Bio-derived poly(thioether)s

Abstract

The present disclosure provides compounds (e.g., bio-derived polymers, and salts, stereoisomers, and isotopically labeled compounds thereof), which may be linear or cross-linked poly(thioethers) and may be provided as a latex or in bulk. The present disclosure also provides compositions, products, and kits comprising the compounds provided herein, as well as methods of preparing, molding, and applying a coating of the compounds provided herein.

Description

BIO-DERIVED POLY(THIOETHER)S CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority under 35 U.S.C. § 119(e) to U.S. Provisional Application, U.S.S.N.63 / 551,893, filed February 9, 2024, titled “Bio-Derived Poly(Thioether)s,” which is incorporated herein by reference. BACKGROUND

[0002] Synthetic rubber is an integral material used in the manufacture of tires, consumer goods, textiles and footwear, electronics, and various other products. However, at every stage of their lifecycle, low-cost, high-volume rubber materials require hazardous chemical modification (vulcanization) to enable reasonable performance. Moreover, reliance on synthetic rubber presents numerous obstacles to sustainability. Synthetic rubber relies on non- renewable petroleum feedstock. Vulcanization is inefficient and energy-intensive, requires hazardous reagents to improve material properties (e.g., the elasticity, resilience, tensile strength, viscosity, and hardness). In addition, vulcanization creates hazardous waste products and renders the resultant rubber non-degradable and non-recyclable. These challenges are compounded by inefficiencies in processing, as well as cosmetic and mechanical failures, that result in up to 30% of rubber-based goods being wasted during manufacturing. Attempts to repurpose and reuse rubber are prohibitively energy-intensive and afford low performance materials. Because synthetic rubber is non-degradable and non-recyclable, synthetic rubber is disposed in landfills at end-of-life. There is a need for materials that afford similar properties to synthetic rubber, but that reduce or eliminate sourcing from crude oil and can be degraded or recycled. SUMMARY OF THE DISCLOSURE

[0003] The present disclosure relates in part to compounds (e.g., bio-derived polymers, and salts, stereoisomers, and isotopically labeled compounds thereof). The compounds provided herein may be linear or cross-linked poly(thioethers) and may be provided as a latex or in bulk. Also provided herein are compositions, products, and kits comprising the compounds provided herein. Also provided herein are methods of preparing, molding, and applying a coating of the compounds provided herein.

[0004] In one aspect, provided herein is a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the polymer is a poly(thioether) comprising:1 / 119 C1723.70000WO00 #13627512v1a diradical derived from a terpene monomer; a diradical derived from a monomer comprising two thiol groups; and optionally a multi-radical derived from a multifunctional cross-linker.

[0005] In another aspect, provided herein is a method of preparing a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, the method comprising reacting a mixture comprising a terpene monomer, a monomer comprising two thiol groups, and optionally a multifunctional cross-linker.

[0006] In another aspect, provided herein is a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, prepared according to a method provided herein.

[0007] In another aspect, provided herein is a composition comprising a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, and an additive.

[0008] In another aspect, provided herein is a kit comprising: a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, or a composition provided herein; and instructions for using the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, or the composition.

[0009] In another aspect, provided herein is a product comprising a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, or a composition provided herein.

[0010] In another aspect, provided herein is a method of injection molding a bio-derived polymer, comprising: introducing a bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, into a screw injection apparatus; melting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; injecting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, into a mold; and cooling the mold.

[0011] In another aspect, provided herein is a method of compression molding a bio-derived polymer, comprising: placing a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, into an open mold; closing the mold and applying heat or pressure to the bio-derived polymer, or a salt,2 / 119 C1723.70000WO00 #13627512v1stereoisomer, or isotopically labeled compound thereof; and cooling the mold.

[0012] In another aspect, provided herein is a method of transfer molding a bio-derived polymer, comprising: transferring a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, into an enclosed mold; applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold.

[0013] In another aspect, provided herein is a method of applying a coating, the method comprising forming a coating layer comprising a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, on a surface.

[0014] The details of certain embodiments of the invention are set forth in the Detailed Description of Certain Embodiments, as described below. Other features, objects, and advantages of the invention will be apparent from the Definitions, Examples, Figures, and Claims. It should be understood that the aspects described herein are not limited to specific embodiments, methods, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying drawings, which constitute a part of this specification, illustrate several embodiments of the invention and together with the description, provide non-limiting examples of the invention.

[0016] FIGs.1A-1C show the characterization of a polymer synthesized from d-limonene and 1,2-ethanedithiol with no cross-linker. FIG.1A shows dynamic light scattering (DLS) traces for the polymer. FIG.1B shows an FTIR spectrum for the polymer. FIG.1C shows an SEM image of the polymer.

[0017] FIGs.2A-2C show the characterization of a polymer synthesized from d-limonene and 1,2-ethanedithiol with the cross-linker β-mycrene. FIG.2A shows DLS traces for the polymer. FIG.2B shows an FTIR spectrum for the polymer. FIG.2C shows an SEM image of the polymer.

[0018] FIGs.3A-3C show the characterization of a polymer synthesized from d-limonene and 1,2-ethanedithiol with the cross-linker trimethylolpropane tris(3-mercaptopropionate). FIG.3 / 119 C1723.70000WO00 #13627512v13A shows DLS traces for the polymer. FIG.3B shows an FTIR spectrum for the polymer. FIG.3C shows an SEM image of the polymer.

[0019] FIGs.4A-4C show the characterization of a polymer synthesized from d-limonene and 1,2-ethanedithiol with the cross-linker pentaerythritol tetrakis(3-mercaptopropionate). FIG. 4A shows DLS traces for the polymer. FIG.4B shows an FTIR spectrum for the polymer. FIG.4C shows an SEM image of the polymer.

[0020] FIGs.5A and 5B show characterization of a polymer synthesized from d-limonene and 1,4-dithiothreitol. FIG.5A shows thermogravimetric analysis (TGA) of the polymer. FIG.5B shows differential scanning calorimetry (DSC) of the polymer.

[0021] FIGs.6A and 6B show characterization of a polymer synthesized from d-limonene and 1,3-propanethiol. FIG.6A shows TGA of the polymer. FIG.6B shows DSC of the polymer. DEFINITIONS

[0022] Definitions of specific functional groups and chemical terms are described in more detail below. The chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75thEd., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Thomas Sorrell, Organic Chemistry, University Science Books, Sausalito, 1999;Michael B. Smith, March’s Advanced Organic Chemistry, 7thEdition, John Wiley & Sons, Inc., New York, 2013; Richard C. Larock, Comprehensive Organic Transformations, John Wiley & Sons, Inc., New York, 2018; and Carruthers, Some Modern Methods of Organic Synthesis, 3rdEdition, Cambridge University Press, Cambridge, 1987.

[0023] Compounds described herein can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and / or diastereomers. For example, the compounds described herein can be in the form of an individual enantiomer, diastereomer or geometric isomer, or can be in the form of a mixture of stereoisomers, including racemic mixtures and mixtures enriched in one or more stereoisomer. Isomers can be isolated from mixtures by methods known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts; or preferred isomers can be prepared by asymmetric syntheses. See, for example, Jacques et al., Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen et al., Tetrahedron 33:2725 (1977); Eliel, E.L. Stereochemistry of Carbon Compounds4 / 119 C1723.70000WO00 #13627512v1(McGraw–Hill, NY, 1962); and Wilen, S.H., Tables of Resolving Agents and Optical Resolutions p.268 (E.L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, IN 1972). The present disclosure additionally encompasses compounds as individual isomers substantially free of other isomers, and alternatively, as mixtures of various isomers.

[0024] The term “isotopes” refers to variants of a particular chemical element such that, while all isotopes of a given element share the same number of protons in each atom of the element, those isotopes differ in the number of neutrons. Unless otherwise provided, formulae and structures depicted herein include compounds that do not include isotopically enriched atoms, and also include compounds that include isotopically enriched atoms. For example, compounds having the present structures except for the replacement of hydrogen by deuterium or tritium, replacement of19F with18F, or the replacement of a carbon by a13C- or14C-enriched carbon are within the scope of the disclosure. Such compounds are useful, for example, as analytical tools or probes in biological assays.

[0025] When a range of values (“range”) is listed, it encompasses each value and sub-range within the range. A range is inclusive of the values at the two ends of the range unless otherwise provided. For example “C1-6 alkyl” encompasses, C1, C2, C3, C4, C5, C6, C1–6, C1–5, C1–4, C1–3, C1–2, C2–6, C2–5, C2–4, C2–3, C3–6, C3–5, C3–4, C4–6, C4–5, and C5–6alkyl.

[0026] The term “aliphatic” refers to alkyl, alkenyl, alkynyl, and carbocyclic groups.

[0027] The term “alkyl” refers to a radical of a straight-chain or branched saturated hydrocarbon group having from 1 to 20 carbon atoms (“C1–20alkyl”). In some embodiments, an alkyl group has 1 to 12 carbon atoms (“C1–12alkyl”). In some embodiments, an alkyl group has 1 to 10 carbon atoms (“C1–10 alkyl”). In some embodiments, an alkyl group has 1 to 9 carbon atoms (“C1–9 alkyl”). In some embodiments, an alkyl group has 1 to 8 carbon atoms (“C1–8alkyl”). In some embodiments, an alkyl group has 1 to 7 carbon atoms (“C1–7alkyl”). In some embodiments, an alkyl group has 1 to 6 carbon atoms (“C1–6 alkyl”). In some embodiments, an alkyl group has 1 to 5 carbon atoms (“C1–5 alkyl”). In some embodiments, an alkyl group has 1 to 4 carbon atoms (“C1–4alkyl”). In some embodiments, an alkyl group has 1 to 3 carbon atoms (“C1–3 alkyl”). In some embodiments, an alkyl group has 1 to 2 carbon atoms (“C1–2 alkyl”). In some embodiments, an alkyl group has 1 carbon atom (“C1 alkyl”). In some embodiments, an alkyl group has 2 to 6 carbon atoms (“C2-6alkyl”). Examples of C1–6alkyl groups include methyl (C1), ethyl (C2), propyl (C3) (e.g., n-propyl, isopropyl), butyl (C4) (e.g., n-butyl, tert-butyl, sec-butyl, isobutyl), pentyl (C5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tert-amyl), and hexyl (C6) (e.g., n-hexyl). Additional examples of alkyl groups include n-heptyl (C7), n-octyl (C8), n-dodecyl (C12), and5 / 119 C1723.70000WO00 #13627512v1the like. Unless otherwise specified, each instance of an alkyl group is independently unsubstituted (an “unsubstituted alkyl”) or substituted (a “substituted alkyl”) with one or more substituents (e.g., halogen, such as F). In certain embodiments, the alkyl group is an unsubstituted C1–12alkyl (such as unsubstituted C1–6alkyl, e.g., −CH3(Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, e.g., unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr)), unsubstituted butyl (Bu, e.g., unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu or s-Bu), unsubstituted isobutyl (i-Bu)). In certain embodiments, the alkyl group is a substituted C1–12 alkyl (such as substituted C1–6 alkyl, e.g., –CH2F, –CHF2, –CF3, –CH2CH2F, –CH2CHF2, –CH2CF3, or benzyl (Bn)).

[0028] The term “alkenyl” refers to a radical of a straight-chain or branched hydrocarbon group having from 1 to 20 carbon atoms and one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 double bonds). In some embodiments, an alkenyl group has 1 to 20 carbon atoms (“C1-20alkenyl”). In some embodiments, an alkenyl group has 1 to 12 carbon atoms (“C1–12alkenyl”). In some embodiments, an alkenyl group has 1 to 11 carbon atoms (“C1–11 alkenyl”). In some embodiments, an alkenyl group has 1 to 10 carbon atoms (“C1–10 alkenyl”). In some embodiments, an alkenyl group has 1 to 9 carbon atoms (“C1–9alkenyl”). In some embodiments, an alkenyl group has 1 to 8 carbon atoms (“C1–8 alkenyl”). In some embodiments, an alkenyl group has 1 to 7 carbon atoms (“C1–7 alkenyl”). In some embodiments, an alkenyl group has 1 to 6 carbon atoms (“C1–6alkenyl”). In some embodiments, an alkenyl group has 1 to 5 carbon atoms (“C1–5alkenyl”). In some embodiments, an alkenyl group has 1 to 4 carbon atoms (“C1–4 alkenyl”). In some embodiments, an alkenyl group has 1 to 3 carbon atoms (“C1–3 alkenyl”). In some embodiments, an alkenyl group has 1 to 2 carbon atoms (“C1–2alkenyl”). In some embodiments, an alkenyl group has 1 carbon atom (“C1 alkenyl”). The one or more carbon- carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl). Examples of C1–4alkenyl groups include methylidenyl (C1), ethenyl (C2), 1-propenyl (C3), 2- propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), butadienyl (C4), and the like. Examples of C1–6 alkenyl groups include the aforementioned C2-4 alkenyl groups as well as pentenyl (C5), pentadienyl (C5), hexenyl (C6), and the like. Additional examples of alkenyl include heptenyl (C7), octenyl (C8), octatrienyl (C8), and the like. Unless otherwise specified, each instance of an alkenyl group is independently unsubstituted (an “unsubstituted alkenyl”) or substituted (a “substituted alkenyl”) with one or more substituents. In certain embodiments, the alkenyl group is an unsubstituted C1-20alkenyl. In certain embodiments, the alkenyl group is a6 / 119 C1723.70000WO00 #13627512v1substituted C1-20alkenyl. In an alkenyl group, a C=C double bond for which the stereochemistry is not specified (e.g., −CH=CHCH3or) may be in the (E)- or (Z)- configuration.

[0029] The term “alkynyl” refers to a radical of a straight-chain or branched hydrocarbon group having from 1 to 20 carbon atoms and one or more carbon-carbon triple bonds (e.g., 1, 2, 3, or 4 triple bonds) (“C1-20 alkynyl”). In some embodiments, an alkynyl group has 1 to 10 carbon atoms (“C1-10 alkynyl”). In some embodiments, an alkynyl group has 1 to 9 carbon atoms (“C1-9alkynyl”). In some embodiments, an alkynyl group has 1 to 8 carbon atoms (“C1-8alkynyl”). In some embodiments, an alkynyl group has 1 to 7 carbon atoms (“C1-7alkynyl”). In some embodiments, an alkynyl group has 1 to 6 carbon atoms (“C1-6 alkynyl”). In some embodiments, an alkynyl group has 1 to 5 carbon atoms (“C1-5 alkynyl”). In some embodiments, an alkynyl group has 1 to 4 carbon atoms (“C1-4alkynyl”). In some embodiments, an alkynyl group has 1 to 3 carbon atoms (“C1-3 alkynyl”). In some embodiments, an alkynyl group has 1 to 2 carbon atoms (“C1-2 alkynyl”). In some embodiments, an alkynyl group has 1 carbon atom (“C1alkynyl”). The one or more carbon- carbon triple bonds can be internal (such as in 2-butynyl) or terminal (such as in 1-butynyl). Examples of C1-4 alkynyl groups include, without limitation, methylidynyl (C1), ethynyl (C2), 1-propynyl (C3), 2-propynyl (C3), 1-butynyl (C4), 2-butynyl (C4), and the like. Examples of C1-6alkenyl groups include the aforementioned C2-4alkynyl groups as well as pentynyl (C5), hexynyl (C6), and the like. Additional examples of alkynyl include heptynyl (C7), octynyl (C8), and the like. Unless otherwise specified, each instance of an alkynyl group is independently unsubstituted (an “unsubstituted alkynyl”) or substituted (a “substituted alkynyl”) with one or more substituents. In certain embodiments, the alkynyl group is an unsubstituted C1-20 alkynyl. In certain embodiments, the alkynyl group is a substituted C1-20 alkynyl.

[0030] The term “heteroalkyl” refers to an alkyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (e.g., inserted between adjacent carbon atoms of) and / or placed at one or more terminal position(s) of the parent chain. In certain embodiments, a heteroalkyl group refers to a saturated group having from 1 to 20 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–20 alkyl”). In certain embodiments, a heteroalkyl group refers to a saturated group having from 1 to 12 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–12 alkyl”). In some embodiments, a heteroalkyl group is a saturated7 / 119 C1723.70000WO00 #13627512v1group having 1 to 11 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–11 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 10 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–10 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 9 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–9 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 8 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–8alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 7 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–7 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 6 carbon atoms and 1 or more heteroatoms within the parent chain (“heteroC1–6alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 5 carbon atoms and 1 or 2 heteroatoms within the parent chain (“heteroC1–5 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 4 carbon atoms and 1or 2 heteroatoms within the parent chain (“heteroC1–4alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 3 carbon atoms and 1 heteroatom within the parent chain (“heteroC1–3 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 to 2 carbon atoms and 1 heteroatom within the parent chain (“heteroC1–2 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 1 carbon atom and 1 heteroatom (“heteroC1 alkyl”). In some embodiments, a heteroalkyl group is a saturated group having 2 to 6 carbon atoms and 1 or 2 heteroatoms within the parent chain (“heteroC2-6alkyl”). Unless otherwise specified, each instance of a heteroalkyl group is independently unsubstituted (an “unsubstituted heteroalkyl”) or substituted (a “substituted heteroalkyl”) with one or more substituents. In certain embodiments, the heteroalkyl group is an unsubstituted heteroC1–12alkyl. In certain embodiments, the heteroalkyl group is a substituted heteroC1–12 alkyl.

[0031] The term “heteroalkenyl” refers to an alkenyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (e.g., inserted between adjacent carbon atoms of) and / or placed at one or more terminal position(s) of the parent chain. In certain embodiments, a heteroalkenyl group refers to a group having from 1 to 20 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–20alkenyl”). In certain embodiments, a heteroalkenyl group refers to a group having from 1 to 12 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–12 alkenyl”). In certain embodiments, a heteroalkenyl group refers to a group having from 1 to 11 carbon atoms, at8 / 119 C1723.70000WO00 #13627512v1least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–11alkenyl”). In certain embodiments, a heteroalkenyl group refers to a group having from 1 to 10 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–10alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 9 carbon atoms at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–9 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 8 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–8alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 7 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–7 alkenyl”). In some embodiments, a heteroalkenyl group has 1to 6 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (“heteroC1–6alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 5 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–5 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 4 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–4 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 3 carbon atoms, at least one double bond, and 1 heteroatom within the parent chain (“heteroC1–3alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 2 carbon atoms, at least one double bond, and 1 heteroatom within the parent chain (“heteroC1–2 alkenyl”). In some embodiments, a heteroalkenyl group has 1 to 6 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–6alkenyl”). Unless otherwise specified, each instance of a heteroalkenyl group is independently unsubstituted (an “unsubstituted heteroalkenyl”) or substituted (a “substituted heteroalkenyl”) with one or more substituents. In certain embodiments, the heteroalkenyl group is an unsubstituted heteroC1–20alkenyl. In certain embodiments, the heteroalkenyl group is a substituted heteroC1–20 alkenyl.

