Self-fortifying hydrophobic polymer networks

Abstract

Disclosed herein are self-fortifying hydrophobic polymer systems including a crosslinked epoxidized lipid / epoxidized-alkoxysilane network. The systems have improved resistance to hydrolytic degradation relative to other polymer systems.

Description

Attorney Docket No.10485-023WO1 SELF-FORTIFYING HYDROPHOBIC POLYMER NETWORKS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 698,318, filed September 24, 2024, which is incorporated by reference herein in its entirety. BACKGROUND

[0001] Polymers that can readily repel high surface tension liquids (such as water) are known as hydrophobic polymers. Due to extreme water repellency of hydrophobic polymers, they have found extensive utility in applications such as water-resistant fabrics, anti-fouling surfaces, self-cleaning coatings, corrosion protection, biomedical devices, liquids separation, packaging materials, non-stick cookware, and ice / frost protection. Among the chemistries that can enable hydrophobic wettability, the polymers with functional groups including methylene (-CH2-), methyl (-CH3), difluoromethylene (-CF2-), and trifluoromethyl (-CF3) are common. While they are effective in reducing solid surface energy and enhancing hydrophobic wettability, these polymers can pose environmental challenges due to their toxicity. In particular, the fluoropolymers consisting of (-CF2-) and (-CF3) functional groups such as per- and polyfluorinated Substances (PFAS) can cause severe health and environmental issues. The production of other synthetic hydrophobic polymers, often derived from petrochemicals, also typically involves significant energy inputs, and requires chemicals with detrimental effects on the environment. Vegetable oil-derived (bio-based) hydrophobic polymers are attractive alternatives for synthetic counterparts as they present readily available and more sustainable resources. These polymers can offer performance similar to their synthetic counterparts while significantly reducing detrimental effects on the environment.

[0002] Similar to other hydrophobic polymers, vegetable oil-derived hydrophobic polymers can experience structural degradation and compromised properties when exposed to environment for sufficiently long time. The factors that can contribute to structural degradation of polymers include water sorption, varying and / or elevated temperatures, as well as physical wear and tear. In particular, extended exposure of these hydrophobic polymers to water either in liquid or vapor form can cause degradation through several mechanisms such as hydrolysis, swelling and plasticization, leading to compromised mechanical and thermal properties.

[0003] There remains a need for improved hydrophobic polymers with enhanced resistance to hydrolytic degradation. There remains a need for hydrophobic polymers that do not include PFAS and other harmful chemicals.Attorney Docket No.10485-023WO1 SUMMARY

[0004] In some implementations, disclosed herein is a self-fortifying polymer obtained by polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy-alkoxysilane.

[0005] In some implementations, also disclosed herein is a self-fortifying crosslinked network comprising a crosslinked epoxidized lipid and crosslinked epoxy-alkoxysilane.

[0006] In some implementations, also disclosed herein is a method of preparing a self- fortifying polymer comprising polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy-alkoxysilane.

[0007] Other systems, methods, features and / or advantages will be or may become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features and / or advantages be included within this description and be protected by the accompanying claims. BRIEF DESCRIPTION OF DRAWINGS

[0008] FIGURE 1 depicts the chemical structure of the materials utilized in the synthesis of the vegetable oil-derived self-fortifying hydrophobic polymers.

[0009] FIGURES 2A-2F depict representative goniometric photos showing the advancing and receding contact angles of different liquids on the polymer prepared using S2 formulation. FIGS. 2A-2B show water, FIGS. 2C-2D show formamide, and FIGS. 2E-2F show rapeseed oil.

[0010] FIGURE 3 depicts a proposed schematic showing self-fortification of polymer structure by forming additional crosslinks when exposed to water in water:ethanol mixture.

[0011] FIGURE 4 depicts a representative photo of the tensile test sample.

[0012] FIGURES 5A-5D depict stress-displacement curves for different polymers obtained from tensile testing. FIG.5A shows S1, FIG.5B shows S2, FIG.5C shows S3, and FIG.5D shows S4.

[0013] FIGURE 6 depicts a representative photo of the compression test sample.

[0014] FIGURES 7A-7D depict stress-displacement curves for different polymers obtained from compression testing. FIG. 7A shows S1, FIG. 7B shows S2, FIG. 7C shows S3, and FIG.7D shows S4.

[0015] FIGURES 8A-8B depict representative photos of a thin mild steel sheet before (FIG.8A) and after (FIG.8B) coating with the polymer.Attorney Docket No.10485-023WO1

[0016] FIGURE 9 depicts Tafel plots obtained from potentiodynamic polarization tests for the polymers. DETAILED DESCRIPTION

[0017] Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or to particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. DEFINITIONS

[0018] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another embodiment includesfrom the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0019] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0020] Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” means “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers or steps. “Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes.

[0021] Disclosed are components that can be used to perform the disclosed methods and systems. These and other components are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed that while specific reference of each various individual and collective combinations and permutation of these may not be explicitly disclosed, each is specifically contemplated and described herein, for all methods and systems. This applies to all aspects of this application including, but not limited to, steps in disclosed methods. Thus, if there are a variety of additional steps that canAttorney Docket No.10485-023WO1 be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods.

[0022] Compounds disclosed herein may be provided in the form of acceptable salts, for example pharmaceutically acceptable salts. Examples of such salts are acid addition salts formed with inorganic acids, for example, hydrochloric, hydrobromic, sulfuric, phosphoric, and nitric acids and the like; salts formed with organic acids such as acetic, oxalic, tartaric, succinic, maleic, fumaric, gluconic, citric, malic, methanesulfonic, p-toluenesulfonic, napthalenesulfonic, and polygalacturonic acids, and the like; salts formed from elemental anions such as chloride, bromide, and iodide; salts formed from metal hydroxides, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, and magnesium hydroxide; salts formed from metal carbonates, for example, sodium carbonate, potassium carbonate, calcium carbonate, and magnesium carbonate; salts formed from metal bicarbonates, for example, sodium bicarbonate and potassium bicarbonate; salts formed from metal sulfates, for example, sodium sulfate and potassium sulfate; and salts formed from metal nitrates, for example, sodium nitrate and potassium nitrate.

[0023] The term "alkyl" refers to a radical of a straight-chain or branched hydrocarbon group having a specified range of carbon atoms (e.g., a "C1-16 alkyl" can have from 1 to 16 carbon atoms). An alkyl group can be a saturated alkyl group or an unsaturated alkyl group, i.e., an alkyl group having one or more carbon-carbon double / triple bonds, i.e., an alkenyl or alkynyl group. Unless specified to the contrary, an “alkyl” group includes both saturated alkyl groups and unsaturated alkyl groups.

[0024] 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 (i.e., inserted between adjacent carbon atoms of) and / or placed at one or more terminal position(s) of the parent chain. By way of example, a heteroC1-6alkyl (which may also be designated a C1-6heteroalkyl) group includes, but is not limited to, the following structures:

[0025] The term “heteroalkyl” preceded by a separate heteroatom refers to a heteroalkyl group bonded through the specified heteroatom. By way of example, a OC1-6heteroalkyl group includes, but it not limited to, the following structures:Attorney Docket No.10485-023WO1

[0026] When a range of values is listed, it is intended to encompass each value and sub- range within the range. For example, "C1-6 alkyl" is intended to encompass 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 C5-6 alkyl.

[0027] Affixing the suffix "-ene" to a group indicates the group is a polyvalent moiety, e.g., boned to two or more groups. Alkylene is the polyvalent 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 (each of which parent groups as defined herein).

[0028] The term "alkoxy" refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0029] 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"). "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.

[0030] "Aralkyl" is a subset of "alkyl" and refers to an alkyl group substituted by an aryl group, wherein the point of attachment is on the alkyl moiety.

[0031] 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 valencyAttorney Docket No.10485-023WO1 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, i.e., either the ring bearing a heteroatom (e.g., 2-indolyl) or the ring that does not contain a heteroatom (e.g., 5-indolyl).

[0032] Exemplary heteroaryl and heterocyclyl rings include: benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH carbazolyl, carbolinyl, chromanyl, chromenyL cirrnolinyl, decahydroquinolinyl, 2H,6H~ 1,5,2-dithiazinyl, dihydrofuro[2,3 b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,4- oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 6H- 1,2,5-thiadiazinyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl, and xanthenyl.

[0033] Unless specified to the contrary, the alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups defined herein (and the “ene” versions of said groups) may be substituted or unsubstituted. AAttorney Docket No.10485-023WO1 substituted group includes a non-hydrogen substituent at a position where in the unsubstituted version a hydrogen atom would be found. Substituents include, but are not limited to, halogen, hydroxy, alkyl, alkoxy, nitro, cyano, oxo, carbocyclyl, carbocycloalkyl, heterocarbocyclyl, heterocarbocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, -NRaRb, -NRaC(=O)Rb, - NRaC(=O)NRaNRb, -NRaC(=O)ORb, - NRaSO2Rb, -C(=O)Ra, -C(=O)ORa, -C(=O)NRaRb, - OC(=O)NRaRb, -ORa, -SRa, -SORa, - S(=O)2Ra, -OS(=O)2Raand -S(=O)2ORa. Raand Rbin this context can be the same or different and independently hydrogen, halogen, hydroxyl, alkyl, alkoxy, alkyl, amino, alkylamino, dialkylamino, carbocyclyl, carbocycloalkyl, heterocarbocyclyl, heterocarbocycloalkyl, aryl, arylalkyl, heteroaryl, or heteroarylalkyl.

[0034] As used herein, the designation of a polyvalent moiety without specifying the specific order of attachment is intended to cover all possible arrangements. By way of example, a compound represented by the formula: A-X-B, wherein X is NHC(=O) embraces both:

[0035] As used herein, a chemical bond depicted: represents either a single, double, ortriple bond, valency permitting. By way of example,

[0036] Some compounds disclosed herein may exist as one or more tautomers. Tautomers are interconvertible structural isomers that differ in the position of one or more protons or other labile atom. By way of example:.

[0037] Unless stated to the contrary, a substituent drawn without explicitly specifying the point of attachment indicates that the substituent may be attached at any possible atom. For example, in a benzofuran depicted:,Attorney Docket No.10485-023WO1 the substituent may be present at any one of the six possible carbon atoms.

[0038] As used herein, the term “null,” when referring to a possible identity of a chemical moiety, indicates that the group is absent, and the two adjacent groups are directly bonded to one another. By way of example, for a genus of compounds having the formula CH3-X-CH3, if X is null, then the resulting compound has the formula CH3-CH3. A group having the subscript ‘0’ is understood to represent a null group as well. By way of example, in the compound CH3-(X)z-CH3, if X is CH2and z is 0, then the compound has the formula CH3-CH3.

[0039] A bracketed functional group with a subscripted variable should be understood to denote the number of repeated bracketed groups present. For example, a number that is selected from 0 or 1 should be interpreted as follows:.

[0040] In certain instances, two or more variable groups may together form a ring. It is understood that any depicted atoms separated the identified groups will themselves form part of the ring:

[0041] When the variable groups are substituted on an aromatic system the new ring will be a fused ring, and unless specified to the contrary may be either aromatic or non-aromatic, carbocyclic or heterocyclic:

[0042] The ring may further be defined by the number of carbon atoms in the specific ring formed by the variable groups, which includes the atoms separating the variable groups:

[0043] Each of the above results when R1and R2together form a six membered (or six atom) ring. Other rings, including 3, 4, 5, 7, and 8-member rings may also be formed, and may be further limited by a specified number of carbon atoms. Although the singular “a ring” mayAttorney Docket No.10485-023WO1 be used to define the group, unless specified to the contrary both monocyclic and polycyclic rings are possible:

[0044] Unless stated to the contrary, a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible isomer, e.g., each enantiomer, diastereomer, and meso compound, and a mixture of isomers, such as a racemic or scalemic mixture. Unless stated to the contrary, a formula depicting one or more stereochemical features does not exclude the presence of other isomers.

