Network toughening of additively manufactured high glass transition temperature materials with sequentially cured interpenetrating polymers

Abstract

Resins and formulations of individual monomers bearing both vinyl ester and epoxy functionalities were synthesized or formulated to blend a vinyl ester component polymerizable by photoinduced free radical polymerization with a step-growth epoxy-amine system that promotes sequential cure. The vinyl ester component was photopolymerized using vat photopolymerization (VPP). Additionally, the preparation of biobased, photocurable thermoset resins with tunable thermal and mechanical properties is provided. All of the monomers and polymers described herein are useful in a variety of applications, including additive manufacturing applications. TIFF2023514315000067.tif95166

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 977,986, filed February 18, 2020, entitled "NETWORK TOUGHENING OF ADDITIVELY MANUFACTURED, HIGH GLASS TRANSITION TEMPERATURE MATERIALS VIA SEQUENTIALLY CURED, INTERPENETRATING POLYMERS," and to U.S. Provisional Patent Application No. 63 / 014,932, filed April 24, 2020, entitled "BIO-BASED ADDITIVE MANUFACTURING RESINS AND METHODS OF MAKING AND USING THE SAME," the disclosures of which are incorporated herein by reference in their entireties.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH This invention was made with government support under Grant Nos. W911NF 14-2-0086, W911NF 17-2-0227, W911NF-16-2-0225, and W911NF 19-2-0152 awarded by the U.S. Army Research Laboratory. The government has certain rights in this invention. [Background technology]

[0003] background Interpenetrating polymer networks (IPNs) are defined as the combination of two or more individual polymer networks, where at least one polymer network is formed in the presence of the other(s). IPNs have been utilized in a wide range of applications, including biomedical materials, sound-deadening and vibration-damping materials, and ion-exchange resins. Numerous types of IPNs exist, including sequential IPNs, simultaneous IPNs, latex IPNs, gradient IPNs, and thermoplastic IPNs, which are formed by different polymerization methods and / or by utilizing different initial blend components in the IPN formulation. Interestingly, IPNs have utility in a variety of additive manufacturing (AM) applications.

[0004] The use of additive manufacturing, a layer-by-layer process more commonly known as 3D printing, is gaining significant momentum in industry, the military, and academia due to its efficient material use, rapid production times, and ability to create complex parts on demand while eliminating the manufacturing constraints typically present with traditional methods. Vat photopolymerization (VPP) is an AM method that creates layers by photopolymerizing liquid resin with ultraviolet / visible light. After localized curing of the resin by laser beam scanning or digital light processing at specific locations on the resin surface, the material is vertically raised or lowered to the desired layer thickness, which ranges from 25 to 200 microns, allowing the resin to backfill and cure a new layer, polymerizing against the previous layer. Parts printed with VPP are typically subjected to post-processing to achieve a higher degree of cure. While mechanical anisotropy typically results from the additive manufacturing process resulting from VPP, VPP-printed parts become substantially isotropic due to the interlayer crosslinks formed during photopolymerization. Typically, readily available VPP resins contain both (meth)acrylate and / or epoxy functional groups, both of which are photopolymerizable. Both functional groups are typically present because (meth)acrylate-based resins can polymerize quickly due to their high cure rate, while (meth)acrylate-based resins typically compromise mechanical properties by reducing part precision and causing overall distortion. Furthermore, epoxy resins exhibit significantly slower cure rates while exhibiting lower shrinkage and more precise geometric shapes, increasing mechanical performance. As a result, most VPP resins are composed of both (meth)acrylate and epoxy functional groups, combining the unique advantages of both.

[0005] Thermosetting polymers, including epoxy and vinyl ester resins, have high glass transition temperatures (T gThey are widely used in commercial and military applications due to their outstanding properties, including high modulus, strength, chemical resistance, and toughness. Epoxy resins feature oxirane moieties that can be polymerized by multiple mechanisms, including ionic polymerization and, more commonly for higher performance materials, epoxy-amine step-growth polymerization. Vinyl ester resins are typically produced by esterifying epoxy resins to incorporate vinyl moieties that can be polymerized by radical-based polymerization mechanisms. While both epoxy and vinyl ester resins are typically cured and molded using conventional thermal procedures, the properties exhibited by epoxy-amine and vinyl ester resins, as well as the polymerization versatility of both resins, make them attractive options for general additive manufacturing. Summary of the Invention

[0006] A brief summary of the disclosure This disclosure describes interpenetrating polymer networks (IPNs) composed of vinyl ester and epoxy-amine components, non-limitingly illustrated in Figure 1, prepared by sequential curing using the VPP method. VPP was utilized to photopolymerize the vinyl ester component and encapsulate the epoxy and amine monomers within a methacrylate-based polymer matrix. Samples were subsequently post-treated to facilitate sequential thermal curing of the epoxy-amine network to form the IPN.

[0007] In various embodiments, an interpenetrating polymer network (IPN) is provided. The IPN comprises the reaction product of a crosslinker containing at least one epoxy curing group and a compound containing at least one vinyl ester functional group and at least one epoxy functional group. The at least one vinyl ester functional group is polymerized by photoinduced free radical polymerization, and the at least one epoxy functional group and the crosslinker are polymerized by step-growth thermal polymerization.

[0008] In various embodiments, a method for preparing an interpenetrating polymer network (IPN) is provided, comprising applying VPP to a mixture of a crosslinker containing at least one epoxy curing group and a monomer, oligomer, or polymer having at least one vinyl ester functional group and at least one epoxy functional group under conditions to photopolymerize the vinyl ester functional group; and exposing the resulting mixture to thermal conditions to effect epoxy-amine polymerization.

[0009] In various embodiments, the compound can be a monomer or a polymer. In various embodiments, the monomer or polymer can be a compound of Formula I, Formula IA, Formula II, Formula III, Formula III-A, or Formula IV, and / or combinations thereof, having the following structure: TIFF0007776427000001.tif74153In formula, A is H, C 1~3 Alkyl, CN, F, Cl, and perfluoroC 1~3 selected from the group consisting of alkyl; X is O or N-R''; Each R is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; Each R' is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; R'' is H or C 1~3 is alkyl; p is an integer between 0 and 100,000; or TIFF0007776427000002.tif49128In formula, Each R 3 are independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl; each Y is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl; n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; or TIFF0007776427000003.tif72154In formula, R 1 teeth TIFF0007776427000004.tif14128; L is selected from the group consisting of a bond, C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl; R 2 is selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl, wherein the substituents are selected from the group consisting of optionally substituted aryl and optionally substituted heteroaryl; Each R 3 are independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl; R 4 teeth TIFF0007776427000005.tif14128; each X is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl; n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; m is 0, 2, 4, 6, or 8. [Brief explanation of the drawings]

[0010] The drawings illustrate generally, by way of example, but not by way of limitation, various aspects of the present application.

[0011] [Figure 1] 1 shows the chemical structures of polymers and monomers used to make interpenetrating polymer networks (IPNs), according to various embodiments. [Figure 2] 1 shows a reaction scheme used to make a polymer having both vinyl and epoxy functionality, according to various embodiments. [Figure 3] Visual representations of a) PM-EM828 network, b) PM-VE828 - Epon828 blend network, c) PM-EM828_025VE828 network, and d) PM-EM828_05Epon828_025VE828 network are shown. [Figure 4] 1 shows near-infrared spectra of PM-EM828 resin and the AM, FC, and PC cure stages of the resin as defined herein, with the spectra vertically offset for clarity. [Figure 5] 1 shows the TGA thermograms in N2 and their respective first derivatives for all IPNs characterized herein. [Figure 6] DMA thermograms of E′ and E″ for all IPNs characterized herein are shown. [Figure 7] 1 shows the tan δ thermograms of all IPNs characterized herein. [Figure 8] The stress / strain curves of all IPNs characterized herein are shown. [Figure 9] The load-displacement curves of all IPNs characterized herein are shown. [Figure 10] FIG. 1 is a schematic diagram showing a two-step, one-pot synthesis of a compound of formula III according to various embodiments. [Figure 11]Figure 1 shows the viscosity of the base PM-NC514sVE uncured resin system with various IM contents (in mole percent) at 25°C. The errors associated with the obtained data are shown in Table 1A. [Figure 12] The calibration curve for PM-NC514sVE 20% IM resin system is shown. [Figure 13] Near infrared spectra of the formulated resin immediately after printing and washing (denoted as AM) and subsequently after post-treatment are shown. [Figure 14] 1 is a photograph of a VPP printed polymer according to various embodiments. [Figure 15] 1 shows TGA (thermogravimetric analysis) thermograms in N2 of post-treated samples containing PM NC514 with various IM weight percentages. [Figure 16] Representative DMA (Dynamic Mechanical Analysis) E' and E'' thermograms are shown for each printed and fully processed (washed and post-treated) resin system containing PM-NC514sVE. [Figure 17] 1 shows representative tan δ thermograms of PM-NC514sVE cured resin systems with various IM weight percentages. [Figure 18] 1 shows stress-strain curves of cured PM-NC514sVE resin systems with various IM weight percentages. [Figure 19] 1 shows the load-displacement curves of the prepared PM-NC514sVE polymers with various IM weight percentages. DETAILED DESCRIPTION OF THE INVENTION

[0012] Detailed Description of Disclosure Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in the context of numbered claims, it will be understood that such subject matter as exemplified is not intended to limit the scope of the claims to the disclosed subject matter.

[0013] Throughout this document, values ​​expressed in range form should be interpreted flexibly to include not only the numerical values ​​expressly recited as the limits of the range, but also all individual numerical values ​​or subranges subsumed within the range, as if each numerical value and subrange were expressly recited. For example, a range such as "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not only about 0.1% to about 5%, but also individual values ​​(e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise indicated, the term "about X to Y" has the same meaning as "about X to about Y." Similarly, unless otherwise indicated, the term "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z."

[0014] In this document, the terms "a," "an," or "the" are used to include one or more unless the context clearly dictates otherwise. The term "or" is used to mean a non-exclusive "or" unless otherwise indicated. The statements "at least one of A and B" or "at least one of A or B" have the same meaning as "A, B, or A and B." Furthermore, words or terms used herein and not defined elsewhere should be understood to be for descriptive purposes only and not for limiting purposes. Any use of section headings is intended to aid in the reading and comprehension of this document and should not be construed as limiting. Information associated with a section heading may occur within or outside that particular section. All publications, patents, and patent documents mentioned in this document are incorporated herein by reference in their entirety, as if individually incorporated by reference.

[0015] In the methods described herein, acts may be performed in any order unless a chronological or operational order is explicitly recited. Furthermore, certain acts may be performed simultaneously unless the express language of the claim requires that they be performed separately. For example, a claimed act of performing X and a claimed act of performing Y may be performed simultaneously in a single operation, and the resulting process is within the literal scope of the claimed process.

[0016] definition As used herein, the term "about" allows for variation of a value or range, for example, within 10%, within 5%, or within 1% of a stated value or stated range limit, and includes the exact value or range stated.

[0017] As used herein, the term "substantially" means "a majority of" or "mostly," similarly meaning at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. As used herein, the term "substantially free" can mean completely free or having an insignificant amount, such that the amount of material present does not affect the material properties of a composition containing the material, and such that the material is between about 0% and about 5%, or between about 0% and about 1%, or not more than about 5%, or less than about 4.5%, equal to, or greater than about 4.5%, or not more than 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or not more than about 0.001% by weight of the composition. The term "substantially free" can mean having an insignificant amount, such that a material is from about 0% to about 5%, or from about 0% to about 1%, or about 5% or less, or less than about 4.5%, equal to, or greater than about 4.5%, or 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001% or less, or about 0% by weight of the composition.

