Rapid gelation of thermoset resins for three-dimensional printing using frontal polymerization

Abstract

Resin compositions including a functionalized alkene, a catalyst, and one or more inhibitors or an antioxidant, the compositions having a pot life of at least 30 days, are provided herein. Polymerization mixtures including the composition and a second catalyst are further provided. Methods of preparing the resin compositions are further provided.

Description

RAPID GELATION OF THERMOSET RESINS FOR THREE-DIMENSIONAL PRINTING USING FRONTAL POLYMERIZATIONSTATEMENT REGARDED FEDERALLY FUNDED RESEARCH

[0001] This invention was made with government support under award DE-SC0023457 awarded by the Department of Energy. The government has certain rights in the invention.TECHNICAL FIELD

[0002] The present disclosure relates to processes of preparing oligomers and polymers from compositions.BACKGROUND

[0003] Frontal polymerization demonstrates great utility as a method of generating high performance thermoset materials and offers a means of three-dimensional printing complex polymer architectures when coupled with direct ink writing. Conventional methods of three- dimensional printing rely on either incubation of the resin for a period of from 2 to 6 hours to attain the viscosity required for printing, or via the addition of rheological modifiers to increase the viscosity of the resin. Rheological modifiers may deteriorate mechanical performance or interact with polymerization co-reagents.

[0004] There is a need for compositions that can quickly form gelled resins. Further there is a need for gelled resins that remain stable for long periods of time after incubation, and available for three-dimensional printing, while retaining thermochemical performance.SUMMARY

[0005] In an example, the present disclosure provides a resin composition, including: a functionalized cycloalkene; a catalyst; a first inhibitor; and a second inhibitor different from the first inhibitor. The pot life of the composition is at least 30 days. The functionalized cycloalkene may be dicyclopentadiene, 1,5-cyclooctadiene, norbornene, 5-ethylidene-2- norbornene, or mixtures thereof. The catalyst may include Ru, Ir, Os, Rh, Mo, or W. The catalyst may be third-generation Grubbs’ catalyst. The first inhibitor may be pyridine, 3- bromopyridine, or 4-dimethylaminopyridine. An amount of the first inhibitor may be in about a 10: 1 molar ratio relative to an amount of the catalyst. The second inhibitor may be a trialkyl phosphite, triphenylphosphine, an aminophosphine, an aryl or alkyl phosphoramidite, or a combination thereof. The trialkyl phosphite may be trimethyl phosphite, triethyl phosphite,tributyl phosphite, or a combination thereof. A molar ratio of an amount of the second inhibitor relative to an amount of the catalyst may be at least 1:1. The molar ratio may be 100:1. The pot life may be at least 120 days. A method of preparing the composition may include: adding the catalyst to the functionalized cycloalkene and the first inhibitor to provide a mixture; agitating the mixture to provide a gelled resin; and treating the gelled resin with the second inhibitor to provide the composition, wherein the treating is after a viscosity of the gelled resin increases to a desired viscosity. A polymerization mixture may include the resin composition and a second catalyst. The second catalyst may be G2.

[0006] In another example, the present disclosure provides a resin composition, including: a functionalized cycloalkene; a catalyst; and an antioxidant. The pot life of the composition is at least 30 days. The functionalized cycloalkene may be selected from the group consisting of dicyclopentadiene, 1,5- cyclooctadiene, norbomene, 5-ethylidene-2-norbornene, and mixtures thereof. The catalyst may be G2. An amount of the catalyst is up to a 10"6: 1 molar ratio relative to an amount of the functionalized cycloalkene. The antioxidant may be a phenolic antioxidant derivative. The antioxidant may be butylated hydroxytoluene (BHT). The antioxidant may be in an amount of up to about 2 mol % relative to an amount of the functionalized cycloalkene. The pot life of the composition may be at least 120 days. A method of preparing the composition may include: cooling the functionalized cycloalkene to about 0 °C; adding the catalyst and the antioxidant to the functionalized cycloalkene to provide a mixture; heating the mixture to initiate the catalyst; and removing the heat from the mixture to provide the composition. The heating may be to a temperature of about 140 °C. A polymerization mixture may include the resin composition and a second catalyst. The second catalyst may be G2.

[0007] Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In order that the present disclosure may be well understood, there will now be described various forms thereof, given by way of example, reference being made to the accompanying drawings. The components in the figures are not necessarily to scale.