[0045] Some compounds disclosed herein may exist as one or more tautomers. Tautomers are interconvertible structural isomers that differ in the position of one or more protons or other labile atom. By way of example:.

[0046] The prevalence of one tautomeric form over another will depend on the specific chemical compound as well as its local chemical environment. Unless specified to the contrary, the depiction of one tautomeric form is inclusive of all possible tautomeric forms. POLYMERS

[0047] Disclosed herein are self-fortifying hydrophobic polymers. The polymers exhibit structural fortification and enhancement of mechanical properties upon exposure to water, in contrast to traditional hydrophobic polymers which are degraded over time by exposure to water.

[0048] In some implementations, the self-fortifying polymer can be obtained by polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy-alkoxysilane. Also disclosed herein are methods of preparing a crosslinked network including the step of crosslinking a mixture including an epoxidized lipid and epoxy- alkoxysilane.

[0049] In some implementations, the epoxidized lipid can be derived from a lipid having an iodine number of 110 or more (e.g., 115 or more, 120 or more, 125 or more, 130 or more, 140 or more, 150 or more, 160 or more, 170 or more, 180 or more, or 190 or more). In some implementations, the epoxidized lipid can be derived from a lipid having an iodine number ofAttorney Docket No.10485-023WO1 200 or less (e.g., 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 125 or less, 120 or less, or 115 or less).

[0050] The epoxidized lipid can be derived from a lipid having an iodine number ranging from any of the minimum values described above to any of the maximum values described above. In some implementations, the epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

[0051] In some implementations the epoxidized lipid can be an epoxidized fatty acid, an epoxidized monoglyceride, an epoxidized diglyceride, an epoxidized triglyceride, or a combination thereof.

[0052] In some implementations the epoxidized lipid comprises an epoxidized drying oil. In some implementations, the epoxidized lipid can include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized poppy seed oil, epoxidized perilla oil, epoxidized walnut oil, epoxidized cod liver oil, epoxidized oiticica oil, epoxidized safflower oil, epoxidized wheat germ oil, epoxidized coconut oil, epoxidized rapeseed oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized sesame oil, epoxidized avocado oil, epoxidized Brazil nut oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized palm oil, epoxidized peanut oil, epoxidized sunflower oil, epoxidized canola oil, epoxidized hempseed oil, epoxidized rice bran oil, or a combination thereof.

[0053] In certain implementations, the epoxidized lipid is epoxidized soybean oil.

[0054] In some implementations the epoxidized lipid can include an epoxidized fatty acid. As used herein, a “fatty acid” includes both conventional fatty acids having at least one carboxylic acid group, but also simple alkyl esters and amides of fatty acids as well. An ester is considered simple if it does not include a glycerol derived moiety. In some implementations the epoxidized lipid can be an epoxidized omega-3 fatty acid, epoxidized omega-6 fatty acid, epoxidized omega-7 fatty acid, epoxidized omega-9 fatty acid, or a combination thereof.

[0055] In some implementations the epoxidized lipid can include epoxidized linoleic acid, epoxidized eicosadienoic acid, epoxidized docosadienoic acid, epoxidized linolenic acid, epoxidized pinolenic acid, epoxidized eleostearic acid, epoxidized dihomo-^-linolenic acid, epoxidized eicosatrienoic acid, epoxidized tetra-unsaturated fatty acids, epoxidized stearidonic acid, epoxidized arachidonic acid, epoxidized eicosatetraenoic acid, epoxidized adrenic acid, epoxidized bosseopentaenoic acid, epoxidized eicosapentaenoic acid, epoxidized ozubondo acid, epoxidized sardine acid, epoxidized tetracosanolpentaenoic acid, epoxidized docosahexaenoic acid, epoxidized herring acid, epoxidized arachidonic acid, or a combination thereof.Attorney Docket No.10485-023WO1

[0056] In some implementations the epoxidized lipid can include a diglyceride or triglyceride derived from at least two different fatty acids, provided the fatty acids in total include at least two carbon-carbon double that can be converted to epoxides.

[0057] In some implementations, the epoxidized lipid includes a diglyceride derived from at least two unsaturated fatty acids. The at least two unsaturated fatty acids can be the same fatty acid or different fatty acids.

[0058] In certain implementations, the epoxidized lipid can include a triglyceride derived from an unsaturated fatty acid. Such a compound may be designated an epoxidized triglyercide. In certain implementations the epoxidized triglyceride can be derived from ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^- linolenic acid, dihomo-^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.

[0059] The epoxy-alkoxysilane can have the formula:, wherein R is a C1-20aliphatic group, R1is C1-4alkyl or OC1-4alkyl, Rais C1-4alkyl, and Rbis C1- 4alkyl, and each of R2, R3, and R4, are independently chosen from H and C1-10aliphatic, wherein any two or more of R, R1, R2, R3, and R4can together form a ring. In certain implementations, R2, R3, and R4each do not include a carbocycloalkyl group. In certain implementations, the ring formed by any two or more of R, R1, R2, R3, and R4does not include a carbocycloalkyl group.

[0060] In some implementations, Raand Rbare both either methyl or ethyl. In some implementations, R1is methoxy when Raand Rbare both methyl. In some implementations, R1is ethoxy when Raand Rbare both ethyl. In other implementations, R1is methyl.

[0061] In certain implementations, R can be a C1-8alkylene group or C1-8heteroalkylene group. In certain implementations, the epoxy-alkoxysilane can have the formula:, wherein Raand Rbare preferably chosen from CH3 and CH2CH3, and R1is preferably chosen from CH3, OCH3and OCH2CH3.Attorney Docket No.10485-023WO1

[0062] The epoxidized lipid and epoxy-alkoxysilane can be combined in the mixture in a variety of weight ratios. In some implementations, the epoxidized lipid:epoxy-alkoxysilane weight ratio can be 1:1 or more (e.g., 2:1 or more, 3:1 or more, 3.95:1 or more, 4:1 or more, 5:1 or more, 6:1 or more, 7:1 or more, 8:1 or more, 8.9:1 or more, 9:1 or more, 10:1 or more, 11:1 or more, 12:1 or more, 13:1 or more, 14:1 or more, 15:1 or more, 16:1 or more, 17:1 or more, 18:1 or more, or 19:1 or more). In some implementations, the epoxidized lipid:epoxy- alkoxysilane weight ratio can be 20:1 or less (e.g., 19:1 or less, 18:1 or less, 17:1 or less, 16:1 or less, 15:1 or less, 14:1 or less, 13:1 or less, 12:1 or less, 11:1 or less, 10:1 or less, 9:1 or less, 8.9:1 or less, 8:1 or less, 7:1 or less, 6:1 or less, 5:1 or less, 4:1 or less, 3.95:1 or less, 3:1 or less, or 2:1 or less).

[0063] The epoxidized lipid:epoxy-alkoxysilane weight ratio can range from any of the minimum values described above to any of the maximum values described above. For example, in some implementations, the epoxidized lipid:epoxy-alkoxysilane weight ratio can be from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:1.

[0064] When the epoxidized lipid comprises a plurality of lipids or alkoxysilanes, the weight ratios refer to the total of each component. Unless stated specifically to the contrary, the unsaturated fatty acids / glycerides that may be present in various oils are not subtracted from the mass of the oil for the purposes of this comparison. By way of example, soybean oil can include approximately 16% of saturated lipids, these saturated lipids are considered part of the epoxidized lipid for the purpose of determining weight ratios. On the other hand, when making reference to a specific epoxidized triglyceride or fatty acid content, any present unsaturated fatty acids and triglycerides are not counted towards the mass of the epoxidized lipid.

[0065] The polymerization may be conducted in the presence of a catalyst. In some implementations the polymerization may be conducted by heating the mixture. In some implementations the polymerization may be conducted by heating the mixture in the presence of a catalyst. In some implementations the polymerization may be conducted using UV irradiation or e-beam irradiation, optionally with heating.

[0066] In some implementations the polymerization is conducted in the presence of a cationic catalyst or an anionic catalyst. Exemplary anionic catalysts include metal alkoxides, metal hydrides, metal amides, and organometals. In certain implementations, the anionic catalyst can include a methoxide salt, an ethoxide salt, or an isopropoxide salt. Exemplary salts include those of Group I metals e.g., sodium methoxide, potassium methoxide, lithium methoxide, cesium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, cesiumAttorney Docket No.10485-023WO1 ethoxide, sodium isopropoxide, potassium isopropoxide, lithium isopropoxide, and cesium isopropoxide.

[0067] In some implementations the polymerization is conducted in the presence of an aluminum compound, a benzyl sulfonium salt catalyst, or a zinc compound. Exemplary catalysts systems include aluminum halides, aluminum alkoxides, aluminum acetylacetonates, and zinc halides.

[0068] In some implementations the catalyst can include triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, , triphenylsulfonium triflate, (4-iodophenyl)diphenylsulfonium triflate, (4-phenylthiophenyl)diphenylsulfonium triflate.

[0069] In some implementations, the catalyst has the formula:, wherein X is a non-coordinating anion, and Raand Rbare independently aryl, heteroaryl, or C1- 6alkyl, or Raand Rbtogether with the sulfur atom form a 5-7 membered ring. In some implementations X is perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis[3,5-bis(trifluoromethyl) phenyl]borate, or triflate.

[0070] In some implementations the catalyst can be a benzyl-p-hydroxylphenyl methylsulfonium salt, a benzyltetrahydrothiophenium salt, a benzyl methyl phenylsulfonium salt, or a 1(p-methoxybenzyl)tetrahydrothiophenium salt. In certain implementations, the salt can be hexafluoroantimonate.

[0071] In some implementations the catalyst can be aluminum chloride, zinc chloride, triphenylsulfonium hexafluorophosphate, , triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4- iodophenyl)diphenylsulfonium triflate, or (4-phenylthiophenyl)diphenylsulfonium triflate.

[0072] The catalyst can be present in the mixture an amount at a concentration of 0.1-5 wt.%, relative to the mass of the epoxidized lipid and epoxy-alkoxysilane. As previously discussed, reference to an epoxidized oil includes saturated components in the mass, while reference to specific epoxidized glycerides and fatty acids does not.

[0073] In some implementations, the catalyst can be present in an amount of 0.001 wt.% or more (e.g., 0.01 wt.% or more, 0.1 wt.% or more, 0.2 wt.% or more, 0.3 wt.% or more, 0.4 wt.% or more, 0.5 wt.% or more, 1 wt.% or more, 1.5 wt.% or more, 2 wt.% or more, 2.5 wt.%Attorney Docket No.10485-023WO1 or more, 3 wt.% or more, 3.5 wt.% or more, 4 wt.% or more, or 4.5 wt.% or more). In some implementations, the catalyst can be present in an amount of 5 wt.% or less (e.g., 4.5 wt.% or less, 4 wt.% or less, 3.5 wt.% or less, 3 wt.% or less, 2.5 wt.% or less, 2 wt.% or less, 1.5 wt.% or less, 1 wt.% or less, 0.5 wt.% or less, 0.4 wt.% or less, 0.3 wt.% or less, 0.2 wt.% or less, 0.1 wt.% or less, or 0.01 wt.% or less).