[0032] The term “heteroalkynyl” refers to an alkynyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (e.g., inserted between adjacent carbon atoms of) and / or placed at one or more terminal position(s) of the parent chain. In certain embodiments, a heteroalkynyl group refers to a group having from 1 to 20 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–20alkynyl”). In certain embodiments, a heteroalkynyl group refers to a group having from 1 to 10 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–10 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 9 carbon atoms, at least one triple bond, and 19 / 119 C1723.70000WO00 #13627512v1or more heteroatoms within the parent chain (“heteroC1–9alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 8 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–8 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 7 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–7 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 6 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (“heteroC1–6alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 5 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–5 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 4 carbon atoms, at least one triple bond, and 1or 2 heteroatoms within the parent chain (“heteroC1–4alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 3 carbon atoms, at least one triple bond, and 1 heteroatom within the parent chain (“heteroC1–3 alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 2 carbon atoms, at least one triple bond, and 1 heteroatom within the parent chain (“heteroC1–2alkynyl”). In some embodiments, a heteroalkynyl group has 1 to 6 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (“heteroC1–6 alkynyl”). Unless otherwise specified, each instance of a heteroalkynyl group is independently unsubstituted (an “unsubstituted heteroalkynyl”) or substituted (a “substituted heteroalkynyl”) with one or more substituents. In certain embodiments, the heteroalkynyl group is an unsubstituted heteroC1–20 alkynyl. In certain embodiments, the heteroalkynyl group is a substituted heteroC1–20alkynyl.

[0033] The term “carbocyclyl” or “carbocyclic” refers to a radical of a non-aromatic cyclic hydrocarbon group having from 3 to 14 ring carbon atoms (“C3-14 carbocyclyl”) and zero heteroatoms in the non-aromatic ring system. In some embodiments, a carbocyclyl group has 3 to 14 ring carbon atoms (“C3-14carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 13 ring carbon atoms (“C3-13 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 12 ring carbon atoms (“C3-12 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 11 ring carbon atoms (“C3-11carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 10 ring carbon atoms (“C3-10 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 8 ring carbon atoms (“C3-8 carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 7 ring carbon atoms (“C3-7carbocyclyl”). In some embodiments, a carbocyclyl group has 3 to 6 ring carbon atoms (“C3-6carbocyclyl”). In some embodiments, a carbocyclyl group has 4 to 6 ring carbon atoms (“C4-6 carbocyclyl”). In some embodiments, a carbocyclyl group has 5 to 6 ring carbon atoms (“C5-6 carbocyclyl”). In some embodiments, a carbocyclyl group has 5 to 10 ring carbon atoms (“C5-10carbocyclyl”).10 / 119 C1723.70000WO00 #13627512v1Exemplary C3-6carbocyclyl groups include cyclopropyl (C3), cyclopropenyl (C3), cyclobutyl (C4), cyclobutenyl (C4), cyclopentyl (C5), cyclopentenyl (C5), cyclohexyl (C6), cyclohexenyl (C6), cyclohexadienyl (C6), and the like. Exemplary C3-8 carbocyclyl groups include the aforementioned C3-6carbocyclyl groups as well as cycloheptyl (C7), cycloheptenyl (C7), cycloheptadienyl (C7), cycloheptatrienyl (C7), cyclooctyl (C8), cyclooctenyl (C8), bicyclo[2.2.1]heptanyl (C7), bicyclo[2.2.2]octanyl (C8), and the like. Exemplary C3-10 carbocyclyl groups include the aforementioned C3-8carbocyclyl groups as well as cyclononyl (C9), cyclononenyl (C9), cyclodecyl (C10), cyclodecenyl (C10), octahydro-1H-indenyl (C9), decahydronaphthalenyl (C10), spiro[4.5]decanyl (C10), and the like. Exemplary C3-8 carbocyclyl groups include the aforementioned C3-10carbocyclyl groups as well as cycloundecyl (C11), spiro[5.5]undecanyl (C11), cyclododecyl (C12), cyclododecenyl (C12), cyclotridecane (C13), cyclotetradecane (C14), and the like. As the foregoing examples illustrate, in certain embodiments, the carbocyclyl group is either monocyclic (“monocyclic carbocyclyl”) or polycyclic (e.g., containing a fused, bridged or spiro ring system such as a bicyclic system (“bicyclic carbocyclyl”) or tricyclic system (“tricyclic carbocyclyl”)) and can be saturated or can contain one or more carbon-carbon double or triple bonds. “Carbocyclyl” also includes ring systems wherein the carbocyclyl ring, as defined above, is fused with one or more aryl or heteroaryl groups wherein the point of attachment is on the carbocyclyl ring, and in such instances, the number of carbons continue to designate the number of carbons in the carbocyclic ring system. Unless otherwise specified, each instance of a carbocyclyl group is independently unsubstituted (an “unsubstituted carbocyclyl”) or substituted (a “substituted carbocyclyl”) with one or more substituents. In certain embodiments, the carbocyclyl group is an unsubstituted C3-14 carbocyclyl. In certain embodiments, the carbocyclyl group is a substituted C3-14carbocyclyl.

[0034] In some embodiments, “carbocyclyl” is a monocyclic, saturated carbocyclyl group having from 3 to 14 ring carbon atoms (“C3-14 cycloalkyl”). In some embodiments, a cycloalkyl group has 3 to 10 ring carbon atoms (“C3-10cycloalkyl”). In some embodiments, a cycloalkyl group has 3 to 8 ring carbon atoms (“C3-8 cycloalkyl”). In some embodiments, a cycloalkyl group has 3 to 6 ring carbon atoms (“C3-6 cycloalkyl”). In some embodiments, a cycloalkyl group has 4 to 6 ring carbon atoms (“C4-6cycloalkyl”). In some embodiments, a cycloalkyl group has 5 to 6 ring carbon atoms (“C5-6cycloalkyl”). In some embodiments, a cycloalkyl group has 5 to 10 ring carbon atoms (“C5-10 cycloalkyl”). Examples of C5-6 cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C5). Examples of C3-6 cycloalkyl groups include the aforementioned C5-6cycloalkyl groups as well as cyclopropyl (C3) and11 / 119 C1723.70000WO00 #13627512v1cyclobutyl (C4). Examples of C3-8cycloalkyl groups include the aforementioned C3-6cycloalkyl groups as well as cycloheptyl (C7) and cyclooctyl (C8). Unless otherwise specified, each instance of a cycloalkyl group is independently unsubstituted (an “unsubstituted cycloalkyl”) or substituted (a “substituted cycloalkyl”) with one or more substituents. In certain embodiments, the cycloalkyl group is an unsubstituted C3-14 cycloalkyl. In certain embodiments, the cycloalkyl group is a substituted C3-14 cycloalkyl. In certain embodiments, the carbocyclyl includes 0, 1, or 2 C=C double bonds in the carbocyclic ring system, as valency permits.

[0035] The term “heterocyclyl” or “heterocyclic” refers to a radical of a 3- to 14-membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“3–14 membered heterocyclyl”). In heterocyclyl groups that contain one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valency permits. A heterocyclyl group can either be monocyclic (“monocyclic heterocyclyl”) or polycyclic (e.g., a fused, bridged or spiro ring system such as a bicyclic system (“bicyclic heterocyclyl”) or tricyclic system (“tricyclic heterocyclyl”)), and can be saturated or can contain one or more carbon- carbon double or triple bonds. Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings. “Heterocyclyl” also includes ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more carbocyclyl groups wherein the point of attachment is either on the carbocyclyl or heterocyclyl ring, or ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring, and in such instances, the number of ring members continue to designate the number of ring members in the heterocyclyl ring system. Unless otherwise specified, each instance of heterocyclyl is independently unsubstituted (an “unsubstituted heterocyclyl”) or substituted (a “substituted heterocyclyl”) with one or more substituents. In certain embodiments, the heterocyclyl group is an unsubstituted 3–14 membered heterocyclyl. In certain embodiments, the heterocyclyl group is a substituted 3–14 membered heterocyclyl. In certain embodiments, the heterocyclyl is substituted or unsubstituted, 3- to 7-membered, monocyclic heterocyclyl, wherein 1, 2, or 3 atoms in the heterocyclic ring system are independently oxygen, nitrogen, or sulfur, as valency permits.

[0036] In some embodiments, a heterocyclyl group is a 5–10 membered non-aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5–10 membered heterocyclyl”).12 / 119 C1723.70000WO00 #13627512v1In some embodiments, a heterocyclyl group is a 5–8 membered non-aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5–8 membered heterocyclyl”). In some embodiments, a heterocyclyl group is a 5–6 membered non-aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5–6 membered heterocyclyl”). In some embodiments, the 5–6 membered heterocyclyl has 1–3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5–6 membered heterocyclyl has 1–2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5–6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur.

[0037] Exemplary 3-membered heterocyclyl groups containing 1 heteroatom include azirdinyl, oxiranyl, and thiiranyl. Exemplary 4-membered heterocyclyl groups containing 1 heteroatom include azetidinyl, oxetanyl, and thietanyl. Exemplary 5-membered heterocyclyl groups containing 1 heteroatom include tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5- dione. Exemplary 5-membered heterocyclyl groups containing 2 heteroatoms include dioxolanyl, oxathiolanyl and dithiolanyl. Exemplary 5-membered heterocyclyl groups containing 3 heteroatoms include triazolinyl, oxadiazolinyl, and thiadiazolinyl. Exemplary 6- membered heterocyclyl groups containing 1 heteroatom include piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl. Exemplary 6-membered heterocyclyl groups containing 2 heteroatoms include piperazinyl, morpholinyl, dithianyl, and dioxanyl. Exemplary 6-membered heterocyclyl groups containing 3 heteroatoms include triazinyl. Exemplary 7-membered heterocyclyl groups containing 1 heteroatom include azepanyl, oxepanyl and thiepanyl. Exemplary 8-membered heterocyclyl groups containing 1 heteroatom include azocanyl, oxecanyl and thiocanyl. Exemplary bicyclic heterocyclyl groups include indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, tetra- hydrobenzothienyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, decahydroisoquinolinyl, octahydrochromenyl, octahydroisochromenyl, decahydronaphthyridinyl, decahydro-1,8-naphthyridinyl, octahydropyrrolo[3,2-b]pyrrole, indolinyl, phthalimidyl, naphthalimidyl, chromanyl, chromenyl, 1H-benzo[e][1,4]diazepinyl, 1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 5,6- dihydro-4H-furo[3,2-b]pyrrolyl, 6,7-dihydro-5H-furo[3,2-b]pyranyl, 5,7-dihydro-4H- thieno[2,3-c]pyranyl, 2,3-dihydro-1H-pyrrolo[2,3-b]pyridinyl, 2,3-dihydrofuro[2,3- b]pyridinyl, 4,5,6,7-tetrahydro-1H-pyrrolo[2,3-b]pyridinyl, 4,5,6,7-tetrahydrofuro[3,2-13 / 119 C1723.70000WO00 #13627512v1c]pyridinyl, 4,5,6,7-tetrahydrothieno[3,2-b]pyridinyl, 1,2,3,4-tetrahydro-1,6-naphthyridinyl, and the like.

[0038] The term “aryl” refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 ^ electrons shared in a cyclic array) having 6–14 ring carbon atoms and zero heteroatoms provided in the aromatic ring system (“C6-14 aryl”). In some embodiments, an aryl group has 6 ring carbon atoms (“C6 aryl”; e.g., phenyl). In some embodiments, an aryl group has 10 ring carbon atoms (“C10aryl”; e.g., naphthyl such as 1–naphthyl and 2-naphthyl). In some embodiments, an aryl group has 14 ring carbon atoms (“C14 aryl”; e.g., anthracyl). “Aryl” also includes ring systems wherein the aryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the radical or point of attachment is on the aryl ring, and in such instances, the number of carbon atoms continue to designate the number of carbon atoms in the aryl ring system. Unless otherwise specified, each instance of an aryl group is independently unsubstituted (an “unsubstituted aryl”) or substituted (a “substituted aryl”) with one or more substituents. In certain embodiments, the aryl group is an unsubstituted C6- 14 aryl. In certain embodiments, the aryl group is a substituted C6-14 aryl.

[0039] The term “heteroaryl” refers to a radical of a 5-14 membered monocyclic or polycyclic (e.g., bicyclic, tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 ^ electrons shared in a cyclic array) having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-14 membered heteroaryl”). In heteroaryl groups that contain one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valency permits. Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings. “Heteroaryl” includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the point of attachment is on the heteroaryl ring, and in such instances, the number of ring members continue to designate the number of ring members in the heteroaryl ring system. “Heteroaryl” also includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more aryl groups wherein the point of attachment is either on the aryl or heteroaryl ring, and in such instances, the number of ring members designates the number of ring members in the fused polycyclic (aryl / heteroaryl) ring system. Polycyclic heteroaryl groups wherein one ring does not contain a heteroatom (e.g., indolyl, quinolinyl, carbazolyl, and the like) the point of attachment can be on either ring, e.g., either the ring bearing a heteroatom (e.g., 2-indolyl) or the ring that does not contain a heteroatom (e.g., 5-indolyl). In14 / 119 C1723.70000WO00 #13627512v1certain embodiments, the heteroaryl is substituted or unsubstituted, 5- or 6-membered, monocyclic heteroaryl, wherein 1, 2, 3, or 4 atoms in the heteroaryl ring system are independently oxygen, nitrogen, or sulfur. In certain embodiments, the heteroaryl is substituted or unsubstituted, 9- or 10-membered, bicyclic heteroaryl, wherein 1, 2, 3, or 4 atoms in the heteroaryl ring system are independently oxygen, nitrogen, or sulfur.

[0040] In some embodiments, a heteroaryl group is a 5-10 membered aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-10 membered heteroaryl”). In some embodiments, a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-8 membered heteroaryl”). In some embodiments, a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1–4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-6 membered heteroaryl”). In some embodiments, the 5- 6 membered heteroaryl has 1–3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1–2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur. Unless otherwise specified, each instance of a heteroaryl group is independently unsubstituted (an “unsubstituted heteroaryl”) or substituted (a “substituted heteroaryl”) with one or more substituents. In certain embodiments, the heteroaryl group is an unsubstituted 5-14 membered heteroaryl. In certain embodiments, the heteroaryl group is a substituted 5-14 membered heteroaryl.

[0041] Exemplary 5-membered heteroaryl groups containing 1 heteroatom include pyrrolyl, furanyl, and thiophenyl. Exemplary 5-membered heteroaryl groups containing 2 heteroatoms include imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5- membered heteroaryl groups containing 3 heteroatoms include triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing 4 heteroatoms include tetrazolyl. Exemplary 6-membered heteroaryl groups containing 1 heteroatom include pyridinyl. Exemplary 6-membered heteroaryl groups containing 2 heteroatoms include pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing 3 or 4 heteroatoms include triazinyl and tetrazinyl, respectively. Exemplary 7- membered heteroaryl groups containing 1 heteroatom include azepinyl, oxepinyl, and thiepinyl. Exemplary 5,6-bicyclic heteroaryl groups include indolyl, isoindolyl, indazolyl,15 / 119 C1723.70000WO00 #13627512v1benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzoisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzthiazolyl, benzisothiazolyl, benzthiadiazolyl, indolizinyl, and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl. Exemplary tricyclic heteroaryl groups include phenanthridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenothiazinyl, phenoxazinyl, and phenazinyl.

[0042] Affixing the suffix “-ene” to a group indicates the group is a divalent moiety, e.g., alkylene is the divalent moiety of alkyl, alkenylene is the divalent moiety of alkenyl, alkynylene is the divalent moiety of alkynyl, heteroalkylene is the divalent moiety of heteroalkyl, heteroalkenylene is the divalent moiety of heteroalkenyl, heteroalkynylene is the divalent moiety of heteroalkynyl, carbocyclylene is the divalent moiety of carbocyclyl, heterocyclylene is the divalent moiety of heterocyclyl, arylene is the divalent moiety of aryl, and heteroarylene is the divalent moiety of heteroaryl.The term “unsaturated bond” refers to a double or triple bond.

[0043] The term “unsaturated” or “partially unsaturated” refers to a moiety that includes at least one double or triple bond.

[0044] The term “saturated” or “fully saturated” refers to a moiety that does not contain a double or triple bond, e.g., the moiety only contains single bonds.

[0045] A group or compound is optionally substituted unless expressly provided otherwise. The term “optionally substituted” refers to being substituted or unsubstituted. In certain embodiments, alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups are optionally substituted. “Optionally substituted” refers to a group which is substituted or unsubstituted (e.g., “substituted” or “unsubstituted” alkyl, “substituted” or “unsubstituted” alkenyl, “substituted” or “unsubstituted” alkynyl, “substituted” or “unsubstituted” heteroalkyl, “substituted” or “unsubstituted” heteroalkenyl, “substituted” or “unsubstituted” heteroalkynyl, “substituted” or “unsubstituted” carbocyclyl, “substituted” or “unsubstituted” heterocyclyl, “substituted” or “unsubstituted” aryl or “substituted” or “unsubstituted” heteroaryl group). In general, the term “substituted” means that at least one hydrogen present on a group is replaced with a permissible substituent, e.g., a substituent which upon substitution results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction. Unless otherwise indicated, a “substituted” group has a substituent at one or more substitutable positions of the group, and when more than one16 / 119 C1723.70000WO00 #13627512v1position in any given structure is substituted, the substituent is either the same or different at each position. The term “substituted” is contemplated to include substitution with all permissible substituents of organic compounds, and includes any of the substituents described herein that results in the formation of a stable compound. The present disclosure contemplates any and all such combinations in order to arrive at a stable compound. For purposes of this disclosure, heteroatoms such as nitrogen may have hydrogen substituents and / or any suitable substituent as described herein which satisfy the valencies of the heteroatoms and results in the formation of a stable moiety. The disclosure is not limited in any manner by the exemplary substituents described herein.