[0018] As used herein, the term "organic group" refers to any carbon-containing functional group. Examples include oxygen-containing groups such as alkoxy groups, aryloxy groups, aralkyloxy groups, and oxo (carbonyl) groups; carboxyl groups, including carboxylic acids, carboxylates, and carboxylic acid esters; sulfur-containing groups such as alkylsulfide groups and arylsulfide groups; and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R), CN, CF, OCF, R, C(O), methylenedioxy, ethylenedioxy, N(R), SR, SOR, SO, SO, N(R), SO, R, C(O)R, C(O)C(O)R, C(O)CHC(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R), OC(O)N(R), C(S)N(R), (CH) 0~2 N(R)C(O)R, (CH2) 0~2 N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N( R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR)R, C(=NOR)R, and substituted or unsubstituted (C1~C 100 ) hydrocarbyl, where R can be hydrogen (in instances containing other carbon atoms) or a carbon-based moiety, which may be substituted or unsubstituted.

[0019] The term "substituted" as used herein with respect to a molecule or organic group as defined herein means that one or more hydrogen atoms therein are replaced with one or more non-hydrogen atoms. As used herein, the term "functional group" or "substituent" refers to a group that can be substituted or is substituted on a molecule or organic group. Examples of substituents or functional groups include, but are not limited to, halogens (e.g., F, Cl, Br, and I); oxygen atoms in groups such as hydroxyl groups, alkoxyl groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxylic acids, carboxylates, and carboxylic acid esters; sulfur atoms in thiol groups, alkylsulfide groups and arylsulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; nitrogen atoms in groups such as amines, hydroxylamine, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that can be attached to a substituted carbon atom (or other atom) include F, Cl, Br, I, OR, OC(O)N(R), CN, NO, NO, ONO, azido, CF, OCF, R, O(oxo), S(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R), SR, SOR, SO, SO, N(R), SO, R, C(O)R, C(O)C(O)R, C(O)CHC(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R), OC(O)N(R), C(S)N(R), (CH) 0~2 N(R)C(O)R, (CH2) 0~2 N(R)N(R), N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R), N(R)SOR, N(R)SON(R), N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R), N(R)C(S)N(R), N(COR)COR, N(OR)R, C(=NH)N(R), C(O)N(OR)R, and C(=NOR)R, where R can be hydrogen or a carbon-based moiety, e.g., R can be hydrogen, (C1-C 100) hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl, or two R groups attached to a nitrogen atom or adjacent nitrogen atoms can be taken together with one or more of the nitrogen atoms to form a heterocyclyl.

[0020] As used herein, the term "alkyl" refers to straight-chain and branched alkyl groups and cycloalkyl groups having 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbon atoms, or in some embodiments, 1 to 8 carbon atoms. Examples of straight-chain alkyl groups include groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl. As used herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and anteisoalkyl groups, as well as other branched forms of alkyl. Representative substituted alkyl groups may be substituted one or more times with any of the groups enumerated herein, such as amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0021] As used herein, the term "alkenyl" refers to straight-chain, branched-chain, and cyclic alkyl groups, as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or from 2 to about 20 carbon atoms, or from 2 to 12 carbon atoms, or in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, vinyl, -CH=C=CCH2, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3)=CH(CH3), -C(CH2CH3)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl, among others.

[0022] The term "alkynyl," as used herein, refers to straight- and branched-chain alkyl groups, as defined herein, except that at least one triple bond exists between two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, from 2 to about 20 carbon atoms, or from 2 to 12 carbon atoms, or in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to, -C≡CH, -C≡C(CH), -C≡C(CHCH), -CHC≡CH, -CHC≡C(CHCH), and -CHC≡C(CHCH), among others.

[0023] The term "acyl," as used herein, refers to a group containing a carbonyl moiety bonded through the carbonyl carbon atom. The carbonyl carbon atom is bonded to a hydrogen forming a "formyl" group or to another carbon atom, which may be part of an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, a cycloalkylalkyl group, a heterocyclyl group, a heterocyclylalkyl group, a heteroaryl group, a heteroarylalkyl group, etc. The acyl group may contain 0 to about 12, 0 to about 20, or 0 to about 40 additional carbon atoms bonded to the carbonyl group. The acyl group may contain a double bond or a triple bond within the meaning herein. An acryloyl group is an example of an acyl group. An acyl group may contain a heteroatom within the meaning herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an acyl group within the meaning herein. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and acryloyl groups. When the group containing the carbon atom bonded to the carbonyl carbon atom contains a halogen, the group is called a "haloacyl" group. An example is the trifluoroacetyl group.

[0024] As used herein, the term "cycloalkyl" refers to cyclic alkyl groups, such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. In some embodiments, cycloalkyl groups can have from 3 to about 8-12 ring members, while in other embodiments, the number of ring carbon atoms ranges from 3 to 4, 5, 6, or 7. Additionally, cycloalkyl groups include polycyclic cycloalkyl groups, such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl, as well as fused rings, such as, but not limited to, decalinyl. Cycloalkyl groups also include rings substituted with straight- or branched-chain alkyl groups, as defined herein. Representative substituted cycloalkyl groups can be mono- or more than twice substituted, such as, but not limited to, 2,2-, 2,3-, 2,4-, 2,5-, or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups. The term "cycloalkenyl," alone or in combination, refers to a cyclic alkenyl group.

[0025] As used herein, the term "aryl" refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms in the ring. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, the aryl group contains from about 6 to about 14 carbon atoms in the ring portion of the group. Aryl groups can be unsubstituted or substituted as defined herein. Representative substituted aryl groups can be mono- or multi-substituted, such as, but not limited to, phenyl groups substituted at any one or more of the 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or naphthyl groups substituted at any one or more of the 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or naphthyl groups substituted at any one or more of the 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring.

[0026] As used herein, the term "aralkyl" refers to an alkyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to an aryl group, as defined herein. Representative aralkyl groups include benzyl and phenylethyl groups, as well as fused (cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. An aralkenyl group refers to an alkenyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to an aryl group, as defined herein.

[0027] As used herein, the term "heterocyclyl" refers to aromatic and non-aromatic ring compounds containing three or more ring members, one or more of which are heteroatoms, such as, but not limited to, N, O, and S. Thus, heterocyclyl can be cycloheteroalkyl, or heteroaryl, or any combination thereof, provided it is polycyclic. In some embodiments, heterocyclyl groups contain from 3 to about 20 ring members, while other similar groups have from 3 to about 15 ring members. The term heterocyclyl includes rings in which one or more C=O groups replace CH groups in the ring, such as those found in cyclic ketones, lactones, and lactams. Examples of heterocyclyl groups containing C=O groups include, but are not limited to, β-propiolactam, γ-butyrolactam, δ-valerolactam, and ε-caprolactam, and the corresponding lactones. A heterocyclyl group referred to as a C2-heterocyclyl can be a 5-membered ring having 2 carbon atoms and 3 heteroatoms, a 6-membered ring having 2 carbon atoms and 4 heteroatoms, etc. Similarly, a C4-heterocyclyl can be a 5-membered ring having 1 heteroatom, a 6-membered ring having 2 heteroatoms, etc. The number of carbon atoms and heteroatoms equals the total number of ring atoms. A heterocyclyl ring may contain one or more double bonds. A heteroaryl ring is an embodiment of a heterocyclyl group. The term "heterocyclyl group" includes fused ring species, including species containing fused aromatic and non-aromatic groups. For example, dioxolanyl rings and benzodioxolanyl ring systems (methylenedioxyphenyl ring systems) are both heterocyclyl groups within the meaning herein. The term also includes polycyclic ring systems containing heteroatoms, such as, but not limited to, quinuclidyl. A heterocyclyl group can be unsubstituted or substituted as described herein.Heterocyclyl groups include, but are not limited to, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, dihydrobenzofuranyl, indolyl, dihydroindolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Representative substituted heterocyclyl groups can be groups such as, but not limited to, mono- or more than twice substituted piperidinyl or quinolinyl groups, which are 2-, 3-, 4-, 5-, or 6-substituted or disubstituted with groups such as those enumerated herein.

[0028] As used herein, the term "heteroaryl" refers to an aromatic ring compound containing five or more ring members, one or more of which are heteroatoms, such as, but not limited to, N, O, and S. For example, heteroaryl rings can have from five to about 8-12 ring members. Heteroaryl groups refer to various heterocyclyl groups with aromatic electronic structures. A heteroaryl group referred to as a C2-heteroaryl can be a five-membered ring with two carbon atoms and three heteroatoms, a six-membered ring with two carbon atoms and four heteroatoms, etc. Similarly, a C4-heteroaryl can be a five-membered ring with one heteroatom, a six-membered ring with two heteroatoms, etc. The sum of the number of carbon atoms and the number of heteroatoms equals the total number of ring atoms. C x~y A heterocyclyl ring, referred to as C, can be any ring containing from "x" to "y" ring members, including all intermediate integers between "x" and "y," and containing one or more heteroatoms as defined herein. x~yIn a ring called C, all non-heteroatom ring members are carbon. x~y The heterocyclyl ring referred to as "heteroaryl" may be a polycyclic ring, such as a bicyclic or tricyclic ring. Heteroaryl groups include, but are not limited to, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, indolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups can be unsubstituted or substituted with groups described herein. Representative substituted heteroaryl groups may be substituted one or more times with groups such as those enumerated herein.

[0029] Further examples of aryl and heteroaryl groups include phenyl, biphenyl, indenyl, naphthyl (1-naphthyl, 2-naphthyl), N-hydroxytetrazolyl, N-hydroxytriazolyl, N-hydroxyimidazolyl, anthracenyl (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophenyl (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl), indolyl, oxadiazolyl, isoxazolyl, quinazolinyl, fluorenyl, xanthenyl, isoindanyl, benzyl, benzo ... hydryl, acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), pyrazolyl (3-pyrazolyl), imidazolyl (1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxazolyl (2-oxazolyl, 4-oxazolyl, 5-oxazolyl), thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl) , pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3-pyridazinyl, 4-pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl (1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), ), benzo[b]furanyl (2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), 2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro-benzo[b]furanyl), 3-(2,3-dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl), 5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl), 7-(2,3-Dihydro-benzo[b]furanyl), benzo[b]thiophenyl (2-benzo[b]thiophenyl, 3-benzo[b]thiophenyl, 4-benzo[b]thiophenyl, 5-benzo[b]thiophenyl, 6-benzo[b]thiophenyl, 7-benzo[b]thiophenyl), 2,3-dihydro-benzo[b]thiophenyl, (2-(2,3-dihydro-benzo[b]thiophenyl), 3-(2,3-dihydro-benzo[b]thiophenyl), 4-(2,3-dihydro-benzo[b]thiophenyl), 5-(2,3-dihydro-benzo[b]thiophenyl) nyl), 6-(2,3-dihydro-benzo[b]thiophenyl), 7-(2,3-dihydro-benzo[b]thiophenyl), indolyl (1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl zolyl, 7-benzimidazolyl, 8-benzimidazolyl), benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl), benzothiazolyl (1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl (1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl), 5H-dibenzo[b,f]azepine (5H-dibenzo[b,f]azepin-1-yl, 5H-dibenzo[b,f]azepin-2-yl, 5 H-dibenzo[b,f]azepin-3-yl, 5H-dibenzo[b,f]azepin-4-yl, 5H-dibenzo[b,f]azepin-5-yl), 10,11-dihydro-5H-dibenzo[b,f]azepine (10,11-dihydro-5H-dibenzo[b,f]azepin-1-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-2-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-3-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-4-yl, 10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl), but are not limited to these.

[0030] As used herein, the term "heterocyclylalkyl" refers to an alkyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group, as defined herein, is replaced with a bond to a heterocyclyl group, as defined herein. Representative heterocyclylalkyl groups include, but are not limited to, furan-2-ylmethyl, furan-3-ylmethyl, pyridin-3-ylmethyl, tetrahydrofuran-2-ylethyl, and indol-2-ylpropyl.