[0074] The catalyst can be present in any amount ranging from any of the minimum values described above to any of the maximum values described above. For example, in some implementations, the catalyst can be present in an amount from 0.1 wt.% to 0.5 wt.%, from 0.1 wt.% to 1 wt.%, from 0.1 wt.% to 2.5 wt.%, from 0.5 wt.% to 1 wt.%, from 0.5 wt.% to 2.5 wt.%, from 1 wt.% to 5 wt.%, or from 1 wt.% to 2.5 wt.%. In some implementations, the catalyst can be present in an amount from 0.001 wt.% to 0.1 wt.%, from 0.001 wt.% to 0.01 wt.%, or from 0.01 wt.% to 0.1 wt.%

[0075] In some implementations, the mixture can include a solvent, for example an alcohol such as methanol, ethanol, n-propanol, isopropanol, or reagent alcohol.

[0076] In some implementations, the mixture can be heated to a temperature of 50°C or more (e.g., 55°C or more, 60°C or more, 65°C or more, 70°C or more, 75°C or more, 80°C or more, 85°C or more, 90°C or more, 95°C or more, 100°C or more, 105°C or more, 110°C or more). In some implementations, the mixture can be heated to a temperature of 110°C or less (e.g., 110°C or less, 105°C or less, 100°C or less, 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, 60°C or less, or 55°C or less).

[0077] The mixture can be heated to a temperature ranging from any of the minimum values described above to any of the maximum values described above. For example, in some implementations, the mixture can be heated to a temperature from 50°C to 110°C, from 75°C to 110°C, from 100°C to 110°C, from 50°C to 100°C, or from 75°C to 100°C.

[0078] Also disclosed herein are crosslinked epoxidized lipid-epoxy-alkoxysilane networks.

[0079] In some implementations, the crosslinked network can be derived from a lipid having an iodine number of 110 or more (e.g., 115 or more, 120 or more, 125 or more, 130 or more, 140 or more, 150 or more, 160 or more, 170 or more, 180 or more, or 190 or more). In some implementations, the crosslinked network can be derived from a lipid having an iodine number of 200 or less (e.g., 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 125 or less, 120 or less, or 115 or less).

[0080] The crosslinked network can be derived from a lipid having an iodine number ranging from any of the minimum values described above to any of the maximum valuesAttorney Docket No.10485-023WO1 described above. For example, in some implementations, the crosslinked network can be derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

[0081] In some implementations the crosslinked network can include a crosslinked epoxidized fatty acid, a crosslinked epoxidized monoglyceride, a crosslinked epoxidized diglyceride, a crosslinked epoxidized triglyceride, or a combination thereof.

[0082] In some implementations the crosslinked network comprises a crosslinked epoxidized drying oil. In some implementations, the crosslinked network can include a crosslinked epoxidized soybean oil, a crosslinked epoxidized linseed oil, a crosslinked epoxidized tung oil, a crosslinked epoxidized poppy seed oil, a crosslinked epoxidized perilla oil, a crosslinked epoxidized walnut oil, a crosslinked epoxidized cod liver oil, a crosslinked epoxidized oiticica oil, a crosslinked epoxidized safflower oil, a crosslinked epoxidized wheat germ oil, a crosslinked epoxidized coconut oil, a crosslinked epoxidized rapeseed oil, a crosslinked epoxidized corn oil, a crosslinked epoxidized cottonseed oil, a crosslinked epoxidized sesame oil, a crosslinked epoxidized avocado oil, a crosslinked epoxidized Brazil nut oil, a crosslinked epoxidized grape seed oil, a crosslinked epoxidized olive oil, epoxidized palm oil, a crosslinked epoxidized peanut oil, a crosslinked epoxidized sunflower oil, a crosslinked epoxidized canola oil, a crosslinked epoxidized hempseed oil, a crosslinked epoxidized rice bran oil, or a crosslinked combination thereof.

[0083] In certain implementations, the network comprises a crosslinked epoxidized soybean oil-epoxy-alkoxysilane network.

[0084] In some implementations the crosslinked network comprises a crosslinked epoxidized fatty acid. As used herein, a “fatty acid” includes both conventional fatty acids having at least one carboxylic acid group, but also simple alkyl esters and amides of fatty acids as well. An ester is considered simple if it does not include a glycerol derived moiety. In some implementations the epoxidized lipid can be an epoxidized omega-3 fatty acid, epoxidized omega-6 fatty acid, epoxidized omega-7 fatty acid, epoxidized omega-9 fatty acid, or a combination thereof.

[0085] In some implementations the crosslinked network can include a crosslinked epoxidized linoleic acid, a crosslinked epoxidized eicosadienoic acid, a crosslinked epoxidized docosadienoic acid, a crosslinked epoxidized linolenic acid, a crosslinked epoxidized pinolenic acid, a crosslinked epoxidized eleostearic acid, a crosslinked epoxidized dihomo-^-linolenic acid, a crosslinked epoxidized eicosatrienoic acid, epoxidized tetra-unsaturated fatty acids, a crosslinked epoxidized stearidonic acid, a crosslinked epoxidized arachidonic acid, epoxidizedAttorney Docket No.10485-023WO1 eicosatetraenoic acid, a crosslinked epoxidized adrenic acid, a crosslinked epoxidized bosseopentaenoic acid, a crosslinked epoxidized eicosapentaenoic acid, a crosslinked epoxidized ozubondo acid, a crosslinked epoxidized sardine acid, a crosslinked epoxidized tetracosanolpentaenoic acid, a crosslinked epoxidized docosahexaenoic acid, a crosslinked epoxidized herring acid, a crosslinked epoxidized arachidonic acid, or a crosslinked combination thereof.

[0086] In some implementations the crosslinked network can include a crosslinked diglyceride or triglyceride derived from at least two different fatty acids, provided the fatty acids in total include at least two carbon-carbon double that can be converted to epoxides.

[0087] In some implementations, the crosslinked network includes a diglyceride derived from at least two unsaturated fatty acids. The at least two unsaturated fatty acids can be the same fatty acid or different fatty acids.

[0088] In certain implementations, the crosslinked network can include a crosslinked triglyceride derived from an unsaturated fatty acid. In crosslinked network can include a crosslinked epoxidized ^-linolenic acid, a crosslinked epoxidized stearidonic acid, a crosslinked epoxidized eicosapentaenoic acid, a crosslinked epoxidized cervonic acid, a crosslinked epoxidized linoleic acid, a crosslinked epoxidized linolelaidic acid, a crosslinked epoxidized ^-linolenic acid, a crosslinked epoxidized dihomo-^-linolenic acid, a crosslinked epoxidized arachidonic acid, a crosslinked epoxidized docosatetraenoic acid, a crosslinked epoxidized palmitoleic acid, a crosslinked epoxidized vaccenic acid, a crosslinked epoxidized paullinic acid, a crosslinked epoxidized oleic acid, a crosslinked epoxidized elaidic acid, a crosslinked epoxidized gondoic acid, a crosslinked epoxidized erucic acid, a crosslinked epoxidized nervonic acid, a crosslinked epoxidized mead acid, or a crosslinked combination thereof.

[0089] The crosslinked epoxy-alkoxysilane can have the formula:, wherein R* is a C1-20aliphatic group, R1*is independently C1-4alkyl or O-*, each of R2*, R3*, and R4*, are independently chosen from H and C1-10aliphatic, wherein any two or more of R*, R1*, R2*, R3*, and R4*can together form a ring, * represents a bond to H, C1-4alkyl, crosslinked lipid, or crosslinked epoxy-alkoxysilane, each wavy line ‘a’ independently represents a bondAttorney Docket No.10485-023WO1 to H, C1-4alkyl, crosslinked lipid or crosslinked epoxy-alkoxysilane, and each wavy line ‘b’ independently represents a bond to H, crosslinked lipid, or crosslinked epoxy-alkoxysilane, provided that at least two of the four wavy lines represent a bond to a crosslinked lipid, or crosslinked epoxy-alkoxysilane. In certain implementations, R2*, R3*, and R4*each do not include a carbocycloalkyl group. In certain implementations, the ring formed by any two or more of R*, R1*, R2*, R3*, and R4*does not include a carbocycloalkyl group.

[0090] In some implementations, the crosslinked epoxy-alkoxysilane comprises a crosslinked glycidylalkoxy silane, for example a crosslinked 3-glycidoxypropyl- trimethoxysilane or crosslinked 3-glycidoxypropyl-triethoxysilane.

[0091] The crosslinked network can include the epoxidized lipid and epoxy-alkoxysilane in a variety of weight ratios. In some implementations, the weight ratio of the epoxidized lipid:epoxy-alkoxysilane in the crosslinked network can be 1:1 or more (e.g., 2:1 or more, 3:1 or more, 3.95:1 or more, 4:1 or more, 5:1 or more, 6:1 or more, 7:1 or more, 8:1 or more, 8.9:1 or more, 9:1 or more, 10:1 or more, 11:1 or more, 12:1 or more, 13:1 or more, 14:1 or more, 15:1 or more, 16:1 or more, 17:1 or more, 18:1 or more, or 19:1 or more). In some implementations, the weight ratio of the epoxidized lipid:epoxy-alkoxysilane in the crosslinked network can be 20:1 or less (e.g., 19:1 or less, 18:1 or less, 17:1 or less, 16:1 or less, 15:1 or less, 14:1 or less, 13:1 or less, 12:1 or less, 11:1 or less, 10:1 or less, 9:1 or less, 8.9:1 or less, 8:1 or less, 7:1 or less, 6:1 or less, 5:1 or less, 4:1 or less, 3.95:1 or less, 3:1 or less, or 2:1 or less).

[0092] The weight ratio of the epoxidized lipid:epoxy-alkoxysilane in the crosslinked network can range from any of the minimum values described above to any of the maximum values described above. For example, in some implementations, the weight ratio of the epoxidized lipid:epoxy-alkoxysilane in the crosslinked network can be from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:1. When the crosslinked network comprises a plurality of lipids or alkoxysilanes, the weight ratios refer to the total of each component.

[0093] Without being bound by any theory, the self-fortifying nature of the networks in the hydrophobic polymer is believed to be due to the hydrolysis and crosslinking of siloxane groups following exposure to water. The crosslinked networks are useful as coatings, especially in coatings expected to be exposed to water, whether due to climate or use conditions. The networks are less susceptible to degradation from exposure to water than conventional polymer and polymer networks. In some implementations, the networks can be used in paints, sealants, protective coatings, and liquid separation membranes.Attorney Docket No.10485-023WO1

[0094] The disclosed polymers are useful in a wide variety of contexts, and may be deployed wherever hydrophobic polymers are used. The polymers can be used in textiles and apparel, electronics, transportation and automotive, construction and building materials, medical devices , agriculture and environmental, consumer products, and optical / imaging. In some implementations the polymers can be used in water-proof textiles and fabrics, electronic components and circuits protection, anti-icing and anti-frosting coatings (e.g., aircraft wings, wind turbines), self-cleaning coatings, coatings for medical devices (e.g., catheters, surgical tools, implants) and lab-on-a-chip medical devices such as microfluidic devices, packaging materials (e.g., moisture-barrier films for food and pharmaceutical packaging), automotive applications (e.g., coatings for windshield, headlights, mirrors), construction materials (e.g., roofing materials to prevent water / moisture sorption), anti-corrosion coatings, marine applications (e.g., ship hull coatings, seawater drag reduction, anti-biofouling), coatings for energy pipelines and fuel storage tanks, optical devices (e.g., coatings for lenses, optical sensors, anti-fogging, etc.), sports equipment (e.g., surfboards, skis). EXAMPLES

[0095] The following examples are for the purpose of illustration of the invention only and are not intended to limit the scope of the present invention in any manner whatsoever. Example 1

[0096] A solution was prepared in a vial by dissolving 100 mg of benzyl(4-hydroxyphenyl) methylsulfonium hexafluoroantimonate (“BHMH”) in 1000 mg of 3-glycidoxypropyl- trimethoxysilane (“GPTMS”). Subsequently, epoxidized soybean oil (“ESO”) (8900 mg) was added, and the vial was stirred for 30 minutes to obtain a transparent solution. For comparison, a solution of only ESO (i.e., without GPTMS) was also prepared by dissolving 100 mg of BHMH in ^50 mg ethanol followed by adding 9900 mg of ESO.

