 M in diethyl ether, Sigma-Aldrich), carbon disulfide (anhydrous, > 99%, Sigma-Aldrich), sodium ethanethiolate (technical grade, Sigma Aldrich), isobutyl vinyl ether (99%, Sigma- Aldrich), sodium hydroxide (certified ACS, Fisher Chemical), sodium chloride (certified ACS, Fisher Chemical), magnesium sulfate (anhydrous, certified powder, Fisher Chemical), boron trifluoride etherate (ca. 48% BF3, Thermo Scientific), tin (IV) chloride (stannic chloride, 99.99% [metals basis], Thermo Scientific), triethylamine (reagent grade, Fisher Chemical), dichloromethane (HPLC grade, Fisher Chemical), ethyl acetate ( certified ACS, Fisher Chemical), hexanes (certified ACS, Fisher Chemical), methanol (Optima, Fisher Chemical), diethyl ether (laboratory grade, Fisher Chemical), tetra hydrofuran (anhydrous, > 99.8%, Thermo Scientific), toluene (anhydrous, 99.8%, Thermo Scientific), dichloromethane (anhydrous, 99.9%, Thermo Scientific), deuterated chloroform (CDCI3, 99.8 atom% D, Thermo Scientific), and deuterated toluene (CzDs, 99.6 atom% D, Cambridge Isotope Laboratories) were used as received.

[0113] Synthesis of 4-methylsyrlngyl vinyl ether (MeSyrVE) 2101715-001297

[0114] Representative synthesis of 1 -bromoethyl-4-methylsyringol: 2.5 g of 4- methylsyringol (1 eq., 14.9 mmol), 5.6 g of 1 ,2-dibromoethane (2 eq., 29.7 mmol), and 1.2 g of sodium hydroxide (2 eq., 29.7 mmol) were sealed in a 20-mL pressurerelief vial with 4.8 mL of deionized water and a stir bar. The mixture was heated to 80 °C, and the reaction proceeded for 24 h with stirring. The contents of the vial then were cooled to 23 °C, transferred to a separatory funnel, and mixed with dichloromethane and deionized water. The aqueous fraction was discarded, and the organic fraction was washed twice more with deionized water and once with a saturated aqueous sodium chloride solution. The organic fraction was retained and dried over magnesium sulfate and, subsequently, the solvent was removed by rotary evaporation. The concentrated, crude oil was run on a flash column to isolate the final product (Biotage Selekt, Biotage Star silica gel column, 0 to 20 vol.% linear gradient of ethyl acetate in hexanes over 10 column volumes, then 20 to 100 vol.% linear gradient of ethyl acetate in hexanes over 6 column volumes). The product fraction was concentrated by rotary evaporation, and trace solvent was removed under dynamic vacuum for 24 h at 23 °C to yield the product as a viscous, clear liquid. Yield: 27 mol%.1H NMR 5 ppm (CDCb, 400 MHz): 6.43 (s, 2H), 5.35 (s, 2H), 4.32 (s, 2H), 3.85 (s, 6H), 2.34 (s,3H). GC-MS: m / z found = 274; m / z expected = 274. 2101715-001297

[0115] -21-

[0116] Representative synthesis of 4-methylsyringyl vinyl ether (MeSyrVE): 2.0 g (1 eq., 8.4 mmol) of 1-bromoethyl-4-methylsyringol was mixed with 2 mL of anhydrous tetrahydrofuran, and the solution was sparged with Ar for 5 min. Then, 7.3 mL (1 eq., 8.4 mmol) of 1 M potassium tert-butoxide in tetrahydrofuran was added dropwise to the solution under Ar flow, and the solution was stirred for 15 min. 1.0 mL (0.1 eq., 1.0 mmol) of additional 1M potassium terf-butoxide in tetra hydrofuran was added dropwise to the solution under Al flow, and the solution was stirred for another 45 min. The solution then was concentrated under rotary evaporation, and the resulting crude product mixture was transferred to a separatory funnel and mixed with dichloromethane and deionized water. The aqueous fraction was discarded, and the organic fraction was washed twice more with deionized water and once with a saturated aqueous sodium chloride solution. The organic fraction then was dried over magnesium sulfate and concentrated by rotary evaporation. The concentrated, crude oil was run on a flash column to isolate the final product (Biotage Selekt, Biotage Star silica gel column, 0 vol.% ethyl acetate hexanes for 2 column volumes, then 0 to 20 vol.% linear gradient of ethyl acetate in hexanes over 10 column volumes, then 20 to 100 vol.% linear gradient of ethyl acetate in hexanes over 6 column volumes). The product fraction was concentrated by rotary evaporation, and trace solvent was removed under dynamic vacuum for 24 h at 60 °C to yield the product as a viscous, clear liquid. Yield: 78 mol%.1H NMR 5 ppm (CDCb, 400 MHz): 6.56 (dd, 1 H), 6.43 (s, 2H), 4.35 (d, 1 H), 4.15 (d, 1 H), 3.83 (s, 6H), 2.34 (s, 3H). GCMS: m / z found= 194; m / z expected = 194.