[0009] FIG. 1 illustrates a NMR spectrum of synthesized GC3-H catalyst;

[0010] FIG. 2 illustrates a plot of viscosity of an example of a gelled resin composition prepared from 95:5 dicyclopentadiene (“DCPD”):5-ethylidene 2-norbornene (“ENB”) mass ratio monomer mixture, with and without tributyl phosphite (“TBP”) added, over ten minutes;

[0011] FIG. 3 illustrates a plot of viscosity of another example of a gelled resin composition prepared from 75:25 DCPD:ENB mass ratio monomer mixture, with and without TBP added, over ten minutes;

[0012] FIG. 4 illustrates a plot of viscosity of yet another example of a gelled resin composition prepared from 50:50 DCPD:ENB mass ratio monomer mixture, with and without TBP added, over ten minutes;

[0013] FIG. 5 illustrates a plot of viscosity of yet another example of a gelled resin composition prepared from 25:75 DCPD:ENB mass ratio monomer mixture, with and without TBP added, over ten minutes;

[0014] FIG. 6 illustrates a plot of time-invariant viscosity of yet another example of a gelled resin composition prepared from 95:5 DCPD:ENB mass ratio monomer mixture;

[0015] FIG. 7 illustrates a plot of time-invariant viscosity of yet another example of a gelled resin composition prepared from 75:25 DCPD:ENB mass ratio monomer mixture;

[0016] FIG. 8 illustrates a plot of time-invariant viscosity of yet another example of a gelled resin composition prepared from 50:50 DCPD:ENB mass ratio monomer mixture;

[0017] FIG. 9 illustrates a plot of time-invariant viscosity of yet another example of a gelled resin composition prepared from 25:75 DCPD:ENB mass ratio monomer mixture;

[0018] FIG. 10 illustrates enthalpy of reaction over time of examples of resins respectively prepared from mixtures of 95:5, 75:25, 50:50, and 25:75 mass ratios of DCPD:ENB monomers;

[0019] FIG. 11 illustrates the results of a creep test to analyze the rheological evolution of reactive ssDCPD as a function of time; and

[0020] FIG. 12 illustrates the storage and loss moduli of an example of a gelled resin composition.

[0021] The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.DETAILED DESCRIPTION

[0022] The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.

[0023] The uses of the terms “a” and “an” and “the” and similar referents in the context of describing the present disclosure (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “plurality of’ is defined by the Applicant in the broadest sense, superseding any other implied definitions or limitations hereinbefore or hereinafter unless expressly asserted by Applicant to the contrary, to mean a quantity of more than one. All methods described herein may be performed in any suitable order unless otherwise indicated herein by context.

[0024] As will be understood by one skilled in the art, for any and all purposes, all ranges recited herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof, as well as the individual values making up the range, particularly integer values. It is therefore understood that each unit between two particular units is also disclosed. For example, if “10 to 15” is disclosed, then 11, 12, 13, and 14 are also disclosed, individually, and as part of a range. A recited range (for example, weight percentages or carbon groups) includes each specific value, integer, decimal, or identity within the range. Any listed range may be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, or tenths. As will also be understood by one skilled in the art, all language such as “up to,” “at least,” “greater than,” “less than,” “more than,” “ or more,” and the like, include the number recited and such terms refer to ranges that may be subsequently broken down into sub-ranges. In the same manner, all ratios recited herein also include all sub-ratios falling within the broader ratio. Accordingly, specific values recited for radicals, substituents, and ranges are for illustration only; the specific values do not exclude other defined values or other values within defined ranges for radicals and substituents. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0025] One skilled in the art will also readily recognize that where members are grouped together in a common manner, such as in a Markush group, the invention encompasses not only the entire group listed as a whole, but each member of the group individually and all possible subgroups of the main group. Additionally, for all purposes, the invention encompasses not only the main group, but also the main group absent one or more of the group members. The invention therefore envisages the explicit exclusion of any one or more of members of a recited group. Accordingly, provisos may apply to any of the disclosed categories or exampleswhereby any one or more of the recited elements, species, or examples may be excluded from such categories or examples, for example, fo ruse in an explicit negative limitation.

[0026] As used herein, the terms “comprise(s),” “include(s),” “having,” “has,” “may,” “contain(s),” and variants thereof, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The present description also contemplates other examples “comprising,” “consisting of,” and “consisting essentially of,” the examples or elements presented herein, whether explicitly set forth or not.

[0027] In describing elements of the present disclosure, the terms “1st,” “2nd,” “first,” “second,” “A,” “B,” “(a),” “(b),” and the like may be used herein. These terms are only used to distinguish one element from another element, but do not limit the corresponding elements irrespective of the nature or order of the corresponding elements.

[0028] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meanings as those generally understood by those skilled in the art to which the present disclosure pertains. Such terms as those defined in a generally used dictionary are to be interpreted as having meanings equal to the contextual meanings in the relevant field of art.

[0029] As used herein, the term “about,” when used in the context of a numerical value or range set forth means a variation of ±15%, or less, of the numerical value. For example, a value differing by ±15%, ±14%, ±10%, or ±5%, among others, would satisfy the definition of “about,” unless more narrowly defined in particular instances.

[0030] The term “alkyl,” by itself or as part of another substituent, refers, unless otherwise stated, to a straight, branched, or cyclic chain aliphatic hydrocarbon (“cycloalkyl”) monovalent radical having the number of carbon atoms designated (in other words, “C1-C20” means one to twenty carbons, and includes C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, and C19). Examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, s ec-butyl, tert-butyl, cyclobutyl, methylcyclopropyl, cyclopropylmethyl, pentyl, neopentyl, hexyl, and cyclohexyl.