[0097] The solutions were poured in cylindrical silicone molds (diameter ^ 0.5 inch, height ^ 0.5 inch). The molds were placed on a hot plate heated to 110°C to perform thermal polymerization. Example 2

[0098] Materials and polymer solutions:

[0099] Materials: The vegetable oil-derived self-fortifying hydrophobic polymer was synthesized using epoxidized soybean oil (ESO) as the main monomer and 3-glycidoxypropyl- trimethoxysilane (GPTMS) as the organosilane monomer. ESO is derived from soybean oil through the epoxidation process [1]. As a replacement for conventional petroleum-based resins, this vegetable oil-derived material has been utilized in preparation of low-cost green bio-basedAttorney Docket No.10485-023WO1 epoxy polymers [2]. The monomer of ESO contains a long hydrocarbon chain consisting of low-solid surface energy Methylene (-CH2-) and Methyl (-CH3) groups, which can introduce hydrophobic wettability. ESO can be readily converted to a high-strength solid epoxy polymer through a ring-opening polymerization reaction [3].

[0100] GPTMS is an organosilane monomer that contains three hydrolyzable alkoxy functional groups (i.e., trialkoxysilyl group) and an epoxy functional organic chain. It can be utilized as an organic binder to increase the strength of a material [4].

[0101] In addition to the monomers, a thermally-latent cationic catalyst / initiator, benzyl(4- hydroxyphenyl) methylsulfonium hexafluoroantimonate (BHMH) was utilized for the synthesis of the polymer [5]. These catalysts / initiators can offer several advantages such as inertness under normal conditions and the ability to release active species only upon stimulation at specific temperatures, which enhances the storage stability of the system[6, 7]. Further, the polymers cured by these catalysts / initiators present lower shrinkage and superior mechanical properties [8]. The chemical structures of the materials are shown in FIG.1.

[0102] Polymer solutions: Polymer solutions with the following compositions of ESO, GPTMS, and BHMH were prepared (TABLE 1): TABLE 1. Composition of polymer solutions.

[0103] First, a polymer solution was prepared in a vial by dissolving BHMH in GPTMS. Subsequently, ESO was added, and the vial was stirred for 30 minutes to obtain a transparent solution. The polymer samples were prepared by thermally curing (polymerization) the polymer solutions on a hotplate at ^110°C. The polymer samples were utilized for a variety of characterization tests as described below.

[0104] Characterization tests:

[0105] Liquid wettability testing: Prior to investigating the liquid wettability, the polymers were coated onto glass substrates. Approximately 500 µL of each polymer solution was cast on glass substrates (size = 7.5 cm × 2.5 cm), followed by heating on a hotplate to completeAttorney Docket No.10485-023WO1 polymerization and obtain solid polymer coatings. The liquid wettability of the polymer coatings was investigated by measuring the dynamic (i.e., advancing and receding) contact angles of water (surface tension, ^lv ^ 72.7 mN / m), formamide (^lv ^ 58.2 mN / m), rapeseed oil (^lv ^ 35.7 mN / m), and n-hexadecane (^lv ^ 27.4 mN / m) at room temperature utilizing a goniometer (Model: Rame hart 210). The maximum advancing and receding contact angles of different liquids obtained on polymers prepared with various compositions are provided in TABLE 2. TABLE 2. Advancing and receding contact angles of different liquids on the polymers.

[0106] The representative goniometric photos obtained during the measurement of advancing and receding contact angles for different liquids are shown in FIG.2.

[0107] All polymer formulations show advancing contact angles for water greater than 90° confirming their hydrophobic wettability. In addition, formamide as another high surface tension liquid is effectively repelled, with advancing contact angles exceeding 76° across all polymer formulations. These results indicate no significant differences in liquid repellency among the tested formulations.

[0108] Shore A hardness testing: The effect of self-fortifying property of the polymer on its mechanical properties was investigated by performing Shore A hardness tests utilizing a DeFelsko PosiTector SHD hardness tester. The Shore A hardness value is expressed as a dimensionless number ranging from 0 to 100. Shore A hardness tests were performed on polymers that had been submerged in 50:50 wt% water:ethanol mixture for 0, 5, 10, and 15 days, and then dried in a dehydrator at 80°F (26.6°C) for 1 day. The measured Shore A hardness values for the polymers are summarized in TABLE 3.Attorney Docket No.10485-023WO1 TABLE 3. Shore A hardness measurements of the polymers.

[0109] These results indicate that the S3 polymer exhibited the greatest increase in Shore A hardness, rising from 79.96^±^0.50 to 89.4^±^0.70 after 10 days of submersion in a water:ethanol mixture. The increase in hardness can be attributed to the hydrolysis reaction at the trialkoxysilyl (-Si-O-CH3) functional groups of GPTMS, leading to formation of silanol groups (-Si-OH). The presence of water in the water:ethanol mixture can initiate this hydrolysis reaction. Subsequently, the condensation reactions between silanol groups caused formation of new silicone-oxygen covalent bonds (Si-O-Si) as additional crosslinks, which can improve the strength of the polymer [9, 10] (FIG.3).

[0110] Note that Shore A hardness could not be measured for the S4 polymer after 10 and 15 days of submersion, as the samples were too brittle and fractured during the hardness testing.

[0111] Tensile testing: The tensile testing samples were prepared by casting the polymer solutions into non-stick rectangular silicone molds (Length= 135 mm, Width= 14 mm, Thickness^ 2 mm). Tensile tests were performed following the ASTM D3039 standard. A benchtop testing equipment (Model: Mark-10 F505) was used and the polymer samples were clamped at both ends using two grips. Testing was performed at a constant strain rate of 2 mm / min during which the load-displacement data were collected. The tensile stress was determined by dividing the measured load by the cross-sectional area of the polymer sample. The representative photo of the tensile test sample is presented in FIG. 4. The plots of tensile stress vs. displacement for different polymer formulations submerged in 50:50 wt% water:ethanol mixture for 0, 5, 10, and 15 days are demonstrated in FIG.5. The ultimate tensile strength (highest tensile stress) values obtained from tensile tests are summarized in TABLE 4.Attorney Docket No.10485-023WO1 TABLE 4. Ultimate tensile strength measurements of the polymers.

[0112] The results of tensile tests show a decrease in ultimate tensile strength values with the increase in the time of submersion in water:ethanol mixture. This reduction may be related to the increased brittleness of the polymers as indicated by the rising hardness values (see TABLE 3), which limits the polymers’ ability to elongate under tensile loading and therefore reduces their tensile strength values.

[0113] The ultimate tensile strength decreased from 0.746 MPa to 0.637 MPa for polymer S1, marking a 0.109 MPa decrease, whereas for polymer S4, it decreased significantly from 1.336 MPa to 0.485 MPa, marking a decrease of 0.851 MPa. This difference can be attributed to a lower concentration of GPTMS in S1 compared to S4. A lower concentration of GPTMS in S1 caused a less pronounced self-fortifying effect resulting in limited increase in hardness and brittleness. In contrast, the higher concentration of GPTMS in S4 caused a significant self- fortifying effect resulting in an excessive increase in hardness and brittleness, which in turn limited the elongation ability and ultimate tensile strength of the polymer.

[0114] Compression testing: The compression testing samples were prepared by casting the polymer solutions into non-stick cylindrical plastic molds (Height^ 10 mm, Diameter= 17.6 mm). Compression tests were conducted using the benchtop testing equipment (Model: Mark- 10 F505). Testing was performed at a constant strain rate of 2 mm / min during which the load- displacement data were collected. The compression stress was determined by dividing the measured load by the cross-sectional area of the cylindrical polymer sample. The representative photo of the compression test sample is presented in FIG. 6. The plots of compression stress vs. displacement for different polymer formulations submerged in 50:50 wt% water:ethanol mixture for 0, 5, 10, and 15 days are demonstrated in FIG.7. The ultimate compression strength (highest compression stress) values obtained from compression tests are summarized in TABLE 5.Attorney Docket No.10485-023WO1 TABLE 5. Ultimate compression strength measurements of the polymers.

[0115] The results of compression tests show that the ultimate compression strength values increased with polymers (S1, S2, and S3) submersion in the water:ethanol mixture. This improvement can be attributed to the increased hardness values (see TABLE 3), which indicate enhanced stiffness and resistance to deformation. These characteristics are particularly beneficial under compressive loading, where the polymers can benefit from a denser network structure. The self-fortifying effect driven by the formation of additional crosslinks resulted in a denser polymer network that could withstand compressive forces more effectively.

[0116] Note that the value of ultimate compression strength generally decreased for the S4 polymer after submersion in the water:ethanol mixture. This reduction is attributed to the high concentration of GPTMS in S4 that caused excessive self-fortifying effect. The resulting brittleness compromised the polymer’s ability to withstand compressive forces.

[0117] Corrosion testing: Corrosion tests were performed using the potentiodynamic polarization method with a three-electrode setup. In this configuration, thin mild steel sheets (Length= 100 mm, Width= 14 mm, Thickness^ 0.65 mm) coated with S1-S4 polymers were utilized as the working electrodes while platinum and Ag / AgCl were used as the counter and reference electrodes, respectively. Saline water (3.5 wt% NaCl in water) was utilized as the corrosive medium (electrolyte). The measurements were performed using a Gamry 1010T potentiostat, and the Tafel plots were recorded at a scan rate of 10 mV / s.

[0118] FIGS. 8A-8B show photos of the thin mild steel sheet before and after coating, respectively. Note that the thickness of the coatings was approximately 0.60 mm.

[0119] FIG.9 shows the Tafel plots obtained from the potentiodynamic polarization tests. The extrapolation method was used to determine the corrosion potential (Ecorr) and corrosion current density (Icorr). The Ecorr and Icorr values obtained for polymers S1-S4 areAttorney Docket No.10485-023WO1 summarized in TABLE 6. Note that a more positive value of Ecorr typically indicates lower corrosion probability, while Icorr is a measure of corrosion rate [11, 12]. TABLE 6. Summary of Ecorrand Icorrvalues for the polymers.

[0120] The results indicate that polymer S2, with the lowest corrosion current density of 0.522 nA / cm2 provides the highest level of corrosion protection in saline water.