[0031] The term "heteroarylalkyl," as used herein, means an alkyl group, as defined herein, in which a hydrogen or carbon bond of the alkyl group is replaced with a bond to a heteroaryl group, as defined herein.

[0032] The term "alkoxy" as used herein refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as defined herein. Examples of linear alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy groups include, but are not limited to, isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy groups include, but are not limited to, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. The alkoxy group can contain about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to the oxygen atom, and can further contain double or triple bonds and heteroatoms. For example, an allyloxy group or a methoxyethoxy group is an alkoxy group within the meaning herein, as is a methylenedioxy group in the context in which two adjacent atoms of the structure are replaced thereby.

[0033] The term "amine" as used herein refers to primary, secondary, and tertiary amines, e.g., having the formula N(group)3, where each group can independently be H or a non-H group, such as alkyl, aryl, etc. Amines include, but are not limited to, R-NH2, e.g., alkylamines, arylamines, alkylarylamines; R2NH, where each R is independently selected, e.g., dialkylamines, diarylamines, aralkylamines, heterocyclylamines, etc.; and RN, where each R is independently selected, e.g., trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, etc. The term "amine" as used herein also includes ammonium ions.

[0034] As used herein, the term "amino group" refers to any of the forms -NH2, -NHR, -NR2, -NR3, where each R is independently selected. + and -NR3, which cannot be protonated. + "Amino" refers to the protonated form of each form except for the following: (a) - (b) - (c) - (d) - (e) - (f) - (g) - (h) - (i) - (j) - (j) - (k) - (k) - (k) - (k) - (i) - (j) - (k) - (k) - (k) - (i ...

[0035] As used herein, the terms "halo," "halogen," or "halide" group by themselves or as part of another substituent mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0036] As used herein, the term "haloalkyl" includes monohaloalkyl groups, polyhaloalkyl groups in which all halo atoms may be the same or different, and perhaloalkyl groups in which all hydrogen atoms are replaced with halogen atoms such as fluoro. Examples of haloalkyl include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, etc. As used herein, a "haloalkoxy" group refers to an alkoxy group substituted with one or more halogen atoms, as in a haloalkyl group.

[0037] As used herein, the term "epoxy-functional" or "epoxy-substituted" refers to a functional group in which the oxygen atoms of the epoxy substituent are directly bonded to two adjacent carbon atoms of a carbon chain or ring system. Examples of epoxy-substituted functional groups include, but are not limited to, 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2,3-epoxypropoxy, epoxypropoxypropyl, 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(glycidoxycarbonyl)propyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxycyclohexyl)ethyl, 2-(2,3-epoxycyclopentyl)ethyl, 2-(4-methyl-3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl, and 5,6-epoxyhexyl.

[0038] As used herein, the term "monovalent" means that the substituent is connected to the substituted molecule by a single bond. If the substituent is monovalent, e.g., F or Cl, then the substituent is attached to the atom it replaces by a single bond.

[0039] As used herein, the term "hydrocarbon" or "hydrocarbyl" refers to a molecule or functional group that contains carbon and hydrogen atoms. The term usually contains both carbon and hydrogen atoms, but can also refer to a molecule or functional group in which all hydrogen atoms have been replaced with other functional groups.

[0040] As used herein, the term "hydrocarbyl" means a functional group derived from a straight chain, branched, or cyclic hydrocarbon, and may be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl, or any combination thereof. A hydrocarbyl group is (C a ~C b For example, (C1-C4) hydrocarbyl means that the hydrocarbyl group can be methyl (C1), ethyl (C2), propyl (C3), or butyl (C4), and (C0-C4) b ) Hydrocarbyl means that in certain embodiments there are no hydrocarbyl groups present.

[0041] As used herein, the term "solvent" means a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents include silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.

[0042] As used herein, the term "(meth)acrylate" refers to a compound that includes at least one methacrylate functional group, at least one acrylate functional group, and any combination thereof. In certain embodiments, a meth(acrylate) includes multiple (meth)acrylate functional groups and / or multiple acrylate functional groups, or any combination thereof.

[0043] The term "monomer" means any individual compound of any molecular weight.

[0044] As used herein, the term "polymer" refers to a molecule composed of repeating structural units typically connected by covalent chemical bonds. The term "polymer" is intended to encompass the terms copolymer and oligomer. In certain embodiments, a polymer comprises a backbone (i.e., the chemical connections defining the central chain of the polymer, including the chemical bonds between the various polymerized monomer units) and side chains (i.e., the chemical connections extending from the backbone). In certain embodiments, the term "oligomer" refers to 0-20, 0-1, or 0-2 repeating units.

[0045] As used herein, the terms "polymerization" or "crosslinking" refer to at least one reaction that consumes at least one functional group in a monomeric, oligomeric, or polymeric molecule to create at least one chemical bond between at least two separate molecules (e.g., an intermolecular bond), at least one chemical bond within the same molecule (e.g., an intramolecular bond), or any combination thereof. The polymerization or crosslinking reaction can consume from about 0% to about 100% of the at least one functional group available in the system. In certain embodiments, the polymerization or crosslinking of at least one functional group consumes about 100% of the at least one functional group. In other embodiments, the polymerization or crosslinking of at least one functional group consumes less than about 100% of the at least one functional group.

[0046] As used herein, the term "reaction conditions" refers to physical treatments, chemical reagents, or a combination thereof, that are necessary or sometimes required to promote a reaction. Non-limiting examples of reaction conditions include electromagnetic radiation (such as, but not limited to, visible and ultraviolet light), heat, catalysts, chemical reagents (such as, but not limited to, acids, bases, electrophiles, or nucleophiles), and buffers.

[0047] As used herein, the term "instructional material" includes publications, records, diagrams, or any other medium of expression that can be used to communicate the usefulness of the disclosed compositions and / or compounds in the kit. The kit's instructional material can, for example, be attached to a container that holds the disclosed compounds and / or compositions or can be shipped together with a container that holds the compounds and / or compositions.

[0048] As used herein, the term "independently selected from" means that the groups referenced are the same, different, or a mixture thereof, unless the context clearly dictates otherwise. Thus, based on this definition, "X 1 , X 2 , and X 3 The phrase "independently selected from the noble gases" is intended to include, for example, X 1 , X 2 , and X 3 scenario where all are the same, X 1 , X 2 , and X 3 scenario where all are different, X 1 and X 2 is the same but X 3 This would include scenarios where the .times. ...

[0049] As used herein, the term "room temperature" means a temperature of about 15°C to 28°C.

[0050] As used herein, the terms "standard temperature" and "standard pressure" mean 20° C. and 101 kPa.

[0051] Composition of interpenetrating polymer networks A. Vinyl and Epoxy Difunctional Monomers and Polymers The compounds of formula I or formula IA or compounds described elsewhere herein can be prepared by the general schemes described herein or by synthetic methods known to those skilled in the art. In some embodiments, the compounds of formula I are polymers or resins. The following examples illustrate non-limiting embodiments of the compounds described herein and their preparation.

[0052] TIFF0007776427000006.tif74153 In the compounds of Formula I and Formula IA, independently: A is H, C 1~3 Alkyl, CN, F, Cl, and perfluoroC 1~3 selected from the group consisting of alkyl; X is O or N-R''; Each R is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; Each R' is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; R'' is H or C 1~3 is alkyl; p is an integer from 0 to 100,000.

[0053] "Perfluoro C 1~3 "Alkyl" means C 1~3 This means that each hydrogen in the alkyl group is replaced with an F (fluorine) atom. In various embodiments, A is CH3. In various embodiments, X is O. In various embodiments, R is CH3. In various embodiments, "p" is an integer between 0 and 1, between 0 and 2, between 0 and 20, between 100 and 100,000, or between 1000 and 100,000. In various embodiments, R' is CH3. In various embodiments, the compound of Formula I has the following structure: TIFF0007776427000007.tif46134

[0054] In various embodiments, the compound of formula IA has the structure: TIFF0007776427000008.tif22128

[0055] In various embodiments, the interpenetrating polymer network (IPN) comprises the reaction product of at least one amine with a compound comprising at least one vinyl ester functional group and at least one epoxy functional group. The compound comprising at least one vinyl ester functional group and at least one epoxy functional group can be a monomer, a polymer, or a combination thereof. The IPN is formed when the at least one vinyl ester functional group is polymerized by photoinduced free radical polymerization and the at least one epoxy functional group and the amine are polymerized by step-growth thermal polymerization.

[0056] In various embodiments, the compound containing at least one vinyl ester functional group and at least one epoxy functional group has the structure of Formula I, Formula IA, or Formula III-A, and combinations thereof. In various embodiments, the vinyl ester functional group in the compound of Formula I, Formula IA, or Formula III-A is photopolymerized using VPP. In various embodiments, the at least one amine is an aromatic diamine. In various embodiments, the epoxy-amine polymerization is accelerated using a thermal post-treatment by exposure to thermal radiation, such as heat under any of the thermal conditions described herein. In various embodiments, the IPN exhibits a tensile stress at break of about 32 to about 40 MPa. In various embodiments, the IPN exhibits a tensile strain at break of about 0.85 to about 0.97%. In various embodiments, the IPN composition is TIFF0007776427000009.tif33128 or a crosslinked product thereof.

[0057] The IM can be crosslinked to any other vinyl (double bond) group in the IPN during, before, or after formation of the IPN. Thus, for example, the IM can be crosslinked to itself and to compounds of Formula I, Formula IA, Formula II, Formula III, or Formula III-A, and combinations thereof.

[0058] B. Bio-based Monomers, Polymers, and Resins In various embodiments, monomers of Formula II, Formula III, Formula III-A, or Formula IV can be polymerized to form bio-based polymers with tunable processing, thermal, and mechanical properties. These monomers are derived from natural biomolecules such as lignin, cardanol (derived from cashew nut shell liquid), and carbohydrates such as isosorbide. Bio-based polymers can be conveniently synthesized using a one-pot, two-step procedure (Figure 10). In one embodiment, the synthesis of the bio-based polymers described herein is solvent-free or substantially solvent-free. In various embodiments, the synthesis of the bio-based polymers described herein does not result in the formation of by-products and does not require workup. In various embodiments, the synthesis of bio-based polymers described herein exhibits an atom efficiency of at least 98%, 99%, 99.5%, 99.9%, 99.99%, or greater than about 98%, 99%, 99.5%, 99.9%, 99.99%, or greater than about 98%, 99%, 99.5%, 99.9%, 99.99%. In various embodiments, the synthesis of bio-based polymers described herein exhibits 100% atom efficiency. In one embodiment, a one-pot synthesis scheme was performed to prepare a resin comprising phenyl methacrylate (PM) and NC-514sVE (NC-514s vinyl ester) in a molar ratio of 1 to 0.5.

[0059] In one embodiment, the monomers of Formula II, Formula III, Formula III-A, and Formula IV have the following structure: TIFF0007776427000010.tif127160In formula, R 1 teeth TIFF0007776427000011.tif14128; L is selected from the group consisting of a bond, C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl; R 2 is selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl, wherein the substituents are selected from the group consisting of optionally substituted aryl and optionally substituted heteroaryl; Each R 3 are independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl; R 4 teeth TIFF0007776427000012.tif14128; each Y is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl; n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; m is 0, 2, 4, 6, or 8.

[0060] In certain embodiments, the monomer of formula II is selected from the group consisting of: TIFF0007776427000013.tif21128In the formula, m is 0, 2, 4, or 6.

[0061] In certain embodiments, the monomer of formula II is a phenyl (meth)acrylate or an optionally substituted phenyl methacrylate.

[0062] In certain embodiments, the monomer of formula III is: TIFF0007776427000014.tif62128.

[0063] In certain embodiments, the monomer of formula III is 2-hydroxy-3-(3-(8-(4-(2-hydroxy-3-(methacryloyloxy)propoxy)phenyl)pentadecyl)phenoxy)propyl methacrylate.