[0031] The term “alkoxy,” by itself or as part of another substituent, refers, unless otherwise stated, an alkyl group having the designated number of carbon atoms, as defined above, connected to the rest of a molecule via an oxygen atom, such as, for example, methoxy, ethoxy, 1 -propoxy, and 2-propoxy (“isopropoxy”).

[0032] The term “halogen” refers to an atom of fluorine, chlorine, bromine, or iodine. The term “halide” refers to an anion of a halogen, and includes fluoride, chloride, bromide, and iodide.

[0033] Each of the terms “alkene” and “olefin,” by itself or as part of another substituent, refers, unless otherwise stated, to a stable mono-unsaturated or di-unsaturated or polyunsaturated straight chain, branched chain, or cyclic hydrocarbon (“cycloalkene”), “unsaturated” meaning a carbon-carbon double bond (-CH=CH-). “Monosubstituted” alkenes include only one bond between an alkene double-bonded carbon, and an adjacent carbon, such as, for example, CH2=CH-C. “Disubstituted” alkenes include two bonds between an alkene double-bonded carbon and adjacent carbons, and the adjacent carbons may be bonded to one (CH2=CC2) or both (C-CH=CH-C) of the alkene double-bonded carbons. “Trisubstituted” alkenes include three bonds between alkene double-bonded carbons and adjacent carbons (CH=CC2). “Tetrasubstituted” alkenes include four bonds between alkene double-bonded carbons and adjacent carbons (CC2=CC2).

[0034] The term “alkenyl,” by itself or as part of another substituent, refers to a stable monounsaturated or di-unsaturated or poly-unsaturated straight chain, branched chain, or cyclic hydrocarbon monovalent radical having the number of carbon atoms designated. Examples may include vinyl, propenyl, allyl, crotyl, isopentenyl, butadienyl, 1,3-pentadienyl, 1,4- pentadienyl, cyclopentenyl, cyclopentadienyl.

[0035] The term “aromatic” generally refers to a carbocycle or heterocycle having one or more polyunsaturated rings having aromatic character (in other words, having (4n+2) delocalized π (pi) electrons where n is an integer).

[0036] The term “aryl,” by itself or in combination with another substituent, refers, unless otherwise stated, to a carbocyclic aromatic system substituent containing one or more rings (typically one, two, or three rings), wherein such rings may be attached together in a pendant manner, such as biphenyl, or may be fused, such as naphthalene. Examples may include phenyl, benzyl, anthracyl, and naphthyl. Preferred are phenyl, benzyl, and naphthyl; most preferred are phenyl and benzyl.

[0037] The terms “heterocyclic,” “heterocycle,” and “heterocyclyl,” by themselves or in combination with another substituent, refer, unless otherwise stated, to a stable mono- or multi- cyclic ring system that consists of carbon atoms and at least one heteroatom independently selected from N, O, Si, and S, wherein each nitrogen and sulfur heteroatom may be optionally oxidized, each nitrogen heteroatom may be optionally quatemized or substituted, and each silicon heteroatom may be optionally substituted. The heterocyclic system may be attached, unless otherwise stated, at any heteroatom or carbon atom that affords a stable structure. Non- limiting examples of monocyclic heterocyclic groups include: aziridine, oxirane, thiirane,azetidine, oxetane, thietane, pyrrolidine, pyrroline, imidazoline, pyrazolidine, dioxolane, sulfolane, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran, thiophane, piperidine, 1, 2,3,6- tetrahydropyridine, piperazine, N -methylpiperazine, morpholine, thiomorpholine, pyran, 2,3- dihydropyran, tetrahydropyran, 1,4-dioxane, 1,3-dioxane, homopiperazine, homopiperidine, 1,3-dioxepane, 4,7-dihydro-l,3-dioxepin, and hexamethyleneoxidine.

[0038] The terms “heteroaryl” and “heteroaromatic,” by themselves or in combination with another substituent, refer, unless otherwise stated, to a heterocyclic having aromatic character. Non-limiting examples of heteroaryl groups include: pyridyl; pyrazinyl; pyrimidinyl, particularly 2- and 4-pyrimidinyl; pyridazinyl; thienyl; furyl; pyrrolyl, particularly 2-pyrrolyl; imidazolyl; thiazolyl; oxazolyl; pyrazolyl, particularly 3- and 5-pyrazolyl; isothiazolyl; 1,2,3- triazolyl; 1,2,4-triazolyl; 1,3,4-triazolyl; tetrazolyl; 1,2,3-thiadiazolyl; 1,2,3-oxadiazolyl; 1,3,4-thiadiazolyl; and 1,3,4-oxadiazolyl.

[0039] The term “aminophosphine” refers to a compound having a molecular formula of R13-nP(NR12)n, where each R1is independently hydrogen, aryl, or alkyl.

[0040] The term “phosphoramidite” refers to a compound having a molecular formula of (R2O)2PNR22, where each R2is independently hydrogen, aryl, or alkyl.