[0117] Synthesis of S-1-isobutoxylethyl-S'-ethyltrithiocarbonate 2101715-001297

[0118] -22-

[0119] 2.1 g (1 eq., 25.0 mmol) of sodium ethanethiolate was mixed with 10 mL of diethyl ether while stirring at 0 °C. 1.6 mL of carbon disulfide (1.1 eq., 27.0 mmol) then was added to this solution over 15 min, and the reaction proceeded for 2 h at 0 °C to generate sodium ethyltrithiocarbonate. Separately, 3.5 mL (1.1 eq., 27.0 mmol) of isobutyl vinyl ether was mixed with 30 mL (1.2 eq., 30.0 mmol) of 1.0 M hydrogen chloride solution in diethyl ether while stirring at 23 °C to generate hydrogen chloride-adducted isobutyl vinyl ether (IBVE-HCI). The IBVE-HCI solution then was added dropwise to the sodium ethyltrithiocarbonate solution over 30 min while stirring at 0 °C. The temperature of the new solution was allowed to rise to 23 °C as the reaction proceeded for 2 h. The reaction solution was diluted with 20 mL of diethyl ether, and the reaction was quenched with 20 mL of aqueous sodium hydroxide (5 wt.%) solution. The reaction solution was transferred to a separatory funnel, the aqueous phase was discarded, and the organic phase was washed with deionized water and a saturated sodium chloride aqueous solution. The organic fraction then was dried with magnesium sulfate, concentrated by rotary evaporation, and dried under dynamic vacuum for 24 h at 23 °C to yield the final product as a yellow liquid. Yield: 64 mol%.1H NMR (400 MHz, CDCh) 5 (ppm): 5.98 (q, 1 H), 3.49-3.23 (m, 4H), 1.84 (m, 1 H), 1.71 (d, 3H), 1.34 (t, 3H), 0.92 (d, 6H). GC-MS: m / z found= 238; m / z expected = 238.

[0120] Cationic polymerization of MeSyrVE

[0121] B.F?or S11CI4 initiator

[0122] Anhydrous solvent, RAFT agent temperature, and length indicated in Table 1

[0123] General procedure: MeSyrVE was added to an oven-dried flask and dried under dynamic vacuum at 50 °C for 16 h prior to polymerization. MeSyrVE then was diluted in anhydrous toluene, tetrahydrofuran, or dichloromethane. In the controlled cationic polymerizations, a stock solution of S-1-isobutoxylethyl-S'- ethyltrithiocarbonate (reversible addition-fragmentation chain transfer agent, RAFT agent) was prepared in the same solvent as the monomer and mixed with the 2101715-001297

[0124] -23- monomer at this point. The molar amount of RAFT agent in the monomer solution was ten times the molar amount of the eventually added initiator. The flask then was sealed, sparged with Ar for 5 min., and brought to the desired polymerization temperature. Polymerizations at -78 °C were maintained in a dry ice and acetone bath; polymerizations at 0 °C were carried out using a recirculating, refrigerated water / ethylene glycol bath (Isotemp 3006S); and polymerizations at 70 °C were maintained in a heated ethylene glycol bath. Boron trifluoride etherate or stannic chloride initiator was dissolved in the same solvent as the monomer to create a stock solution and then injected into the flask to initiate polymerization. The reaction was stirred for the indicated time and then quenched by addition of 20 vol.% triethylamine in dichloromethane. The polymer solution was diluted in dichloromethane, and the polymer was precipitated into -20 °C methanol. Then, the mixture was centrifuged, and the supernatant was decanted to isolate the polymer. This purification process - dissolution of the polymer in dichloromethane, precipitation in -20 °C methanol, centrifugation, and decantation of supernatant- was repeated to yield the final purified polymer, poly(4-methylsyringyl vinyl ether) (pMeSyrVE).

[0125] Compatible and incompatible reaction conditions for the above general procedure can be found in Table 1.

[0126]

[0127] Table 1: Cationic polymerization conditions for MeSyrVE

[0128] 2101715-001297

[0129] -25-

[0130] Proton (1H) and carbon (13C) nuclear magnetic resonance (NMR) spectroscopy

[0131] NMR spectroscopy was carried out on Bruker Neo 400 MHz and Bruker Neo 600 MHz spectrometers. Small-molecule samples and polymerization aliquots to analyze conversions were dissolved in CDCh for analysis by1H NMR spectroscopy. Conversions for MeSyrVE polymerizations were determined by comparing integrations of a monomer methylidene peak at 6 = 4.35 ppm to a broad polymer aromatic peak centered at 5 of about 6.20 ppm. Polymer samples to analyze tacticity were dissolved in CzDs and heated to 80 °C in situ for analysis by13C NMR spectroscopy. Background subtractions and phase corrections were performed in Mnova software (version 15.0.0, Mestrelab Research), and peak fitting of13C spectra to Lorentzian curves for analysis of tacticity was performed in Origin software (version 2023b, OriginLab).

[0132] Gas chromatography-mass spectrometry (GC-MS)

[0133] Products of small-molecule synthesis were analyzed on a Shimadzu QP2020 gas chromatograph with an Rtx-5MS column connected to a flame ionization detector and a mass spectrometer. Solutions were injected with an AOC- 20i autosampler at 300 °C under He flow with a 30:1 split ratio into a column set to 50 °C, held at 50 °C for 1 min, and then ramped linearly to 315 °C at a rate of 15 °C / min.