[0064] In certain embodiments, the monomer of formula IV is: TIFF0007776427000015.tif32128.

[0065] In certain embodiments, the monomer of formula IV is (3R,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-diyl bis(2-methylacrylate). The monomer of formula IV is also known as isosorbide dimethacrylate (IM).

[0066] Compounds of formula III-A can be prepared by methods described herein and art-recognized methods. In various embodiments, compounds of formula III-A can be prepared in a manner similar to that of preparing compounds of formula I, for example, according to Reaction Scheme 1. TIFF0007776427000016.tif94155 Scheme 1

[0067] The compounds described herein are synthesized using any suitable procedure starting from compounds available from commercial sources or prepared using the procedures described herein.

[0068] In certain embodiments, reactive functional groups such as hydroxyl, amino, imino, thio, or carboxy groups are protected to prevent their undesired participation in reactions. Protecting groups are used to block some or all reactive moieties, preventing the group from participating in chemical reactions until the protecting group is removed. In other embodiments, each protecting group is removable by a different means. The need for differential removal is met by protecting groups that are cleaved under completely different reaction conditions.

[0069] In certain embodiments, protecting groups are removed by acid, base, reducing conditions (e.g., hydrogenolysis), and / or oxidative conditions. Groups such as trityl, dimethoxytrityl, acetal, and t-butyldimethylsilyl are acid labile and are used to protect carboxy- and hydroxy-reactive moieties in the presence of amino groups protected with the hydrogenolysis-removable Cbz group and the base-labile Fmoc group. Carboxylic acid- and hydroxy-reactive moieties are blocked with base-labile groups such as, but not limited to, methyl, ethyl, and acetyl in the presence of amines blocked with acid-labile groups such as t-butyl carbamate, or with carbamates that are both acid- and base-stable but removable by hydrolysis.

[0070] In certain embodiments, carboxylic acid- and hydroxy-reactive moieties are blocked with hydrolytically removable protecting groups such as benzyl groups, while amine groups capable of hydrogen bonding with acids are blocked with base-labile groups such as Fmoc. Carboxylic acid-reactive moieties are protected by conversion to simple ester compounds exemplified herein, including conversion to alkyl esters, or are blocked with oxidatively removable protecting groups such as 2,4-dimethoxybenzyl, while concurrent amino groups are blocked with fluoride-labile silyl carbamates.

[0071] Allyl blocking groups are useful in the presence of acid- and base-protecting groups because the former are stable and can be subsequently removed by metal or pi-acid catalysts. For example, allyl-blocking carboxylic acids are deprotected by palladium catalysis in the presence of acid-labile t-butyl carbamate or base-labile acetate amine protecting groups. Yet another form of protecting group is a resin to which a compound or intermediate is attached. As long as the residue is attached to the resin, the functional group is blocked and cannot react. Upon release from the resin, the functional group becomes available for reaction.

[0072] Typically, blocking / protecting groups may be selected from: TIFF0007776427000017.tif80137.

[0073] Other protecting groups, along with detailed descriptions of techniques applicable to the creation and removal of protecting groups, are described in Greene & Wuts, Protective Groups in Organic Synthesis, 3rd Ed., John Wiley & Sons, New York, NY, 1999 and Kocienski, Protective Groups, Thieme Verlag, New York, NY, 1994, the disclosures of which are incorporated herein by reference.

[0074] How to make an IPN A. Vinyl and Epoxy Bifunctional Monomers, Polymers, and Resins as IPN Precursors In various aspects, a method for preparing an interpenetrating polymer network (IPN) is provided, the method comprising: subjecting a mixture of a crosslinker and a monomer, oligomer, or polymer having at least one vinyl ester functional group and at least one epoxy functional group to vat photopolymerization (VPP) under conditions such that the vinyl ester functional group is photopolymerized; and exposing the resulting mixture to thermal conditions under which epoxy-amine polymerization occurs. Includes:

[0075] In various embodiments, the monomer or polymer having at least one vinyl ester functional group and at least one epoxy functional group includes compounds of Formula I, Formula IA, Formula III-A, and combinations thereof. The method includes performing stereolithography on a mixture that may include additional agents, such as a photoinitiator that promotes free-radical polymerization of the vinyl groups and a thermal initiator that promotes thermal polymerization of the epoxy and amine groups. The mixture may further include compounds of Formula II, Formula III, and Formula IV, or mixtures thereof. In various embodiments, the stereolithography is performed in the absence of a solvent. Advantageously, a solvent is not required to perform the methods described herein. In various embodiments, the exposing step is performed in situ. Thus, the formation of the IPN can be performed in a so-called one-pot, two-step process, in which the reaction components are not transferred to a separate vessel or separately purified after the photoinitiated polymerization (stereolithography) is complete. In various embodiments, the formation of the IPN described herein does not result in the formation of by-products and does not require workup.

[0076] In various embodiments, composite materials are provided that include the IPNs described herein. Composite materials that may suitably include the IPNs described herein include, but are not limited to, automotive composites, boating composites, aircraft composites, automotive coatings, powder coatings, radiation curable coatings, waterborne coating resins, industrial and protective finishes, appliance and hardware finishes, and the like.

[0077] In various embodiments, a first crosslinked product of a compound of Formula I or Formula IA is provided. The first crosslinked product can be obtained, for example, using VPP. In some embodiments, the first crosslinked product of a compound of Formula I or Formula IA can be obtained by photopolymerization with a photoinitiator. In certain embodiments, the photoinitiator is reactive when exposed to light in the infrared (700-1,000,000 nm) range, the visible (400-700 nm) range, or the ultraviolet (10-400 nm) range. In various embodiments, the photoinitiator is a compound belonging to a class selected from the group consisting of acylphosphines, ketones, diimidazoles, acylgermaniums, thioketones, dithiocarbonates, trithiocarbonates, camphorquinones, and camphoramines. Suitable photoinitiators include 1-hydroxy-cyclohexylphenyl ketone (HCPK), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP), diphenyl(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), acetophenone, benzophenone, 2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, TIFF0007776427000018.tif48128. Photoinitiators can be used in amounts of about 0.01 to about 5% by weight of the formulated mass including the compound of Formula I or Formula IA. In various embodiments, the photoinitiator is present in an amount of about 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, or about 5% by weight of the formulated mass including the compound of Formula I. In various embodiments, the photoinitiator is TPO. In various embodiments, the photoinitiator is present in an amount of about 1.0 to about 3.0% by weight of the formulation including the compound of Formula I or Formula IA.

[0078] In various embodiments, the formulations comprising the compound of Formula I or Formula IA include the compound of Formula I or Formula IA, at least one photoinitiator, and at least one amine crosslinker capable of crosslinking epoxy groups. In various embodiments, the formulations comprising the compound of Formula I or Formula IA are solvent-free. In various embodiments, the compound of Formula I or Formula IA is present in the formulation in an amount of about 1 to about 99% by weight, or at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight of the formulation comprising the compound of Formula I or Formula IA. 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight, or greater than about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight.

[0079] In some embodiments, the crosslinker comprises at least one epoxy curing group. Suitable epoxy curing groups include amines, thiols, and the like. In some embodiments, the crosslinker can have one, two, three, or four amine groups. In some embodiments, the crosslinker can have one, two, three, or four thiol groups. The crosslinker can have two or more epoxy curing groups in the same molecule; for example, the crosslinker can have an amine group and a thiol group in the same molecule. In various embodiments, the amine is the epoxy curing agent. In various embodiments, the crosslinker is an aromatic diamine. Suitable amine crosslinkers include, but are not limited to, 2,4-diethyl-5-methylbenzene-1,3-diamine (sold under the trade name EPIKURE™ W), 4,4-diaminodiphenylmethane (DDM), m-xylylenediamine (m-XDA), and the like, or combinations thereof. Suitable thiol crosslinkers include, but are not limited to, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), 2,2'-(ethylenedioxy)diethanethiol, and the like, and combinations thereof. In various embodiments, suitable crosslinkers include (4,4-diaminodicyclohexylmethane), phenalkamines, polyetheramines, diethylenetriamine, isophoronediamine, substituted dianilines, anhydride epoxy curing agents, and the like, and combinations thereof. In various embodiments, the amine crosslinker is capable of crosslinking the epoxide moiety in the compound of Formula I or Formula IA. The amine crosslinker may be present in an amount of about 1 to about 50 wt. % of the formulation containing the compound of Formula I or Formula IA. In various embodiments, the amine crosslinker can be present in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or about 50% by weight of the formulation including the compound of Formula I.

[0080] In various embodiments, the first crosslinked product comprises crosslinks between vinyl (alkene) moieties in the compound of Formula I or Formula IA, and is substantially free of crosslinks between epoxy moieties in the compound of Formula I or Formula IA. In various embodiments, crosslinking of the vinyl moieties can be initiated by light exhibiting a wavelength of about 200 nm to about 400 nm.

[0081] In various embodiments, a formulation including a compound of Formula I or Formula IA can be thermally cured to form a final resin by exposing the formulation to heat. In various embodiments, the heat is at a temperature of about 80 to about 220° C. In various embodiments, the heat is about 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, or about 220° C. In various embodiments, thermal curing involves exposing the formulation including a compound of Formula I or Formula IA to heat for about 0.5 to about 4 hours, or for 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or about 4 hours.

[0082] In various embodiments, the final resin exhibits a tensile strain at break of at least about 0.85%. In various embodiments, the final resin exhibits a tensile strain at break of about 0.85 to about 0.97%. In various embodiments, the final resin exhibits a tensile strain at break of about or at least about 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, or about 0.97%.

[0083] In various embodiments, the final resin exhibits a tensile stress at break of at least about 32 MPa. In various embodiments, the final resin exhibits a tensile stress at break of about 32 to about 40 MPa. In various embodiments, the final resin exhibits a tensile stress at break of about or at least about 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, or about 40 MPa.

[0084] In various embodiments, pre-VPP resins of compounds of Formula I or Formula IA described herein exhibit a viscosity at room temperature of about 250 to about 5000 cPs, or a viscosity at room temperature of about 250, 500, 750, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, 4800, or about 5000 cPs.

[0085] B. Bio-based Monomers, Polymers, and Resins Compounds of formula III-A can be used to prepare IPNs using the same procedures, amounts, conditions, and reagents as used with compounds of formula I, as described herein.

[0086] In certain embodiments, the monomers, polymers, and combinations thereof described herein are useful in a wide variety of applications, such as, for example, automotive composites, boating composites, aircraft composites, automotive coatings, powder coatings, radiation curable coatings, waterborne coating resins, industrial and protective finishes, appliance and hardware finishes, adhesives, electrical laminates, plastic modifiers (PVC (polyvinyl chloride), PET (polyethylene terephthalate), engineering thermoplastics, rubber), 3D printing resins, VPP printing resins, and additive manufacturing. In other embodiments, the monomers, polymers, and combinations thereof described herein can be used as additives in the production of monofunctional oligomers and polymers to add dual functionality to the oligomers and polymers by forming end caps on the oligomers and polymers.

[0087] In various embodiments, a formulation is provided that includes a compound of Formula III-A, at least one photoinitiator, and at least one amine crosslinker capable of crosslinking epoxy groups, prior to VPP with a compound of Formula III-A. In various embodiments, the formulation including the compound of Formula III-A is solvent-free. In various embodiments, the compound of Formula III-A is present in the formulation in an amount of about 1 to about 99% by weight, or at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight of the formulation including the compound of Formula III-A. The compound of formula III-A is present in an amount of about 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight, or greater than about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight. Formulations containing a compound of formula III-A may include at least one compound of formula II, formula III, formula IV, and combinations thereof. Formulations may include thermal initiators, redox initiators, and combinations thereof.