[0041] The term “functionalized,” in the context of alkenes, refers, unless otherwise stated, to a an alkene being ring-strained or having a nonhydrocarbon substituent on one or more of the carbons of the moiety of the alkene. Examples of functionalized alkenes may include:cyclooctatetraene; or any combination thereof.

[0042] Examples of functionalized alkenes may also include heterocyclic alkenes. Examples of heterocyclic alkenes may include:(Z)-2,2-diisopropyl-5,8-dihydro-4H -1,3,2-dioxasilocine;2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine;(Z)-2-isopropyl-5,8-dihydro-4H -1,3-dioxocine;2-isopropyl-4,7-dihydro-l,3-dioxepine; or any combination thereof.

[0043] Examples of functionalized alkenes may also include polymer- functionalized alkenes.Examples of polymer-functionalized alkenes may include:norbornenylethyl terminated polydimethylsiloxane;trisilanol phenyl polyhedral oligomeric silsesquioxane ("POSS");trisilanol vinyl polyhedral oligomeric silsesquioxane ("POSS"); or any combination thereof.

[0044] Examples of functionalized alkenes may also include compounds of formula (I), or combinations thereof:wherein R3and R4are independently selected from hydrogen, halogen, substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted aryl, (C1-C10)alkylsulfonate, tri(C1- C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy, or R3and R4, together with the carbon atoms to which R3and R4are bonded, form a substituted or unsubstituted cyclopentyl or cyclohexyl ring; wherein the substituted (C1-C10)alkyl, substituted aryl, substituted cyclopentyl ring, or substituted cyclohexyl ring is substituted with one or more substituents independently selected from halogen, (C1-C10)alkyl, (C1-C10)alkylsulfonate, tri(C1-C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; provided that the compound of formula (I) includes only one double bond. Each aryl or aryloxy group may independently be a heteroaryl or heteroaryloxy group.

[0045] Examples of compounds of formula (I) may include:2,3,3a,4,4a,5,8,8a,9,9a-decahydro-l / / -4,9:5,8-dimethanocyclopenta[6]naphthalene ("H2-TCPD").H2-TCPD may be present as an isomer selected from endo-endo-endo-Hi-TCPD, endo-endo- exo-H2-TCPD, endo-exo-endo-H2-TCPD, endo-exo-exo-H2-TCPD, exo-endo-endo-H2-TCPD, exo-endo-exo-H2-TCPD, exo-exo-endo-H2-TCPD, exo-exo-exo-H2-TCPD, or any mixtures thereof in any relative proportions:

[0046] Examples of compounds of formula (I) may further include:1 ,4, 4a, 5, 6, 7, 8, 8a, 9, 9a, 10,10a-dodecahydro- 1 ,4 :9, 10-dimethanoanthracene; which may be present as an isomer selected from endo-endo-endo, endo-endo-exo, endo-exo- endo, endo-exo-exo, exo-endo-endo. exo-endo-exo, exo-exo-endo, and exo- exo- exo (with structures analogous to the structures of the corresponding isomers of H2-TCPD disclosed above), or any mixtures thereof in any relative proportions.

[0047] Examples of compounds of formula (I) may further include:1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene ("NB-CPD"), which may be present as one isomer selected from exo-exo-NB-CPD, exo-exo-NB-CPD, endo- exo-NB-CPD, or endo -endo -NB-CPD, or any mixture of exo-exo-NB-CPD, exo-endo -NB- CPD, endo -exo-NB-CPD, and / or endo-endo-NB-CPD in any proportion;

[0048] Examples of compounds of formula (I) may further include:2-methyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2-ethyl- 1 ,2 , 3 ,4 ,4a, 5 , 8 , 8 a-octahydro- 1 ,4 : 5 , 8 -dimethanonaphthalene ;2,3 -dimethyl- 1 ,2,3,4,4a,5,8,8a-octahydro- 1 ,4:5,8-dimethanonaphthalene;R3a= CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, cyclopentyl, cyclohexyl, Ph;R3b= CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, cyclopentyl, cyclohexyl, Ph;R4a= halogen, OSO2R3a, R3a, Si(R3a)2R3b, OR3a;

[0049] The term “ring- strained,” in the context of cycloalkenes, refers, unless otherwise stated, to the relative higher energy of a cycloalkene as a result of the number of carbons making up one or more of the cyclic moieties of the cycloalkene causing compression or “strain” to thenatural angles between acyclic carbon-carbon bonds at each carbon atom of the one or more cyclic moieties, wherein the compression or strain would be alleviated (and the energy would be decreased) were the one or more cyclic moieties to undergo a reaction that would “open” the ring at the alkene bond.