[0046] Exemplary carbon atom substituents include halogen, −CN, −NO2, −N3, −SO2H, −SO3H, −OH, −ORaa, −ON(Rbb)2, −N(Rbb)2, −N(Rbb)3+X−, −N(ORcc)Rbb, −SH, −SRaa, −SSRcc, −C(=O)Raa, −CO2H, −CHO, −C(ORcc)2, −CO2Raa, −OC(=O)Raa, −OCO2Raa, −C(=O)N(Rbb)2, −OC(=O)N(Rbb)2, −NRbbC(=O)Raa, −NRbbCO2Raa, −NRbbC(=O)N(Rbb)2, −C(=NRbb)Raa, −C(=NRbb)ORaa, −OC(=NRbb)Raa, −OC(=NRbb)ORaa, −C(=NRbb)N(Rbb)2, −OC(=NRbb)N(Rbb)2, −NRbbC(=NRbb)N(Rbb)2, −C(=O)NRbbSO2Raa, −NRbbSO2Raa, −SO2N(Rbb)2, −SO2Raa, −SO2ORaa, −OSO2Raa, −S(=O)Raa, −OS(=O)Raa, −Si(Raa)3,−P(ORcc)3+X−, −P(Rcc)4, −P(ORcc)4, −OP(Rcc)2, −OP(Rcc)3+X−, −OP(ORcc)2, −OP(ORcc)3+X−, −OP(Rcc)4, −OP(ORcc)4, −B(Raa)2, −B(ORcc)2, −BRaa(ORcc), C1–20 alkyl, C1–20 perhaloalkyl, C1–20 alkenyl, C1–20 alkynyl, heteroC1–20 alkyl, heteroC1–20 alkenyl, heteroC1–20 alkynyl, C3-10 carbocyclyl, 3-14 membered heterocyclyl, C6-14aryl, and 5-14 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rddgroups; wherein X−is a counterion; or two geminal hydrogens on a carbon atom are replaced with the group =O, =S, =NN(Rbb)2, =NNRbbC(=O)Raa, =NNRbbC(=O)ORaa, =NNRbbS(=O)2Raa, =NRbb, or =NORcc; wherein: each instance of Raais, independently, selected from C1–20alkyl, C1–20perhaloalkyl, C1–20 alkenyl, C1–20 alkynyl, heteroC1–20 alkyl, heteroC1–20alkenyl, heteroC1–20alkynyl, C3-10 carbocyclyl, 3-14 membered heterocyclyl, C6-14 aryl, and 5- 14 membered heteroaryl, or two Raagroups are joined to form a 3-14 membered17 / 119 C1723.70000WO00 #13627512v1heterocyclyl or 5-14 membered heteroaryl ring, wherein each of the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rddgroups; each instance of Rbbis, independently, selected from hydrogen, −OH, −ORaa, −N(Rcc)2, −CN, −C(=O)Raa, −C(=O)N(Rcc)2, −CO2Raa, −SO2Raa, −C(=NRcc)ORaa, −C(=NRcc)N(Rcc)2, −SO2N(Rcc)2, −SO2Rcc, −SO2ORcc, −SORaa, −C(=S)N(Rcc)2, −C(=O)SRcc, −C(=S)SRcc, −P(=O)(Raa)2, −P(=O)(ORcc)2, −P(=O)(N(Rcc)2)2, C1–20alkyl, C1–20 perhaloalkyl, C1–20 alkenyl, C1–20 alkynyl, heteroC1–20alkyl, heteroC1– 20alkenyl, heteroC1–20alkynyl, C3-10 carbocyclyl, 3-14 membered heterocyclyl, C6-14 aryl, and 5-14 membered heteroaryl, or two Rbbgroups are joined to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rddgroups; each instance of Rccis, independently, selected from hydrogen, C1–20alkyl, C1–20 perhaloalkyl, C1–20 alkenyl, C1–20 alkynyl, heteroC1–20 alkyl, heteroC1–20 alkenyl, heteroC1–20 alkynyl, C3-10 carbocyclyl, 3-14 membered heterocyclyl, C6-14 aryl, and 5- 14 membered heteroaryl, or two Rccgroups are joined to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rddgroups; each instance of Rddis, independently, selected from halogen, −CN, −NO2, −N3, −SO2H, −SO3H, −OH, −ORee, −ON(Rff)2, −N(Rff)2, −N(Rff)3+X−, −N(ORee)Rff, −SH, −SRee, −SSRee, −C(=O)Ree, −CO2H, −CO2Ree, −OC(=O)Ree, −OCO2Ree, −C(=O)N(Rff)2, −OC(=O)N(Rff)2, −NRffC(=O)Ree, −NRffCO2Ree, −NRffC(=O)N(Rff)2, −C(=NRff)ORee, −OC(=NRff)Ree, −OC(=NRff)ORee, −C(=NRff)N(Rff)2, −OC(=NRff)N(Rff)2, −NRffC(=NRff)N(Rff)2, −NRffSO2Ree, −SO2N(Rff)2, −SO2Ree, −SO2ORee, −OSO2Ree, −S(=O)Ree, −Si(Ree)3, −OSi(Ree)3, −C(=S)N(Rff)2, −C(=O)SRee, −C(=S)SRee, −SC(=S)SRee, −P(=O)(ORee)2, −P(=O)(Ree)2, −OP(=O)(Ree)2, −OP(=O)(ORee)2, C1–10 alkyl, C1–10 perhaloalkyl, C1–10 alkenyl, C1–10 alkynyl, heteroC1–10alkyl, heteroC1–10alkenyl, heteroC1–10alkynyl, C3-10carbocyclyl, 3- 10 membered heterocyclyl, C6-10aryl, and 5-10 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 518 / 119 C1723.70000WO00 #13627512v1Rgggroups, or two geminal Rddsubstituents are joined to form =O or =S; wherein X−is a counterion; each instance of Reeis, independently, selected from C1–10 alkyl, C1–10 perhaloalkyl, C1–10alkenyl, C1–10alkynyl, heteroC1–10alkyl, heteroC1–10alkenyl, heteroC1–10 alkynyl, C3-10 carbocyclyl, C6-10 aryl, 3-10 membered heterocyclyl, and 3- 10 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rgggroups; each instance of Rffis, independently, selected from hydrogen, C1–10 alkyl, C1–10perhaloalkyl, C1–10alkenyl, C1–10alkynyl, heteroC1–10alkyl, heteroC1–10alkenyl, heteroC1–10alkynyl, C3-10carbocyclyl, 3-10 membered heterocyclyl, C6-10aryl, and 5- 10 membered heteroaryl, or two Rffgroups are joined to form a 3-10 membered heterocyclyl or 5-10 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 Rgggroups; each instance of Rggis, independently, halogen, −CN, −NO2, −N3, −SO2H, −SO3H, −OH, −OC1–6alkyl, −ON(C1–6alkyl)2, −N(C1–6alkyl)2, −N(C1–6alkyl)3+X−, −NH(C1–6 alkyl)2+X−, −NH2(C1–6 alkyl)+X−, −NH3+X−, −N(OC1–6 alkyl)(C1–6 alkyl), −N(OH)(C1–6 alkyl), −NH(OH), −SH, −SC1–6 alkyl, −SS(C1–6 alkyl), −C(=O)(C1–6 alkyl), −CO2H, −CO2(C1–6alkyl), −OC(=O)(C1–6alkyl), −OCO2(C1–6alkyl), −C(=O)NH2, −C(=O)N(C1–6alkyl)2, −OC(=O)NH(C1–6alkyl), −NHC(=O)( C1–6alkyl), −N(C1–6 alkyl)C(=O)( C1–6 alkyl), −NHCO2(C1–6 alkyl), −NHC(=O)N(C1–6 alkyl)2, −NHC(=O)NH(C1–6 alkyl), −NHC(=O)NH2, −C(=NH)O(C1–6 alkyl), −OC(=NH)(C1–6alkyl), −OC(=NH)OC1–6alkyl, −C(=NH)N(C1–6alkyl)2, −C(=NH)NH(C1–6 alkyl), −C(=NH)NH2, −OC(=NH)N(C1–6 alkyl)2, −OC(NH)NH(C1– 6 alkyl), −OC(NH)NH2, −NHC(NH)N(C1–6 alkyl)2, −NHC(=NH)NH2, −NHSO2(C1–6 alkyl), −SO2N(C1–6alkyl)2, −SO2NH(C1–6alkyl), −SO2NH2, −SO2C1–6alkyl, −SO2OC1–6 alkyl, −OSO2C1–6 alkyl, −SOC1–6 alkyl, −Si(C1–6 alkyl)3, −OSi(C1–6 alkyl)3 −C(=S)N(C1–6 alkyl)2, C(=S)NH(C1–6 alkyl), C(=S)NH2, −C(=O)S(C1–6 alkyl), −C(=S)SC1–6alkyl, −SC(=S)SC1–6alkyl, −P(=O)(OC1–6alkyl)2, −P(=O)(C1–6alkyl)2, −OP(=O)(C1–6alkyl)2, −OP(=O)(OC1–6alkyl)2, C1–10alkyl, C1–10perhaloalkyl, C1–10alkenyl, C1–10 alkynyl, heteroC1–10 alkyl, heteroC1–10 alkenyl, heteroC1–10 alkynyl, C3- 10 carbocyclyl, C6-10 aryl, 3-10 membered heterocyclyl, or 5-10 membered heteroaryl; or two geminal Rggsubstituents can be joined to form =O or =S; and19 / 119 C1723.70000WO00 #13627512v1each X−is a counterion.

[0047] The term “thiol” or “thio” refers to the group –SH. The term “substituted thiol” or “substituted thio,” by extension, refers to a thiol group wherein the sulfur atom directly attached to the parent molecule is substituted with a group other than hydrogen, and includes groups selected from –SRaa, –S=SRcc, –SC(=S)SRaa, –SC(=S)ORaa, –SC(=S) N(Rbb)2, –wherein Raaand Rccare as defined herein.

[0048] In certain embodiments, the substituent present on a sulfur atom is a sulfur protecting group (also referred to as a “thiol protecting group”). In some embodiments, each sulfur protecting group is selected from the group consisting of −Raa, −N(Rbb)2, −C(=O)SRaa,−S(=O)Raa, −SO2Raa, −Si(Raa)3, −P(Rcc)2, −P(Rcc)3+X−, −P(ORcc)2, −P(ORcc)3+X−, −P(=O)(Raa)2, −P(=O)(ORcc)2, and −P(=O)(N(Rbb) 2)2, wherein Raa, Rbb, and Rccare as defined herein. Sulfur protecting groups are well known in the art and include those described in detail in Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3rdedition, John Wiley & Sons, 1999, incorporated herein by reference.

[0049] A “counterion” or “anionic counterion” is a negatively charged group associated with a positively charged group in order to maintain electronic neutrality. An anionic counterion may be monovalent (e.g., including one formal negative charge). An anionic counterion may also be multivalent (e.g., including more than one formal negative charge), such as divalent or trivalent. Exemplary counterions include halide ions (e.g., F–, Cl–, Br–, I–), NO3–, ClO4–, OH–, H2PO4–, HCO − 3 , HSO4–, sulfonate ions (e.g., methansulfonate, trifluoromethanesulfonate, p–toluenesulfonate, benzenesulfonate, 10–camphor sulfonate, naphthalene–2–sulfonate, naphthalene–1–sulfonic acid–5–sulfonate, ethan–1–sulfonic acid– 2–sulfonate, and the like), carboxylate ions (e.g., acetate, propanoate, benzoate, glycerate, lactate, tartrate, glycolate, gluconate, and the like), BF4−, PF4–, PF6–, AsF6–, SbF6–, B[3,5- (CF3)2C6H3]4]–, B(C6F5)4−, BPh4–, Al(OC(CF3)3)4–, and carborane anions (e.g., CB11H12–or (HCB11Me5Br6)–). Exemplary counterions which may be multivalent include CO32−, HPO42−, PO 3− 4 , B4O72−, SO42−, S2O32−, carboxylate anions (e.g., tartrate, citrate, fumarate, maleate, malate, malonate, gluconate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, salicylate, phthalates, aspartate, glutamate, and the like), and carboranes.

[0050] Use of the phrase “at least one instance” refers to 1, 2, 3, 4, or more instances, but also encompasses a range, e.g., for example, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 4, from 2 to 3, or from 3 to 4 instances, inclusive.20 / 119 C1723.70000WO00 #13627512v1

[0051] The disclosure is not intended to be limited in any manner by the above exemplary listing of substituents. Additional terms may be defined in other sections of this disclosure.

[0052] As used herein, the term “salt” refers to any and all salts, and encompasses pharmaceutically acceptable salts. Salts include ionic compounds that result from the neutralization reaction of an acid and a base. A salt is composed of one or more cations (positively charged ions) and one or more anions (negative ions) so that the salt is electrically neutral (without a net charge). Salts of the compounds of the present disclosure include those derived from inorganic and organic acids and bases. Examples of acid addition salts are salts of an amino group formed with inorganic acids, such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, and perchloric acid, or with organic acids, such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, or malonic acid or by using other methods known in the art such as ion exchange. Other salts include adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2–hydroxy–ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2– naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3–phenylpropionate, phosphate, picrate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate, hippurate, and the like. Salts derived from appropriate bases include alkali metal, alkaline earth metal, ammonium and N+(C1–4 alkyl)4 salts. Representative alkali or alkaline earth metal salts include sodium, lithium, potassium, calcium, magnesium, and the like. Further salts include ammonium, quaternary ammonium, and amine cations formed using counterions such as halide, hydroxide, carboxylate, sulfate, phosphate, nitrate, lower alkyl sulfonate, and aryl sulfonate.

[0053] It is also to be understood that compounds that have the same molecular formula but differ in the nature or sequence of bonding of their atoms or the arrangement of their atoms in space are termed “isomers”. Isomers that differ in the arrangement of their atoms in space are termed “stereoisomers”.

[0054] Stereoisomers that are not mirror images of one another are termed “diastereomers” and those that are non-superimposable mirror images of each other are termed “enantiomers”. When a compound has an asymmetric center, for example, it is bonded to four different groups, a pair of enantiomers is possible. An enantiomer can be characterized by the absolute21 / 119 C1723.70000WO00 #13627512v1configuration of its asymmetric center and is described by the R- and S-sequencing rules of Cahn and Prelog, or by the manner in which the molecule rotates the plane of polarized light and designated as dextrorotatory or levorotatory (i.e., as (+) or (−)-isomers respectively). A chiral compound can exist as either individual enantiomer or as a mixture thereof. A mixture containing equal proportions of the enantiomers is called a “racemic mixture”.

[0055] The term “terpene” refers to a class of compounds derived from isoprene, which has the molecular formula C5H8, or is produced by combining isoprene units. The basic molecular formula for terpenes comprises multiples of C5H8, that is, (C5H8)n1 where n1 is the number of linked isoprene units. The isoprene units may be linked together head to head to form linear chains, or they may be arranged to form rings. The terpenes may be classified by the number of terpene units in the molecule. The terpenes include hemiterpenes which comprise a single isoprene unit (e.g., isoprene); monoterpenes which comprise two isoprene units and are represented by the formula C10H16 (e.g., pinene, limonene); sesquiterpenes which comprise three isoprene units and are represented by the formula C15H24(e.g., farnesene); diterpenes which comprise four isoprene units and are represented by the formula C20H32 (e.g., cembrene, taxadiene); sesterterpenes which comprise five isoprene units and have 25 carbon atoms (e.g., geranylfarnesol); triterpenes which comprise six isoprene units and are represented by the formula C30H48 (e.g., squalene); tetraterpenes which comprise eight terpene units and are represented by the formula C40H64 (e.g., acylic lycopene, monocyclic gamma-carotene, alpha-carotene, beta-carotene). In some embodiments, the terpene is optionally substituted. In some embodiments, the terpene is a modified terpene comprising one or more oxygen atoms. In some embodiments, the terpene is a modified terpene lacking one or more methyl groups.

[0056] The term “polymer” refers to a compound comprising covalently connected repeating units. In some embodiments, a polymer comprises eleven or more covalently connected repeating units. The term “oligomer” refers to a compound comprising two to ten covalently connected repeating units. In some embodiments, the polymer is an oligomer. In certain embodiments, a polymer or oligomer is naturally occurring. In certain embodiments, a polymer or oligomer is synthetic (i.e., not naturally occurring).

[0057] The term “initiator” refers to a substance or molecule, other than a reactant, that initiates a reaction, such as in polymerization. In some embodiments, the initiator initiates chain-growth polymerization. Typically, the initiator decomposes to form radical, anionic or cationic species that serve as reactive sites for propagation of polymerization.

[0058] The term “linear polymer” refers to a polymer having molecules arranged in a linear22 / 119 C1723.70000WO00 #13627512v1fashion, in the form of a single straight chain without cross-links or branches.

[0059] The term “multifunctional cross-linker” refers to a cross-linker having at least three reactive functional groups that can undergo a reaction that provides a cross-link between at least two polymer chains. In some embodiments, inclusion of a multifunctional cross-linker affords a cross-linked polymer.

[0060] The term “cross-linked polymer” refers to a polymer in which the polymer chains are linked together by chemical covalent bonds, generally through molecules or groups that cross-link together to form a polymer network. In some embodiments, multiple polymer chains may be cross-linked to each other at points within their structures, not limited to the ends of the polymer chains. The cross-linked polymer is generally characterized as insoluble but may be swollen with suitable solvents.

[0061] The term “radical” refers to the point of attachment on a particular moiety. Accordingly, the term “diradical” refers to a moiety having two points of attachment. The term “a diradical derived from a terpene monomer” refers to a moiety that has two points of attachment that is obtained from a terpene monomer upon its incorporation into a polymer. The term “a diradical derived from a monomer comprising two thiol groups” refers to a moiety that has two points of attachment that is obtained from a monomer comprising two thiol groups upon its incorporation into a polymer. In some embodiments, the term “a diradical derived from a monomer comprising two thiol groups” refers to a moiety that has two points of attachment that is obtained from a monomer having two thiol groups upon its incorporation into a polymer. The term “a multi-radical derived from a multifunctional cross- linker” refers to a moiety that has at least two points of attachment that is obtained from a multifunctional cross-linker. In some embodiments, the term “a multi-radical derived from a multifunctional cross-linker” refers to a moiety that has at least three points of attachment that is obtained from a multifunctional cross-linker.

[0062] The term “additive” refers to a substance that is added to a compound provided herein (e.g., a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof) to modify its properties. In some embodiments, an additive is added at a lower weight percentage than the compound itself. An additive can be any kind of molecular, polymeric, inorganic, or organic substance. For example, additives include, but are not limited to, plasticizers, lubricants, mold release agents, viscosity reducing agents, antioxidants, solvents, pigments, flame retardants, acid scavengers, light stabilizers, thermal stabilizers, anti-static agents, slip agents, fillers, reinforcements, and the like.

[0063] The term “latex” refers to an emulsion of polymer microparticles in water. In some23 / 119 C1723.70000WO00 #13627512v1embodiments, a latex solidifies by coalescence of the polymer particles as the water evaporates.

[0064] The terms “composition” and “formulation” are used interchangeably.

[0065] The term “injection molding” refers to the process of injecting molten polymer within a cavity to produce an article. The heated polymer is forced under pressure into the cavity, which is created by parts of the mold, which may be clamped together. The cavity generally has an inverse shape to the desired article of manufacture. Upon cooling, the mold is released, and the solidified article can be removed. In some embodiments, injection molding is compatible with thermoplastic materials. In some embodiments, injection molding is compatible with both thermoplastic and thermoset materials.