[0134] Gel permeation chromatography (GPC)

[0135] Relative GPC profiles were obtained using a Tosoh EcoSEC HLC-8320 with a TSKgel HHR-H guard column, two TSKgel GMHHR-N columns in series, and a refractive index detector. Tetrahydrofuran was used as the eluent with a flow rate of 1.0 mL / min. The GPC columns were heated to 40 °C during analysis. Relative molecular weights were obtained by GPC calibration to polystyrene standards (PStQuick C and PstQuick D, Tosoh Bioscience). Number-average molecular weights, weight-average molecular weights, and dispersities were calculated using SECview software (version 1.2.1757).

[0136] Absolute molecular weights were determined from GPC profiles captured on a chromatograph equipped with an Agilent isocratic pump, degasser, and autosampler; a Viscogel l-series 5 pm guard column; two ViscoGel l-series G3078 2101715-001297

[0137] -26- mixed bed columns; a Wyatt Optilab T-rEX refractive index detector; and a Wyatt miniDAWN Treos light scattering detector operating at 690 nm. Tetrahydrofuran was used as the eluent with a flow rate of 1.0 mL / min. The GPC columns were held at 25 °C during analysis. Absolute molecular weights and molecular mass distributions were calculated using Wyatt ASTRA software, and the refractive index increment (dn / dc) was calculated assuming 100% mass recovery.

[0138] Differential scanning calorimetry (DSC)

[0139] DSC experiments were conducted on a TA Instruments Discovery differential scanning calorimeter. pMeSyrVE was heated from 30 °C to 150 °C at 15 °C / min, held at 150 °C for 2 min., cooled at 15 °C / min to -50 °C, and heated to 150 °C at 15 °C / min. The reported glass transition temperature is taken from the second heating profile. pMeSyrVE was heated from 30 °C to 150 °C at 10 °C / min, annealed at 150 °C for 5 min, cooled at 10 °C / min to -20 °C, and heated to 150 °C at 10 °C / min. The sample then was annealed at 150 °C for 5 min, cooled to -20 °C and heated to 150 °C at 10 °C / min over four more cycles, for a total of six annealing, heating, and cooling cycles.

[0140] Thermogravi metric analysis (TGA)

[0141] TGA experiments were conducted on a TA Instruments TGA 5500. Thermal decomposition profiles were obtained using a 10 °C / min linear heating ramp from 50 °C to 600 °C under N2 or air flow.

[0142] X-ray diffraction (XRD)

[0143] XRD experiments were performed on a Bruker D8 instrument with a monochromatic Cu KaX-ray source (A = 1.54 A) and a 1.2 mm slit width. Data were collected in 20 = 0.05° increments with 1 s exposure per data point and averaged over five scans. No smoothing or other manipulation of the spectra was performed. Background subtractions and Gaussian peak fittings for analysis of crystallinity were performed using Origin software (version 2023b, OriginLab).

[0144] Wide-angle X-ray scattering (WAXS)

[0145] WAXS experiments were performed on a XENOCS Xuess 2.0 instrument with a monochromatic Cu KaX-ray source (A = 1.54 A) and a Dectris PILATUS 300K detector. pMeSyrVE was mounted between Kapton tape and placed in the sample chamber under dynamic vacuum to minimize background scattering from 2101715-001297

[0146] -27- air. A sample-to-detector distance of 72 mm was used for WAXS experiments. The WAXS profile of Kapton tape was subtracted as background from the pMeSyrVE 2D WAXS profile. The data were otherwise unmanipulated. The transformation of the 2D WAXS profile to a 1D profile was performed using instrument software.

[0147] Solubility Analysis Calculations

[0148] Hansen solubility parameters for pMeSyrVE were calculated using group contribution methods to first estimate the van der Waals molar volume of pMeSyrVE and then determine the dispersive (bd), dipolar (<5P), and hydrogenbonding (bh) contributions of pMeSyrVE to solubility. Data for calculations were taken from "Polymer Handbook," J. Brandrup, E.H. Immergut, E.A Grulke, 4thedition, John Wiley & Sons, 1999. A molar volume of 130 cm3 / mol was calculated for pMeSyrVE, and, in turn, solubility parameters of 5d = 24.4 MPa1 / 2, 5P= 5.4 MPa1 / 2, and bh = 8.3 MPa1 / 2were calculated for pMeSyrVE. The Hansen distance (Ra„ "The three dimensional solubility parameter and solvent diffusion coefficient," C. M. Hansen, Technical University of Denmark, 1967) between pMeSyrVe and organic solvents was calculated according to:

[0149] Ra values between pMeSyrVE and several organic solvents are tabulated in Table 2.