[0050] The term “frontal polymerization,” refers, unless otherwise stated, to a process in which the polymerization reaction propagates through a vessel or a substance. There are three types of frontal polymerizations: thermal frontal polymerization (“TFP”) that uses an external thermal energy source to initiate the front; photofrontal polymerization (“PFP”), in which the localized reaction is driven by an external UV source; and isothermal frontal polymerization (“IFP”), which relies on the Norrish-Trommsdorff, or gel effect, that occurs when monomer and initiator diffuse into a polymer seed (small piece of polymer). Thermal frontal polymerization begins when a heat source contacts a solution of monomer or a gel and a thermal initiator or catalyst. Alternatively, a UV source may be applied if a photoinitiator is also present. The area of contact (or UV exposure) has a faster polymerization rate, and the energy from the exothermic polymerization diffuses into the adjacent region, raising the temperature and increasing the reaction rate in that location. The result is a localized reaction zone that propagates down the reaction vessel as a thermal wave.

[0051] The term “ring-opening metathesis polymerization” (“ROMP”), refers, unless otherwise stated, to a type of olefin metathesis chain-growth polymerization that may produce industrially important products. The driving force of the reaction is relief of ring strain in cyclic olefins, which may be functionalized cycloalkenes. Thus, “frontal ring-opening metathesis polymerization” (“FROMP”) entails the conversion of a monomer into a polymer via a localized exothermic reaction zone that propagates through the coupling of thermal diffusion and Arrhenius reaction kinetics. The pot life, gel time, and reaction kinetics may be controlled through various modifications of the polymerization chemistry.

[0052] The term “pot life” refers to the amount of time between the mixing of monomer and initiator or catalyst and the point at which extrusion of the reaction product is no longer possible due to viscosity being too high, and the reaction product has a viscosity approaching the viscosity of a viscoelastic solid. “Pot life” may also refer to the amount of time it takes for an initial viscosity of a composition to multiply by about 100. Timing starts from the mixing of the composition, and is measured at room temperature. Examples of pot life may include amounts of time of at least 1 hour, at least 2 hours, at least 4 hours, at least 8 hours, at least 12 hours, at least 16 hours, at least 20 hours, at least 24 hours, at least 48 hours, at least 72 hours,at least 96 hours, at least 120 hours, at least 6 days, at least 7 days, at least 8 days, at least 9 days, at least 10 days, at least 20 days, at least 30 days, at least 2 months (in other words, at least about 60 days), at least 3 months (in other words, at least about 90 days), at least 4 months (in other words, at least about 120 days), at least 5 months (in other words, at least about 150 days), at least 6 months (in other words, at least about 180 days), at least 9 months, at least 1 year, at least 1.5 years, at least 2 years, at least 2.5 years, at least 3 years, at least 3.5 years, at least 4 years, at least 4.5 years, at least about 5 years, or longer; including at least about amounts of time less than any of the above-mentioned amounts of time.

[0053] The term “inhibitor” refers to a chemical species that interacts with a catalyst so as to decrease the activity of the catalyst, which may have an effect on a chemical reaction catalyzed by the catalyst, including, for example, decreasing the rate of the chemical reaction. Examples of inhibitors may include:bis(2-cyanoethyl) diisopropylphosphoramidite;tricyclohexylphosphane;andtriphenylphosphine; or any combination thereof.Examples of trialkyl phosphite may include trimethyl phosphite, triethyl phosphite, triisopropryl phosphite, tributyl phosphite, tris(l,l,l,3,3,3-hexafluoropropan-2-yl) phosphite, tris(2,2,2-trifluoroethyl) phosphite, or any combination thereof. In certain examples, a first inhibitor and a second inhibitor may be used. The second inhibitor may be the same as, or different from, the first inhibitor.

[0054] The term “solvent” refers to a substance that dissolves a compound homogeneously, resulting in a solution.

[0055] Examples of catalysts may include catalysts including one or more Ru, Ir, Os, Rh, Mo, and / or W nuclei. In certain examples, the catalyst may be a Grubbs’ third- generation catalyst (“GC3-H”):In other examples, the catalyst may be Grubbs’ second-generation catalyst (“G2” or “GC2”).

[0056] An amount of an inhibitor may be included in a composition in an amount greater than or less than an amount of the catalyst. A molar ratio of an amount of an inhibitor to an amount of a catalyst, or an amount of a catalyst to an amount of an inhibitor, may be about 1:1, or greater than about 1:1, or about 2:1, or about 3:1, or about 4:1, or about 5:1, or about 6:1, or about 7:1, or about 8:1, or about 9:1, or about 10:1, or about 15:1, or about 20:1, or about 25:1, or about 30: 1 , or about 35: 1 , or about 40: 1 , or about 45: 1 , or about 50: 1 , or about 55: 1 , or about60:1, or about 65:1, or about 70:1, or about 75:1, or about 80:1, or about 85:1, or about 90:1, or about 95:1, or about 100:1; or a molar ratio greater than or less than any of the aforementioned ratios.

[0057] Examples of antioxidants may include phenolic antioxidants and derivatives thereof, and non-phenolic antioxidants and derivatives thereof. Examples of antioxidants may include:2octadecyl 3-(3,5-di-tert-butyl4-hydroxyphenyl)propanoate (“Irganox-1076”);l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-l,3,5-triazinane-2,4,6-trione (“Irganox-3114”);4,4’-methylenebis(2,6-di-tert-butylphenol) (“lonox 220”).