[0121] Distinct features of polymers: While self-strengthening polymers have been reported in prior studies [9, 10, 13-17], in these works, the self-strengthening mechanism was also attributed to the hydrolysis and condensation of the alkoxysilyl (-Si-O-CH3) functional groups, resulting in formation of additional crosslinks, which enables progressive improvement in mechanical properties of polymers. However, the current work differs from those prior studies in several aspects as summarized below.

[0122] Unlike conventional polymers, completely different monomers were used in the present work, which include Epoxidized soybean oil (ESO) and 3-glycidoxypropyl- trimethoxysilane (GPTMS). Furthermore, the organosilane monomer used in the present work is 3-glycidoxypropyl-trimethoxysilane (GPTMS), which also contains alkoxysilyl moiety. Unlike conventional polymers, the head group in GPTMS consists only of an epoxide ring.

[0123] The hydrolysis and condensation of the alkoxysilyl functional groups that cause self-fortifying in the polymer developed in present work is also initiated by submersion in a liquid containing water (e.g., water-ethanol mixture). Additionally, the polymer developed in this work partially undergoes self-fortification during the thermal polymerization process when exposed to heat.

[0124] Unlike conventional polymers, the catalyst / initiator used in the present work is a thermally-latent cationic initiator (heat-responsive catalyst / initiator), benzyl(4-hydroxyphenyl) methylsulfonium hexafluoroantimonate (BHMH). This catalyst / initiator can undergo thermal decomposition to release protons that can initiate polymerization

[0018] . These catalysts / initiators offer several advantages such as inertness under normal conditions and theAttorney Docket No.10485-023WO1 ability to release active species when stimulated at specific temperatures, which enhances the storage stability of the system[6, 7]. Further, the polymers cured by these catalysts / initiators present lower shrinkage and superior mechanical properties [8].

[0125] The polymer developed in the present work is hydrophobic (water-repelling). As such, the self-fortifying hydrophobic polymer developed in the present work can be used for applications such as hydrophobic protective coatings, corrosion protection, and liquids separation. EXAMPLE ASPECTS

[0126] Example 1: A self-fortifying polymer obtained by polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy- alkoxysilane.

[0127] Example 2: The polymer according to any examples herein, wherein the epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

[0128] Example 3: The polymer according to any examples herein, wherein the epoxidized lipid comprises an epoxidized fatty acid, an epoxidized monoglyceride, an epoxidized diglyceride, an epoxidized triglyceride, or a combination thereof.

[0129] Example 4: The polymer according to any examples herein, wherein the epoxidized lipid comprises an epoxidized drying oil.

[0130] Example 5: The polymer according to any examples herein, wherein the epoxidized lipid comprises epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized poppy seed oil, epoxidized perilla oil, epoxidized walnut oil, epoxidized cod liver oil, epoxidized oiticica oil, epoxidized safflower oil, epoxidized wheat germ oil, epoxidized coconut oil, epoxidized rapeseed oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized sesame oil, epoxidized avocado oil, epoxidized Brazil nut oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized palm oil, epoxidized peanut oil, epoxidized sunflower oil, epoxidized canola oil, epoxidized hempseed oil, epoxidized rice bran oil, or a combination thereof.

[0131] Example 6: The polymer according to any examples herein, wherein the epoxidized lipid comprises epoxidized soybean oil.

[0132] Example 7: The polymer according to any examples herein, wherein the epoxidized lipid comprises an epoxidized fatty acid.Attorney Docket No.10485-023WO1

[0133] Example 8: The polymer according to any examples herein, wherein the epoxidized lipid comprises an epoxidized omega-3 fatty acid, epoxidized omega-6 fatty acid, epoxidized omega-7 fatty acid, epoxidized omega-9 fatty acid, or a combination thereof.

[0134] Example 9: The polymer according to any examples herein, wherein the epoxidized lipid comprises an epoxidized linoleic acid, epoxidized eicosadienoic acid, epoxidized docosadienoic acid, epoxidized linolenic acid, epoxidized pinolenic acid, epoxidized eleostearic acid, epoxidized dihomo-^-linolenic acid, epoxidized eicosatrienoic acid, epoxidized tetra-unsaturated fatty acids, epoxidized stearidonic acid, epoxidized arachidonic acid, epoxidized eicosatetraenoic acid, epoxidized adrenic acid, epoxidized bosseopentaenoic acid, epoxidized eicosapentaenoic acid, epoxidized ozubondo acid, epoxidized sardine acid, epoxidized tetracosanolpentaenoic acid, epoxidized docosahexaenoic acid, epoxidized herring acid, epoxidized arachidonic acid, or a combination thereof.

[0135] Example 10: The polymer according to any examples herein, wherein the epoxidized lipid comprises a diglyceride or triglyceride derived from at least two unsaturated fatty acids.

[0136] Example 11: The polymer according to any examples herein, wherein the epoxidized lipid comprises a diglyceride derived from at least two unsaturated fatty acids.

[0137] Example 12: The polymer according to any examples herein, wherein the epoxidized lipid comprises a triglyceride derived from an unsaturated fatty acid.

[0138] Example 13: The polymer according to any examples herein, wherein the epoxidized lipid comprises an epoxidized triglyceride, wherein the triglyceride is derived from an unsaturated fatty acid, wherein the fatty acid comprises ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^-linolenic acid, dihomo- ^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.

[0139] Example 14: The polymer according to any examples herein, wherein the epoxy- alkoxysilane has the formula:,Attorney Docket No.10485-023WO1 wherein R is a C1-20aliphatic group, R1is C1-4alkyl or OC1-4alkyl, Rais C1-4alkyl, and Rbis C1- 4alkyl, and each of R2, R3, and R4, are independently chosen from H and C1-10aliphatic, wherein any two or more of R1, R2, R3, and R4can together form a ring.

[0140] Example 15: The polymer according to any examples herein, wherein R2, R3, and R4each do not comprise a carbocycloalkyl group.

[0141] Example 16: The polymer according to any examples herein, wherein the ring formed by any two or more of R, R1, R2, R3, and R4does not comprise a carbocycloalkyl group.

[0142] Example 17: The polymer according to any examples herein, wherein R is a C1-8alkylene group or C1-8heteroalkylene group.

[0143] Example 18: The polymer according to any examples herein, wherein the epoxy- alkoxysilane has the formula:, wherein Raand Rbare preferably chosen from CH3 and CH2CH3, and R1is preferably chosen from CH3, OCH3 and OCH2CH3.

[0144] Example 19: The polymer according to any examples herein, wherein the epoxidized lipid and epoxy-alkoxysilane are present in the mixture with an epoxidized lipid:epoxy-alkoxysilane weight ratio from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:1.

[0145] Example 20: The polymer according to any examples herein, wherein the polymerization is conducted in the presence of a catalyst, UV irradiation, e-beam irradiation, heat, or a combination thereof.

[0146] Example 21: The polymer according to any examples herein, wherein the polymerization is conducted in the presence of a catalyst.

[0147] Example 22: The polymer according to any examples herein, wherein the polymerization is conducted in the presence of a cationic catalyst or an anionic catalyst.

[0148] Example 23: The polymer according to any examples herein, wherein the anionic catalyst comprises a metal alkoxide, a metal hydride, a metal amide, or an organometal.

[0149] Example 24: The polymer according to any examples herein, wherein the anionic catalyst comprises a methoxide, an ethoxide, an isopropoxide,Attorney Docket No.10485-023WO1

[0150] Example 25: The polymer according to any examples herein, wherein the polymerization is conducted in the presence of an aluminum compound, a benzyl sulfonium salt catalyst, or a zinc compound.

[0151] Example 26: The polymer according to any examples herein, wherein the catalyst comprises aluminum halide, aluminum alkoxide, aluminum acetylacetonate, zinc chloride.

[0152] Example 27: The polymer according to any examples herein, wherein the catalyst comprises triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4- iodophenyl)diphenylsulfonium triflate, (4-phenylthiophenyl)diphenylsulfonium triflate.

[0153] Example 28: The polymer according to any examples herein, wherein the catalyst has the formula:, wherein X is a non-coordinating anion, and Raand Rbare independently aryl, heteroaryl, or C1-6alkyl, or Raand Rbtogether with the sulfur atom form a 5-7 membered ring.

[0154] Example 29: The polymer according to any examples herein, wherein the catalyst has the formula:

[0155] Example 30: The polymer according to any examples herein, wherein X is perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis[3,5- bis(trifluoromethyl) phenyl]borate, or triflate.

[0156] Example 31: The polymer according to any examples herein, wherein the catalyst comprises aluminum chloride, zinc chloride, triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4-iodophenyl)diphenylsulfonium triflate, or (4- phenylthiophenyl)diphenylsulfonium triflate.

[0157] Example 32: The polymer according to any examples herein, wherein the catalyst is present in the mixture in an amount at a concentration of 0.1 wt.% to 5 wt.%.Attorney Docket No.10485-023WO1

[0158] Example 33: The polymer according to any examples herein, wherein the mixture further comprises a solvent.

[0159] Example 34: The polymer according to any examples herein, wherein the solvent comprises an alcohol.

[0160] Example 35: The polymer according to any examples herein, wherein the mixture is heated to a temperature from 50°C to 110°C, from 75°C to 110°C, from 100°C to 110°C, from 50°C to 100°C, or from 75°C to 100°C

[0161] Example 36: A self-fortifying crosslinked network comprising a crosslinked epoxidized lipid and crosslinked epoxy-alkoxysilane.

[0162] Example 37: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

[0163] Example 38: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized fatty acid, a crosslinked epoxidized monoglyceride, a crosslinked epoxidized diglyceride, a crosslinked epoxidized triglyceride, or a crosslinked combination thereof.

[0164] Example 39: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized drying oil.

[0165] Example 40: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises crosslinked epoxidized soybean oil, crosslinked epoxidized linseed oil, crosslinked epoxidized tung oil, crosslinked epoxidized poppy seed oil, crosslinked epoxidized perilla oil, crosslinked epoxidized walnut oil, crosslinked epoxidized cod liver oil, crosslinked epoxidized oiticica oil, crosslinked epoxidized safflower oil, crosslinked epoxidized wheat germ oil, crosslinked epoxidized coconut oil, crosslinked epoxidized rapeseed oil, crosslinked epoxidized corn oil, crosslinked epoxidized cottonseed oil, crosslinked epoxidized sesame oil, crosslinked epoxidized avocado oil, crosslinked epoxidized Brazil nut oil, crosslinked epoxidized grape seed oil, crosslinked epoxidized olive oil, crosslinked epoxidized palm oil, crosslinked epoxidized peanut oil, crosslinked epoxidized sunflower oil, crosslinked epoxidized canola oil, crosslinked epoxidized hempseed oil, crosslinked epoxidized rice bran oil, or a crosslinked combination thereof.

[0166] Example 41: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises crosslinked epoxidized soybean oil.

[0167] Example 42: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized fatty acid.Attorney Docket No.10485-023WO1

[0168] Example 43: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized omega-3 fatty acid, a crosslinked epoxidized omega-6 fatty acid, a crosslinked epoxidized omega-7 fatty acid, a crosslinked epoxidized omega-9 fatty acid, or a crosslinked combination thereof.