[0150] Table 2: Hansen distances between pMeSyrVE and common organic solvents 2101715-001297

[0151] -28-

[0152] Results and Discussion

[0153] Synthesis of 4-methylsyringyl vinyl ether (MeSyrVE) from lignin-derivable 4-methylsyringol

[0154] MeSyrVE was synthesized as described above through a Williamson ether reaction of 4-methylsyringol and 1,2-dibromoethane to form a halogenated intermediate followed by an elimination reaction with potassium tert-butoxide to obtain the final product (see FIG. 1). The design of MeSyrVE to include substitutions at both phenolic ortho positions and the para position was conceived to minimize undesired intra- and intermolecular Friedel-Crafts reactions during cationic polymerization. Other synthetic routes can also be used to obtain MeSyrVE, including iridium-catalyzed transfer vinylations or the reaction of acetylene or calcium carbide with 4-methylsyringol in the presence of a base.

[0155] Synthesis of MeSyrVE polymers

[0156] MeSyrVE then was polymerized to pMeSyrVE via conventional and controlled cationic methods (see Table 1). Cationic polymerizations are commonly performed at dry ice temperatures (-78 °C) to suppress chain transfer and termination events while achieving stereoregularity. Unusually, no conversion was noted in the polymerization of MeSyrVE at -78 °C over 4-6 hours, potentially suggesting an energetic barrier in the propagation of the sterically bulky monomers. In contrast, polymerization of MeSyrVE reached 28-84% conversion at temperatures ranging 0 - 70 °C over 1 to 96 h (Table 1). The ability to polymerize MeSyrVE under these conditions - especially at ambient temperature - provides insight into leveraging monomer design to reduce energy inputs for cationic polymerizations by removing requirements to maintain low temperatures.

[0157] Relative number-average molecular weights ( / Wn) and dispersities (£>m) of pMeSyrVE polymers in Table 1 were calculated from molecular weight distributions captured by gel permeation chromatography (GPC) against polystyrene standards. 2101715-001297

[0158] -29-

[0159] MnS and 0ms of pMeSyrVE samples synthesized by conventional cationic methods range from 7.1 to 13.5 kg mol'1and 1.4 to 2.7, respectively, with the exception of two polymerizations that gelled (entries 6 and 11 in Table 1). Of note, reported calculated molecular weights and dispersities are influenced by tailing in the GPC profiles and this tailing could be influenced by (and subsequently was mitigated by) solvent choice for GPC, but it could not be eliminated. Two polymers also were synthesized by cationic reversible addition-fragmentation chain transfer (RAFT) to examine the fidelity of the MeSyrVE monomer in controlled polymerization methods and to obtain pMeSyrVE samples with narrow molecular mass distributions for determination of absolute molecular weight. Evaluation of absolute molecular weight by multi-angle light scattering for a pMeSyrVE sample (entry 14 of Table 1 , dn / dc = 0.14) synthesized by cationic RAFT returned Mnand £>m values of 18.8 kg mol'1and 1 .2, respectively; the corresponding Mnand £>m values calculated by relative GPC were 5.9 kg mol'1and 1.5, respectively.

[0160] Prototypical alkyl and benzyl vinyl ethers form isotactic-enriched ( / .e., meso diad-enriched, m diad-enriched) polymers upon cationic polymerization due to the presence of a bulky counteranion near the cationic propagating species that imparts a preferential monomer addition face. For example, a typical isobutyl vinyl ether polymerization by living cationic methods leads to a polymer with m = 68%. Significant work in initiator and co-catalyst design has demonstrated pathways to enhance the degree of isotacticity in poly(vinyl ethers) to m > 90%. In contrast, syndiotactic poly(vinyl ethers) are unusual and primarily result from the polymerization of bulky monomers in polar solvents. The chemistry of the active polymer chain end is hypothesized to play a more significant role in mediating the stereochemistry of monomer addition in these cases than in prototypical vinyl ether polymerizations, in which the chemistry of the free counterion dominates.

[0161] The tacticity of poly(vinyl ethers) can be estimated through13C nuclear magnetic resonance (NMR) spectroscopic analysis of the backbone methine protons at a downfield shift near 37 - 45 ppm. Methine peaks spanning about 37 to 41 ppm are typically assignable to m diads, and methine peaks spanning about 41 to 45 ppm are typically assignable to racemic (r) diads. A representative13C NMR spectra of pMeSyrVE in FIG. 2 showed a significant syndiotactic character (r = 2101715-001297

[0162] -30-

[0163] 71%) in comparison to conventional poly(alkyl or benzyl vinyl ethers). The syndiotactic enrichment was consistent among pMeSyrVE samples synthesized over the range of polymerization temperatures, solvents, and polymerization strategies, suggesting that the monomer chemistry ( / .e., bulkiness and polarity from tri-substituted aromatic chemistry) likely played a substantial role in controlling pMeSyrVE tacticity.

[0164] Understanding the solubilities and thermal properties of polymers are critical for determining appropriate material applications and processing methods. These polymer characteristics are particularly relevant for material handling when melt processing is inaccessible based on polymer transition and decomposition temperatures. The Hansen distance (F?a), a measure of the distance between Hansen solubility parameters for a solute and its solvent in Hansen space, offers a numerical method for assessing polymer solubility in organic solvents. Dispersive (<5d), dipolar (<5P), and hydrogen-bonding (<5h) components of solubility were calculated for pMeSyrVE by group contribution methods as discussed above to obtain 5d= 24.4 MPa1 / 2, <5P= 5.4 MPa1 / 2, and <5h= 8.3 MPa1 / 2(Table 2). These calculated values support visually observed solubility of pMeSyrVE in a broad range of organic solvents, including tetrahydrofuran (Ra= 15.2 MPa1 / 2), chloroform (Ra= 13.6 MPa1 / 2), toluene (F?a= 14.8 MPa1 / 2), acetone (F?a= 18.5 MPa1 / 2), and dichloromethane (Ra= 15.0 MPa1 / 2).