[0058] Herein is described a resin composition that is formed by rapid gelation from functionalized cycloalkene and a catalyst. The resin composition surprisingly and unexpectedly demonstrates a pot life of at least 30 days at room temperature. As illustrated in Scheme 1 below, by adding an excess of a ligand to the catalyst, the reactivity profile of the catalyst may be significantly reduced, which limits the likelihood of spontaneous polymerization of the resin composition and thereby increases the pot life of the resin composition. Alternatively, by heating a mixture of the catalyst and the functionalized cycloalkene to activate the catalyst to the maximum activity of the catalyst, rapid gelation may occur to attain a desired rheology and / or molecular weight, after which the catalyst is thermally deactivated, which limits the likelihood of spontaneous polymerization of the resin composition and thereby increases the pot life of the resin composition. The resin composition may be stored indefinitely prior ttoo activation of frontal polymerization. An example of activation of frontal polymerization is illustrated in Scheme 2.Scheme 2

[0059] Enablement of three-dimensional printing of resin compositions that may advantageously possess an extended pot life is described herein. The resin compositions are stable at room temperature for at least 30 days prior to printing. A mixture including the resin composition and a catalyst may be extruded through a die to form an “extrudate,” for example, from a print head onto a heated surface. As the printing continues, a propagating polymerization front forms and propagates through the extrudate.

[0060] In an example, a resin composition may include a functionalized cycloalkene, a catalyst, a first inhibitor, and a second inhibitor different from the first inhibitor. In certain examples, the pot life of the composition may be at least 30 days.

[0061] In another example, a resin composition may include a functionalized cycloalkene, a catalyst, and an antioxidant. In certain examples, the pot life of the composition may be least 30 days.

[0062] In an example, a polymerization mixture may include an example of a resin composition and a second catalyst. In certain examples, the second catalyst may be G2.

[0063] In an example, a method of preparing a resin composition may include: adding a catalyst to a functionalized cycloalkene and a first inhibitor to provide a mixture; agitating the mixture to provide a gelled resin; and treating the gelled resin with a second inhibitor to provide the composition. The treating may be performed after a viscosity of the gelled resin increases to a desired viscosity. Agitating may ensure uniform mixture of catalyst throughout the resin.

[0064] In another example, a method of preparing a resin composition may include: cooling a functionalized cycloalkene to about 0° C; adding a catalyst and an antioxidant to the functionalized cycloalkene to provide a mixture; heating the mixture to initiate the catalyst;and removing the heat from the mixture to provide the composition. In certain examples, the heating may be to a temperature of about 140° C.

[0065] The compositions and processes described above may be better understood in connection with the following Examples. In addition, the following non-limiting examples are an illustration. The illustrated methods are applicable to other examples of compounds of formula (I) of the present disclosure. The procedures described as general methods describe what is believed will be typically effective to prepare the compositions indicated. However, the person skilled in the art will appreciate that it may be necessary to vary the procedures for any given examples of the present disclosure, for example, vary the order or steps and / or the chemical reagents used.EXAMPLES

[0066] L Materials.

[0067] ULTRENE™ 99 Dicyclopentadiene (“DCPD,” >99%) was received from Cymetech. 5-Ethylidene-norbomene (“ENB,” 99%, contains 100-200 ppm BHT) and Grubbs’ 2ndgeneration catalyst (M204, G2) were purchased from Millipore Sigma. Tributyl phosphite (>93%, “TBP” or P(OtBu)3) was purchased from TCI Chemicals. Grubbs’ 2ndgeneration catalyst (>98%, M204, G2) starting material for the synthesis of Grubbs’ 3rdgeneration catalyst was purchased from Chemscene. Anhydrous bottles of toluene, hexanes, and pyridine were purchased from Millipore Sigma. All materials were used as received unless otherwise stated.

[0068] II. Experimental Procedures and Analyses,

[0069] A. Synthesis of Grubbs’ 3rdGeneration Catalyst.

[0070] In a 20-milliliter vial, 2009.2 mg of Grubbs’ Second Generation Catalyst (“G2”) was stirred with 19 milliliters of pyridine for 2 - 3 minutes, until a color change from red to green was observed. The entire solution was transferred to a 500-milliliter flask containing 100 milliliters of hexanes. The flask was transferred to a freezer at -20 °C to crystallize for 2 - 3 hours. The green solid precipitate at the bottom of the flask was filtered out and washed with200 mL of hexanes. The mother liquor was again transferred to the freezer, then filtered, and the filtrate washed. The filtered and washed precipitate was dried overnight under vacuum and transferred to a septa vial kept under nitrogen for storage. The synthesized GC3-H, a fine green powder, was obtained at a yield of 83% (1667.6 mg) and stored in a refrigerator. A1H NMR (500 MHz, CDCh) of the synthesized GC3-H is illustrated in FIG. 1.