[0088] In various embodiments, the photoinitiator is acetophenone, benzophenone, 2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, TIFF0007776427000019.tif47128.

[0089] In various embodiments, the thermal initiator is 4,4'-diaminodicyclohexylmethane, tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-2,5-dimethyl-3-hexyne), ... tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.

[0090] In various embodiments, the redox initiator is selected from the group consisting of sodium iodide / hydrogen peroxide, potassium iodide / hydrogen peroxide, benzoyl peroxide / dimethylaniline, benzoyl peroxide / N,N-dimethyl p-toluidine, benzoyl peroxide / 4-N,N-dimethylaminophenethyl alcohol, benzoyl peroxide / ethyl 4-dimethylaminobenzoate, glucose oxidase / oxygen / iron(II) sulfate, and copper(II) sulfate / sodium ascorbate.

[0091] In various embodiments, the monomer of formula III can be from about 1 to about 99% of the formulation, or from about 50% to about 85% by weight of the composition. In various embodiments, the monomer of formula III can be at least or about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight of the formulation including the compound of formula III-A, or can be greater than about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight.

[0092] In various embodiments, the monomer of formula II can be from about 1 to about 99% of the formulation, or from about 15% to about 30% by weight of the composition. In various embodiments, the monomer of formula II can be at least or about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight of the formulation including the compound of formula III-A, or can be greater than about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight.

[0093] In various embodiments, the monomer of formula IV can be from about 1 to about 99% of the formulation, or from about 1% to about 40% by weight of the formulation. In various embodiments, the monomer of formula IV can be at least or about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight of the formulation including the compound of formula III-A, or can be greater than about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 97, 98, or 99% by weight.

[0094] In various embodiments, formulations including compounds of formula III-A are light-curable within about 0-20 seconds, or within about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 seconds. In various embodiments, the pre-VPP resin of the compounds of Formula III-A described herein has a viscosity at room temperature of about 250 to about 5000 cPs, or a viscosity at room temperature of about 250, 500, 750, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, 3400, 3600, 3800, 4000, 4200, 4400, 4600, 4800, or about 5000 cPs.

[0095] In various embodiments, the final resin comprising a compound of Formula III-A, and optionally a compound of Formula II, Formula III, Formula IV, or a combination thereof, exhibits a tensile strain at break of at least about 0.65%. In various embodiments, the final resin exhibits a tensile strain at break of about 0.65 to about 0.97%. In various embodiments, the final resin exhibits a tensile strain at break of about or at least about 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, or about 0.97%.

[0096] In various embodiments, the final resin exhibits a tensile stress at break of at least about 25 MPa. In various embodiments, the final resin exhibits a tensile stress at break of about 32 to about 40 MPa, or about 25 MPa to about 40 MPa. In various embodiments, the final resin exhibits a tensile stress at break of about or at least about 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5, or about 40 MPa.

[0097] kit In a further aspect, kits are provided that include one or more compounds described herein. In certain embodiments, the kits include a composition containing at least one monomer selected from the group consisting of at least one monomer of Formula I, a monomer of Formula IA, a monomer of Formula II, a monomer of Formula III, a monomer of Formula III-A, and a monomer of Formula IV, and combinations thereof, and instructional materials for its use. In certain embodiments, the composition further includes at least one polymerization initiator.

[0098] In certain embodiments, the kit further comprises a light source capable of generating light sufficient to activate the photoinitiator. In other embodiments, the kit further comprises a light source capable of emitting light in the infrared (700-1,000,000 nm) range, the visible (400-700 nm) range, or the ultraviolet (10-400 nm) range. In still other embodiments, the kit further comprises a heat source capable of generating heat sufficient to activate the thermal initiator. In other embodiments, the kit further comprises a heat source capable of heating the composition of the present disclosure to a temperature of about 30°C to about 200°C.

[0099] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures, embodiments, claims, and examples described herein. These equivalents are considered to be within the scope of this disclosure and are considered to be covered by the claims appended hereto. For example, it should be understood that modification of reaction conditions, including but not limited to reaction time, reaction size / volume, experimental reagents such as solvents, catalysts, pressure, atmospheric conditions, e.g., nitrogen atmosphere, and reducing / oxidizing agents, using art-recognized substitutes and no more than routine experimentation, is within the scope of this application.

[0100] Wherever values ​​and ranges are given herein, it should be understood that all values ​​and ranges subsumed within those values ​​and ranges are intended to be encompassed within the scope of the present disclosure. Moreover, all values ​​within these ranges, as well as the upper or lower limits of a range of values, are also contemplated by the present application.

[0101] The following examples further illustrate aspects of the present disclosure, but in no way limit the teachings or disclosure of the present disclosure set forth herein. [Example]

[0102] Various aspects of the present application can be better understood with reference to the following examples, which are provided by way of illustration and not limitation of the scope of the present application.

[0103] material Phenol (99.5%), 4-dimethylaminopyridine (DMAP, 99%), and NMR-grade chloroform-d3 were purchased from Acros Organics. Methacrylic anhydride (94%) was purchased from Alfa Aesar. AMC-2 catalyst (a chromium(III)-based catalyst) was purchased from AMPAC Fine Chemicals. Diphenyl(2,4,5-trimethylbenzoyl)phosphine oxide (TPO) was purchased from TCI. Isopropyl alcohol (IPA) was purchased from VWR. Compressed nitrogen (N2, 99.998%) and compressed argon (Ar, 99.999%) were purchased from Airgas. EPON™ Resin 828 (diglycidyl ether of bisphenol A, DGEBA) and EPIKURE™ W curing agent (diethyltoluenediamine) were obtained from Hexion. NC-514s was provided by Cardolite Corporation (Bristol, PA, USA). Isosorbide dimethacrylate (IM) was prepared as described in the literature. EPON 828 was converted to the bismethacrylic glycidyl ether of bisphenol A using a literature method, which showed similar chemical and physical characterization results. This is designated as vinyl ester 828 (VE828). All chemicals were used as received.

[0104] Resin synthesis and formulation A. Vinyl and Epoxy Dual Functional Polymers / Resins The resin was synthesized using a one-pot, two-step reaction methodology, as shown in Figure 2. Phenol (200.00 g) and DMAP (13.11 g) were added to a three-necked round-bottom flask equipped with a mechanical mixer. The mixture was purged with argon for 10 minutes, after which methacrylic anhydride (330.91 g) was added. The reaction mixture was heated to 50-55 °C with continuous stirring. After 24 h, the reaction mixture was cooled to room temperature, and the second step of the synthetic procedure, partial methacrylation of Epon™ 828, was carried out by adding a stoichiometric amount of EPON™ 828 (804.75 g) along with AMC-2 catalyst (1.00 g). The mixture was then heated to 70 °C and monitored for completion by acid number titration (when the free acid number was less than 10, corresponding to approximately 3% acidity). The final synthesis, PM-EM828, consisted of a 1:1 molar ratio of the monofunctional monomer phenyl methacrylate (PM) and the difunctional crosslinker partially methacrylated bisphenol A epoxy (EM828). A fully methacrylated vinyl ester resin similar to the PM-EM828 system was also prepared for comparison purposes. Here, Epon828 was added at a molar ratio of 0.5 to methacrylic acid to promote complete conversion of Epon828 to the corresponding difunctional vinyl ester, VE828.

[0105] Resins containing epoxy moieties were blended with a stoichiometric amount of Epikure W (i.e., one amine nitrogen per epoxide) to promote curing of the epoxy-amine network. Additionally, resin formulations were prepared by mixing all components in a Thinky centrifugal mixer at the specific molar compositions shown in Table 1. PM-VE828 resin alone served as the basis for comparison for this study.

[0106] (Table 1) Resin composition TIFF0007776427000020.tif45170

[0107] The effect of network connectivity was evaluated by comparing PM-EM828 with a PM-VE828-Epon828 blend. This comparison was made due to the fact that these two systems have identical molar concentrations of reactive epoxy and methacrylate groups. However, in the PM-EM828 system, the vinyl ester and epoxy-amine networks are chemically connected to each other by the EM828 monomer, which has both functional groups on the same molecule, whereas in the PM-VE828-Epon828 blend, these connections are made at the molecular level.

[0108] Furthermore, to evaluate the effect of the molecular distance between the connections of the vinyl ester and the epoxy-amine network on the overall polymer properties, PM-EM828 was blended with VE828, or VE828 and Epon828, in the molar amounts listed in Table 1. A visual representation of the formed network is shown in Figure 3.

[0109] B. Bio-based Monomers, Polymers, and Resins The resin was synthesized using a modified one-pot reaction methodology described in our previous work. Phenol (50.00 g) and DMAP (3.28 g) were added to a three-neck round-bottom flask equipped with a mechanical mixer. The mixture was purged with argon for 10 minutes, after which methacrylic anhydride (82.73 g) was added. The reaction mixture was heated to 50–55 °C with continuous stirring. After 24 h, the reaction mixture was cooled to room temperature, and NC-514s (224.47 g) was added along with AMC-2 catalyst (0.27 g). The mixture was then heated to 70 °C and monitored by acid value titration until completion (when the free acid number was less than 10, corresponding to approximately 3% acidity). The synthesized resin (PM-NC514sVE) consisted of the monofunctional monomer phenyl methacrylate (PM) and the crosslinker NC514sVE in a molar ratio of 1:0.5. The complete reaction scheme is shown in Figure 10. PM-NC514sVE resin was utilized as the sole resin and also blended with both 10 wt % and 20 wt % IM to determine the effect of increasing IM content on resin properties.

[0110] Resin Characterization The synthesized resin 1 Characterization was performed by H-NMR (400.15 MHz, 32 scans at 298 K) using a Varian 400 MHz FT-NMR spectrometer. Viscosity of resins and formulations was obtained using a TA Instruments Discovery Hybrid Rheometer (DHR-2) at 25°C with a 1° 40 mm cone geometry. The shear rate was ramped logarithmically, with a ramp time of 1 s. -1 100 seconds from -1 rises to 100 seconds -1 1 second from -1 It fell to.

[0111] Resin Additive Manufacturing All resins, polymers, and monomers were prepared for free-radical photopolymerization with VPP by adding TPO as a photoinitiator at 2 wt% of the total resin formulation. The resins were mixed with TPO in a planetary mixer for 15 minutes and degassed for 2 minutes. Digital models were prepared for viscoelastic, tensile, and fracture testing. The final models were uploaded to an SLA 3D printer. A layer thickness of 100 μm was selected. After printing, the printed samples were washed with isopropyl alcohol for 20 minutes to remove any unreacted resin from the surface of the printed samples. These samples are referred to as AM samples. The samples were further post-treated with UV / visible light (λ = 405 nm) and heat (80 °C) for 2 hours (FC) and then further post-cured in a thermal oven at 180 °C for 2 hours (PC).

[0112] Polymer properties Thermogravimetric analysis was performed using a Thermogravimetric Analyzer 550. 10 mg of sample was placed on a platinum pan and heated under N2 (inert) and air (oxidizing) atmospheres (balance gas flow rate 40 mL / min). -1 , sample gas flow rate 25 mL / min -1 ) at a rate of 10°C / min -1 The initial decomposition temperature (IDT), the temperature at which 50% by weight of the mixture was decomposed (T 50% ), the temperature at maximum decomposition (T max ), and charcoal content are reported.

[0113] The viscoelastic properties of all cured resins were evaluated using a dynamic mechanical analyzer (DMA). A single cantilever geometry with a frequency of 1.0 Hz, a Poisson's ratio of 0.35, and a deflection amplitude of 7.5 μm was used. The heating ramp was from 0 °C to 250 °C at 2 °C per minute.

[0114] Rheology A. Vinyl and Epoxy Difunctional Monomers, Polymers, and Resins All resin compositions exhibited Newtonian behavior. The viscosity of each resin was determined by averaging three steady-state points at different shear rates and is shown in Table 2.