[0165] In complement, the thermal properties of pMeSyrVE were investigated. pMeSyrVE exhibited a Tgof 100 °C, as determined by differential scanning calorimetry (DSC) (FIG. 3). Assessment of pMeSyrVE thermal decomposition by thermogravimetric analysis (TGA) in N2 identified temperatures of 5% mass loss (Td,5%) and 50% mass loss (Td,so%) at 304 and 348 °C, respectively (FIG. 4). Further, Td,s% and Td,so% of pMeSyrVE in air are determined to be 305 and 353 °C, respectively (FIG. 5). The near-identical Td values for pMeSyrVE in N2 and air indicate that the thermal decomposition mechanisms for pMeSyrVE at temperatures below about 360 °C are independent of atmospheric influences. No melting temperature (Tm) was noted by DSC below the pMeSyrVE degradation temperatures determined by TGA. However, the two-thirds empirical relationship between Tgand Tm (in Kelvin) would estimate that the Tmof a semi-crystalline 2101715-001297

[0166] -31- pMeSyrVE is about 285 °C, so the absence of a melting event in the DSC profile is not expected to be conclusive of an amorphous polymer. In total, the thermal and solubility properties of pMeSyrVE imply that pMeSyrVE is suitable for processing by solvent-based methods and has a significant window of thermal stability.

[0167] The ability to achieve stereoregularity in polymer design through cationic synthesis offers a pathway toward obtaining semi-crystalline chain-growth polymers from lignin-derivable monomers. X-ray diffraction (XRD) and wide-angle X-ray scattering (WAXS) patterns of pMeSyrVE showed distinct crystalline peaks emerging from an amorphous halo (see FIG. 6) which indicated that pMeSyrVE is a semi-crystalline polymer. A 24% degree of crystallinity was estimated for pMeSyrVE by comparing the area under Gaussian fits of the crystalline peaks to the area of the amorphous halo region. This value is on par with reported about 30% crystallinities for poly(al kyl vinyl ethers) calculated by X-ray methods. As another point of comparison, crystallinities of syndiotactic polystyrene samples range from about 10 to 60%. Syndiotactic polystyrene is widely reported to be brittle and have a low impact strength. pMeSyrVE is similarly qualitatively observed to be brittle and, therefore, could be useful in composites or polymer blends parallel to those in which syndiotactic polystyrene is currently used, such as glass fiber composites, clay nanocomposites, and elastomer-thermoplastic blends.

[0168] The percent crystallinity of pMeSyrVE was also estimated from the change in the polymer’s heat capacity (ACP) at its Tg(see FIG. 7). pMeSyrVE does not have a known ACPat Tgfor a 100% amorphous sample, so the mobile bead approximation, which assumes an average increase in CPat Tgof 11.5 ± 1.7 J mol-1K’1, was used. The closest polymer structure to pMeSyrVE with a reported ACPis poly(p-methylstyrene), which has a ACPof 34.6 J mol-1K'1. By accounting for the three additional mobile beads in pMeSyrVE, in comparison to poly(p-ethylstyrene), 100% amorphous pMeSyrVE has an estimated ACPof 69.1 ± 5.1 J mol'1K'1. This ACPis likely an underestimation given that poly(p-methylstyrene) and polystyrene have the same number of small and large mobile beads, yet polystyrene only has a ACPof 30.8 J mol'1K'1. By accounting for the heat capacity of the oxygen atoms bound to the phenyl ring similarly to the methyl carbon in poly(p-methylstyrene), this brings the estimated ACPof pMeSyrVE to 76.7 ± 5.1 J mol'1K'1(0.395 ± 0.026 2101715-001297

[0169] -32-

[0170] J g'1K'1). A ACPof 0.355 J g-1K'1while heating through the Tgin a second heating cycle of pMeSyrVE corresponded to a 10.1 ± 6.6% crystalline polymer. Further, the ACPat Tgdecreased over several rounds of annealing (5 min isotherms at 150 °C); by the sixth heating cycle, a ACPof 0.331 J g-1K'1at Tgof pMeSyrVE indicated a 6% relative increase in the degree of crystallinity of the sample, equating to a 16.2% crystalline polymer. In total, analysis of XRD, WAXS, and DSC profiles of pMeSyrVE confirms that pMeSyrVE is semi-crystalline with a 10-24% degree of crystallinity.