[0071] B. Rapid Viscosity Modification Procedure.

[0072] A small amount of synthesized GC3-H (1 mg) was weighed out and the required amount of pyridine (1.1 μL for a 10:1 molar ratio with GC3-H) was added. The mixture was diluted with 1 mL of toluene in a glass vial. The volume of the mixture corresponding to the required concentration of GC3-H in DCPD:ENB monomer was pipetted out into the liquid monomer while under agitation in a vortex mixer.

[0073] The viscosity began to build rapidly and could be measured on a shear rheometer or estimated via “proto-rheology” techniques (180° vial tip test). Once the desired viscosity was obtained, 2.1 μL of TBP diluted in 100 μL of toluene was pipetted into the reaction mixture. The TBP halted the rapid viscosity increase and produced a time-invariant resin of DCPD:ENB with a negligible amount (1 ppm) of G2-like catalyst species that achieves catalyst death over time through an oxidation pathway.

[0074] C. Characterization of Viscosity Evolution

[0075] The effect of the addition of the tributyl phosphite ligand on “gating” the initiation of ROMP was measured by observing the viscosity evolution over 10 minutes, before and after the addition of the tributyl phosphite. A flow peak hold at 1 s-1for 600 seconds was conducted on a TA Instruments Discovery Series Hybrid Rheometer. FIGs. 2 5 illustrate the effect of addition of tributyl phosphite to viscosity of resins prepared from mixtures of 95:5, 75:25, 50:50, and 25:75 mass ratios of DCPD:ENB, respectively. The viscosity of the resins is controlled by the amount of time between catalyst addition and inhibitor addition.

[0076] To measure the time-invariant properties of the resin, the viscosity of resins prepared from respective mixtures of 95:5, 75:25, 50:50, and 25:75 mass ratios of DCPD:ENB was monitored over 5 months. A creep test was conducted at 25° C to measure viscosity. A 1 Pa loading was applied for 180 seconds and a 0 Pa unloading was applied for 90 seconds. An average of instantaneous viscosity values was calculated from the linear slope portion of the compliance vs. time graph, and the Weissenberg number calculated over the same interval, to verify that Wi«l (zero-shear viscosity). FIGs. 6 - 9 illustrate the time-invariant viscosity of the resins respectively prepared from mixtures of 95:5, 75:25, 50:50, and 25:75 mass ratios ofDCPD:ENB. It is apparent that inhibitor addition determines the pot life of the resin. A shear rate sweep was conducted from 1 s-1to 100 s-1, and a zero-shear viscosity estimated by fitting to the Carreau- Yasuda model. FIG. 10 illustrates enthalpy of reaction over time of each of the resins respectively prepared from mixtures of 95:5, 75:25, 50:50, and 25:75 mass ratios of DCPD:ENB.

[0077] D. Rapid Viscosity Through Thermal Deactivation

[0078] The rheological evolution of reactive ssDCPD was probed at 140° C. The apparent viscosity was measured as a surrogate metric to evaluate polymer network evolution using a series of creep test. The sample was loaded on the rheometer at room temperature, and a shear stress of 1 Pa was applied to measure the apparent viscosity as a function of time. The temperature was ramped to 140° C in approximately 180 seconds. The test was terminated upon reaching a final viscosity plateau (within 250 seconds). FIG. 11 illustrates the results of the creep experiment. The initial viscosity corresponds to the viscosity of the monomer (DCPD). The reaction stopped once all reactive monomers were consumed, which is reflected by the terminal plateaus in the graph, indicating that the ssDCPD process is complete and no further reaction is expected. Therefore, without other factors such as aging or oxidation, the ssDCPD is shelf stable.

[0079] To prepare self- suspended DCPD (“ssDCPD”) gel, the DCPD monomer was first preconditioned to suppress unwanted catalytic activity before the reaction, which may be done by bringing the temperature of DCPD down to about 0° C. The desired amount of a metathesis catalyst (for example, GC2) was then added to the preconditioned DCPD monomer. A solvent (for example, 1 -methylnaphthalene) may be used to dissolve the metathesis catalyst for better dispersion and for higher precision in catalyst loading due to providing for significantly low concentration of catalyst. While stirred, the catalyst-loaded DCPD solution was then brought to a higher temperature close to the DCP decomposition (about 140° C) to start the reaction. The high temperature favors the decomposition pathway illustrated below in Scheme 3 to irreversibly decompose the catalyst, thus halting the reaction. For example, for a 150 mL batch size of DCPD monomer with 0.6 ppm GC2 loading, the reaction time is about 5 minutes. Once the reaction is complete, the gel is allowed to cool down at room temperature before storing. High temperature promotes beta-hydride-mediated decomposition of the metathesis catalyst. Alternatively, oxygen may also decompose the catalyst, as illustrated below in Scheme 4.Scheme 4

[0080] For a 150 mL batch size of DCPD monomer with 0.6 ppm GC2 loading, the reaction time was about 5 minutes. Once the reaction was complete, the gel was allowed to cool to ambient temperature before storing.