[0066] The term “compression molding” refers to a method of forming an article by applying heat or pressure to a polymer in a mold. In some embodiments, heat or pressure is applied such that the polymer does not melt. If both heat and pressure are applied, the application of heat and pressure can occur simultaneously or sequentially. Methods of compression molding include, but are not limited to, isostatic molding, direct forming and sintering.

[0067] The term “transfer molding” refers to a method of forming an article from a polymer by transferring the polymer from a separate receptacle through a gate to a fixed mold cavity, from which the article may be removed after molding.

[0068] Other than in the examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein should be understood as modified in all instances by the term “about.” “About” and “approximately” shall generally mean an acceptable degree of error for the quantity measured given the nature or precision of the measurements. Exemplary degrees of error are within 20 percent (%), typically, within 10%, or more typically, within 5%, 4%, 3%, 2%, or 1% of a given value or range of values.

[0069] Unless otherwise required by context, singular terms shall include pluralities, and plural terms shall include the singular. DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

[0070] The present disclosure provides compounds (e.g., bio-derived polymers, and salts, stereoisomers, and isotopically labeled compounds thereof), as well as compositions, products, and kits thereof. The compounds provided herein may be linear or cross-linked poly(thioethers) and may be provided as a latex or in bulk. Also provided herein are methods of preparing, molding, and applying a coating of the compounds provided herein.24 / 119 C1723.70000WO00 #13627512v1Compounds

[0071] In one aspect, provided herein is a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the polymer is a poly(thioether) comprising: a diradical derived from a terpene monomer; a diradical derived from a monomer comprising two thiol groups; and optionally a multi-radical derived from a multifunctional cross-linker.

[0072] In some embodiments, the bio-derived polymer is a poly(thioether) consisting of: a diradical derived from a terpene monomer; and a diradical derived from a monomer comprising two thiol groups.

[0073] In some embodiments, the bio-derived polymer is a poly(thioether) consisting of: a diradical derived from a terpene monomer; a diradical derived from a monomer comprising two thiol groups; and a multi-radical derived from a multifunctional cross-linker.

[0074] In some embodiments, the bio-derived polymer is a poly(thioether) comprising: a diradical derived from a terpene monomer; a diradical derived from a monomer having two thiol groups; and optionally a multi-radical derived from a multifunctional cross-linker.

[0075] In some embodiments, the bio-derived polymer is a poly(thioether) consisting of: a diradical derived from a terpene monomer; and a diradical derived from a monomer having two thiol groups.

[0076] In some embodiments, the bio-derived polymer is a poly(thioether) consisting of: a diradical derived from a terpene monomer; a diradical derived from a monomer having two thiol groups; and a multi-radical derived from a multifunctional cross-linker.

[0077] In some embodiments, the bio-derived polymer is a latex. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is provided in bulk. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of a brick. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of a roll. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of a pellet.

[0078] In some embodiments, the bio-derived polymer comprises one or more instances of formula (i):25 / 119 C1723.70000WO00 #13627512v1wherein A is a diradical derived from a terpene monomer, Z is a diradical derived from a monomer comprising two thiol groups, and n is an integer from 1 to 1,000 inclusive.

[0079] In some embodiments, the diradical derived from a terpene monomer comprises optionally substituted C1-20 alkylene, optionally substituted C1-20 alkenylene, optionally substituted C1-20alkynylene, optionally substituted C1-20heteroalkylene, optionally substituted C1-20heteroalkenylene, optionally substituted C1-20heteroalkynylene, optionally substituted C3-15 carbocycylene, optionally substituted 3- to 10-memebered heterocyclylene, optionally substituted C6-10arylene, optionally substittued C5-10heteroarylene, or any combination thereof. In some embodiments, the diradical derived from a terpene monomer comprises optionally substituted C1-20 alkylene, optionally substituted C1-20 alkenylene, optionally substituted C1-20 alkynylene, optionally substituted C3-15 carbocycylene, or any combination thereof. In some embodiments, the diradical derived from a terpene monomer comprises optionally substituted C1-20alkylene, optionally substituted C1-20alkenylene, optionally substituted C3-15 carbocycylene, or any combination thereof. In some embodiments, the diradical derived from a terpene monomer comprises C1-20alkylene, C1-20alkenylene, C3-15carbocycylene, or any combination thereof, wherein the alkylene, alkenylene, or carbocyclene is optionally substituted with -OH or -Me. In some embodiments, the diradical derived from a terpene monomer comprises optionally substituted C1-20alkylene, optionally substituted C1-20alkenylene, optionally substituted C3-15carbocycylene, or any combination thereof, wherein The diradical derived from a terpene monomer comprises a double bond. In some embodiments, the diradical derived from a terpene monomer comprises C1-20alkylene, C3-15carbocycylene, or any combination thereof, wherein the alkylene or carbocyclene is optionally substituted with -OH or -Me. In some embodiments, the diradical derived from a terpene monomer comprises C1-20 alkylene, wherein the alkylene is optionally substituted with -OH or -Me. In some embodiments, the diradical derived from a terpene monomer comprises C3-15carbocycylene, wherein the carbocyclene is optionally substituted with -OH or -Me. In some embodiments, the diradical derived from a terpene monomer comprises C3-15carbocycylene, wherein the carbocyclene is monocyclic. In some embodiments, the diradical derived from a terpene monomer comprises C3-15 carbocycylene, wherein the carbocyclene is bicyclic. In some embodiments, the diradical derived from a terpene monomer comprises C3-15 carbocycylene, wherein the carbocyclene is bridged.26 / 119 C1723.70000WO00 #13627512v1

[0080] In some embodiments, the diradical derived from a terpene monomer is a diradical derived from a terpene monomer having two double bonds. In some embodiments, the diradical derived from a terpene monomer has the formula:In some embodiments, the diradical derived from a terpene monomer has the formula:27 / 119 C1723.70000WO00 #13627512v1

[0081] In some embodiments, the diradical derived from a terpene monomer has the formula:some embodiments, the diradical derived fromembodiments, the diradical derived from a terpene monomer has the formula:,28 / 119 C1723.70000WO00 #13627512v1some embodiments, the diradical derived from a terpenemonomer has the formula:some embodiments, the diradical derived from a terpene monomer hasthe formula:some embodiments, the diradical derived from a terpene monomer hassome embodiments, the diradical derived from a terpene monomer has the formula:embodiments, the diradical derived from a terpene monomer has the formula:29 / 119 C1723.70000WO00 #13627512v1. In some embodiments, the diradical derived from a terpeneembodiments, the diradical derived from a terpene monomer has the formula:

[0082] In some embodiments, the diradical derived from a terpene monomer has the formula:embodiments, the diradical derived from a terpene monomer has the formula:30 / 119 C1723.70000WO00 #13627512v1

[0083] In some embodiments, the diradical derived from a terpene monomer has the formula:some embodiments, the diradical derived from a terpene monomer has theterpene monomer has the formula:someembodiments, the diradical derived from a terpene monomer has the formula:31 / 119 C1723.70000WO00 #13627512v1derived from a terpene monomer has the formula: some embodiments,the diradical derived from a terpene monomer has the formula:some embodiments, the diradical derived from a terpene monomer has the formula:some embodiments, the diradical derived from a terpene monomer has the formula:. In some embodiments, the diradical derived from a terpene monomer has the formula:.

[0084] In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula , wherein L1comprises optionally substituted C1-20 alkylene, optionally substituted C1-20alkenylene, optionally substituted C1-20alkynylene, optionally substituted C1-20heteroalkylene, optionally substituted C1-20heteroalkenylene, optionally substituted C1-20 heteroalkynylene, optionally substituted C3-10 carbocycylene, optionally substituted 3- to 10-memebered heterocyclylene, optionally substituted C6-10arylene, optionally substittued C5-10heteroarylene, or any combination thereof. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula , wherein L1is optionally substituted C1-20alkylene or optionally substituted C1-20 heteroalkylene. In some embodiments, L1is optionally substituted C1-10 alkylene or optionally substituted C1-10heteroalkylene. In some embodiments, L1is optionally substituted C2-10alkylene or optionally substituted C2-10heteroalkylene. In some embodiments, L1is optionally substituted C2-10 alkylene or optionally substituted C2-10 heteroalkylene, wherein the heteroalkylene or optional substitutent comprises one or more oxygen atoms. In some embodiments, L1is optionally substituted C2-10alkylene, wherein the32 / 119 C1723.70000WO00 #13627512v1optional substituent comprises one or more oxygen atoms. In some embodiments, L1is unsubstituted C2-10 alkylene. In some embodiments, L1is C2-10 alkylene optionally substitued with =O, -OH, or C1-6 alkoxy. In some embodiments, L1is C2-10 alkylene optionally substitued with -OH. In some embodiments, L1is optionally substituted C2-10heteroalkylene, wherein the heteroalkylene comprises one or more oxygen atoms. In some embodiments, L1is C2-10 heteroalkylene optionally substituted with =O, -OH, or C1-6 alkoxy.

[0085] In some embodiments, the bio-derived polymer comprises one or more instances of formula (i-1):wherein A, L1, and n are as provided herein.

[0086] In some embodiments, the diradical derived from a monomer comprising two thiol groups is a diradical derived from a monomer having two thiol groups. In some embodiments, the diradical derived from a monomer comprising two thiol groups has themonomer comprising two thiol groups has the formula:,33 / 119 C1723.70000WO00 #13627512v1embodiments, the diradical derived from a monomer comprising two thiol groups has thethe diradicalderived from a monomer comprising two thiol groups has the ,embodiments, the diradical derived from a monomer comprising two thiol groups has theor. In some embodiments, the diradical derived from amonomer comprising two thiol groups has the formula:or. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:or. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the34 / 119 C1723.70000WO00 #13627512v1formula: . In some embodiments, the diradical derived from a monomercomprising two thiol groups has the formula: . In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:. In some embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:embodiments, the diradical derived from a monomer comprising two thiol groups has the formula:.

[0087] In some embodiments, the bio-derived polymer does not comprise a multi-radical derived from a multifunctional cross-linker. In some embodiments, the bio-derived polymer is a linear polymer.

[0088] In some embodiments, the bio-derived polymer comprises a multi-radical derived from a multifunctional cross-linker. In some embodiments, the bio-derived polymer is a cross-linked polymer. In some embodiments, the bio-derived polymer comprises a multi- radical derived from a multifunctional cross-linker, wherein the multifunctional cross-linker has reacted to form a bond to the bio-derived polymer at each available position. In some embodiments, the bio-derived polymer comprises a multi-radical derived from a multifunctional cross-linker, wherein the multifunctional cross-linker has reacted to form a bond to the bio-derived polymer at more than two available positions. In some embodiments, the bio-derived polymer comprises a multi-radical derived from a multifunctional cross- linker, wherein the multifunctional cross-linker has reacted to form a bond to the bio-derived polymer at three or more available positions.

[0089] In some embodiments, the multi-radical derived from a multifunctional cross-linker is derived from a compound comprising one or more thiol moieties. In some embodiments, the35 / 119 C1723.70000WO00 #13627512v1multi-radical derived from a multifunctional cross-linker is derived from a compound comprising at least three thiol moieties.

[0090] In some embodiments, the bio-derived polymer further comprises one or more instances of formula (ii) or (iii):(iii), wherein A is a diradical derived from a terpene monomer, Z is a diradical derived from a monomer comprising two thiol groups, Y is a multi-radical derived from a multifunctional cross-linker, and m is an integer from 2 to 6, inclusive.

[0091] In some embodiments, the bio-derived polymer further comprises one or more instances of formula (ii) or (iii):wherein A is a diradical derived from a terpene monomer, Z is a diradical derived from a monomer comprising two thiol groups, Y is a multi-radical derived from a multifunctional cross-linker, m is an integer from 2 to 6, inclusive, and each instance of X is independently a bond to the bio-derived polymer, hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or two adjacent instances of X are joined to form a double bond. In some embodiments, the bio-derived polymer further comprises one or more instances of formula (ii′):wherein A is a diradical derived from a terpene monomer, Y is a multi-radical derived from a multifunctional cross-linker, m is an integer from 2 to 6, inclusive, and each instance of X is independently a bond to the bio-derived polymer, hydrogen, or a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups). In some embodiments, the bio-derived polymer further comprises one or more instances of formula (iii):wherein Z is a diradical derived from a monomer comprising two thiol groups, Y is a multi- radical derived from a multifunctional cross-linker, m is an integer from 2 to 6, inclusive, and36 / 119 C1723.70000WO00 #13627512v1each instance of X is independently a bond to the bio-derived polymer, hydrogen, or two adjacent instances of X are joined to form a double bond.

[0092] In some embodiments, the bio-derived polymer further comprises one or more instances of formula (ii-1):wherein each instance of n is independently an integer from 1 to 1,000, inclusive.

[0093] In some embodiments, the bio-derived polymer further comprises one or more instances of formula (ii-2):wherein each instance of n is independently an integer from 1 to 1,000, inclusive.

[0094] In some embodiments, the bio-derived polymer further comprises one or more instances of formula (iii-1):wherein each instance of n is independently an integer from 1 to 1,000, inclusive.

[0095] In some embodiments, n is an integer from 1 to 1,000, inclusive. In some embodiments, n is an integer from 1 to 800, inclusive. In some embodiments, n is an integer from 1 to 600, inclusive. In some embodiments, n is an integer from 1 to 400, inclusive. In some embodiments, n is an integer from 1 to 200, inclusive. In some embodiments, n is an integer from 1 to 100, inclusive. In some embodiments, n is an integer from 10 to 1,000, inclusive. In some embodiments, n is an integer from 10 to 800, inclusive. In some embodiments, n is an integer from 10 to 600, inclusive. In some embodiments, n is an integer from 10 to 400, inclusive. In some embodiments, n is an integer from 10 to 200, inclusive. In some embodiments, n is an integer from 10 to 100, inclusive. In some embodiments, n is an integer from 50 to 250, inclusive. In some embodiments, n is an integer from 100 to 300, inclusive. In some embodiments, n is an integer from 200 to 400, inclusive. In some embodiments, n is an integer from 300 to 500, inclusive. In some embodiments, n is an37 / 119 C1723.70000WO00 #13627512v1integer from 400 to 600, inclusive. In some embodiments, n is an integer from 500 to 750, inclusive. In some embodiments, n is an integer from 750 to 1,000, inclusive. In some embodiments, n is an integer from 10 to 100, inclusive. In some embodiments, n is an integer from 50 to 150, inclusive. In some embodiments, n is an integer from 100 to 200, inclusive. In some embodiments, n is an integer from 150 to 250, inclusive. In some embodiments, n is an integer from 200 to 300, inclusive. In some embodiments, n is an integer from 250 to 350, inclusive. In some embodiments, n is an integer from 300 to 400, inclusive. In some embodiments, n is an integer from 350 to 450, inclusive. In some embodiments, n is an integer from 500 to 600, inclusive. In some embodiments, n is an integer from 550 to 650, inclusive. In some embodiments, n is an integer from 600 to 700, inclusive. In some embodiments, n is an integer from 650 to 750, inclusive. In some embodiments, n is an integer from 700 to 800, inclusive. In some embodiments, n is an integer from 750 to 850, inclusive. In some embodiments, n is an integer from 800 to 900, inclusive. In some embodiments, n is an integer from 850 to 950, inclusive. In some embodiments, n is an integer from 900 to 1,000, inclusive.

[0096] In some embodiments, m is an integer from 2 to 5, inclusive. In some embodiments, m is an integer from 2 to 4, inclusive. In some embodiments, m is an integer from 3 to 6, inclusive. In some embodiments, m is an integer from 3 to 5, inclusive. In some embodiments, m is an integer from 4 to 6, inclusive. In some embodiments, m is 2 or 3. In some embodiments, m is 3 or 4. In some embodiments, m is 4 or 5. In some embodiments, m is 5 or 6. In some embodiments, m is 2. In some embodiments, m is 3. In some embodiments, m is 4. In some embodiments, m is 5. In some embodiments, m is 6.

[0097] In some embodiments, the multi-radical derived from a multifunctional cross-linkerleast three instances of X are a bond to the bio-derived polymer, and the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a38 / 119 C1723.70000WO00 #13627512v1multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the multi-radical derived from a multifunctional cross-linker has the formula:,least three instances of X are a bond to the bio-derived polymer, and the other instances of X are each independently hydrogen. In some embodiments, the multi-radical derived from a multifunctional cross-linker has the formula:,.

[0098] In some embodiments, the multi-radical derived from a multifunctional cross-linker has the formula:39 / 119 C1723.70000WO00 #13627512v1wherein at least three instances of X are a bond to the bio-derived polymer, and the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the multi-radical derivedderived polymer, and the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the multi-radical derived from a multifunctional cross-linker has the formula: :40 / 119 C1723.70000WO00 #13627512v1of X is independently hydrogen or a bond to the bio-derived polymer, provided that at least three instances of X are a bond to the bio-derived polymer. In some embodiments, the multi- radical derived from a multifunctional cross-linker has the formula:,X is independently hydrogen or a bond to the bio-derived polymer, provided that at least three instances of X are a bond to the bio-derived polymer.

[0099] In some embodiments, the bio-derived polymer further comprises a diradical derived from a multifunctional cross-linker. In some embodiments, the bio-derived polymer comprises a diradical derived from a multifunctional cross-linker, wherein the multifunctional cross-linker has reacted to form a bond to the bio-derived polymer at two available positions.41 / 119 C1723.70000WO00 #13627512v1

[0100] In some embodiments, the diradical derived from a multifunctional cross-linker is derived from a compound comprising one or more thiol moieties. In some embodiments, the diradical derived from a multifunctional cross-linker is derived from a compound comprising at least three thiol moieties. In some embodiments, the diradical derived from a multifunctional cross-linker has the formula:,instances of X are a bond to the bio-derived polymer, and the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the diradical derived from a multifunctionalinstance of X is independently hydrogen or a bond, provided that two instances of X are a bond to the bio-derived polymer and the remaining instances of X are hydrogen.

[0101] In some embodiments, the diradical derived from a multifunctional cross-linker has42 / 119 C1723.70000WO00 #13627512v1wherein two instances of X are a bond to the bio-derived polymer, and the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the diradical derived from a multifunctional cross-linker has the formula:of X is independently hydrogen or a bond to the bio-derived polymer, provided that two instances of X are a bond to the bio-derived polymer and the remaining instances of X are hydrogen.

[0102] In some embodiments, the diradical derived from a multifunctional cross-linker hasthe formula:43 / 119 C1723.70000WO00 #13627512v1X are a bond to the bio-derived polymer, and the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the diradical derived from a multifunctional cross-linker has the formula:X is independently hydrogen or a bond to the bio-derived polymer, provided that two instances of X are a bond to the bio-derived polymer and the remaining instances of X are hydrogen.