[0171] Conclusions

[0172] The design of monomers from lignin-derivable phenolics offers a promising route towards incorporating sustainable feedstocks into polymer synthesis and imparting desirable properties on derivative polymers. In this example, lignin- derivable MeSyrVE was synthesized and polymerized to pMeSyrVE by conventional and controlled cationic methods. The design of a vinyl ether monomer from a tri-substituted phenolic suppressed termination during cationic polymerization at low molecular weights, and MeSyrVE achieved high polymerization conversions at mild temperatures (0 to 70 °C). Surprisingly, pMeSyrVE exhibited high degrees of syndiotacticity (r= 71%), departing from the isotactic-rich nature of prototypical poly(alkyl or benzyl vinyl ethers). The broad solubility of pMeSyrVE can enable its processability by solvent-based methods, and the high glass-transition temperature (Tg= 100 °C) and thermal stability (Td, 5% of about 305 °C in N2 and air) of pMeSyrVE offer application utility over a wide range of temperatures. Finally, pMeSyrVE was demonstrated to be semi-crystalline, addressing a long-standing challenge for chain-growth lignin-derivable materials.

[0173] Example 2

[0174] Synthesis of 4-methylsyringyl vinyl ether (Me ere 60 °CSanhydrous D F 2101715-001297

[0175] 23 °C, 1 h

[0176] 1 -broewethyi-4- ethy feyri n§o i 4- mafhylsyringyl vieyt ether

[0177] Representative synthesis of 1 -bromoethyl-4-methylsyringol: 250 mL round bottom flask (RBF) was equipped with a magnetic PTFE stir bar and sealed with a septum and sparged with nitrogen for 10 min. 2 g of methyl syringol (1 eq., 11.9 mmol) and 80 mL of anhydrous dimethylformamide was passed into the sealed flask using a syringe and a needle. After the complete dissolution of the methyl syringol, 13.1 g of anhydrous potassium carbonate (8 eq., 95.1 mmol) was transferred into the flask. The flask's content was allowed to stir for 1 h to enhance the dissolution of potassium carbonate and sufficient deprotonation of the methylsyringol. Afterwards, 17.9 g of 1,2- dibromoethane (8 eq., 95.1 mmol) was added dropwise over 30 minutes into the flask content while stirring at 1000 revolutions per minute. The mixture was heated to 60 °C and the reaction proceeded for 24 h while stirring. The contents of the vial were then cooled to 23°C and poured into 100 ml of deionized water. The mixture was then transferred into a separatory funnel and extracted with ethyl acetate. The aqueous fraction was discarded and the organic fraction was washed with deionized water and brine solution. The washed organic fraction was dried over magnesium sulfate and, subsequently, the solvent was removed by rotary evaporation. The concentrated, crude oil was run in a flash column to isolate the final product (Biotage Selekt, Biotage Star silica gel column, 0 to 20 vol% linear gradient of ethyl acetate in hexanes over 10 column volumes, then 20 to 100 vol.% linear gradient of ethyl acetate in hexanes over 6 column volumes). The product fraction was concentrated by rotary evaporation, and trace solvent was removed under dynamic vacuum for 24 h at 23°C to yield the product as a viscous, clear liquid: 66 mol%.1H NMR 5 ppm (CDCh, 400 MHz): 6.43 (s, 2H), 6.43 (s, 2H), 4.35 (d, 1 H), 4.15 (d, 1 H), 3.83 (s, 6H), 2.34 (s, 3H). GC MS: m / z found = 275; m / z expected = 275. 2101715-001297

[0178] -34-

[0179] Representative synthesis of 4-methylsyringyl vinyl ether (MeSyrVE): A 100- ml RBF equipped with a magnetic PTFE stir bar was sealed with a septum and sparged with Ar. for 10 min. 2.0 g (1 eq., 7.3 mmol) of 1-bromoethyl-4- methylsyringol and 2 mL of anhydrous tetrahydrofuran (THF) were passed into the sealed flask using a syringe and a needle. The solution was sparged with Ar for 5 min. Then, 7.3 mL (1 eq., 7.3 mmol) of 1 M KOtBu in THF was added dropwise to the solution under Ar flow, and the solution was stirred for 15 min. 1.0 mL (0.1 eq., 0.7 mmol) of additional 1 M KOtBu in THF was added dropwise to the solution under Ar flow, and the solution was stirred for another 45 min. The solution was then concentrated under rotary evaporation, and the resulting crude product mixture was transferred to a 250-ml beaker containing 50 ml of deionized water. The resulting solution was then transferred into a separatory funnel and extracted with ethyl acetate. The aqueous fraction was discarded, and the organic fraction was washed twice more with deionized water and once with brine solution. The organic fraction was then dried over magnesium sulfate and concentrated by rotary evaporation. The concentrated crude oil was run on a flash column to isolate the final product (Biotage Selekt, Biotage Star silica gel column, 0 vol.% ethyl acetate hexanes for 2 column volumes, then 0 to 20 vol. % linear gradient of ethyl acetate in hexanes over 10 column volumes, then 20 to 100 vol. % linear gradient of ethyl acetate in hexanes over 6 column volumes). The product fraction was concentrated by rotary evaporation and trace solvent was removed under a dynamic vacuum for 24 h at 60 °C to yield the product as a viscous, clear liquid. Yield: 83 mol%.1H NMR 5 ppm (CDCb, 400 MHz): 6.56 (dd, 1 H), 6.43 (s, 2H), 4.35 (d, 1 H), 4.15 (d, 1 H), 3.83 (s, 6H), 2.34 (s, 3H).