[0115] (Table 2) Resin viscosity at 25°C TIFF0007776427000021.tif49153

[0116] As the overall molar concentration of the crosslinker, EM828, Epon828, or VE828, increased, the viscosity of each resin system increased. Interestingly, although the PM-EM828 resin and the PM-VE828-Epon828 blend resin contain the exact same molar amounts of PM, crosslinker, and bisphenol content, as well as identical molar amounts of methacrylate and epoxy moieties, the PM-EM828 system exhibits a significantly reduced viscosity compared to its blend counterpart. This is because the EM828 monomer alone has a viscosity of 1.1x10 5 While the cP is shown, the VE828 (6x10 7 cP) and Epon828 (1.3x10 4 An equimolar blend of 100 and 100 cP has a viscosity of approximately 3x10 based on the logarithmic simple compound rule. 7 Therefore, preparation of multifunctional EM828 reduces resin viscosity for the same molar content of reactive functional groups, thus potentially increasing processability.

[0117] B. Bio-based Monomers, Polymers, and Resins To determine the viability of bio-based resins in VPP, the viscosity of the uncured resins was obtained. The results are shown in Figure 11 and Table 1A. In Figure 11, the weight percent of IM was converted to mole percent for comparison with the predicted viscosity based on the logarithmic simple compound rule. The viscosity of each uncured resin formulation was determined using the average of three steady-state points at various shear rates. Based on the rheological data obtained, all resins exhibited Newtonian behavior. A viscosity below 3000 cP at room temperature is generally recommended for resin processing with VPP. Therefore, as seen in Table 1A, the resin blends meet the viscosity requirements of VPP. In various embodiments, the viscosity of the resin system decreased as the concentration of IM increased. Without being bound by theory, this is believed to be because the IM, which has a viscosity of approximately 157 cP by itself at room temperature, acts as a reactive diluent. The experimental viscosities were similar to those of PM-NC514sVE (PM alone = 3.1 cP, NC514s = 2.9x10). 7 This is predicted based on the logarithmic simple compounding rule of the individual viscosities of the IM and the IM.

[0118] The calibration curve parameter E C (the amount of exposure per unit area required for the resin to reach its gel point) and D p (The depth at which the irradiance becomes 13.5% of the irradiance at the interface where the laser contacts the resin) is defined as E max The resin system parameters were estimated by OLS regression of cure depth as a function of the natural logarithm of . The estimated values ​​for all resin system parameters are shown in Table 2A.

[0119] Table 1A: Viscosity of base PM-NC514sVE uncured resin system with various IM weight percentages TIFF0007776427000022.tif31164

[0120] Table 2A: Calibration curve parameters D for PM NC514sVE resin systems with various IM weight percentages P and E C TIFF0007776427000023.tif31164

[0121] As can be seen in Figure 12, the calibration curve model fits the data well. The resin blends show a general trend of decreasing calibration curve parameters with increasing IM content. The addition of IM increases the overall methacrylate concentration in the resin formulation, ultimately resulting in a decrease in E C The overall photosensitivity decreases as observed by the decrease in D. p and higher methacrylate concentrations lead to higher crosslink density in the thermoset polymer network, thus reducing the penetration depth of light through the cured resin surface.

[0122] degree of hardening A. Vinyl and Epoxy Difunctional Monomers, Polymers, and Resins The degree of cure of the material after printing (AM), post-processing (FC), and post-curing (PC) was determined by near-infrared (near-IR) spectroscopy. The uncured resin was contained in a 3 mm thick glass container. Resolution: 2 cm -1 Sixty-four cumulative scans at 6165 cm were collected. The cured resins had a thickness of 2.5 mm, and their near-infrared spectra were acquired in the same manner as the uncured resin. The methacrylate peak was observed at approximately 6165 cm before and after curing. -1 Measured at 5900cm, which is not affected by polymerization -1 The peak was compared to the reference peak at approximately 4530 cm. If present, the oxirane ring of the epoxy was -1 The amine peak was measured at approximately 5000 cm -1 and approximately 6600 cm -1 Figure 4 shows typical near-infrared spectra of the cured and uncured resins.

[0123] Table 3. Degree of cure of resin measured by near-infrared spectroscopy at various cure stages taken at room temperature TIFF0007776427000024.tif121158

[0124] The only photopolymerizable group in the resin is the 6165 cm -1The ratio between the methacrylate peak before the curing process and the methacrylate peak after the curing process is 5900 cm -1 The degree of cure of the methacrylate network was calculated by comparing it with the unreacted control peak at approximately 4530 cm. Similarly, the oxirane ring on the epoxy and amine reacted at approximately 4530 cm. -1 , about 5000cm -1 , and approximately 6600 cm -1 The near-infrared absorption spectra were used to determine the degree of cure of the epoxy-amine network. After printing, the degree of cure of the methacrylate functional groups in all resins was 75–90%. Furthermore, because the epoxy-amine reaction was not initiated during VPP printing, all epoxy conversions were 0%. Therefore, the epoxy and amine monomers are plasticized within the shell of the methacrylate network.

[0125] The addition of a post-curing step at 80 °C with UV / visible light irradiation around the printed area further increased the methacrylate cure degree to approximately 90%. Furthermore, the FC step at 80 °C initiated the epoxy-amine cure, a temperature within the typical epoxy-amine cure range. The overall epoxy cure degree was shown to increase to 65-83% for all samples, demonstrating that the step-cure approach using VPP with thermal post-cure allows for in situ IPN formation, where the epoxy-amine monomer is first plasticized within the VPP-printed methacrylate polymer matrix, followed by curing during FC. A traditional post-cure at 180 °C was further used to accelerate the conversion of the epoxy-amine network.

[0126] This post-cure was not used for the fully methacrylated PM-VE828 due to the absence of epoxy-amine reactivity. Interestingly, PM-EM828 and PM-VE828-Epon828 blends, which contain the exact same molar amounts of PM, crosslinker, and bisphenol content, and the same molar amounts of methacrylate and epoxy moieties, show similar degrees of cure for the methacrylate, but with a difference of about 16% in the degree of cure for the epoxy-amine network. Because the two networks are not connected in the PM-VE828-Epon828 blend, the fully methacrylated moieties exhibit a higher T than all other prepared IPNs after AM. g This likely results in a polymer with a higher T than the polymer after AM, thus causing the network to vitrify earlier, which reduces the degree of cure of the epoxy-amine network in this sample. g As a result of the addition of methacrylate and epoxy functional groups, which affect the vitrification and result in changes in the vitrification, both components show similar degree of cure values, intermediate between those of PM-EM828 and PM-VE828-Epon828 blends.

[0127] B. Bio-based Monomers, Polymers, and Resins Near-infrared spectroscopy was used to determine the degree of cure for the formulated resins immediately after printing and washing (denoted as AM) and subsequently after post-treatment. Representative near-infrared spectra are shown in Figure 13, and the resulting degree of cure values ​​are listed in Table 3A.

[0128] Table 3A: Degree of cure before and after FC for printed samples of PM-NC514sVE resin system with various IM weight percentages. TIFF0007776427000025.tif35164

[0129] The polymerizable methacrylate group is at 6165 cm -1The ratio between the methacrylate peak before the curing step and the methacrylate peak after the curing step was calculated based on the reference peak (5900 cm -1 ) and calculated the degree of cure. Generally, all resin formulations showed similar degrees of cure both after printing and washing and after post-treatment. The addition of FC (post-treatment), which acts as a traditional post-cure while also irradiating the material with UV light, increased the overall degree of cure by approximately 16%, approaching full conversion, thus definitely eliminating the effect of degree of cure on the polymer properties presented and discussed herein.

[0130] Polymer properties A. Vinyl and Epoxy Difunctional Monomers, Polymers, and Resins The resulting polymer was a hard, glassy, ​​gray-green / brown sample. All cured resins were analyzed for thermal degradation. TGA thermograms are shown in Figure 5. 50% , T max , and the values ​​of charcoal content are reported in Table 4.

[0131] Table 4. Thermogravimetric properties of all IPNs in N2 TIFF0007776427000026.tif43162

[0132] In general, all IPNs exhibit comparable thermogravimetric properties, with IDT values ​​of approximately 320 °C and T 50% Value and T max The values ​​were approximately 400°C, with charcoal contents ranging from 5 to 12%. The fully methacrylate-based PM-VE828 was the only sample that showed a decrease in IDT. The decrease in IDT for the methacrylate-based PM-VE828 may be a result of the absence of a secondary network structure, which likely contributes to an increase in the IDT value of the IPN and prevents premature degradation of the bulk material. A similar thermogravimetric trend was observed in oxidizing environments, the only difference being the decrease in charcoal content due to the combustion of charcoal at high temperatures.

[0133] The viscoelastic properties of all IPNs were evaluated using DMA. Figure 6 shows representative storage modulus (E') and loss modulus (E'') thermograms for all IPN samples. Figure 7 shows the tan δ thermograms for each IPN. Table 5 shows the specific thermomechanical properties of all cured IPNs.

[0134] Table 5. Viscoelastic properties of all IPNs TIFF0007776427000027.tif57170

[0135] The differences in E' at 25°C were not statistically significant for all samples, and these samples exhibited E' values ​​comparable to conventional styrene-diluted vinyl esters at 25°C and higher than typical epoxy-amine thermosets (about 2.5 GPa) due to the methacrylate nature of their networks. Using both the E'' peak and the tan δ peak, T g The temperature at which the polymer changes from a glassy state to a rubbery state was determined. Comparing PM-EM828 and PM-VE828-Epon828 blends containing identical molar amounts of PM, crosslinker, and bisphenol content, and identical molar amounts of methacrylate and epoxy moieties, PM-EM828 achieved a higher degree of cure than the PM-VE828-Epon828 blend, resulting in an approximately 10°C higher T g Furthermore, by adding VE828 to PM-EM828 resin, the crosslinker content in the entire system is increased, resulting in a material with T g Although T increases by approximately 11°C further relative to the E'' peak, both VE828 and Epon828 formulations (i.e., PM-EM828_05Epon828_025VE828) g Therefore, the increase in the molecular distance between the methacrylate and epoxy-amine network connections does not result in a further increase in T g Nevertheless, all the prepared IPNs exhibited similar T values ​​to those of the styrene-diluted vinyl ester resins. g Indicates the value.

[0136] The width of the tan δ peak is related to the heterogeneity of the polymer network. A broader peak indicates a more heterogeneous network and a broader distribution of relaxation modes. The tan δ thermograms of all IPNs showed similar widths, indicating that all IPNs exhibited similar levels of homogeneity. The maximum value of tan δ can be used to gain insight into the overall polymer chain segmental mobility, with higher peaks indicating higher chain transfer potential. In general, the prepared IPNs are likely to exhibit a high degree of heterogeneity depending on the IPN composition and the resulting M c The difference in values ​​indicates slight differences in the segmental mobility of the polymer chains. The maximum value of tan δ is M c The difference in interconnectivity between the two networks, and the difference in molecular spacing, therefore shows only a small effect on the segmental mobility of the polymer chains.

[0137] M c was calculated using rubber elasticity theory and is shown in Table 5. Comparing the fully methacrylate-based PM-VE828 with all other polymers prepared, it was found that PM-VE828 had the lowest M among all the prepared polymers. c It is observed that the PM-VE828-Epon828 blend exhibited the highest M among all the samples. c This is likely a result of a reduced degree of cure of the epoxy-amine network.

[0138] All interconnect IPNs for PM-EM828, PM-EM828_025VE828, and PM-EM828_05Epon828_025VE828 are similar M c This result is due to the fact that all crosslinkers (EM828, VE828, and Epon828) have similar molecular weights. The increase in molecular distance between the methacrylate and epoxy-amine network connections is related to the M cThis does not affect the numerical M c exists independently of the IPN connections, and in this case, M c Because it means...