[0169] Example 44: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises crosslinked epoxidized linoleic acid, crosslinked epoxidized eicosadienoic acid, crosslinked epoxidized docosadienoic acid, crosslinked epoxidized linolenic acid, crosslinked epoxidized pinolenic acid, crosslinked epoxidized eleostearic acid, crosslinked epoxidized dihomo-^-linolenic acid, crosslinked epoxidized eicosatrienoic acid, crosslinked epoxidized tetra-unsaturated fatty acids, crosslinked epoxidized stearidonic acid, crosslinked epoxidized arachidonic acid, crosslinked epoxidized eicosatetraenoic acid, crosslinked epoxidized adrenic acid, crosslinked epoxidized bosseopentaenoic acid, crosslinked epoxidized eicosapentaenoic acid, crosslinked epoxidized ozubondo acid, crosslinked epoxidized sardine acid, crosslinked epoxidized tetracosanolpentaenoic acid, crosslinked epoxidized docosahexaenoic acid, crosslinked epoxidized herring acid, crosslinked epoxidized arachidonic acid, or a crosslinked combination thereof.

[0170] Example 45: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked diglyceride or crosslinked triglyceride derived from at least two unsaturated fatty acids.

[0171] Example 46: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked diglyceride derived from at least two unsaturated fatty acids.

[0172] Example 47: The crosslinked network according to any examples herein, wherein the crosslinked epoxidized lipid comprises a crosslinked triglyceride derived from an unsaturated fatty acid.

[0173] Example 48: The crosslinked network according to any examples herein, wherein the epoxidized lipid comprises a crosslinked epoxidized triglyceride, wherein the triglyceride is derived from an unsaturated fatty acid, wherein the fatty acid comprises ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^- linolenic acid, dihomo-^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.Attorney Docket No.10485-023WO1

[0174] Example 49: The crosslinked network according to any examples herein, wherein the epoxy-alkoxysilane has the formula:, wherein R* is a C1-20aliphatic group, R1*is independently C1-4alkyl or O-*, each of R2*, R3*, and R4*, are independently chosen from H and C1-10aliphatic, wherein any two or more of R*, R1*, R2*, R3*, and R4*can together form a ring, * represents a bond to H, C1-4alkyl, crosslinked lipid, or crosslinked epoxy-alkoxysilane, each wavy line ‘a’ independently represents a bond to H, C1-4alkyl, crosslinked lipid or crosslinked epoxy-alkoxysilane, and each wavy line ‘b’ independently represents a bond to H, crosslinked lipid, or crosslinked epoxy-alkoxysilane, provided that at least two of the four wavy lines represent a bond to a crosslinked lipid, or crosslinked epoxy-alkoxysilane.

[0175] Example 50: The crosslinked network according to any examples herein, wherein R2*, R3*, and R4*each do not comprise a carbocycloalkyl group.

[0176] Example 51: The crosslinked network according to any examples herein, wherein the ring formed by any two or more of R*, R1*, R2*, R3*, and R4*does not comprise a carbocycloalkyl group.

[0177] Example 52: The crosslinked network according to any examples herein, wherein R* is a C1-8alkylene group or C1-8heteroalkylene group.

[0178] Example 53: The crosslinked network according to any examples herein, wherein the crosslinked epoxy-alkoxysilane comprises a crosslinked glycidylalkoxy silane.

[0179] Example 54: The crosslinked network according to any examples herein, wherein the crosslinked epoxy-alkoxysilane comprises crosslinked 3-glycidoxypropyl- trimethoxysilane or crosslinked 3-glycidoxypropyl-triethoxysilane.

[0180] Example 55: The crosslinked network according to any examples herein, comprising the crosslinked epoxidized lipid and crosslinked epoxy-alkoxysilane in a weight ratio from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:1.

[0181] Example 56: A method of preparing a self-fortifying polymer comprising polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy-alkoxysilane.Attorney Docket No.10485-023WO1

[0182] Example 57: The method according to any examples herein, wherein the epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

[0183] Example 58: The method according to any examples herein, wherein the epoxidized lipid comprises an epoxidized fatty acid, an epoxidized monoglyceride, an epoxidized diglyceride, an epoxidized triglyceride, or a combination thereof.

[0184] Example 59: The method according to any examples herein, wherein the epoxidized lipid comprises an epoxidized drying oil.

[0185] Example 60: The method according to any examples herein, wherein the epoxidized lipid comprises epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized poppy seed oil, epoxidized perilla oil, epoxidized walnut oil, epoxidized cod liver oil, epoxidized oiticica oil, epoxidized safflower oil, epoxidized wheat germ oil, epoxidized coconut oil, epoxidized rapeseed oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized sesame oil, epoxidized avocado oil, epoxidized Brazil nut oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized palm oil, epoxidized peanut oil, epoxidized sunflower oil, epoxidized canola oil, epoxidized hempseed oil, epoxidized rice bran oil, or a combination thereof.

[0186] Example 61: The method according to any examples herein, wherein the epoxidized lipid comprises epoxidized soybean oil.

[0187] Example 62: The method according to any examples herein, wherein the epoxidized lipid comprises an epoxidized fatty acid.

[0188] Example 63: The method according to any examples herein, wherein the epoxidized lipid comprises an epoxidized omega-3 fatty acid, epoxidized omega-6 fatty acid, epoxidized omega-7 fatty acid, epoxidized omega-9 fatty acid, or a combination thereof.

[0189] Example 64: The method according to any examples herein, wherein the epoxidized lipid comprises an epoxidized linoleic acid, epoxidized eicosadienoic acid, epoxidized docosadienoic acid, epoxidized linolenic acid, epoxidized pinolenic acid, epoxidized eleostearic acid, epoxidized dihomo-^-linolenic acid, epoxidized eicosatrienoic acid, epoxidized tetra-unsaturated fatty acids, epoxidized stearidonic acid, epoxidized arachidonic acid, epoxidized eicosatetraenoic acid, epoxidized adrenic acid, epoxidized bosseopentaenoic acid, epoxidized eicosapentaenoic acid, epoxidized ozubondo acid, epoxidized sardine acid, epoxidized tetracosanolpentaenoic acid, epoxidized docosahexaenoic acid, epoxidized herring acid, epoxidized arachidonic acid, or a combination thereof.Attorney Docket No.10485-023WO1

[0190] Example 65: The method according to any examples herein, wherein the epoxidized lipid comprises a diglyceride or triglyceride derived from at least two unsaturated fatty acids.

[0191] Example 66: The method according to any examples herein, wherein the epoxidized lipid comprises a diglyceride derived from at least two unsaturated fatty acids.

[0192] Example 67: The method according to any examples herein, wherein the epoxidized lipid comprises a triglyceride derived from an unsaturated fatty acid.

[0193] Example 68: The method according to any examples herein, wherein the epoxidized lipid comprises an epoxidized triglyceride, wherein the triglyceride is derived from an unsaturated fatty acid, wherein the fatty acid comprises ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^-linolenic acid, dihomo- ^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.

[0194] Example 69: The method according to any examples herein, wherein the epoxy- alkoxysilane has the formula:wherein R is a C1-20aliphatic group, R1is C1-4alkyl or OC1-4alkyl, Rais C1-4alkyl, and Rbis C1-4alkyl, and each of R2, R3, and R4, are independently chosen from H and C1-10aliphatic, wherein any two or more of R1, R2, R3, and R4can together form a ring.

[0195] Example 70: The method according to any examples herein, wherein R2, R3, and R4each do not comprise a carbocycloalkyl group.

[0196] Example 71: The method according to any examples herein, wherein the ring formed by any two or more of R, R1, R2, R3, and R4does not comprise a carbocycloalkyl group.

[0197] Example 72: The method according to any examples herein, wherein R is a C1- 8alkylene group or C1-8heteroalkylene group.

[0198] Example 73: The method according to any examples herein, wherein the epoxy- alkoxysilane has the formula:,Attorney Docket No.10485-023WO1 wherein Raand Rbare preferably chosen from CH3 and CH2CH3, and R1is preferably chosen from CH3, OCH3 and OCH2CH3.

[0199] Example 74: The method according to any examples herein, wherein the epoxidized lipid and epoxy-alkoxysilane are present in the mixture with an epoxidized lipid:epoxy-alkoxysilane weight ratio from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:1.

[0200] Example 75: The method according to any examples herein, wherein the polymerization is conducted in the presence of a catalyst, UV irradiation, e-beam irradiation, heat, or a combination thereof.

[0201] Example 76: The method according to any examples herein, wherein the polymerization is conducted in the presence of a catalyst.

[0202] Example 77: The method according to any examples herein, wherein the polymerization is conducted in the presence of a cationic catalyst or an anionic catalyst.

[0203] Example 78: The method according to any examples herein, wherein the anionic catalyst comprises a metal alkoxide, a metal hydride, a metal amide, or an organometal.

[0204] Example 79: The method according to any examples herein, wherein the anionic catalyst comprises a methoxide, an ethoxide, or an isopropoxide,

[0205] Example 80: The method according to any examples herein, wherein the polymerization is conducted in the presence of an aluminum compound, a benzyl sulfonium salt catalyst, or a zinc compound.

[0206] Example 81: The method according to any examples herein, wherein the catalyst comprises aluminum halide, aluminum alkoxide, aluminum acetylacetonate, zinc chloride.

[0207] Example 82: The method according to any examples herein, wherein the catalyst comprises triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4- iodophenyl)diphenylsulfonium triflate, (4-phenylthiophenyl)diphenylsulfonium triflate.

[0208] Example 83: The method according to any examples herein, wherein the catalyst has the formula:,Attorney Docket No.10485-023WO1 wherein X is a non-coordinating anion, and Raand Rbare independently aryl, heteroaryl, or C1-6alkyl, or Raand Rbtogether with the sulfur atom form a 5-7 membered ring.

[0209] Example 84: The method according to any examples herein, wherein the catalyst has the formula:.

[0210] Example 85: The method according to any examples herein, wherein X is perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis[3,5- bis(trifluoromethyl) phenyl]borate, or triflate.

[0211] Example 86: The method according to any examples herein, wherein the catalyst comprises aluminum chloride, zinc chloride, triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate,, triphenylsulfonium triflate, (4-iodophenyl)diphenylsulfonium triflate, or (4- phenylthiophenyl)diphenylsulfonium triflate.

[0212] Example 87: The method according to any examples herein, wherein the catalyst is present in the mixture in an amount at a concentration of 0.1 wt.% to 5 wt.%.

[0213] Example 88: The method according to any examples herein, wherein the mixture further comprises a solvent.

[0214] Example 89: The method according to any examples herein, wherein the solvent comprises an alcohol.

[0215] Example 90: The method according to any examples herein, wherein the mixture is heated to a temperature from 50°C to 110°C, from 75°C to 110°C, from 100°C to 110°C, from 50°C to 100°C, or from 75°C to 100°C.

[0216] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of theAttorney Docket No.10485-023WO1 compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches.