[0180] Synthesis of 2,6-dimethoxy-4-methyl-2-phenoxy ethyl N,N-diethyl dithiocarbamate 2101715-001297

[0181] -35- anhydrous acetonitrile

[0182] 24 h ethyl

[0183] Representative synthesis of 2,6-dimethoxy-4-methyl-2-phenoxy ethyl N, Indiethyl dithiocarbamate: A 25-ml RBF sealed with a septum and equipped with PTFE magnetic stir bar was degassed for 10 min. with Ar. 1 .0 g (1 eq., 3.6 mmol) of 1-bromoethyl-4-methylsyringol and 10 mL of anhydrous acetonitrile were passed into the sealed flask using a syringe and a needle. Then, 0.7 g (1.2 eq., 4.4 mmol) of sodium diethyl dithiocarbamate was added to the flask and the solution was allowed to stir at 200 RPM at 23°C for 24 h. Afterward, the solution was transferred into 20 mL of deionized water. The mixture was then transferred into a separatory funnel and extracted with ethyl acetate. The aqueous fraction was discarded, and the organic fraction was washed with deionized water and brine solution. The washed organic fraction was dried over magnesium sulfate, and 2101715-001297

[0184] -36- subsequently, the solvent was removed by rotary evaporation. The concentrated crude oil was run in a flash column to isolate the final product (Biotage Selekt, Biotage Star silica gel column, 0 to 20 vol% linear gradient of ethyl acetate in hexanes over 10 column volumes, then 20 to 100 vol.% linear gradient of ethyl acetate in hexanes over 6 column volumes). The product fraction was concentrated by rotary evaporation, and trace solvent was removed under dynamic vacuum for 24 h at 23°C to yield the product as a viscous, clear liquid: 96 mol%.1H NMR 5 ppm (CDCh, 400 MHz): 6.3 (s, 2H), 4.1 (t, 2H), 3.97 (q, 2H), 3.8 (s, 6H), 3.7 (q, 2H), 3.62 (q, 2H), 2.2 (s, 3H), 1.2 (dt, 6H).

[0185] Differential scanning calorimetry (DSC)

[0186] DSC experiments were conducted on a TA instrument Discovery differential scanning calorimeter. In FIG. 8, exemplary pMeSyrVE polymers were heated at 10 °C / min heating / cooling between 0 °C and 200 °C under N2 flow for two heat / cool cycles and Tgreported on second heating. The DSC data of the exemplary pMeSyrVE polymers are provided in Table 3.

[0187] Table 3: DSC data of Tgfor exemplary pMeSyrVE polymers.

[0188] TgExpected MnMALS Mn

[0189] Sample Name D

[0190] (°C) (kg / mol) (kg / mol)

[0191] 200 DP 70% conv 104 28.0 24.3 1.76

[0192] 500 DP 25% conv 106 25.3 28.8 1.99

[0193] 500 DP 50% conv 115 48.6 77.1 5.97

[0194] 750 DP 40% conv 117 55.3 68.2 6.34

[0195] Thermogravimetric analysis (TGA)

[0196] TGA experiments were conducted on a TA instrument TGA 5500. Thermal decomposition profiles are shown in FIG. 9 and provided in Table 4. TGA data were obtained using a 10 °C / min linear heating ramp from 30 °C to 700 °C under N2 flow.

[0197] Table 4: TGA data of Td ,5% for different molecular weights of exemplary pMeSyrVE polymers 2101715-001297

[0198] -37-

[0199] Td,s% Expected MnMALS Mn

[0200] Sample Name D

[0201] (°C) (kg / mol) (kg / mol)

[0202] 200 DP 70% conv 291 28.0 24.3 1.76

[0203] 500 DP 25% conv 309 25.3 28.8 1.99

[0204] 500 DP 50% conv 306 48.6 77.1 5.97

[0205] 750 DP 40% conv 300 55.3 68.2 6.34

[0206] Wide-angle X-ray scattering (WAXS)

[0207] WAXS experiments were performed on a XENOCS Xuess 20 instrument with a monochromatic Cu K« X-ray source (2 = 1.54 A) and a Dectris PILATUS 300K detector. pMeSyrVE was mounted between Kapton tape and placed in the sample chamber under dynamic vacuum to minimize background scattering from air. A sample-to-detector of 72 mm was used for WAXS experiments. The WAXS profile of Kapton tape was substracted as background form the pMeSyrVE 2D WAXS profiles are shown in FIG. 10 and XRD data is shown in Table 5. Table 5: XRD of exemplary pMeSyrVE polymers of differing molecular weights with peak dimension identified

[0208] MALS

[0209] Sample Expected Mn

[0210] Peak 1 Peak 2 Peak 3 Mn

[0211] Name (kg / moi)

[0212] (kg / mol)

[0213] 500 DP

[0214] 7.1 7.1 7.1 25.3 28.8

[0215] 25% conv

[0216] 500 DP

[0217] 13.7 14.1 13.6 48.6 77.1

[0218] 50% conv

[0219] 750 DP

[0220] 23.4 23.5 23.7 55.3 68.2

[0221] 40% conv

[0222] It will be appreciated by those skilled in the art that the present disclosure can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the disclosure is indicated by the appended claims rather than the foregoing 2101715-001297

[0223] -38- description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced therein.