[0103] In some embodiments, the other instances of X are each independently hydrogen, a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups), or a bond to a radical derived from a terpene monomer. In some embodiments, the other instances of X are each independently hydrogen or a bond to another S-atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups). In some embodiments, the other instances of X are each independently hydrogen or a bond to a radical derived from a terpene monomer. In some embodiments, the other instances of X are each independently a bond to another S-atom (e.g., an S-atom of a44 / 119 C1723.70000WO00 #13627512v1multifunctional crosslinker or of a monomer comprising two thiol groups) or a bond to a radical derived from a terpene monomer. In some embodiments, the other instances of X are each hydrogen. In some embodiments, the other instances of X are each a bond to another S- atom (e.g., an S-atom of a multifunctional crosslinker or of a monomer comprising two thiol groups). In some embodiments, the other instances of X are each a bond to a radical derived from a terpene monomer.

[0104] In some embodiments, the multi-radical derived from a multifunctional cross-linker is derived from a terpene comprising three or more double bonds. In some embodiments, the multi-radical derived from a multifunctional cross-linker has the formula:45 / 119 C1723.70000WO00 #13627512v1

[0105] In some embodiments, the multi-radical derived from a multifunctional cross-linkerthe multi-radical derived from a multifunctional cross-linker has the formula:,46 / 119 C1723.70000WO00 #13627512v1some embodiments, the multi-radical derived from amultifunctional cross-linker has the formula:,some embodiments, the multi-radical derived from a multifunctional cross-linker has the formula:multifunctional cross-linker has the formula:embodiments, the multi-radical derived from a multifunctional cross-linker has the formula:

[0106] In some embodiments, the diradical derived from a multifunctional cross-linker is derived from a compound comprising one or more alkene moieties. In some embodiments, the diradical derived from a multifunctional cross-linker is derived from a compound comprising at least three alkene moieties. In some embodiments, the diradical derived from a multifunctional cross-linker is derived from a terpene comprising one or more alkene moieties. In some embodiments, the diradical derived from a multifunctional cross-linker is derived from a terpene comprising at least three alkene moieties.

[0107] In some embodiments, the diradical derived from a multifunctional cross-linker has47 / 119 C1723.70000WO00 #13627512v1other instances of X are each independently hydrogen, a radical derived from a monomer comprising two thiol groups, or two adjacent instances of X are joined to form a double bond. In some embodiments, the diradical derived from a multifunctional cross-linker has the formula:wherein each instance of X is independently hydrogen or a bond to the bio-derived polymer, or two adjacent instances of X are joined to form a double bond, provided that two instances of X are a bond to the bio-derived polymer. In some embodiments, the other instances of X are each independently hydrogen, a radical derived from a monomer comprising two thiol groups, or two adjacent instances of X are joined to form a double bond. In some embodiments, the other instances of X are each independently hydrogen or two adjacent instances of X are joined to form a double bond. In some embodiments, the other instances of X are each independently hydrogen or a radical derived from a monomer comprising two thiol groups.

[0108] In some embodiments, the diradical derived from a terpene monomer is limonene, and the diradical derived from a monomer comprising two thiol groups is dithiothreitol, propanedithiol, or ethanediol. In some embodiments, the diradical derived from a terpene monomer is limonene, and the diradical derived from a monomer comprising two thiol groups is dithiothreitol or propanedithiol. In some embodiments, the diradical derived from a terpene monomer is limonene, and the diradical derived from a monomer comprising two thiol groups is dithiothreitol. In some embodiments, the diradical derived from a terpene monomer is limonene and the diradical derived from a monomer comprising two thiol groups is propanedithiol. In some embodiments, the diradical derived from a terpene monomer is48 / 119 C1723.70000WO00 #13627512v1limonene, and the diradical derived from a monomer comprising two thiol groups is ethanediol.

[0109] In some embodiments, the bio-derived polymer further comprises hydrogen end- groups.

[0110] In another aspect, provided herein is a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, prepared according to a method provided herein, including according to the examples herein. Compositions, Kits, and Products

[0111] In another aspect, provided herein is a composition comprising a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, and an additive. In some embodiments, the composition comprises one or more additives.

[0112] In some embodiments, the additive is a plasticizer, pigment, flame retardant, antioxidant, acid scavenger, light stabilizer, thermal stabilizer, lubricant, anti-static agent, slip agent, filler, or reinforcement. In some embodiments, the additive prevents degradation of the composition. In some embodiments, the additive improves the stability of the composition. In some embodiments, the additive improves the stability of the composition relative to a composition of the bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, without the additive. In some embodiments, the additive is an antioxidant, acid scavenger, light stabilizer, or thermal stabilizer. In some embodiments, the additive improves one or more material properties of the composition. In some embodiments, the additive is a plasticizer, pigment, flame retardant, lubricant, anti- static agent, slip agent, filler, or reinforcement.

[0113] In some embodiments, the composition is in the form of a brick. In some embodiments, the composition is in the form of a roll. In some embodiments, the composition is in the form of a pellet.

[0114] In another aspect, provided herein is a kit comprising: a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, or a composition provided herein; and instructions for using the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, or the composition.

[0115] In another aspect, provided herein is a product comprising a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, or a composition provided herein.49 / 119 C1723.70000WO00 #13627512v1

[0116] In some embodiments, the product is a footwear sole or midsole, paint, coating, film, adhesive, oil or gas fracturing fluid, drilling fluid, shale-plugging agent, nano-propellant, lubricant, pacifier, teething ring, nightguard, tire, tire component, seal, trim, insulation, glove, condom, bandage, catheter, tubing, toy, rubber band, gasket, O-ring, belt, textile, bag, packaging, emulsifier, tackifier, or nanoparticle.

[0117] In some embodiments, the product is non-toxic or biocompatible. In some embodiments, the product is non-toxic. In some embodiments, the product is biocompatible. In some embodiments, the product is antibacterial or antimicrobial. In some embodiments, the product is antibacterial. In some embodiments, the product is antimicrobial. In some embodiments, the product releases an antibacterial or antimicrobial agent. In some embodiments, the product releases an antibacterial or antimicrobial agent upon degradation. In some embodiments, the antibacterial or antimicrobial agent is a terpene. In some embodiments, the antibacterial or antimicrobial agent is limonene. In some embodiments, the antibacterial or antimicrobial agent is d-limonene. Methods and Uses

[0118] In another aspect, provided herein is a method of preparing a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, the method comprising reacting a mixture comprising a terpene monomer, a monomer comprising two thiol groups, and optionally a multifunctional cross-linker. In some embodiments, provided herein is a method of preparing a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, the method comprising reacting a mixture comprising a terpene monomer, a monomer having two thiol groups, and optionally a multifunctional cross-linker.

[0119] In some embodiments, the method comprises the steps of: a. preparing a solution of surfactant in solvent; b. adding to the solution terpene monomer, monomer comprising two thiol groups, and optionally a multifunctional cross-linker to afford a mixture; c. purging the mixture with an inert gas; d. heating the mixture; and e. adding an initiator.

[0120] In some embodiments, the method comprises the steps of: a. preparing a solution of surfactant in solvent; b. adding to the solution terpene monomer, monomer having two thiol groups, and optionally a multifunctional cross-linker to afford a mixture;50 / 119 C1723.70000WO00 #13627512v1c. purging the mixture with an inert gas; d. heating the mixture; and e. adding an initiator.

[0121] In some embodiments, the reaction is performed in a solvent. In some embodiments, the solvent is a polar solvent. In some embodiments, the solvent is a polar aprotic solvent. In some embodiments, the solvent is acetone. In some embodiments, the solvent is a polar protic solvent. In some embodiments, the solvent is water.

[0122] In some embodiments, the mixture comprises a surfactant in solution. In some embodiments, the surfactant is a fatty acid, or a salt thereof. In some embodiments, the surfactant is sodium dodecyl sulfate.

[0123] In some embodiments, the solution of surfactant has a concentration of about 1 mM to about 30 mM. In some embodiments, the solution of surfactant has a concentration of about 1 mM to about 10 mM. In some embodiments, the solution of surfactant has a concentration of about 10 mM to about 20 mM. In some embodiments, the solution of surfactant has a concentration of about 20 mM to about 30 mM. In some embodiments, the solution of surfactant has a concentration of about 5 mM to about 20 mM. In some embodiments, the solution of surfactant has a concentration of about 5 mM to about 10 mM. In some embodiments, the solution of surfactant has a concentration of about 6 mM to about 9 mM. In some embodiments, the solution of surfactant has a concentration of about 7.5 mM to about 8.5 mM. In some embodiments, the solution of surfactant has a concentration of about 1 mM, about 2 mM, about 4 mM, 5 mM, about 6 mM, about 7 mM, about 8 mM, about 9 mM, about 10 mM, about 11 mM, about 12 mM, about 13 mM, about 14 mM, about 15 mM, about 20 mM, about 25 mM, or about 30 mM. In some embodiments, the solution of surfactant has a concentration of about 5 mM. In some embodiments, the solution of surfactant has a concentration of about 6 mM. In some embodiments, the solution of surfactant has a concentration of about 7 mM. In some embodiments, the solution of surfactant has a concentration of about 8 mM. In some embodiments, the solution of surfactant has a concentration of about 9 mM. In some embodiments, the solution of surfactant has a concentration of about 10 mM.

[0124] In some embodiments, the terpene monomer is one or more of:51 / 119 C1723.70000WO00 #13627512v1. In some embodiments, the terpene monomer is one or more of:,. In some embodiments, the terpene monomersome embodiments, the terpene monomersome embodiments, the terpene monomersome embodiments, the terpene monomersome embodiments, the terpene monomersome embodiments, the terpene monomer is. In some embodiments, the terpene monomer isIn some52 / 119 C1723.70000WO00 #13627512v1embodiments, the terpene monomer some embodiments, the terpene

[0125] In some embodiments, the terpene monomer has a final concentration of about 50- 500 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 100-400 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 50-100 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 100-200 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 200- 300 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 300-400 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 400-500 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 50 mM, about 100 mM, about 150 mM, about 200 mM, about 250 mM, about 300 mM, about 350 mM, about 400 mM, about 450 mM, or about 500 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 200 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 250 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 300 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 350 mM in the mixture. In some embodiments, the terpene monomer has a final concentration of about 400 mM in the mixture.53 / 119 C1723.70000WO00 #13627512v1

[0126] In some embodiments, the monomer comprising two thiol groups is a monomer having two thiol groups. In some embodiments, the monomer comprising two thiol groups is ,. In some embodiments, the monomer comprising two thiol groups is one or more of:, , ,some embodiments, the monomer comprising two thiol groups is one or more of:,embodiments, the monomer comprising two thiol groups is one or more of:,embodiments, the monomer comprising two thiol groups is one or more of:In some embodiments, the monomer comprising two thiol groups is one or more of:In some embodiments, the monomer comprising two thiol groups is one or more of:54 / 119 C1723.70000WO00 #13627512v1embodiments, the monomer comprising two thiol groups is one or more of:. In some embodiments, the monomer comprising two thiol groups is one or more of:. In some embodiments, the monomer comprising two thiol groups is. In some embodiments, the monomer comprising two thiol groups is. In some embodiments, the monomer comprising two thiol groups is. In someembodiments, the monomer comprising two thiol groups is . In someembodiments, the monomer comprising two thiol groups is . In some embodiments, the monomer comprising two thiol groups is. In some embodiments, the monomer comprising two thiol groups is. In some embodiments, the monomer comprising two thiol groups is. In some embodiments, the monomer comprising two thiol groups is.

[0127] In some embodiments, the monomer comprising two thiol groups has a final concentration of about 50-500 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 100-400 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 50-100 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 100-200 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 200-300 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 300-400 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 400-500 mM in the mixture. In55 / 119 C1723.70000WO00 #13627512v1some embodiments, the monomer comprising two thiol groups has a final concentration of about 50 mM, about 100 mM, about 150 mM, about 200 mM, about 250 mM, about 300 mM, about 350 mM, about 400 mM, about 450 mM, or about 500 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 200 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 250 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 300 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 350 mM in the mixture. In some embodiments, the monomer comprising two thiol groups has a final concentration of about 400 mM in the mixture.

[0128] In some embodiments, the multifunctional cross-linker is one or more ofembodiments, the multifunctional cross-linker is one or more of56 / 119 C1723.70000WO00 #13627512v1embodiments, the multifunctional cross-linker is one or more of:multifunctional cross-linker is one or more of:57 / 119 C1723.70000WO00 #13627512v1.

[0129] In some embodiments, the multifunctional cross-linker issome embodiments, the multifunctional cross-linker is , . In some58 / 119 C1723.70000WO00 #13627512v1embodiments, the multifunctional cross-linker is . In some embodiments, the multifunctional cross-linkersome embodiments, the multifunctional cross-linkersome embodiments, the multifunctionalis. In some embodiments, the multifunctional cross-linker is59 / 119 C1723.70000WO00 #13627512v1.

[0130] In some embodiments, the multifunctional cross-linker is one or more of:

[0131] In some embodiments, the multifunctional cross-linker is one or more of:60 / 119 C1723.70000WO00 #13627512v1some embodiments, the multifunctional cross-linker is one or more of: ,

[0132] In some embodiments, the inert gas is nitrogen. In some embodiments, the inert gas is argon.

[0133] In some embodiments, the mixture is heated to about 20 ºC to about 100 ºC. In some embodiments, the mixture is heated to about 50 ºC to about 90 ºC. In some embodiments, the mixture is heated to about 50 ºC to about 70 ºC. In some embodiments, the mixture is heated to about 55 ºC to about 75 ºC. In some embodiments, the mixture is heated to about 60 ºC to about 80 ºC. In some embodiments, the mixture is heated to about 65 ºC to about 85 ºC. In some embodiments, the mixture is heated to about 70 ºC to about 90 ºC. In some embodiments, the mixture is heated to about 50 ºC, about 55 ºC, about 60 ºC, about 65 ºC, about 70 ºC, about 75 ºC, about 80 ºC, about 85 ºC, about 90 ºC, about 95 ºC, or about 10061 / 119 C1723.70000WO00 #13627512v1ºC. In some embodiments, the mixture is heated to about 50 ºC. In some embodiments, the mixture is heated to about 55 ºC. In some embodiments, the mixture is heated to about 60 ºC. In some embodiments, the mixture is heated to about 65 ºC. In some embodiments, the mixture is heated to about 70 ºC. In some embodiments, the mixture is heated to about 75 ºC. In some embodiments, the mixture is heated to about 80 ºC. In some embodiments, the mixture is heated to about 85 ºC. In some embodiments, the mixture is heated to about 90 ºC. In some embodiments, the mixture is heated to about 95 ºC. In some embodiments, the mixture is heated to about 100 ºC.

[0134] In some embodiments, the mixture comprises an initiator. In some embodiments, the initiator is a radical initiator. In some embodiments, the initiator is water soluble. In some embodiments, the initiator is potassium persulfate.

[0135] In some embodiments, the initiator is added as a solution. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 0.1 mM to about 100 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 0.5 mM to about 50 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 1 mM to about 10 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 2 mM to about 8 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 3 mM to about 7 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 4 mM to about 6 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 0.5 mM, about 1 mM, about 1.5 mM, about 2 mM, about 2.5 mM, about 3 mM, about 3.5 mM, about 4 mM, abou 4.5 mM, about 5 mM, about 5.5 mM, about 6 mM, about 6.5 mM, about 7 mM, about 7.5 mM, about 8 mM, about 8.5 mM, about 9.0 mM, or about 10 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 1 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 2 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 3 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 3.5 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 4 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 4.5 mM in the mixture. In some62 / 119 C1723.70000WO00 #13627512v1embodiments, adding the initiator to the mixture affords a final initiator concentration of about 5 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 5.5 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 6 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 6.5 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 7 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 7.5 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 8 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 8.5 mM in the mixture. In some embodiments, adding the initiator to the mixture affords a final initiator concentration of about 9.0 mM in the mixture.

[0136] In some embodiments, the method further comprises the step of isolating the bio- derived polymer. In some embodiments, the isolating is performed by centrifuging the mixture. In some embodiments, the isolating is performed by coagulation. In some embodiments, the isolating is performed by adding a salt to the mixture and decanting the solvent. In some embodiments, the coagulating is performed by adding a salt to the mixture. In some embodiments, the coagulating is performed by adding a salt to the mixture and decanting the solvent. In some embodiments, the salt is calcium chloride, sodium chloride, potassium chloride, magnesium sulfate, magnesium chloride, calcium nitrate, barium chloride, aluminum sulfate, iron (III) chloride, or iron (III) sulfate. In some embodiments, the salt is calcium chloride. In some embodiments, the salt is sodium chloride. In some embodiments, the salt is potassium chloride. In some embodiments, the salt is magnesium sulfate. In some embodiments, the salt is magnesium chloride. In some embodiments, the salt is calcium nitrate. In some embodiments, the salt is barium chloride. In some embodiments, the salt is aluminum sulfate. In some embodiments, the salt is iron (III) chloride. In some embodiments, the salt is iron (III) sulfate. In some embodiments, the method further comprises filtering the bio-derived polymer. In some embodiments, the method further comprises filtering the bio-derived polymer away from the solvent. In some embodiments, the method further comprises filtering the bio-derived polymer away from the reaction mixture.

[0137] In some embodiments, the method further comprises resuspending or washing the bio-derived polymer with a second solvent. In some embodiments, the method further63 / 119 C1723.70000WO00 #13627512v1comprises resuspending the bio-derived polymer with a second solvent. In some embodiments, the method further comprises washing the bio-derived polymer with a second solvent. In some embodiments, the second solvent is the same solvent. In some embodiments, the second solvent is a different solvent. In some embodiments, the second solvent is a polar solvent. In some embodiments, the second solvent is a polar aprotic solvent. In some embodiments, the second solvent is acetone. In some embodiments, the second solvent is a polar protic solvent. In some embodiments, the second solvent is water.

[0138] In some embodiments, the method further comprises drying the bio-derived polymer. In some embodiments, the drying is performed by heating. In some embodiments, the drying is performed at about 20 °C to about 150 °C. In some embodiments, the drying is performed at about 20 °C to about 80 °C. In some embodiments, the drying is performed at about 20 °C to about 65 °C. In some embodiments, the drying is performed at about 20 °C to about 40 °C. In some embodiments, the drying is performed at about 40 °C to about 60 °C. In some embodiments, the drying is performed at about 60 °C to about 80 °C. In some embodiments, the drying is performed at about 80 °C to about 100 °C. In some embodiments, the drying is performed at about 100 °C to about 120 °C. In some embodiments, the drying is performed at about 120 °C to about 150 °C. In some embodiments, the drying is performed under reduced pressure.