[0217] The following patents, applications and publications as listed below and throughout this document are hereby incorporated by reference in their entirety herein. Reference List [1] Z. S. Petrovi^, et al., "Epoxidation of soybean oil in toluene with peroxoacetic and peroxoformic acids—kinetics and side reactions," European Journal of Lipid Science and Technology, vol.104, no.5, pp.293-299, 2002. [2] A. Sobhan, et al., "Derivation and characterization of epoxidized soybean oil and epoxy resin film produced using a three step-washing neutralization process," Industrial Crops and Products, vol.198, p.116675, 2023 / 08 / 01 / 2023. [3] X. Huang, et al., "Enhancement of Hydrophobic Properties of Cellulose Fibers via Grafting with Polymeric Epoxidized Soybean Oil," ACS Sustainable Chemistry & Engineering, vol.5, no.2, pp.1619-1627, 2017 / 02 / 062017. [4] L. Chu, et al., "Use of (Glycidoxypropyl)trimethoxysilane as a Binder in Colloidal Silica Coatings," Chemistry of Materials, vol.9, no.11, pp.2577-2582, 1997 / 11 / 011997. [5] T. Tsujimoto, et al., "Biodegradable shape memory polymeric material from epoxidized soybean oil and polycaprolactone," Polymers, vol.7, no.10, pp.2165-2174, 2015. [6] S.-J. Park, et al., "Cationic polymerization and physicochemical properties of a biobased epoxy resin initiated by thermally latent catalysts," European Polymer Journal, vol. 41, no.2, pp.231-237, 2005 / 02 / 01 / 2005.Attorney Docket No.10485-023WO1 [7] S.-J. Park, et al., "Synthesis and Thermal Properties of Epoxidized Vegetable Oil," Macromolecular Rapid Communications, vol.25, no.6, pp.724-727, 2004. [8] S. Malburet, C. et al., "Sustainable access to fully biobased epoxidized vegetable oil thermoset materials prepared by thermal or UV-cationic processes," RSC advances, vol.10, no.68, pp.41954-41966, 2020. [9] L. Song, Q et al., "Mimicking nature: Self-strengthening properties in a dental adhesive," Acta Biomaterialia, vol.35, pp.138-152, 2016 / 04 / 15 / 2016.

[0010] M. Ezazi, et al., "Autonomous-Strengthening Adhesive Provides Hydrolysis- Resistance and Enhanced Mechanical Properties in Wet Conditions," Molecules, vol. 27, no. 17, p.5505, 2022.

[0011] M. Ezazi, et al., "Self-healable superomniphobic surfaces for corrosion protection," ACS applied materials & interfaces, vol.11, no.33, pp.30240-30246, 2019.

[0012] Z. Zhan, et al., "Superhydrophobic Al surfaces with properties of anticorrosion and reparability," ACS omega, vol.3, no.12, pp.17425-17429, 2018.

[0013] E. Demirel, et al., "Engineering Interfacial Integrity with Hydrolytic-Resistant, Self-Reinforcing Dentin Adhesive," International Journal of Molecular Sciences, vol. 25, no. 13, p.7061, 2024.

[0014] L. Song, et al., "Multifunctional monomer acts as co-initiator and crosslinker to provide autonomous strengthening with enhanced hydrolytic stability in dental adhesives," Dental Materials, vol.36, no.2, pp.284-295, 2020 / 02 / 01 / 2020.

[0015] L. Song, et al., "New silyl-functionalized BisGMA provides autonomous strengthening without leaching for dental adhesives," Acta Biomaterialia, vol.83, pp.130-139, 2019 / 01 / 01 / 2019.

[0016] L. Song, et al., "Fabrication of hybrid crosslinked network with buffering capabilities and autonomous strengthening characteristics for dental adhesives," Acta Biomaterialia, vol.67, pp.111-121, 2018 / 02 / 01 / 2018.

[0017] L. Song, et al., "Self-strengthening hybrid dental adhesive via visible-light irradiation triple polymerization," RSC advances, vol.6, no.57, pp.52434-52447, 2016.

[0018] M. Matsubara et al., "Proton-assisted low-temperature sintering of Cu fine particles stabilized by a proton-initiating degradable polymer," RSC Advances, 10.1039 / C5RA21402E vol.5, no.124, pp.102904-102910, 2015.

[0019] K. L. Van Landuyt, et al., "The role of HEMA in one-step self-etch adhesives," Dental Materials, vol.24, no.10, pp.1412-1419, 2008 / 10 / 01 / 2008.Attorney Docket No.10485-023WO1

[0020] B. Liang, et al., "Bio-based organic-inorganic hybrid UV-curable hydrophobic coating prepared from epoxidized vegetable oils," Industrial Crops and Products, vol. 163, p. 113331, 2021 / 05 / 01 / 2021.

Claims

Attorney Docket No.10485-023WO1 CLAIMS What is claimed is:

1. A self-fortifying polymer obtained by polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy-alkoxysilane. The polymer according to any preceding claim, wherein the epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

3. The polymer according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized fatty acid, an epoxidized monoglyceride, an epoxidized diglyceride, an epoxidized triglyceride, or a combination thereof.

4. The polymer according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized drying oil.

5. The polymer according to any preceding claim, wherein the epoxidized lipid comprises epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized poppy seed oil, epoxidized perilla oil, epoxidized walnut oil, epoxidized cod liver oil, epoxidized oiticica oil, epoxidized safflower oil, epoxidized wheat germ oil, epoxidized coconut oil, epoxidized rapeseed oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized sesame oil, epoxidized avocado oil, epoxidized Brazil nut oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized palm oil, epoxidized peanut oil, epoxidized sunflower oil, epoxidized canola oil, epoxidized hempseed oil, epoxidized rice bran oil, or a combination thereof. The polymer according to any preceding claim, wherein the epoxidized lipid comprises epoxidized soybean oil. The polymer according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized fatty acid.Attorney Docket No.10485-023WO1 8. The polymer according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized omega-3 fatty acid, epoxidized omega-6 fatty acid, epoxidized omega-7 fatty acid, epoxidized omega-9 fatty acid, or a combination thereof.

9. The polymer according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized linoleic acid, epoxidized eicosadienoic acid, epoxidized docosadienoic acid, epoxidized linolenic acid, epoxidized pinolenic acid, epoxidized eleostearic acid, epoxidized dihomo-^-linolenic acid, epoxidized eicosatrienoic acid, epoxidized tetra-unsaturated fatty acids, epoxidized stearidonic acid, epoxidized arachidonic acid, epoxidized eicosatetraenoic acid, epoxidized adrenic acid, epoxidized bosseopentaenoic acid, epoxidized eicosapentaenoic acid, epoxidized ozubondo acid, epoxidized sardine acid, epoxidized tetracosanolpentaenoic acid, epoxidized docosahexaenoic acid, epoxidized herring acid, epoxidized arachidonic acid, or a combination thereof.

10. The polymer according to any preceding claim, wherein the epoxidized lipid comprises a diglyceride or triglyceride derived from at least two unsaturated fatty acids.

11. The polymer according to any preceding claim, wherein the epoxidized lipid comprises a diglyceride derived from at least two unsaturated fatty acids.

12. The polymer according to any preceding claim, wherein the epoxidized lipid comprises a triglyceride derived from an unsaturated fatty acid.

13. The polymer according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized triglyceride, wherein the triglyceride is derived from an unsaturated fatty acid, wherein the fatty acid comprises ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^-linolenic acid, dihomo- ^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.

14. The polymer according to any preceding claim, wherein the epoxy-alkoxysilane has the formula:Attorney Docket No.10485-023WO1, wherein R is a C1-20aliphatic group, R1is C1-4alkyl or OC1-4alkyl, Rais C1-4alkyl, and Rbis C1-4alkyl, and each of R2, R3, and R4, are independently chosen from H and C1- 10aliphatic, wherein any two or more of R1, R2, R3, and R4can together form a ring.

15. The polymer according to any preceding claim, wherein R2, R3, and R4each do not comprise a carbocycloalkyl group.

16. The polymer according to any preceding claim, wherein the ring formed by any two or more of R, R1, R2, R3, and R4does not comprise a carbocycloalkyl group.

17. The polymer according to any preceding claim, wherein R is a C1-8alkylene group or C1-8heteroalkylene group.

18. The polymer according to any preceding claim, wherein the epoxy-alkoxysilane has the formula:, wherein Raand Rbare preferably chosen from CH3and CH2CH3, and R1is preferably chosen from CH3, OCH3and OCH2CH3.

19. The polymer according to any preceding claim, wherein the epoxidized lipid and epoxy-alkoxysilane are present in the mixture with an epoxidized lipid:epoxy-alkoxysilane weight ratio from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:

1.

20. The polymer according to any preceding claim, wherein the polymerization is conducted in the presence of a catalyst, UV irradiation, e-beam irradiation, heat, or a combination thereof.Attorney Docket No.10485-023WO1 21. The polymer according to any preceding claim, wherein the polymerization is conducted in the presence of a catalyst.

22. The polymer according to any preceding claim, wherein the polymerization is conducted in the presence of a cationic catalyst or an anionic catalyst.

23. The polymer according to any preceding claim, wherein the anionic catalyst comprises a metal alkoxide, a metal hydride, a metal amide, or an organometal.

24. The polymer according to any preceding claim, wherein the anionic catalyst comprises a methoxide, an ethoxide, an isopropoxide, 25. The polymer according to any preceding claim, wherein the polymerization is conducted in the presence of an aluminum compound, a benzyl sulfonium salt catalyst, or a zinc compound.

26. The polymer according to any preceding claim, wherein the catalyst comprises aluminum halide, aluminum alkoxide, aluminum acetylacetonate, zinc chloride.

27. The polymer according to any preceding claim, wherein the catalyst comprises triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4- iodophenyl)diphenylsulfonium triflate, (4-phenylthiophenyl)diphenylsulfonium triflate.

28. The polymer according to any preceding claim, wherein the catalyst has the formula:, wherein X is a non-coordinating anion, and Raand Rbare independently aryl, heteroaryl, or C1-6alkyl, or Raand Rbtogether with the sulfur atom form a 5-7 membered ring.

29. The polymer according to any preceding claim, wherein the catalyst has the formula:Attorney Docket No.10485-023WO130. The polymer according to any preceding claim, wherein X is perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis[3,5- bis(trifluoromethyl) phenyl]borate, or triflate.

31. The polymer according to any preceding claim, wherein the catalyst comprises aluminum chloride, zinc chloride, triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, , triphenylsulfonium triflate, (4-iodophenyl)diphenylsulfonium triflate, or (4-phenylthiophenyl)diphenylsulfonium triflate.

32. The polymer according to any preceding claim, wherein the catalyst is present in the mixture in an amount at a concentration of 0.1 wt.% to 5 wt.%.

33. The polymer according to any preceding claim, wherein the mixture further comprises a solvent.

34. The polymer according to any preceding claim, wherein the solvent comprises an alcohol.

35. The polymer according to any preceding claim, wherein the mixture is heated to a temperature from 50°C to 110°C, from 75°C to 110°C, from 100°C to 110°C, from 50°C to 100°C, or from 75°C to 100°C 36. A self-fortifying crosslinked network comprising a crosslinked epoxidized lipid and crosslinked epoxy-alkoxysilane.Attorney Docket No.10485-023WO1 37. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

38. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized fatty acid, a crosslinked epoxidized monoglyceride, a crosslinked epoxidized diglyceride, a crosslinked epoxidized triglyceride, or a crosslinked combination thereof.

39. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized drying oil.

40. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises crosslinked epoxidized soybean oil, crosslinked epoxidized linseed oil, crosslinked epoxidized tung oil, crosslinked epoxidized poppy seed oil, crosslinked epoxidized perilla oil, crosslinked epoxidized walnut oil, crosslinked epoxidized cod liver oil, crosslinked epoxidized oiticica oil, crosslinked epoxidized safflower oil, crosslinked epoxidized wheat germ oil, crosslinked epoxidized coconut oil, crosslinked epoxidized rapeseed oil, crosslinked epoxidized corn oil, crosslinked epoxidized cottonseed oil, crosslinked epoxidized sesame oil, crosslinked epoxidized avocado oil, crosslinked epoxidized Brazil nut oil, crosslinked epoxidized grape seed oil, crosslinked epoxidized olive oil, crosslinked epoxidized palm oil, crosslinked epoxidized peanut oil, crosslinked epoxidized sunflower oil, crosslinked epoxidized canola oil, crosslinked epoxidized hempseed oil, crosslinked epoxidized rice bran oil, or a crosslinked combination thereof.

41. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises crosslinked epoxidized soybean oil.

42. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized fatty acid.

43. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked epoxidized omega-3 fatty acid, a crosslinkedAttorney Docket No.10485-023WO1 epoxidized omega-6 fatty acid, a crosslinked epoxidized omega-7 fatty acid, a crosslinked epoxidized omega-9 fatty acid, or a crosslinked combination thereof.

44. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises crosslinked epoxidized linoleic acid, crosslinked epoxidized eicosadienoic acid, crosslinked epoxidized docosadienoic acid, crosslinked epoxidized linolenic acid, crosslinked epoxidized pinolenic acid, crosslinked epoxidized eleostearic acid, crosslinked epoxidized dihomo-^-linolenic acid, crosslinked epoxidized eicosatrienoic acid, crosslinked epoxidized tetra-unsaturated fatty acids, crosslinked epoxidized stearidonic acid, crosslinked epoxidized arachidonic acid, crosslinked epoxidized eicosatetraenoic acid, crosslinked epoxidized adrenic acid, crosslinked epoxidized bosseopentaenoic acid, crosslinked epoxidized eicosapentaenoic acid, crosslinked epoxidized ozubondo acid, crosslinked epoxidized sardine acid, crosslinked epoxidized tetracosanolpentaenoic acid, crosslinked epoxidized docosahexaenoic acid, crosslinked epoxidized herring acid, crosslinked epoxidized arachidonic acid, or a crosslinked combination thereof.

45. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked diglyceride or crosslinked triglyceride derived from at least two unsaturated fatty acids.

46. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked diglyceride derived from at least two unsaturated fatty acids.

47. The crosslinked network according to any preceding claim, wherein the crosslinked epoxidized lipid comprises a crosslinked triglyceride derived from an unsaturated fatty acid.

48. The crosslinked network according to any preceding claim, wherein the epoxidized lipid comprises a crosslinked epoxidized triglyceride, wherein the triglyceride is derived from an unsaturated fatty acid, wherein the fatty acid comprises ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^-linolenic acid, dihomo- ^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.Attorney Docket No.10485-023WO1 49. The crosslinked network according to any preceding claim, wherein the epoxy- alkoxysilane has the formula:, wherein R* is a C1-20aliphatic group, R1*is independently C1-4alkyl or O-*, each of R2*, R3*, and R4*, are independently chosen from H and C1-10aliphatic, wherein any two or more of R*, R1*, R2*, R3*, and R4*can together form a ring, * represents a bond to H, C1-4alkyl, crosslinked lipid, or crosslinked epoxy-alkoxysilane, each wavy line ‘a’ independently represents a bond to H, C1-4alkyl, crosslinked lipid or crosslinked epoxy-alkoxysilane, and each wavy line ‘b’ independently represents a bond to H, crosslinked lipid, or crosslinked epoxy-alkoxysilane, provided that at least two of the four wavy lines represent a bond to a crosslinked lipid, or crosslinked epoxy-alkoxysilane.

50. The crosslinked network according to any preceding claim, wherein R2*, R3*, and R4*each do not comprise a carbocycloalkyl group. The crosslinked network according to any preceding claim, wherein the ring formed by any two or more of R*, R1*, R2*, R3*, and R4*does not comprise a carbocycloalkyl group.

52. The crosslinked network according to any preceding claim, wherein R* is a C1-8alkylene group or C1-8heteroalkylene group.

53. The crosslinked network according to any preceding claim, wherein the crosslinked epoxy-alkoxysilane comprises a crosslinked glycidylalkoxy silane.

54. The crosslinked network according to any preceding claim, wherein the crosslinked epoxy-alkoxysilane comprises crosslinked 3-glycidoxypropyl-trimethoxysilane or crosslinked 3-glycidoxypropyl-triethoxysilane.Attorney Docket No.10485-023WO1 55. The crosslinked network according to any preceding claim, comprising the crosslinked epoxidized lipid and crosslinked epoxy-alkoxysilane in a weight ratio from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:

1.

56. A method of preparing a self-fortifying polymer comprising polymerizing a mixture comprising (1) an epoxidized lipid having at least two epoxide groups and (2) an epoxy- alkoxysilane.

57. The method according to any preceding claim, wherein the epoxidized lipid is derived from a lipid having an iodine number from 110 to 200, from 115 to 150, from 120 to 150, or from 125 to 150.

58. The method according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized fatty acid, an epoxidized monoglyceride, an epoxidized diglyceride, an epoxidized triglyceride, or a combination thereof.

59. The method according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized drying oil.

60. The method according to any preceding claim, wherein the epoxidized lipid comprises epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized poppy seed oil, epoxidized perilla oil, epoxidized walnut oil, epoxidized cod liver oil, epoxidized oiticica oil, epoxidized safflower oil, epoxidized wheat germ oil, epoxidized coconut oil, epoxidized rapeseed oil, epoxidized corn oil, epoxidized cottonseed oil, epoxidized sesame oil, epoxidized avocado oil, epoxidized Brazil nut oil, epoxidized grape seed oil, epoxidized olive oil, epoxidized palm oil, epoxidized peanut oil, epoxidized sunflower oil, epoxidized canola oil, epoxidized hempseed oil, epoxidized rice bran oil, or a combination thereof.

61. The method according to any preceding claim, wherein the epoxidized lipid comprises epoxidized soybean oil.

62. The method according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized fatty acid.Attorney Docket No.10485-023WO1 63. The method according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized omega-3 fatty acid, epoxidized omega-6 fatty acid, epoxidized omega-7 fatty acid, epoxidized omega-9 fatty acid, or a combination thereof.

64. The method according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized linoleic acid, epoxidized eicosadienoic acid, epoxidized docosadienoic acid, epoxidized linolenic acid, epoxidized pinolenic acid, epoxidized eleostearic acid, epoxidized dihomo-^-linolenic acid, epoxidized eicosatrienoic acid, epoxidized tetra-unsaturated fatty acids, epoxidized stearidonic acid, epoxidized arachidonic acid, epoxidized eicosatetraenoic acid, epoxidized adrenic acid, epoxidized bosseopentaenoic acid, epoxidized eicosapentaenoic acid, epoxidized ozubondo acid, epoxidized sardine acid, epoxidized tetracosanolpentaenoic acid, epoxidized docosahexaenoic acid, epoxidized herring acid, epoxidized arachidonic acid, or a combination thereof.

65. The method according to any preceding claim, wherein the epoxidized lipid comprises a diglyceride or triglyceride derived from at least two unsaturated fatty acids.

66. The method according to any preceding claim, wherein the epoxidized lipid comprises a diglyceride derived from at least two unsaturated fatty acids.

67. The method according to any preceding claim, wherein the epoxidized lipid comprises a triglyceride derived from an unsaturated fatty acid.

68. The method according to any preceding claim, wherein the epoxidized lipid comprises an epoxidized triglyceride, wherein the triglyceride is derived from an unsaturated fatty acid, wherein the fatty acid comprises ^-linolenic acid, stearidonic acid, eicosapentaenoic acid, cervonic acid, linoleic acid, linolelaidic acid, ^-linolenic acid, dihomo-^-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, vaccenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid, or a combination thereof.

69. The method according to any preceding claim, wherein the epoxy-alkoxysilane has the formula:Attorney Docket No.10485-023WO1, wherein R is a C1-20aliphatic group, R1is C1-4alkyl or OC1-4alkyl, Rais C1-4alkyl, and Rbis C1-4alkyl, and each of R2, R3, and R4, are independently chosen from H and C1- 10aliphatic, wherein any two or more of R1, R2, R3, and R4can together form a ring.

70. The method according to any preceding claim, wherein R2, R3, and R4each do not comprise a carbocycloalkyl group.

71. The method according to any preceding claim, wherein the ring formed by any two or more of R, R1, R2, R3, and R4does not comprise a carbocycloalkyl group.

72. The method according to any preceding claim, wherein R is a C1-8alkylene group or C1-8heteroalkylene group.

73. The method according to any preceding claim, wherein the epoxy-alkoxysilane has the formula:, wherein Raand Rbare preferably chosen from CH3and CH2CH3, and R1is preferably chosen from CH3, OCH3and OCH2CH3.

74. The method according to any preceding claim, wherein the epoxidized lipid and epoxy-alkoxysilane are present in the mixture with an epoxidized lipid:epoxy-alkoxysilane weight ratio from 1:1 to 20:1, from 1:1 to 10:1, from 2:1 to 10:1, from 2:1 to 9:1, from 2:1 to 8.9:1, from 3:1 to 9:1, from 4:1 to 9:1, from 3.95:1 to 9:1, or from 3.95:1 to 8.9:

1.

75. The method according to any preceding claim, wherein the polymerization is conducted in the presence of a catalyst, UV irradiation, e-beam irradiation, heat, or a combination thereof.Attorney Docket No.10485-023WO1 76. The method according to any preceding claim, wherein the polymerization is conducted in the presence of a catalyst.

77. The method according to any preceding claim, wherein the polymerization is conducted in the presence of a cationic catalyst or an anionic catalyst.

78. The method according to any preceding claim, wherein the anionic catalyst comprises a metal alkoxide, a metal hydride, a metal amide, or an organometal.

79. The method according to any preceding claim, wherein the anionic catalyst comprises a methoxide, an ethoxide, or an isopropoxide, 80. The method according to any preceding claim, wherein the polymerization is conducted in the presence of an aluminum compound, a benzyl sulfonium salt catalyst, or a zinc compound.

81. The method according to any preceding claim, wherein the catalyst comprises aluminum halide, aluminum alkoxide, aluminum acetylacetonate, zinc chloride.

82. The method according to any preceding claim, wherein the catalyst comprises triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4- iodophenyl)diphenylsulfonium triflate, (4-phenylthiophenyl)diphenylsulfonium triflate.

83. The method according to any preceding claim, wherein the catalyst has the formula:, wherein X is a non-coordinating anion, and Raand Rbare independently aryl, heteroaryl, or C1-6alkyl, or Raand Rbtogether with the sulfur atom form a 5-7 membered ring.

84. The method according to any preceding claim, wherein the catalyst has the formula:Attorney Docket No.10485-023WO1.

85. The method according to any preceding claim, wherein X is perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, tetrakis[3,5- bis(trifluoromethyl) phenyl]borate, or triflate.

86. The method according to any preceding claim, wherein the catalyst comprises aluminum chloride, zinc chloride, triphenylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium triflate, (4- iodophenyl)diphenylsulfonium triflate, or (4-phenylthiophenyl)diphenylsulfonium triflate.

87. The method according to any preceding claim, wherein the catalyst is present in the mixture in an amount at a concentration of 0.1 wt.% to 5 wt.%.

88. The method according to any preceding claim, wherein the mixture further comprises a solvent.

89. The method according to any preceding claim, wherein the solvent comprises an alcohol.

90. The method according to any preceding claim, wherein the mixture is heated to a temperature from 50°C to 110°C, from 75°C to 110°C, from 100°C to 110°C, from 50°C to 100°C, or from 75°C to 100°C.

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