Claims

1. 2101715-001297-39-CLAIMS:

1. A method for the synthesis of a poly(vinyl ether) polymer, the method comprising: obtaining one or more phenolic compounds from a source; synthesizing one or more vinyl ether-functionalized monomers from the obtained one or more phenolic compounds; and polymerizing the one or more vinyl ether-functionalized monomers to form the poly(vinyl ether) polymer.

2. The method of claim 1, wherein the source is a lignin source selected from the group consisting of an herbaceous plant, a softwood source, a hardwood source, agriculture residues, food wastes, pulp or paper wastes, and other lignincontaining sources.

3. The method of claim 1, wherein the one or more phenolic compounds are selected from the group consisting of2101715-001297-40-wherein R is selected from H, H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups.

4. The method of claim 1 , wherein the polymerization is performed in an anhydrous solvent and in a presence of polymerization initiator.

5. The method of claim 4, wherein the polymerization catalyst is selected from a Lewis acid, a protic acid, a carbonium salt or ionizing radiation.

6. The method of claim 4, wherein the anhydrous solvent is selected from the group consisting of chloroform, toluene, dichloromethane, tetra hydrofuran, and acetone.2101715-001297-41-7. The method of claim 1, wherein the polymerization is performed at a temperature ranging from about -78°C to about 200°C.

8. The method of claim 1, wherein the polymerization is performed for at most about 1 week.

9. The method of claim 1, wherein the polymerization is performed in a presence of a Reversible Addition-Fragmentation Chain Transfer (RAFT) agent.

10. The method of claim 1 , wherein the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds comprises: first reacting the one or more phenolic compounds with a 1 ,2-halogenated ethane to create an intermediate possessing one of the following structures:2101715-001297-42-wherein: R is selected from H, H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C2 to C10 linear or branched alkyne optionally substituted with one or more functional groups;2101715-001297-43-X is a halogen; and using an elimination mechanism to obtain the one or more vinyl ether- functionalized monomers, such as elimination by a base such as potassium tert- butoxide.

11. The method of claim 1 , wherein the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds comprises: reacting the obtained one or more phenolic compounds with a base or metal catalyst in acetylene.

12. The method of claim 1 , wherein the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds comprises: reacting the obtained one or more phenolic compounds with vinyl acetate in the presence of a catalyst and / or a base.

13. The method of claim 1 , wherein the synthesis of the one or more vinyl ether- functionalized monomers from the obtained one or more phenolic compounds comprises: reacting the obtained one or more phenolic compounds with a metal carbide, optionally in a presence of a catalyst.

14. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses a crystallinity of about 0 to about 50%.

15. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses a glass transition temperature ranging from about 0°C to about 200°C.

16. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses a degradation temperature ranging from about 250°C to about 350°C.2101715-001297-44-17. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses a dispersity ranging from about 1.0 to about 15.0.

18. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses a number-average molecular weight ranging from about 1 kg / mol to about 500 kg / mol.

19. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses a weight-average molecular weight ranging from about 1 kg / mol to about 7500 kg / mol.

20. The method of claim 1 , wherein the poly(vinyl ether) polymer possesses greater than 50% racemic diads.

21. A poly(vinyl ether) polymer possessing the following structure:(Formula I) wherein:R1is selected from -H or -OCH3;R2is selected from -H or -OCH3;R3is selected from -H or -OCH3;R4is selected from -H or -OCH3;R5is selected from H, OH, NH2, COOH, CHO, a Ci to C10 linear or branched alkyl optionally substituted with one or more functional groups, a C2 to C10 linear or branched alkene optionally substituted with one or more functional groups, or a C22101715-001297-45- to C10 linear or branched alkyne optionally substituted with one or more functional groups; n is an integer that is at least 10, wherein the polyvinyl ether polymer possesses a crystallinity of about 0 to about 50%.

22. The poly(vinyl ether) polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses a glass transition temperature ranging from about 0°C to about 200°C.

23. The poly(vinyl ether) polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses a degradation temperature ranging from about 250°C to about 350°C.

24. The poly(vinyl ether) polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses a dispersity ranging from about 1.0 to about 15.0.

25. The poly(vinyl ether) polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses a number-average molecular weight ranging from about 1 kg / mol to about 500 kg / mol.

26. The poly(vinyl ether) polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses a weight-average molecular weight ranging from about 1 kg / mol to about 7500 kg / mol.

27. The polyvinyl ether polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses greater than 50% racemic diads.

28. The polyvinyl ether polymer of claim 21 , wherein the poly(vinyl ether) polymer possesses a Hansen distance (Ra) in a solvent that ranges from about 10.0 to about 40.0.2101715-001297-46-29. A composition comprising: a polyvinyl ether polymer of claim 21 ; and one or more additives.

30. The composition of claim 29, wherein the one or more additives are selected from the group consisting of polymer modifiers, performance enhancers and processing aids.

31. An article or product comprising a poly(vinyl ether) polymer of claim 21.

Images