[0139] In some embodiments, the method further comprises curing the bio-derived polymer. In some embodiments, a curing agent is added to the bio-derived polymer. In some embodiments, the curing agent is a peroxide, a metal oxide, or a photoinitiator. In some embodiments, the curing agent is a peroxide. In some embodiments, the curing agent is dicumyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide (MEKP), cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxide, di-tert-butyl peroxide, or a peroxyacetal. In some embodiments, the curing agent is dicumyl peroxide. In some embodiments, the curing agent is benzoyl peroxide. In some embodiments, the curing agent is methyl ethyl ketone peroxide (MEKP). In some embodiments, the curing agent is cumene hydroperoxide. In some embodiments, the curing agent is t-butyl peroxybenzoate. In some embodiments, the curing agent is t-butyl peroxide. In some embodiments, the curing agent is di-tert-butyl peroxide. In some embodiments, the curing agent is peroxyacetal. In some embodiments, the curing agent is a metal oxide. In some embodiments, the curing agent is zinc oxide or magnesium oxide. In some embodiments, the curing agent is a photoinitiator. In some embodiments, the curing agent is benzophenone, igracure, or a derivative thereof.

[0140] In some embodiments, the curing agent is present in an amount of about 0.1% to64 / 119 C1723.70000WO00 #13627512v1about 10% w / w. In some embodiments, the curing agent is present in an amount of about 0.1% to about 1% w / w. In some embodiments, the curing agent is present in an amount of about 1% to about 2% w / w. In some embodiments, the curing agent is present in an amount of about 2% to about 4% w / w. In some embodiments, the curing agent is present in an amount of about 4% to about 6% w / w. In some embodiments, the curing agent is present in an amount of about 6% to about 8% w / w. In some embodiments, the curing agent is present in an amount of about 8% to about 10% w / w.

[0141] In some embodiments, the curing is performed at or above the decomposition temperature of the curing agent. In some embodiments, the curing is performed at about the decomposition temperature of the curing agent. In some embodiments, the curing is performed above the decomposition temperature of the curing agent. In some embodiments, the curing is performed at below about 200 °C. In some embodiments, the curing is performed at about 20 °C to about 200 °C. In some embodiments, the curing is performed at about 20 °C to about 100 °C. In some embodiments, the curing is performed at about 50 °C to about 150 °C. In some embodiments, the curing is performed at about 100 °C to about 200 °C. In some embodiments, the curing is performed at about 20 °C to about 40 °C. In some embodiments, the curing is performed at about 30 °C to about 50 °C. In some embodiments, the curing is performed at about 40 °C to about 60 °C. In some embodiments, the curing is performed at about 50 °C to about 70 °C. In some embodiments, the curing is performed at about 60 °C to about 80 °C. In some embodiments, the curing is performed at about 70 °C to about 90 °C. In some embodiments, the curing is performed at about 80 °C to about 100 °C. In some embodiments, the curing is performed at about 90 °C to about 110 °C. In some embodiments, the curing is performed at about 100 °C to about 120 °C. In some embodiments, the curing is performed at about 110 °C to about 130 °C. In some embodiments, the curing is performed at about 120 °C to about 140 °C. In some embodiments, the curing is performed at about 130 °C to about 150 °C. In some embodiments, the curing is performed at about 140 °C to about 160 °C. In some embodiments, the curing is performed at about 150 °C to about 170 °C. In some embodiments, the curing is performed at about 160 °C to about 180 °C. In some embodiments, the curing is performed at about 170 °C to about 190 °C. In some embodiments, the curing is performed at about 180 °C to about 200 °C.

[0142] In some embodiments, the method further comprises hardening the bio-derived polymer. In some embodiments, the method further comprises hardening the bio-derived polymer by heating the bio-derived polymer. In some embodiments, the method further65 / 119 C1723.70000WO00 #13627512v1comprises hardening the bio-derived polymer by heating the bio-derived polymer at about 20 °C to about 200 °C. In some embodiments, the hardening is performed by heating the bio- derived polymer at about 20 °C to about 200 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 20 °C to about 100 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 50 °C to about 150 °C. In some embodiments, the hardening is performed by heating the bio- derived polymer at about 100 °C to about 200 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 20 °C to about 40 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 30 °C to about 50 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 40 °C to about 60 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 50 °C to about 70 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 60 °C to about 80 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 70 °C to about 90 °C. In some embodiments, the hardening is performed by heating the bio- derived polymer at about 80 °C to about 100 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 90 °C to about 110 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 100 °C to about 120 °C. In some embodiments, the hardening is performed by heating the bio- derived polymer at about 110 °C to about 130 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 120 °C to about 140 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 130 °C to about 150 °C. In some embodiments, the hardening is performed by heating the bio- derived polymer at about 140 °C to about 160 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 150 °C to about 170 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 160 °C to about 180 °C. In some embodiments, the hardening is performed by heating the bio- derived polymer at about 170 °C to about 190 °C. In some embodiments, the hardening is performed by heating the bio-derived polymer at about 180 °C to about 200 °C.

[0143] In another aspect, provided herein is a method of injection molding a bio-derived polymer, comprising: introducing a bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, into a screw injection apparatus; melting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled66 / 119 C1723.70000WO00 #13627512v1compound thereof; injecting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, into a mold; and cooling the mold.

[0144] In some embodiments, melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 100 ºC to about 300 ºC. In some embodiments, melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 100 ºC to about 150 ºC. In some embodiments, melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 150 ºC to about 200 ºC. In some embodiments, melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 200 ºC to about 250 ºC. In some embodiments, melting comprises heating the bio- derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 250 ºC to about 300 ºC. In some embodiments, melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 130 ºC, about 140 ºC, about 150 ºC, about 160 ºC, about 170 ºC, about 180 ºC, about 190 ºC, about 200 ºC, about 210 ºC, or about 220 ºC.

[0145] In some embodiments, the injecting step is performed at an injection speed of about 10 mm / s to about 200 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 20 mm / s to about 150 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 30 mm / s to about 100 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 10 mm / s to about 20 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 20 mm / s to about 30 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 30 mm / s to about 40 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 40 mm / s to about 50 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 50 mm / s to about 60 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 60 mm / s to about 70 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 70 mm / s to about 80 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 80 mm / s to about 90 mm / s. In some embodiments, the injecting step is performed at an injection speed of about 90 mm / s to about 100 mm / s.

[0146] In some embodiments, the injecting step is performed at an injection pressure of67 / 119 C1723.70000WO00 #13627512v1about 100 bar to about 2000 bar. In some embodiments, the injecting step is performed at an injection pressure of about 500 bar to about 1500 bar. In some embodiments, the injecting step is performed at an injection pressure of about 100 bar to about 400 bar. In some embodiments, the injecting step is performed at an injection pressure of about 400 bar to about 800 bar. In some embodiments, the injecting step is performed at an injection pressure of about 800 bar to about 1200 bar. In some embodiments, the injecting step is performed at an injection pressure of about 1200 bar to about 1600 bar. In some embodiments, the injecting step is performed at an injection pressure of about 1600 bar to about 2000 bar.

[0147] In some embodiments, the mold is clamped at a force of about 1 tons to about 2000 tons. In some embodiments, the mold is clamped at a force of about 50 tons to about 1000 tons. In some embodiments, the mold is clamped at a force of about 75 tons to about 750 tons. In some embodiments, the mold is clamped at a force of about 100 tons to about 500 tons. In some embodiments, the mold is clamped at a force of about 50 tons to about 150 tons. In some embodiments, the mold is clamped at a force of about 100 tons to about 200 tons. In some embodiments, the mold is clamped at a force of about 150 tons to about 250 tons. In some embodiments, the mold is clamped at a force of about 200 tons to about 300 tons. In some embodiments, the mold is clamped at a force of about 250 tons to about 350 tons. In some embodiments, the mold is clamped at a force of about 300 tons to about 400 tons. In some embodiments, the mold is clamped at a force of about 350 tons to about 450 tons. In some embodiments, the mold is clamped at a force of about 400 tons to about 500 tons.

[0148] In some embodiments, the cooling step is performed for about 1 second to about 1 hour. In some embodiments, the cooling step is performed for about 5 seconds to about 30 minutes. In some embodiments, the cooling step is performed for about 10 seconds to about 10 minutes. In some embodiments, the cooling step is performed for about 1 second to about 10 seconds. In some embodiments, the cooling step is performed for about 10 seconds to about 30 seconds. In some embodiments, the cooling step is performed for about 30 seconds to about 60 seconds. In some embodiments, the cooling step is performed for about 1 minute to about 5 minutes. In some embodiments, the cooling step is performed for about 5 minutes to about 10 minutes. In some embodiments, the cooling step is performed for about 10 minutes to about 30 minutes. In some embodiments, the cooling step is performed for about 30 minutes to about 1 hour.

[0149] In another aspect, provided herein is a method of compression molding a bio-derived polymer, comprising:68 / 119 C1723.70000WO00 #13627512v1placing a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, into an open mold; closing the mold and applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold.

[0150] In another aspect, provided herein is a method of transfer molding a bio-derived polymer, comprising: transferring a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, into an enclosed mold; applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold.

[0151] In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 100 ºC to about 300 ºC. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 100 ºC to about 150 ºC. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 150 ºC to about 200 ºC. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 200 ºC to about 250 ºC. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 250 ºC to about 300 ºC. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 130 ºC, about 140 ºC, about 150 ºC, about 160 ºC, about 170 ºC, about 180 ºC, about 190 ºC, about 200 ºC, about 210 ºC, or about 220 ºC.

[0152] In some embodiments, pressure of about 100 psi to about 10,000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 2000 psi to about 8000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 1000 psi to about 5000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 100 psi to about 1000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some69 / 119 C1723.70000WO00 #13627512v1embodiments, pressure of about 1000 psi to about 2000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 1500 psi to about 2500 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 2000 psi to about 3000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 2500 psi to about 3500 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 3000 psi to about 4000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 3500 psi to about 4500 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 4000 psi to about 5000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 4500 psi to about 5500 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 5000 psi to about 6000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 6000 psi to about 7000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 7000 psi to about 8000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. In some embodiments, pressure of about 8000 psi to about 10000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof.

[0153] In some embodiments, the mold is compressed for a period of about 1 second to about 30 minutes. In some embodiments, the mold is compressed for a period of about 30 seconds to about 10 minutes. In some embodiments, the mold is compressed for a period of about 1 minute to about 5 minutes. In some embodiments, the mold is compressed for a period of about 30 seconds to 1 minute. In some embodiments, the mold is compressed for a period of about 1 minute to about 2 minutes. In some embodiments, the mold is compressed for a period of about 2 minutes to about 3 minutes. In some embodiments, the mold is compressed for a period of about 3 minutes to about 4 minutes. In some embodiments, the mold is compressed for a period of about 4 minutes to about 5 minutes. In some embodiments, the mold is compressed for a period of about 5 minutes to about 6 minutes. In70 / 119 C1723.70000WO00 #13627512v1some embodiments, the mold is compressed for a period of about 6 minutes to about 8 minutes. In some embodiments, the mold is compressed for a period of about 8 minutes to about 10 minutes. In some embodiments, the mold is compressed for a period of about 10 minutes to about 15 minutes. In some embodiments, the mold is compressed for a period of about 15 minutes to about 20 minutes. In some embodiments, the mold is compressed for a period of about 20 minutes to about 30 minutes.

[0154] In some embodiments, the mold is cooled for about 30 seconds to about 3 hours. In some embodiments, the mold is cooled for about 1 minute to about 2 hours. In some embodiments, the mold is cooled for about 5 minutes to about 1 hour. In some embodiments, the mold is cooled for about 5 minutes to about 30 minutes. In some embodiments, the mold is cooled for about 30 minutes to about 1.5 hours. In some embodiments, the mold is cooled for about 30 seconds to about 5 minutes. In some embodiments, the mold is cooled for about 5 minutes to about 15 minutes. In some embodiments, the mold is cooled for about 15 minutes to about 30 minutes. In some embodiments, the mold is cooled for about 30 minutes to about 45 minutes. In some embodiments, the mold is cooled for about 45 minutes to about 1 hour. In some embodiments, the mold is cooled for about 1 hour to about 1.5 hours.

[0155] In some embodiments, the transferring step occurs with a transfer time of about 1 second to about 30 minutes. In some embodiments, the transferring step occurs with a transfer time of about 10 seconds to about 20 minutes. In some embodiments, the transferring step occurs with a transfer time of about 30 seconds to about 10 minutes. In some embodiments, the transferring step occurs with a transfer time of about 30 seconds to about 2 minutes. In some embodiments, the transferring step occurs with a transfer time of about 2 minutes to about 4 minutes. In some embodiments, the transferring step occurs with a transfer time of about 4 minutes to about 6 minutes. In some embodiments, the transferring step occurs with a transfer time of about 6 minutes to about 8 minutes. In some embodiments, the transferring step occurs with a transfer time of about 8 minutes to about 10 minutes. In some embodiments, the transferring step occurs with a transfer time of about 10 minutes to about 15 minutes. In some embodiments, the transferring step occurs with a transfer time of about 15 minutes to about 20 minutes. In some embodiments, the transferring step occurs with a transfer time of about 20 minutes to about 30 minutes.

[0156] In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of granules, pellets, sheets, or liquid. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of pellets. In some embodiments, the bio-derived polymer,71 / 119 C1723.70000WO00 #13627512v1or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of sheets. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of liquid. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of granules or pellets for injection molding. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of pellets or sheets for compression molding. In some embodiments, the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of granules or pellets for transfer molding.

[0157] In another aspect, provided herein is a method of applying a coating, the method comprising forming a coating layer comprising a bio-derived polymer provided herein, or a salt, stereoisomer, or isotopically labeled compound thereof, on a surface.

[0158] In some embodiments, the coating layer is formed via dip coating, spray coating, or liquid coating. In some embodiments, the coating layer is formed via dip coating. In some embodiments, the dip coating is performed via submersion. In some embodiments, the coating layer is formed via spray coating. In some embodiments, the spray coating is performed via aerosolization. In some embodiments, the spray coating is performed via brushing and spraying. In some embodiments, the coating layer is formed via liquid coating.

[0159] In some embodiments, the method of applying a spray coating further comprises vulcanizing the coating. In some embodiments, a vulcanization agent is added to the bio- derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof.

[0160] In some embodiments, vulcanizing the coating further comprises heating the coating to about 50 ºC to about 250 ºC. In some embodiments, vulcanizing the coating further comprises heating the coating to about 50 ºC to about 100 ºC. In some embodiments, vulcanizing the coating further comprises heating the coating to about 100 ºC to about 150 ºC. In some embodiments, vulcanizing the coating further comprises heating the coating to about 150 ºC to about 200 ºC. In some embodiments, vulcanizing the coating further comprises heating the coating to about 200 ºC to about 250 ºC. In some embodiments, vulcanizing the coating further comprises heating the coating to about 250 ºC to about 300 ºC.

[0161] As can be appreciated by the skilled artisan, methods of molding or applying a coating of the compounds provided herein (e.g., a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof) will be evident to those of ordinary skill in the art, including the embodiments in the schemes and examples herein, which are72 / 119 C1723.70000WO00 #13627512v1representative of the transformations, processing methods, reagents, and conditions for methods of molding and applying a coating of the compounds, and salts, stereoisomers, and isotopically labeled compounds thereof, delineated herein. Additionally, the various processing steps may be performed in an alternate sequence or order to give the desired properties. In addition, the temperatures, reagents, pressures, etc. delineated herein are for purposes of illustration only and one of ordinary skill in the art will recognize that variation of the conditions can be used in the methods of the present disclosure. For example, representative procedures are provided in: Injection and Compression Molding Fundamentals, 1st ed.; Isayev, A. L. CRC Press, 1987; Handbook of Polymer Reaction Engineering; Meyer, T.; Keurentjes, J. WILEY-VCH Verlag GmbH & Co. KGaA, 2005. DOI: 10.1002 / 9783527619870; and Rubber Science A Modern Approach; Ikeda, Y.; Kato, A.; Kohjiya, S.; Nakajima, Y. Springer, 2018. DOI: 10.1007 / 978-981-10-2938-7; each of which is incorporated herein by reference in its entirety. EXAMPLES

[0162] In order that the present disclosure may be more fully understood, the following examples are set forth. The synthetic and biological examples described in this application are offered to illustrate the compounds, pharmaceutical compositions, and methods provided herein and are not to be construed in any way as limiting in their scope. Example 1

[0163] X-linker can be any multifunctional terpene or thiol (containing three or more double bonds or thiols).

[0164] Example lab scale procedure73 / 119 C1723.70000WO00 #13627512v1

[0165] 18.77 mL of deionized water was added to a 25 mL dried round bottom flask. SDS (23.1 mg, 0.080 mmol, 1.6 eq) was added to the water in one portion with stirring. D- limonene (0.809 mL, 2.50 mmol, 50 eq.) and ethanedithiol (0.419 mL, 2.50 mmol, 50 eq.) were subsequently added to the reaction mixture, along with any cross-linker (0.125 mmol, 2.5 eq.). The flask was sealed with a rubber septum and deoxygenated by purging with nitrogen gas for at least 30 minutes. After purging, the flask was submerged in an oil bath and heated to 70 °C. 1 mL of deoxygenated KPS solution (13.5 mg / mL) was syringed into the flask via an airtight syringe to initiate the reaction. The reaction was allowed to progress for 2 hours with stirring and stopped by removing the septum and cooling the flask to room temperature. SDS was removed from the mixture by two repeated centrifugation and resuspension cycles at 4000 g. Example 2

[0166] 10 mL of deionized water was added to a 15 mL dried Schlenk flask. SDS (23.1 mg, 0.080 mmol) was added to the water in one portion with stirring. D-limonene (0.405 mL, 2.50 mmol) and ethanedithiol (0.210 mL, 2.50 mmol) were subsequently added to the reaction mixture. The flask was sealed with a rubber septum and deoxygenated by purging with nitrogen gas for at least 30 minutes. After purging, the flask was submerged in an oil bath and heated to 70 °C. 1 mL of deoxygenated KPS solution (13.5 mg / mL) was syringed into the flask via an airtight syringe to initiate the reaction. The reaction was allowed to progress for 2 hours with stirring and stopped by removing the septum and cooling the flask to room temperature. SDS was removed from the mixture by two repeated centrifugation and resuspension cycles at 4000 g.

[0167] Characterization data for the resulting polymer is shown in FIGs. 1A-1C.74 / 119 C1723.70000WO00 #13627512v1Example 3

[0168] 10 mL of deionized water was added to a 15 mL dried Schlenk flask. SDS (23.1 mg, 0.080 mmol) was added to the water in one portion with stirring. D-limonene (0.364 mL, 2.25 mmol), ethanedithiol (0.210 mL, 2.50 mmol), and β-myrcene (0.043 mL, 0.25 mmol) were subsequently added to the reaction mixture. The flask was sealed with a rubber septum and deoxygenated by purging with nitrogen gas for at least 30 minutes. After purging, the flask was submerged in an oil bath and heated to 70 °C. 1 mL of deoxygenated KPS solution (13.5 mg / mL) was syringed into the flask via an airtight syringe to initiate the reaction. The reaction was allowed to progress for 2 hours with stirring and stopped by removing the septum and cooling the flask to room temperature. SDS was removed from the mixture by two repeated centrifugation and resuspension cycles at 4000 g.