[0139] Tensile tests were performed to determine the effect of the IPN connection on the resulting mechanical properties of the polymer. Figure 8 shows the stress-strain curves for all samples. All samples exhibited linear behavior up to failure. Table 6 shows the tensile property data for all cured polymers.

[0140] Table 6. Tensile test values ​​for all IPNs TIFF0007776427000028.tif53165

[0141] Young's modulus, a measure of polymer stiffness, is directly correlated with the overall monomer structure, degree of crosslinking, and macromolecular architecture of the polymer network. The differences in Young's modulus were not statistically significant for most samples, with the exception of PM-EM828_05Epon828_025VE828. This is likely due to the increased epoxy content resulting from the addition of VE828 and Epon828, thus increasing the molecular distance between the two formed networks. The fully methacrylate-based PM-VE828 generally exhibited the lowest tensile strain and stress at break. The PM-VE828-Epon828 blend IPN produced results nearly identical to the fully methacrylate-based PM-VE828.

[0142] Unexpectedly, the interconnected IPN, PM-EM828, yielded materials with significantly improved tensile properties compared with PM-VE828-Epon828 blends containing identical molar amounts of resin components and reactive species. Thus, the interconnection of vinyl ester and epoxy-amine networks demonstrated a significant increase in tensile strength, likely as a result of increased cure. However, the addition of VE828 to the PM-EM828 resin (PM-EM828_025VE828) resulted in an overall decrease in the tensile properties of the resulting IPN. This is the result of an increased number of crosslinks within the methacrylate network and a subsequent decrease in the molecular distance between network-level connections.

[0143] However, the addition of Epon 828 (PM-EM828_05Epon828_025VE828) offsets this, increasing both the epoxy properties and the molecular distance between the two interconnected networks that form. As noted previously, this increase in molecular distance results in a slight decrease in Young's modulus, but the change in network connectivity significantly improves all other measured tensile properties, including energy at maximum force, force at break, tensile strain at break, and tensile stress at break. This indicates that increased interconnectivity and molecular distance within the IPN increases toughness.

[0144] Furthermore, the results obtained by the tensile tests are confirmed by fracture toughness experiments. As shown in Figure 9, all specimens showed linear deformation leading to failure. The plane-strain fracture toughness K 1C and the critical strain energy release rate G 1C The results are shown in Table 7.

[0145] Table 7. Fracture toughness K of all IPNs 1C value and G 1C value TIFF0007776427000029.tif49128

[0146] The fully methacrylate-based PM-VE828 system exhibited fracture toughness similar to that of the styrene-diluted vinyl esters. The PM-VE828-Epon 828 blend exhibited the lowest fracture toughness of all the IPNs prepared. Interestingly, the PM-VE828-Epon 828 blend exhibited intermediate fracture properties relative to the individual components of the network, where the PM-VE828 components are as shown in Table 7 (G 1C is 222J m -2 ), Epon828-EPIKURE(TM) W G 1C is 135J m -2 This is shown in the literature.

[0147] This intermediate fracture toughness is the result of the formation of a non-interconnected mesh-like IPN and a low degree of cure. However, PM-EM828, an interconnected IPN containing the exact same molar amounts of PM, crosslinker, and bisphenol content as the PM-VE828-Epon828 blend, and the same molar amounts of methacrylate and epoxy moieties, exhibited a significant increase in fracture toughness as a result of interconnection of the vinyl ester and epoxy amine network by the dual functionality of the EM828 monomer, resulting in a G 1C is 668J m -2 is increasing.

[0148] By adding VE828 to PM-EM828 resin, 1C is 283J m -2 This is due to an increase in the number of crosslinks within the methacrylate network, resulting in a decrease in the molecular distance between network-level connections. However, the addition of Epon 828 offsets the decrease in toughness due to the addition of VE828, where the PM-EM828_05Epon828_025VE828 system had a toughness of 790 J m -2 It is shown that the IPN has a high fracture energy of 1.0 times higher than the conventional IPN. This is a result of the increase in the total molecular distance between the two interconnected networks. 1C 790J m -2The fracture toughness is comparable to that of thermoset rubber and / or particle-toughened vinyl ester resins and epoxy resins. g It is important to note that this is achieved without a decrease in . This is typical of rubber toughening systems since the particles exhibit a plasticizing effect.

[0149] B. Bio-based Monomers, Polymers, and Resins The resulting VPP printed polymer was glassy at room temperature and brown in color, primarily due to the color of the NC-514s utilized in the resin synthesis. A representative photograph of the sample is shown in Figure 14.

[0150] TGA was performed on all post-treated samples to determine their thermal stability. Thermograms of the post-treated samples in N2 are shown in Figure 15. IDT, T 50% , T max , and charcoal content values ​​are shown in Table 4A.

[0151] Table 4A: Thermogravimetric properties of PM-NC514sVE cured resin systems with various IM weight percentages in N. TIFF0007776427000030.tif38164

[0152] Generally, all samples have IDT, T within the error range of each other. 50% , T max , and charcoal content values. Therefore, the addition of IM to the base PM-NC514sVE resin does not significantly affect thermal stability. Viscoelastic properties were evaluated using DMA. Representative storage modulus (E') and loss modulus (E'') thermograms for each sample are shown in Figure 16, and tan δ thermograms are shown in Figure 17. Table 5A contains the thermomechanical property values ​​for each resin system, printed and fully processed (washed and post-treated).

[0153] The cured PM-NC514sVE resin system exhibits the lowest E' of 3.5 GPa at -40 °C and 1.0 GPa at 25 °C due to the flexibility of the CNSL-derived NC514sVE. The addition of IM increases E' at -40 °C and 25 °C as expected, as the cured IM alone exhibits an E' of 4 GPa at 25 °C (see Table 5A). The T of the samples was determined using both the E'' peak and the tan δ peak. g , the temperature at which the polymer changes from a rigid state to a more flexible, rubbery state upon heating. Generally, the peak in E'' indicates a relatively modest T g The value of α is obtained, while the peak of tanδ provides an upper limit. Because of concerns about peak overlap due to intermittent β relaxation of the long alkyl chain of NC514sVE, the peak of tanδ is used for comparison. g Overall, T g follows the same trend as E', where the base PM-NC514sVE cured resin system has a T of 63°C. g The addition of 10 wt% and 20 wt% IM resulted in T values ​​of 91°C and 109°C, respectively. g A cured resin system having the following structure was obtained.

[0154] Table 5A. Thermomechanical results of PM-NC514sVE samples with various IM weight percentages. TIFF0007776427000031.tif46158

[0155] The width of the tan δ peak is related to the heterogeneity of the thermoset polymer network, where a broader peak indicates a more heterogeneous network and a broader distribution of relaxation modes. The incorporation of IM into the PM-NC514sVE resin system results in the presence of three distinct components with significantly different molecular structures within the polymer matrix, increasing the heterogeneity of the formulation, thereby increasing the width of the tan δ peak. The segmental mobility of the polymer chain is determined by the maximum value of tan δ, where a higher peak indicates higher chain segment mobility. As the IM content in the resin formulation increases, the rigidity of the IM structure restricts chain mobility to the interior of the entire thermoset polymer network, thus decreasing the tan δ peak height, as shown in Figure 17.

[0156] Table 5A shows the calculated Mc values ​​using rubber elasticity theory. In various embodiments, as the IM concentration increases, the M c This is due to the low molecular weight of the IM and the high crosslink density of the resulting polymer matrix (M c Similarly, when the IM content increases, the crosslink density increases and the M c The decrease in β correlates directly with the increase in bulk polymer density (see Table 5A).

[0157] Tensile tests were performed to determine the effect of increasing IM content on the tensile properties of VPP-printed thermoset polymers. Figure 18 shows representative stress-strain curves for the prepared polymers. Tensile test properties, including energy at maximum force, Young's modulus, force at break, tensile strain, and tensile stress, are reported in Table 6A.

[0158] Table 6A: Tensile test results for cured PM-NC514sVE resin systems with various IM weight percentages TIFF0007776427000032.tif50164

[0159] The cured PM-NC514sVE resin system exhibited the lowest Young's modulus of 543 MPa and the highest tensile strain at break of 9.44%. The low Young's modulus and high strain at break values ​​are due to the chemical structure of the NC514sVE component, which is known to exhibit elastic behavior and result in low modulus materials. However, upon addition of IM, the Young's modulus significantly increases, while the strain at break significantly decreases. As can be seen in Tables 5A and 6A, and in general, the M c As the results show, the cured resin system follows this trend, where the addition of IM increases the Young's modulus by 100%. c This resulted in a decrease in Young's modulus, which is directly correlated to an increase in Young's modulus and a decrease in strain at break. However, although the addition of IM substantially increased the overall material strength, it also embrittled the material, as indicated by a significant decrease in the energy at maximum force.

[0160] The tensile test results were also confirmed by fracture toughness experiments. As shown in Figure 19, all specimens showed linear deformation leading to failure. Plane-strain fracture toughness K 1C and the critical strain energy release rate G 1C are reported in Table 7A. Generally, as the IM content increases, K 1C and G 1C The cured PM-NC514sVE resin system without IM showed a decrease in K 1C Value 0.55 MPa m 1 / 2 and G 1C Value 729J m -2 This indicates that the resin system was the toughest of the thermosetting polymers printed and tested. The weakest cured resin system was PM-NC514sVE 20% IM, with K 1C is 0.50 MPa m 1 / 2 , G 1C is 160J m -2 It was.

[0161] The decrease in toughness is due to the increased crosslink density (M cThis is because it produces a thermosetting matrix that exhibits a decrease in Tg (a decrease in Young's modulus) and an overall decrease in aliphatic content, which typically results in toughening. When comparing the performance of the three SLA-printed bio-based resins, the addition of IM to the cured polymer network decreased flexibility, as indicated by an increase in Tg and Young's modulus, and also decreased toughness.

[0162] Table 7A: Fracture toughness K of PM-NC514sVE with various IM weight percentages 1C and G 1C value TIFF0007776427000033.tif31128