[0169] Characterization data for the resulting polymer is shown in FIGs. 2A-2C. Example 4

[0170] 10 mL of deionized water was added to a 15 mL dried Schlenk flask. SDS (23.1 mg, 0.080 mmol) was added to the water in one portion with stirring. D-limonene (0.405 mL, 2.5075 / 119 C1723.70000WO00 #13627512v1mmol), ethanedithiol (0.189 mL, 2.25 mmol), and trimethylolpropane tris(3- mercaptopropionate) (0.082 mL, 0.25 mmol) were subsequently added to the reaction mixture. The flask was sealed with a rubber septum and deoxygenated by purging with nitrogen gas for at least 30 minutes. After purging, the flask was submerged in an oil bath and heated to 70 °C. 1 mL of deoxygenated KPS solution (13.5 mg / mL) was syringed into the flask via an airtight syringe to initiate the reaction. The reaction was allowed to progress for 2 hours with stirring and stopped by removing the septum and cooling the flask to room temperature. SDS was removed from the mixture by two repeated centrifugation and resuspension cycles at 4000 g.

[0171] Characterization data for the resulting polymer is shown in FIGs. 3A-3C. Example 5

[0172] 10 mL of deionized water was added to a 15 mL dried Schlenk flask. SDS (23.1 mg, 0.080 mmol) was added to the water in one portion with stirring. D-limonene (0.405 mL, 2.50 mmol), ethanedithiol (0.189 mL, 2.25 mmol), and pentaerythritol tetrakis(3- mercaptopropionate) (0.095 mL, 0.25 mmol) were subsequently added to the reaction mixture. The flask was sealed with a rubber septum and deoxygenated by purging with nitrogen gas for at least 30 minutes. After purging, the flask was submerged in an oil bath and heated to 70 °C. 1 mL of deoxygenated KPS solution (13.5 mg / mL) was syringed into the flask via an airtight syringe to initiate the reaction. The reaction was allowed to progress for 2 hours with stirring and stopped by removing the septum and cooling the flask to room temperature. SDS was removed from the mixture by two repeated centrifugation and76 / 119 C1723.70000WO00 #13627512v1resuspension cycles at 4000 g.

[0173] Characterization data for the resulting polymer is shown in FIGs. 4A-4C. Example 6

[0174] Polymer was prepared from d-limonene and 1,4-dithiothreitol according to the procedures of Examples 1-5, except that the resulting polymer was isolated via coagulation according to the following procedure (rather than via centrifugation / resuspension). Following reaction completion, a solution of calcium chloride (CaCl2) was prepared in water (1-20% w / v). The reaction mixture was allowed to cool to room temperature and 1-20 mL of CaCl2 solution was slowly added to the stirring reaction mixture. Visible flocculation was observed. Once coagulation of polymer particles was complete, stirring was halted and the supernatant containing water, SDS, and unreacted monomer was decanted. Coagulated polymer particles were collected by filtration, washed, and dried. Drying was performed at room temperature overnight or by heating the coagulated to low temperatures (40-60 °C) in an oven.

[0175] 1 gram of coagulated and dried polymer was added to a vial along with 30 mg of dicumyl peroxide powder (DCP) (3% w / w). The two substances were mechanically mixed, and the polymer was cured by setting the vial on a hot plate at 150 °C for 20 min. The sample was then heated at 100 °C for 30 minutes for post-cure hardening.

[0176] Characterization data for the resulting polymer is shown in FIGs. 5A and 5B. Example 7

[0177] Polymer was prepared from d-limonene and 1,3-propanethiol according to the procedures of Examples 1-5, except that the resulting polymer was isolated via coagulation and cured according to the procedure of Example 6.

[0178] Characterization data for the resulting polymer is shown in FIGs. 6A and 6B.77 / 119 C1723.70000WO00 #13627512v1References: 1. US Patent No.9,441,084 2. US Patent No.10,144,840 3. US Application Publication No.2019-0100664 4. Constant E, King O, Weems AC. Bioderived 4D Printable Terpene Photopolymers from Limonene and β-Myrcene. Biomacromolecules.2022 Jun 13;23(6):2342-2352. doi: 10.1021 / acs.biomac.2c00085. Epub 2022 May 24. 5. Durham OZ, Chapman DV, Krishnan S, Shipp DA. Redical Mediated Thiol-Ene Emulsion Polymerizations. Macromolecules.2017 Jan 26;50(3):775-783. doi: 10.1021 / acs.macromol.6b02228. 6. Hearon K, Nash LD, Rodriguez JN, Lonnecker AT, Raymond JE, Wilson TS, Wooley KL, Maitland DJ. A high-performance recycling solution for polystyrene achieved by the synthesis of renewable poly(thioether) networks derived from D-limonene. Adv Mater.2014 Mar 12;26(10):1552-8. doi: 10.1002 / adma.201304370. Epub 2013 Nov 19. 7. Weems A, Delle Chiaie, KR, Worch JC, Stubbs CJ, Dove AP. Terpene- and terpenoid-based polymeric resins for stereolithography 3D printing. Polymer Chemistry.2019 Sep; 10(44):5941-6064. doi: 10.1039 / c9py00950g. 8. Injection and Compression Molding Fundamentals, 1st ed.; Isayev, A. L. CRC Press, 1987. 9. Handbook of Polymer Reaction Engineering; Meyer, T.; Keurentjes, J. WILEY-VCH Verlag GmbH & Co. KGaA, 2005. DOI: 10.1002 / 9783527619870. 10. Rubber Science A Modern Approach; Ikeda, Y.; Kato, A.; Kohjiya, S.; Nakajima, Y. Springer, 2018. DOI: 10.1007 / 978-981-10-2938-7. LISTING OF EMBODIMENTS 1. A bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the polymer is a poly(thioether) comprising: a diradical derived from a terpene monomer; a diradical derived from a monomer comprising two thiol groups; and optionally a multi-radical derived from a multifunctional cross-linker.78 / 119 C1723.70000WO00 #13627512v12. The bio-derived polymer of embodiment 1, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer is a latex. 3. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises one or more instances of formula (i):wherein A is a diradical derived from a terpene monomer, Z is a diradical derived from a monomer comprising two thiol groups, and n is an integer from 1 to 1,000, inclusive. 4. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer comprises optionally substituted C1-20alkylene, optionally substituted C1-20alkenylene, optionally substituted C3-15carbocycylene, or any combination thereof. 5. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer comprises C1-20 alkylene, C3-15 carbocycylene, or any combination thereof, wherein the alkylene or carbocyclene is optionally substituted with -OH or -Me. 6. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer is a diradical derived from a terpene monomer having two double bonds. 7. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer has the formula:79 / 119 C1723.70000WO00 #13627512v18. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer has the formula:80 / 119 C1723.70000WO00 #13627512v19. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula , wherein L1comprises optionally substituted C1-20 alkylene, optionally substituted C1-20 alkenylene, optionally substituted C1-20 alkynylene, optionally substituted C1-20 heteroalkylene, optionally substituted C1-20heteroalkenylene, optionally substituted C1-20heteroalkynylene, optionally substituted C3-10 carbocycylene, optionally substituted 3- to 10-memebered heterocyclylene, optionally substituted C6-10 arylene, optionally substittued C5-10 heteroarylene, or any combination thereof. 10. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula , wherein L1is optionally substituted C1-20alkylene or optionally substituted C1-20heteroalkylene. 11. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula:. 12. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula:81 / 119 C1723.70000WO00 #13627512v1. 13. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer does not comprise a multi-radical derived from a multifunctional cross-linker. 14. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer is a linear polymer. 15. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises a multi-radical derived from a multifunctional cross-linker. 16. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises one or more instances of formula (ii) or (iii):wherein Y is a multi-radical derived from a multifunctional cross-linker, and m is an integer from 2 to 6, inclusive. 17. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker is derived from a compound comprising one or more thiol moieties.82 / 119 C1723.70000WO00 #13627512v118. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises one or more instances of formula (ii′):wherein each instance of X is independently a bond to the bio-derived polymer, hydrogen, or a bond to another S-atom. 19. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:20. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:83 / 119 C1723.70000WO00 #13627512v1wherein each instance of X is independently hydrogen or a bond, provided that at least three instances of X are a bond to the bio-derived polymer. 21. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer further comprises a diradical derived from a multifunctional cross-linker. 22. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a multifunctional cross-linker has the formula:, wherein each instance of X is independently hydrogen or a bond to the bio-derived polymer, provided that two instances of X are a bond to the bio- derived polymer. 23. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a84 / 119 C1723.70000WO00 #13627512v1multifunctional cross-linker has the formula:X is independently hydrogen or a bond to the bio-derived polymer, provided that two instances of X are a bond to the bio-derived polymer. 24. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker is derived from a terpene comprising three or more double bonds. 25. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer further comprises one or more instances of formula (iii′):wherein each instance of X is independently a bond to the bio-derived polymer, hydrogen, or two adjacent instances of X are joined to form a double bond.85 / 119 C1723.70000WO00 #13627512v126. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:86 / 119 C1723.70000WO00 #13627512v127. The bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:28. The bio-derived polymer of any the preceding embodimentsembodiments 21-27, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a multifunctional cross-linker has the formula:, wherein each instance of X is independently hydrogen or a bond to the bio-derived polymer, or two adjacent instances of X are joined to form a double bond, provided that two instances of X are a bond to the bio-derived polymer. 29. A method of preparing a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, the method comprising reacting a mixture comprising a terpene monomer, a monomer comprising two thiol groups, and optionally a multifunctional cross-linker. 30. The method of embodiment 29, wherein the method comprises the steps of: a. preparing a solution of surfactant in solvent; b. adding to the solution terpene monomer, monomer comprising two thiol groups, and optionally a multifunctional cross-linker to afford a mixture;87 / 119 C1723.70000WO00 #13627512v1c. purging the mixture with an inert gas; d. heating the mixture; and e. adding an initiator. 31. The method of any of the preceding embodiments, wherein the reaction is performed in a solvent. 32. The method of any of the preceding embodiments, wherein the solvent is water. 33. The method of any of the preceding embodiments, wherein the mixture comprises a surfactant in solution. 34. The method of any of the preceding embodiments, wherein the surfactant is a fatty acid, or a salt thereof. 35. The method of any of the preceding embodiments, wherein the surfactant is sodium dodecyl sulfate. 36. The method of any of the preceding embodiments, wherein the solution of surfactant has a concentration of about 5 mM to about 20 mM. 37. The method of any of the preceding embodiments, wherein the solution of surfactant has a concentration of about 8 mM. 38. The method of any of the preceding embodiments, wherein the terpene monomer is one or more of:39. The method of any of the preceding embodiments, wherein the terpene monomer has a88 / 119 C1723.70000WO00 #13627512v1final concentration of about 100-400 mM in the mixture. 40. The method of any of the preceding embodiments, wherein the terpene monomer has a final a concentration of about 250 mM in the mixture. 41. The method of any of the preceding embodiments, wherein the monomer comprising two thiol groups is one or more of:. 42. The method of any of the preceding embodiments, wherein the monomer comprising two thiol groups has a final concentration of about 200-300 mM in the mixture. 43. The method of any of the preceding embodiments, wherein the monomer comprising two thiol groups has a final concentration of about 250 mM in the mixture. 44. The method of any of the preceding embodiments, wherein the multifunctional cross- linker is one or more of:89 / 119 C1723.70000WO00 #13627512v145. The method of any of the preceding embodiments, wherein the multifunctional cross- linker is one or more of:46. The method of any of the preceding embodiments, wherein the inert gas is nitrogen. 47. The method of any of the preceding embodiments, wherein the mixture is heated to about 60 ºC to about 80 ºC. 48. The method of any of the preceding embodiments, wherein the mixture is heated to about 70 ºC. 49. The method of any of the preceding embodiments, wherein the mixture comprises an initiator. 50. The method of any of the preceding embodiments, wherein the initiator is a radical initiator. 51. The method of any of the preceding embodiments, wherein the initiator is water soluble. 52. The method of any of the preceding embodiments, wherein the initiator is potassium persulfate.90 / 119 C1723.70000WO00 #13627512v153. The method of any of the preceding embodiments, wherein the initiator is added as a solution. 54. The method of any of the preceding embodiments, wherein adding the initiator to the mixture affords a final initiator concentration of about 1 mM to about 10 mM in the mixture. 55. The method of any of the preceding embodiments, wherein adding the initiator to the mixture affords a final initiator concentration of about 5 mM in the mixture. 56. The method of any of the preceding embodiments, wherein the method further comprises the step of isolating the bio-derived polymer. 57. The method of any of the preceding embodiments, wherein the isolating is performed by centrifuging the mixture. 58. The method of any of the preceding embodiments, wherein the isolating is performed by coagulation. 59. The method of any of the preceding embodiments, wherein the isolating is performed by adding a salt to the mixture and decanting the solvent. 60. The method of any of the preceding embodiments, wherein the salt is calcium chloride, sodium chloride, potassium chloride, magnesium sulfate, magnesium chloride, calcium nitrate, barium chloride, aluminum sulfate, iron (III) chloride, or iron (III) sulfate. 61. The method of any of the preceding embodiments, wherein the salt is calcium chloride. 62. The method of any of the preceding embodiments, wherein the method further comprises filtering the bio-derived polymer. 63. The method of any of the preceding embodiments, wherein the method further comprises resuspending or washing the bio-derived polymer with a second solvent.91 / 119 C1723.70000WO00 #13627512v164. The method of any of the preceding embodiments, wherein the second solvent is water. 65. The method of any of the preceding embodiments, wherein the method further comprises drying the bio-derived polymer. 66. The method of any of the preceding embodiments, wherein the drying is performed at about 20 °C to about 80 °C. 67. The method of any of the preceding embodiments, wherein the drying is performed at about 20 °C to about 65 °C. 68. The method of any of the preceding embodiments, wherein the method further comprises curing the bio-derived polymer. 69. The method of any of the preceding embodiments, wherein a curing agent is added to the bio-derived polymer. 70. The method of any of the preceding embodiments, wherein the curing agent is a peroxide, a metal oxide, or a photoinitiator. 71. The method of any of the preceding embodiments, wherein the curing agent is a peroxide. 72. The method of any of the preceding embodiments, wherein the curing agent is dicumyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide (MEKP), cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxide, di-tert-butyl peroxide, or a peroxyacetal. 73. The method of any of the preceding embodiments, wherein the curing agent is dicumyl peroxide. 74. The method of any of the preceding embodiments, wherein the curing agent is a metal oxide. 75. The method of any of the preceding embodiments, wherein the curing agent is zinc oxide92 / 119 C1723.70000WO00 #13627512v1or magnesium oxide. 76. The method of any of the preceding embodiments, wherein the curing agent is a photoinitiator. 77. The method of any of the preceding embodiments, wherein the curing agent is benzophenone, igracure, or a derivative thereof. 78. The method of any of the preceding embodiments, wherein the curing agent is present in an amount of about 0.1% to about 10% w / w. 79. The method of any of the preceding embodiments, wherein the curing agent is present in an amount of about 2% to about 4% w / w. 80. The method of any of the preceding embodiments, wherein the curing is performed at or above the decomposition temperature of the curing agent. 81. The method of any of the preceding embodiments, wherein the curing is performed at about 20 °C to about 200 °C. 82. The method of any of the preceding embodiments, wherein the curing is performed at about 140 °C to about 160 °C. 83. The method of any of the preceding embodiments, wherein the method further comprises hardening the bio-derived polymer. 84. The method of any of the preceding embodiments, wherein the hardening is performed by heating the bio-derived polymer at about 20 °C to about 200 °C. 85. The method of any of the preceding embodiments, wherein the hardening is performed by heating the bio-derived polymer at about 90 °C to about 110 °C. 86. A bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, prepared according to the method of any of the preceding embodiments.93 / 119 C1723.70000WO00 #13627512v187. A composition comprising a bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, and an additive. 88. The composition of embodiment 87, wherein the additive is a plasticizer, pigment, flame retardant, antioxidant, acid scavenger, light stabilizer, thermal stabilizer, lubricant, anti- static agent, slip agent, filler, or reinforcement. 89. A kit comprising: a bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, or the composition of any of the preceding embodiments; and instructions for using the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, or the composition. 90. A product comprising the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, of any of the preceding embodiments, or the composition of any of the preceding embodiments. 91. The product of any of the preceding embodiments, wherein the product is a footwear sole or midsole, paint, coating, film, adhesive, oil or gas fracturing fluid, drilling fluid, shale- plugging agent, nano-propellant, lubricant, pacifier, teething ring, nightguard, tire, tire component, seal, trim, insulation, glove, condom, bandage, catheter, tubing, toy, rubber band, gasket, O-ring, belt, textile, bag, packaging, emulsifier, tackifier, or nanoparticle. 92. The product of any of the preceding embodiments, wherein the product is non-toxic or biocompatible. 93. The product of any of the preceding embodiments, wherein the product is antibacterial or antimicrobial. 94. The product of any of the preceding embodiments, wherein the product releases an antibacterial or antimicrobial agent upon degradation.94 / 119 C1723.70000WO00 #13627512v195. The product of any of the preceding embodiments, wherein the antibacterial or antimicrobial agent is limonene. 96. The product of any of the preceding embodiments, wherein the antibacterial or antimicrobial agent is d-limonene. 97. A method of injection molding a bio-derived polymer, comprising: introducing a bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, into a screw injection apparatus; melting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; injecting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, into a mold; and cooling the mold. 98. The method of any of the preceding embodiments, wherein melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 150 ºC to about 200 ºC. 99. The method of any of the preceding embodiments, wherein the injecting step is performed at an injection speed of about 30 mm / s to about 100 mm / s. 100. The method of any of the preceding embodiments, wherein the injecting step is performed at an injection pressure of about 500 bar to about 1500 bar. 101. The method of any of the preceding embodiments, wherein the mold is clamped at a force of about 100 tons to about 500 tons. 102. The method of any of the preceding embodiments, wherein the cooling step is performed for about 10 seconds to about 10 minutes. 103. A method of compression molding a bio-derived polymer, comprising: placing a bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, into an open mold;95 / 119 C1723.70000WO00 #13627512v1closing the mold and applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold. 104. The method of any of the preceding embodiments, wherein the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 150 ºC to about 200 ºC. 105. The method of any of the preceding embodiments, wherein pressure of about 1000 psi to about 5000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. 106. The method of any of the preceding embodiments, wherein the mold is compressed for a period of about 1 minute to about 5 minutes. 107. The method of any of the preceding embodiments, wherein the mold is cooled for about 5 minutes to about 1 hour. 108. A method of transfer molding a bio-derived polymer, comprising: transferring a bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, into an enclosed mold; applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold. 109. The method of any of the preceding embodiments, wherein the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 150 ºC to about 200 ºC. 110. The method of any of the preceding embodiments, wherein pressure of about 1000 psi to about 5000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. 111. The method of any of the preceding embodiments, wherein the transferring step occurs96 / 119 C1723.70000WO00 #13627512v1with a transfer time of about 30 seconds to about 10 minutes. 112. The method of any of the preceding embodiments, wherein the mold is cooled for about 5 minutes to about 1 hour. 113. The method of any of the preceding embodiments, wherein the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of pellets, sheets, or liquid. 114. A method of applying a coating, the method comprising forming a coating layer comprising a bio-derived polymer of any of the preceding embodiments, or a salt, stereoisomer, or isotopically labeled compound thereof, on a surface. 115. The method of any of the preceding embodiments, wherein the coating layer is formed via dip coating, spray coating, or liquid coating. 116. The method of any of the preceding embodiments, wherein dip coating is performed via submersion. 117. The method of any of the preceding embodiments, wherein spray coating is performed via aerosolization. 118. The method of any of the preceding embodiments, wherein the spray coating is performed via brushing and spraying. 119. The method of any of the preceding embodiments, further comprising vulcanizing the coating. 120. The method of any of the preceding embodiments, wherein a vulcanization agent is added to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof. 121. The method of any of the preceding embodiments, wherein vulcanizing the coating further comprises heating the coating to about 150 ºC to about 200 ºC.97 / 119 C1723.70000WO00 #13627512v1EQUIVALENTS AND SCOPE

[0179] In the claims articles such as “a,” “an,” and “the” may mean one or more than one unless indicated to the contrary or otherwise evident from the context. Claims or descriptions that include “or” between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The present disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The present disclosure includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[0180] Furthermore, the present disclosure encompasses all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim. Where elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should it be understood that, in general, where the present disclosure, or aspects of the present disclosure, is / are referred to as comprising particular elements and / or features, certain embodiments of the present disclosure or aspects of the present disclosure consist, or consist essentially of, such elements and / or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. It is also noted that the terms “comprising” and “containing” are intended to be open and permits the inclusion of additional elements or steps. Where ranges are given, endpoints are included. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the present disclosure, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0181] This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. If there is a conflict between any of the incorporated references and the instant specification, the specification shall control. In addition, any particular embodiment of the present disclosure that falls within the prior art may be explicitly excluded from any one or more of the claims. Because such embodiments are deemed to be known to one of ordinary skill in the art, they98 / 119 C1723.70000WO00 #13627512v1may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the present disclosure can be excluded from any claim, for any reason, whether or not related to the existence of prior art.