[0163] Numbered Aspects Numbered aspects are presented below, but the numbering should not be construed as indicating a level of importance. Aspect 1 is comprising the reaction product of a crosslinker comprising at least one epoxy curing group and a compound comprising at least one vinyl ester functional group and at least one epoxy functional group; the at least one vinyl ester functional group is polymerized by photoinduced free radical polymerization; the at least one epoxy functional group and the crosslinker are polymerized by step-growth thermal polymerization; An interpenetrating polymer network (IPN) is provided. Embodiment 2 is the IPN of embodiment 1, wherein the compound has the structure of Formula I or Formula IA: TIFF0007776427000034.tif89134In formula, A is H, C 1~3 Alkyl, CN, F, Cl, and perfluoroC 1~3 selected from the group consisting of alkyl; X is O or N-R''; Each R is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; Each R' is independently H, C 1~3Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; Each R'' is independently H or C 1~3 is alkyl; p is an integer between 0 and 100,000 to provide. Embodiment 3 provides the IPN of embodiment 1, wherein R is CH3. Embodiment 4 provides the IPN of embodiment 1, wherein R' is CH3. Embodiment 5 is the IPN of embodiment 1, wherein the compound of formula I has the structure: Provide TIFF0007776427000035.tif46134. Embodiment 6 relates to the IPN of embodiment 1, wherein the compound has the structure of formula III-A: TIFF0007776427000036.tif56128In formula, Each R 3 are independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl; each Y is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl; n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 to provide. Example 7 provides the IPN of Example 6, wherein the vinyl ester functional groups are photopolymerized using vat photopolymerization (VPP). Example 8 provides the IPN of Example 1, wherein the vinyl ester functional groups are photopolymerized using VPP. Example 9 provides the IPN of Example 1, wherein the crosslinker is an epoxy curing agent. Embodiment 10 provides the IPN of embodiment 1, wherein the epoxy-crosslinker polymerization is accelerated using a thermal post-treatment. Embodiment 11 is the IPN of embodiment 1, further comprising: Provide TIFF0007776427000037.tif32128. Embodiment 12 is a method of preparing an interpenetrating polymer network (IPN), comprising: applying VPP to a mixture of a crosslinker containing at least one amine functional group and a monomer, oligomer, or polymer having at least one vinyl ester functional group and at least one epoxy functional group under conditions such that the vinyl ester functional group is photopolymerized; and exposing the resulting mixture to thermal conditions under which epoxy-amine polymerization occurs. A method comprising: to provide. Embodiment 13 relates to the method of embodiment 12, wherein the monomer has a structure of formula IA: TIFF0007776427000038.tif30128In formula, A is H, C 1~3 Alkyl, CN, F, Cl, and perfluoroC 1~3 selected from the group consisting of alkyl; X is O or N-R''; R is H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; R' is H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; R'' is H or C 1~3 is alkyl; p is an integer between 0 and 100,000 to provide. Example 14 is the method of example 12, wherein the polymer has a structure of Formula I: TIFF0007776427000039.tif46134In formula, A is H, C 1~3 Alkyl, CN, F, Cl, and perfluoroC 1~3 selected from the group consisting of alkyl; X is O or N-R''; Each R is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; Each R' is independently H, C 1~3 Alkyl, F, and Perfluoro C 1~3 selected from the group consisting of alkyl; Each R'' is independently H or C 1~3 is alkyl; p is an integer between 0 and 100,000 to provide. Embodiment 15 provides the method of embodiment 12, wherein the applying step is carried out in the absence of a solvent. Embodiment 16 provides the method of embodiment 12, wherein the exposing step is performed in situ. Example 17 provides the method of Example 12, wherein the crosslinking agent is an epoxy curing agent. Embodiment 18 provides a composite material comprising the IPN of embodiment 1. Embodiment 19 is a composition comprising at least one monomer selected from the group consisting of: TIFF0007776427000040.tif72155In formula, R 1 teeth TIFF0007776427000041.tif14128; L is selected from the group consisting of a bond, C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl; R 2 is selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl, wherein the substituents are selected from the group consisting of optionally substituted aryl and optionally substituted heteroaryl; Each R 3 are independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl; R 4 teeth TIFF0007776427000042.tif14128; each X is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl; n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; m is 0, 2, 4, 6, or 8 to provide. Embodiment 20 is the composition of embodiment 19, wherein the monomer of formula II is selected from the group consisting of: TIFF0007776427000043.tif26128 where m is 0, 2, 4, or 6 to provide. Example 21 is the composition of example 19, wherein the monomer of formula III is: Provide TIFF0007776427000044.tif63128. Embodiment 22 is the composition of embodiment 19, wherein the monomer of formula IV is: Provide TIFF0007776427000045.tif33128. Example 23 is the composition of Example 21, further comprising at least one polymerization initiator. Example 24 provides the composition of Example 21, wherein the polymerization initiator is at least one selected from the group consisting of a photoinitiator, a thermal initiator, and a redox initiator. Example 25 provides the composition of Example 24, wherein the photoinitiator is reactive when exposed to light in the infrared, visible, or ultraviolet spectrum. Aspect 26 is a photoinitiator selected from the group consisting of acetophenone, benzophenone, 2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, TIFF0007776427000046.tif47128. Embodiment 27 is directed to a method for preparing a tertiary amine compound, the method comprising the steps of: preparing a tertiary amine compound (TMA), ... 25. The composition of claim 24, wherein the peroxy group is selected from the group consisting of 1,1-bis(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate. Example 28 provides the composition of example 24, wherein the redox initiator is selected from the group consisting of sodium iodide / hydrogen peroxide, potassium iodide / hydrogen peroxide, benzoyl peroxide / dimethylaniline, benzoyl peroxide / N,N-dimethyl p-toluidine, benzoyl peroxide / 4-N,N-dimethylaminophenethyl alcohol, benzoyl peroxide / ethyl 4-dimethylaminobenzoate, glucose oxidase / oxygen / iron(II) sulfate, and copper(II) sulfate / sodium ascorbate. Example 29 provides the composition of Example 19, wherein the monomer of Formula III comprises about 50% to about 85% by weight of the composition. Example 30 provides the composition of Example 19, wherein the monomer of Formula II comprises about 15% to about 30% by weight of the composition. Example 31 provides the composition of Example 19, wherein the monomer of Formula IV comprises from about 0% to about 40% by weight of the composition. Embodiment 32 provides the composition of embodiment 19, wherein the composition is light curable within about 0 to 20 seconds. Embodiment 33 provides the composition of embodiment 19, having a viscosity of about 250 to about 5000 cPs at room temperature. Example 34 provides a kit comprising the composition of example 1 or example 19 and instructional materials for forming a polymer network using the composition of the kit. Embodiment 35 relates to a monomer comprising Formula II, Formula III, Formula III-A, or Formula IV: TIFF0007776427000047.tif127147In formula, R 1 teeth TIFF0007776427000048.tif14128; L is selected from the group consisting of a bond, C1-C6 alkyl, C2-C6 alkenyl, and C2-C6 alkynyl; R 2 is selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl, wherein the substituents are selected from the group consisting of optionally substituted aryl and optionally substituted heteroaryl; Each R3 are independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, and optionally C2-C6 alkynyl; R 4 teeth TIFF0007776427000049.tif14128; each y is independently selected from the group consisting of optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally C2-C6 alkynyl, optionally C1-C6 alkoxy, optionally C1-C6 aminoalkyl, optionally C1-C6 haloalkoxy, and optionally C1-C6 haloalkyl; n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; m is 0, 2, 4, 6, or 8 to provide.

Claims

1. a crosslinker comprising at least one epoxy curing group; At least one compound comprising at least one vinyl ester functional group and at least one epoxy functional group, the compound having the structure of Formula III-A: (In the formula, each R 3 is independently selected from the group consisting of optionally substituted C 1 -C 6 alkylene, optionally substituted C 2 -C 6 alkenylene, and optionally C 2 -C 6 alkynylene; each Y is independently selected from the group consisting of optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally C 2 -C 6 alkynyl, optionally C 1 -C 6 alkoxy, optionally C 1 -C 6 aminoalkyl, optionally C 1 -C 6 haloalkoxy, and optionally C 1 -C 6 haloalkyl; and n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) and at least one compound having an interpenetrating polymer network (IPN) comprising the reaction product of a mixture comprising: the at least one vinyl ester functional group is polymerized by photoinduced free radical polymerization; the at least one epoxy functional group and the crosslinker are polymerized by step-growth thermal polymerization; Interpenetrating polymer networks (IPNs).

2. The IPN of claim 1, wherein the mixture further comprises at least one compound having a structure of Formula I or Formula IA: During the ceremony, A is H, C 1～3 Alkyl, CN, F, Cl, and perfluoroC 1～3 selected from the group consisting of alkyl; X is O or N-R''; Each R is independently H, C 1～3 Alkyl, F, and Perfluoro C 1～3 selected from the group consisting of alkyl; Each R' is independently H, C 1～3 Alkyl, F, and Perfluoro C 1～3 selected from the group consisting of alkyl; Each R'' is independently H or C 1～3 is alkyl; and p is an integer between 0 and 100,000.

3. R is CH 3 3. The IPN of claim 2, wherein:

4. R' is CH 3 4. The IPN of claim 2 or 3, wherein:

5. The IPN of claim 2, wherein the compound of formula I has the structure: 。

6. 6. The IPN of any one of claims 1 to 5, wherein the vinyl ester functional groups are photopolymerized using vat photopolymerization (VPP).

7. The IPN of any one of claims 1 to 6, wherein the crosslinking agent is an epoxy curing agent.

8. 8. The IPN of any one of claims 1 to 7, wherein the epoxy-crosslinker polymerization is accelerated using a thermal post-treatment.

9. The IPN of any one of claims 1 to 8, further comprising: 。

10. 1. A method for preparing an interpenetrating polymer network (IPN), comprising: a crosslinker comprising at least one amine functional group; optionally at least one polymerization initiator; At least one monomer having at least one vinyl ester functional group and at least one epoxy functional group, having the structure of Formula III-A: (In the formula, each R 3 is independently selected from the group consisting of optionally substituted C 1 -C 6 alkylene, optionally substituted C 2 -C 6 alkenylene, and optionally C 2 -C 6 alkynylene; each Y is independently selected from the group consisting of optionally substituted C 1 -C 6 alkyl, optionally substituted C 2 -C 6 alkenyl, optionally C 2 -C 6 alkynyl, optionally C 1 -C 6 alkoxy, optionally C 1 -C 6 aminoalkyl, optionally C 1 -C 6 haloalkoxy, and optionally C 1 -C 6 haloalkyl; and n is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) and at least one monomer having applying VPP to the mixture under conditions to photopolymerize the vinyl ester functional groups in the at least one monomer; and exposing the resulting mixture to thermal conditions under which epoxy-amine polymerization occurs. A method comprising:

11. The method of claim 10, wherein the mixture further comprises a monomer having a structure of formula IA: During the ceremony, A is H, C 1～3 Alkyl, CN, F, Cl, and perfluoroC 1～3 selected from the group consisting of alkyl; X is O or N-R''; R is H, C 1～3 Alkyl, F, and Perfluoro C 1～3 selected from the group consisting of alkyl; R' is H, C 1～3 Alkyl, F, and Perfluoro C 1～3 selected from the group consisting of alkyl; R'' is H or C 1～3 is alkyl; p is an integer between 0 and 100,000.

12. The method of claim 10, wherein the mixture further comprises a compound having a structure of Formula I: During the ceremony, A is H, C 1～3 Alkyl, CN, F, Cl, and perfluoroC 1～3 selected from the group consisting of alkyl; X is O or N-R''; Each R is independently H, C 1～3 Alkyl, F, and Perfluoro C 1～3 selected from the group consisting of alkyl; Each R' is independently H, C 1～3 Alkyl, F, and Perfluoro C 1～3 selected from the group consisting of alkyl; Each R'' is independently H or C 1～3 is alkyl; p is an integer between 0 and 100,000.

13. 13. The method of any one of claims 10 to 12, wherein the applying step is carried out in the absence of a solvent.

14. 14. The method of any one of claims 10 to 13, wherein the exposing step is performed in situ.

15. 15. The method of any one of claims 10 to 14, wherein the cross-linking agent is an epoxy curing agent.

16. The method of claim 10, wherein the polymerization initiator is at least one selected from the group consisting of a photoinitiator, a thermal initiator, and a redox initiator.

17. The method of claim 16, wherein the photoinitiator is reactive when exposed to light in the infrared spectrum, the visible spectrum, or the ultraviolet spectrum.

18. The photoinitiator is selected from the group consisting of acetophenone, benzophenone, 2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-methyl-(4-methylthienyl)-2-morpholinyl-1-propan-1-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, 17. The method of claim 16, selected from the group consisting of:

19. The thermal initiator is 4,4'-diaminodicyclohexylmethane, tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy) 17. The method of claim 16, wherein the peroxide is selected from the group consisting of tert-butyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.

20. The method of claim 16, wherein the redox initiator is selected from the group consisting of sodium iodide / hydrogen peroxide, potassium iodide / hydrogen peroxide, benzoyl peroxide / dimethylaniline, benzoyl peroxide / N,N-dimethyl p-toluidine, benzoyl peroxide / 4-N,N-dimethylaminophenethyl alcohol, benzoyl peroxide / ethyl 4-dimethylaminobenzoate, glucose oxidase / oxygen / iron(II) sulfate, and copper(II) sulfate / sodium ascorbate.

21. A composite material comprising the IPN of any one of claims 1 to 9.

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