[0182] Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments described herein. The scope of the present embodiments described herein is not intended to be limited to the above Description, but rather is as set forth in the appended claims. Those of ordinary skill in the art will appreciate that various changes and modifications to this description may be made without departing from the spirit or scope of the present disclosure, as defined in the following claims.99 / 119 C1723.70000WO00 #13627512v1

Claims

CLAIMS What is claimed is:

1. A bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the polymer is a poly(thioether) comprising: a diradical derived from a terpene monomer; a diradical derived from a monomer comprising two thiol groups; and optionally a multi-radical derived from a multifunctional cross-linker.

2. The bio-derived polymer of claim 1, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer is a latex.

3. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises one or more instances of formula (i):wherein A is a diradical derived from a terpene monomer, Z is a diradical derived from a monomer comprising two thiol groups, and n is an integer from 1 to 1,000, inclusive.

4. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer comprises optionally substituted C1-20 alkylene, optionally substituted C1-20 alkenylene, optionally substituted C3-15carbocycylene, or any combination thereof.

5. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer comprises C1-20alkylene, C3-15carbocycylene, or any combination thereof, wherein the alkylene or carbocyclene is optionally substituted with -OH or -Me.

6. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer is a diradical derived from a terpene monomer having two double bonds.100 / 119 C1723.70000WO00 #13627512v17. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer has the formula:101 / 119 C1723.70000WO00 #13627512v18. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a terpene monomer has the formula:

9. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula , wherein L1comprises optionally substituted C1-20 alkylene, optionally substituted C1-20 alkenylene, optionally substituted C1-20alkynylene, optionally substituted C1-20heteroalkylene, optionally substituted C1-20heteroalkenylene, optionally substituted C1-20heteroalkynylene, optionally substituted C3-10 carbocycylene, optionally substituted 3- to 10-memebered heterocyclylene, optionally substituted C6-10arylene, optionally substittued C5-10heteroarylene, or any combination thereof.

10. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula , wherein L1is optionally substituted C1-20alkylene or optionally substituted C1-20heteroalkylene.

11. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula:102 / 119 C1723.70000WO00 #13627512v1.

12. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a monomer comprising two thiol groups has the formula:.

13. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer does not comprise a multi-radical derived from a multifunctional cross-linker.

14. The bio-derived polymer of claim 13, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer is a linear polymer.

15. The bio-derived polymer of any one of claims 1-12, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises a multi-radical derived from a multifunctional cross-linker.

16. The bio-derived polymer of claim 15, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises one or more instances of formula (ii) or (iii):103 / 119 C1723.70000WO00 #13627512v1wherein Y is a multi-radical derived from a multifunctional cross-linker, and m is an integer from 2 to 6, inclusive.

17. The bio-derived polymer of claim 15 or 16, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker is derived from a compound comprising one or more thiol moieties.

18. The bio-derived polymer of any one of claims 15-17, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer comprises one or more instances of formula (ii′):wherein each instance of X is independently a bond to the bio-derived polymer, hydrogen, or a bond to another S-atom.

19. The bio-derived polymer of any one of claims 15-18, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:

20. The bio-derived polymer of any one of claims 15-18, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a104 / 119 C1723.70000WO00 #13627512v1multifunctional cross-linker has the formula:instance of X is independently hydrogen or a bond, provided that at least three instances of X are a bond to the bio-derived polymer.

21. The bio-derived polymer of any one of the preceding claims, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer further comprises a diradical derived from a multifunctional cross-linker.

22. The bio-derived polymer of claim 21, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a multifunctional cross-linker has the formula:, wherein each instance of X is independently hydrogen or a bond to the bio-derived polymer, provided that two instances of X are a bond to the bio- derived polymer.105 / 119 C1723.70000WO00 #13627512v123. The bio-derived polymer of claim 21, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a multifunctional cross-linker has the formula:X is independently hydrogen or a bond to the bio-derived polymer, provided that two instances of X are a bond to the bio-derived polymer.

24. The bio-derived polymer of any one of claims 15-23, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker is derived from a terpene comprising three or more double bonds.

25. The bio-derived polymer of any one of claims 15-24, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the bio-derived polymer further comprises one or more instances of formula (iii′):wherein each instance of X is independently a bond to the bio-derived polymer, hydrogen, or two adjacent instances of X are joined to form a double bond.106 / 119 C1723.70000WO00 #13627512v126. The bio-derived polymer of any one of claims 15-25, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:107 / 119 C1723.70000WO00 #13627512v127. The bio-derived polymer of any one of claims 15-26, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the multi-radical derived from a multifunctional cross-linker has the formula:

28. The bio-derived polymer of any one of claims 21-27, or a salt, stereoisomer, or isotopically labeled compound thereof, wherein the diradical derived from a multifunctional cross-linker has the formula:, wherein each instance of X is independently hydrogen or a bond to the bio-derived polymer, or two adjacent instances of X are joined to form a double bond, provided that two instances of X are a bond to the bio-derived polymer.

29. A method of preparing a bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, the method comprising reacting a mixture comprising a terpene monomer, a monomer comprising two thiol groups, and optionally a multifunctional cross-linker.

30. The method of claim 29, wherein the method comprises the steps of: a. preparing a solution of surfactant in solvent; b. adding to the solution terpene monomer, monomer comprising two thiol groups, and optionally a multifunctional cross-linker to afford a mixture;108 / 119 C1723.70000WO00 #13627512v1c. purging the mixture with an inert gas; d. heating the mixture; and e. adding an initiator.

31. The method of claim 29 or 30, wherein the reaction is performed in a solvent.

32. The method of any one of claims 29-31, wherein the solvent is water.

33. The method of any one of claims 29-32, wherein the mixture comprises a surfactant in solution.

34. The method of claim 33, wherein the surfactant is a fatty acid, or a salt thereof.

35. The method of claim 33 or 34, wherein the surfactant is sodium dodecyl sulfate.

36. The method of any one of claims 30-35, wherein the solution of surfactant has a concentration of about 5 mM to about 20 mM.

37. The method of any one of claims 30-36, wherein the solution of surfactant has a concentration of about 8 mM.

38. The method of any one of claims 29-37, wherein the terpene monomer is one or more of: ,39. The method of any one of claims 29-38, wherein the terpene monomer has a final concentration of about 100-400 mM in the mixture.

40. The method of any one of claims 29-39, wherein the terpene monomer has a final a concentration of about 250 mM in the mixture.109 / 119 C1723.70000WO00 #13627512v141. The method of any one of claims 29-40, wherein the monomer comprising two thiol groups is one or more of:.

42. The method of any one of claims 29-41, wherein the monomer comprising two thiol groups has a final concentration of about 200-300 mM in the mixture.

43. The method of any one of claims 29-42, wherein the monomer comprising two thiol groups has a final concentration of about 250 mM in the mixture.

44. The method of any one of claims 29-43, wherein the multifunctional cross-linker is one or more of:110 / 119 C1723.70000WO00 #13627512v145. The method of any one of claims 29-44, wherein the multifunctional cross-linker is one or more of:

46. The method of any one of claims 30-45, wherein the inert gas is nitrogen.

47. The method of any one of claims 29-46, wherein the mixture is heated to about 60 ºC to about 80 ºC.

48. The method of any one of claims 29-47, wherein the mixture is heated to about 70 ºC.

49. The method of any one of claims 29-48, wherein the mixture comprises an initiator.

50. The method of any one of claims 30-49, wherein the initiator is a radical initiator.

51. The method of any one of claims 30-50, wherein the initiator is water soluble.

52. The method of any one of claims 30-51, wherein the initiator is potassium persulfate.

53. The method of any one of claims 30-52, wherein the initiator is added as a solution.

54. The method of any one of claims 30-53, wherein adding the initiator to the mixture affords a final initiator concentration of about 1 mM to about 10 mM in the mixture.

55. The method of any one of claims 30-54, wherein adding the initiator to the mixture affords a final initiator concentration of about 5 mM in the mixture.

56. The method of any one of claims 29-55, wherein the method further comprises the step of isolating the bio-derived polymer.111 / 119 C1723.70000WO00 #13627512v157. The method of claim 56, wherein the isolating is performed by centrifuging the mixture.

58. The method of claim 56 or 57, wherein the isolating is performed by coagulation.

59. The method of any one of claims 56-58, wherein the isolating is performed by adding a salt to the mixture and decanting the solvent.

60. The method of claim 59, wherein the salt is calcium chloride, sodium chloride, potassium chloride, magnesium sulfate, magnesium chloride, calcium nitrate, barium chloride, aluminum sulfate, iron (III) chloride, or iron (III) sulfate.

61. The method of claim 59 or 60, wherein the salt is calcium chloride.

62. The method of any one of claims 29-61, wherein the method further comprises filtering the bio-derived polymer.

63. The method of any one of claims 29-62, wherein the method further comprises resuspending or washing the bio-derived polymer with a second solvent.

64. The method of claim 63, wherein the second solvent is water.

65. The method of any one of claims 29-64, wherein the method further comprises drying the bio-derived polymer.

66. The method of claim 65, wherein the drying is performed at about 20 °C to about 80 °C.

67. The method of claim 65 or 66, wherein the drying is performed at about 20 °C to about 65 °C.

68. The method of any one of claims 29-67, wherein the method further comprises curing the bio-derived polymer.

69. The method of claim 68, wherein a curing agent is added to the bio-derived polymer.112 / 119 C1723.70000WO00 #13627512v170. The method of claim 69, wherein the curing agent is a peroxide, a metal oxide, or a photoinitiator.

71. The method of claim 69 or 70, wherein the curing agent is a peroxide.

72. The method of any one of claims 69-71, wherein the curing agent is dicumyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide (MEKP), cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxide, di-tert-butyl peroxide, or a peroxyacetal.

73. The method of any one of claims 69-72, wherein the curing agent is dicumyl peroxide.

74. The method of claim 69 or 70, wherein the curing agent is a metal oxide.

75. The method of claim 74, wherein the curing agent is zinc oxide or magnesium oxide.

76. The method of claim 69 or 70, wherein the curing agent is a photoinitiator.

77. The method of claim 76, wherein the curing agent is benzophenone, igracure, or a derivative thereof.

78. The method of any one of claims 69-77, wherein the curing agent is present in an amount of about 0.1% to about 10% w / w.

79. The method of any one of claims 69-78, wherein the curing agent is present in an amount of about 2% to about 4% w / w.

80. The method of any one of claims 69-79, wherein the curing is performed at or above the decomposition temperature of the curing agent.

81. The method of any one of claims 68-80, wherein the curing is performed at about 20 °C to about 200 °C.

82. The method of any one of claims 68-81, wherein the curing is performed at about 140 °C to about 160 °C.113 / 119 C1723.70000WO00 #13627512v183. The method of any one of claims 29-82, wherein the method further comprises hardening the bio-derived polymer.

84. The method of claim 83, wherein the hardening is performed by heating the bio-derived polymer at about 20 °C to about 200 °C.

85. The method of claim 83 or 84, wherein the hardening is performed by heating the bio- derived polymer at about 90 °C to about 110 °C.

86. A bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, prepared according to the method of any one of claims 29-85.

87. A composition comprising a bio-derived polymer of any one of claims 1-28 or 86, or a salt, stereoisomer, or isotopically labeled compound thereof, and an additive.

88. The composition of claim 87, wherein the additive is a plasticizer, pigment, flame retardant, antioxidant, acid scavenger, light stabilizer, thermal stabilizer, lubricant, anti- static agent, slip agent, filler, or reinforcement.

89. A kit comprising: a bio-derived polymer of any one of claims 1-28 or 86, or a salt, stereoisomer, or isotopically labeled compound thereof, or the composition of claim 87 or 88; and instructions for using the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, or the composition.

90. A product comprising the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, of any one of claims 1-28 or 86, or the composition of claim 87 or 88.

91. The product of claim 90, wherein the product is a footwear sole or midsole, paint, coating, film, adhesive, oil or gas fracturing fluid, drilling fluid, shale-plugging agent, nano-propellant, lubricant, pacifier, teething ring, nightguard, tire, tire component, seal, trim, insulation, glove, condom, bandage, catheter, tubing, toy, rubber band, gasket, O-114 / 119 C1723.70000WO00 #13627512v1ring, belt, textile, bag, packaging, emulsifier, tackifier, or nanoparticle.

92. The product of claim 90 or 91, wherein the product is non-toxic or biocompatible.

93. The product of any one of claims 90-92, wherein the product is antibacterial or antimicrobial.

94. The product of any one of claims 90-93, wherein the product releases an antibacterial or antimicrobial agent upon degradation.

95. The product of claim 94, wherein the antibacterial or antimicrobial agent is limonene.

96. The product of claim 94 or 95, wherein the antibacterial or antimicrobial agent is d- limonene.

97. A method of injection molding a bio-derived polymer, comprising: introducing a bio-derived polymer of any one of claims 1-28 or 86, or a salt, stereoisomer, or isotopically labeled compound thereof, into a screw injection apparatus; melting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; injecting the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, into a mold; and cooling the mold.

98. The method of claim 97, wherein melting comprises heating the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, to a temperature of about 150 ºC to about 200 ºC.

99. The method of claim 97 or 98, wherein the injecting step is performed at an injection speed of about 30 mm / s to about 100 mm / s.

100. The method of any one of claims 97-99, wherein the injecting step is performed at an injection pressure of about 500 bar to about 1500 bar.115 / 119 C1723.70000WO00 #13627512v1101. The method of any one of claims 97-100, wherein the mold is clamped at a force of about 100 tons to about 500 tons.

102. The method of any one of claims 97-101, wherein the cooling step is performed for about 10 seconds to about 10 minutes.

103. A method of compression molding a bio-derived polymer, comprising: placing a bio-derived polymer of any one of claims 1-29 or 86, or a salt, stereoisomer, or isotopically labeled compound thereof, into an open mold; closing the mold and applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold.

104. The method of claim 103, wherein the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 150 ºC to about 200 ºC.

105. The method of claim 103 or 104, wherein pressure of about 1000 psi to about 5000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof.

106. The method of any one of claims 103-105wherein the mold is compressed for a period of about 1 minute to about 5 minutes.

107. The method of any one of claims 103-106, wherein the mold is cooled for about 5 minutes to about 1 hour.

108. A method of transfer molding a bio-derived polymer, comprising: transferring a bio-derived polymer of any one of claims 1-28 or 86, or a salt, stereoisomer, or isotopically labeled compound thereof, into an enclosed mold; applying heat or pressure to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof; and cooling the mold.116 / 119 C1723.70000WO00 #13627512v1109. The method of claim 108, wherein the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is heated to a temperature of about 150 ºC to about 200 ºC.

110. The method of claim 108 or 109, wherein pressure of about 1000 psi to about 5000 psi is applied to the bioderived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof.

111. The method of any one of claims 108-110, wherein the transferring step occurs with a transfer time of about 30 seconds to about 10 minutes.

112. The method of any one of claims 108-111, wherein the mold is cooled for about 5 minutes to about 1 hour.

113. The method of any one of claims 108-112, wherein the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof, is in the form of pellets, sheets, or liquid.

114. A method of applying a coating, the method comprising forming a coating layer comprising a bio-derived polymer of any of claims 1-28 or 86, or a salt, stereoisomer, or isotopically labeled compound thereof, on a surface.

115. The method of claim 114, wherein the coating layer is formed via dip coating, spray coating, or liquid coating.

116. The method of claim 115, wherein dip coating is performed via submersion.

117. The method of claim 115, wherein spray coating is performed via aerosolization.

118. The method of claim 115, wherein the spray coating is performed via brushing and spraying.

119. The method of any one of claims 114-118, further comprising vulcanizing the coating.117 / 119 C1723.70000WO00 #13627512v1120. The method of claim 119, wherein a vulcanization agent is added to the bio-derived polymer, or a salt, stereoisomer, or isotopically labeled compound thereof.

121. The method of claim 119 or 120, wherein vulcanizing the coating further comprises heating the coating to about 150 ºC to about 200 ºC.118 / 119 C1723.70000WO00 #13627512v1

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