[0081] E. Characterization of Linear Viscoelasticity of the ssDCPD

[0082] The rheological stability of ssDCPD was measured. Linear viscoelasticity (“LVE”) was picked as a surrogate probing metric to demonstrate temporal stability of the gel rheology (or evolution, if any). Specifically, downward frequency sweep from 100 to 0.1 1 / s at a smallstrain (1%) amplitude was used to ensure linear viscoelasticity by measuring the storage (G’) and loss (G”) moduli. FIG. 12 illustrates that both G’ and G” traces, which remained unchanged over 4 months, signifying the temporal stability of the ssDCPD gels. The circles in PIG. 12 represent Day 0 measurements, and the triangles represent Day 2 measurements. The filled circles and triangles represent storage (G’) modulus and the unfilled circles and triangles represent loss (G”) modulus. All measurements were performed on a stress-controlled rheometer (MCR702 - Anton Paar) using a Couette geometry with a sand-blasted cup. All measurements were performed at 25°C.

[0083] Although the present disclosure has been described with reference to examples and the accompanying drawings, the present disclosure is not limited thereto, but may be variously modified and altered by those skilled in the art to which the present disclosure pertains without departing from the spirit and scope of the present disclosure.

[0084] The subject-matter of the disclosure may also relate, among others, to the following aspects:

[0085] A first aspect relates to a resin composition, comprising: a functionalized alkene; a catalyst; a first inhibitor; and a second inhibitor different from the first inhibitor; wherein the pot life of the composition is at least 30 days.

[0086] A second aspect relates to the composition of aspect 1, wherein the functionalized alkene is a cycloalkene, a heterocyclic alkene, a polymer-functionalized alkene, or a mixture thereof.

[0087] A third aspect relates to the composition of any preceding aspect, wherein the functionalized alkene is selected from the group consisting of dicyclopentadiene, 1,5- cyclooctadiene, norbomene, 5-ethylidene-2-norbomene, cyclooctene, cyclooctatetraene, 2,3- dihydrofuran, 2-(4-methoxyphenyl)-2,3-dihydrofuran, 2-(ethoxymethyl)-2,3-dihydrofuran, 3- methyl-2,3-dihydrofuran, 2-phenyl-2,3-dihydrofuran, 1,3-dioxole, 2,5-dihydrofuran, (Z)-2,2- di i sopropyl -5 , 8-di hydro-4 / 7- 1 ,3 ,2-dioxasilocine, 2,2-diisopropyl-4,7 -dihydro- 1,3,2- dioxasilepine, (Z)-2-isopropyl-5,8-dihydro-4H -1,3-dioxocine, 2-isopropyl-4,7-dihydro-l,3- dioxepine, norbomenylethyl terminated polydimethylsiloxane, trisilanol phenyl polyhedral oligomeric silsesquioxane, trisilanol vinyl polyhedral oligomeric silsesquioxane, and mixtures thereof.

[0088] A fourth aspect relates to the composition of aspect 1 or 2, wherein the functionalized alkene is a compound of formula (I)wherein R3and R4are independently selected from hydrogen, halogen, substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted aryl, (C1-C10)alkylsulfonate, tri(C1- C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; or R3and R4, together with the carbon atoms to which R3and R4are bonded, form a substituted or unsubstituted cyclopentyl or cyclohexyl ring; wherein the substituted (C1-C10)alkyl, substituted aryl, substituted cyclopentyl ring, or substituted cyclohexyl ring is substituted with one or more substituents independently selected from halogen, (C1-C10)alkyl, (C1-C10)alkylsulfonate, tri(C1-C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; provided that the compound of formula (I) comprises only one double bond; and wherein the composition does not comprise a solution of the compound of formula (I) in a solvent.

[0089] A fifth aspect relates to the composition of aspect 4, comprising two or more compounds of formula (I).

[0090] A sixth aspect relates to the composition of aspect 4 or 5, wherein the compound of formula (I) comprises2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H -4,9:5,8-dimethanocyclopenta[b]naphthalene (H2-TCPD).

[0091] A seventh aspect relates to the composition of aspects 4 to 6, wherein the compound of formula (I) comprises a compound selected from the group consisting of:l,4,4a,5,6,7,8,8a,9,9a,10,10a-dodecahydro-l,4:9,10-dimethanoanthracene;1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (NB-CPD;2-methyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2-ethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2,3-dimethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;wherein each R3aand R3bis independently selected from CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, cyclopentyl, cyclohexyl, or phenyl; and wherein each R4ais independently selected from halogen, OSO2R3a, Si(R3a)2R3b, or OR3a.

[0092] An eighth aspect relates to the composition of any preceding aspect, wherein the catalyst comprises Ru, Ir, Os, Rh, Mo, or W.

[0093] A ninth aspect relates to the composition of any preceding aspect, wherein the catalyst is third-generation Grubbs’ Catalyst (“GC3-H”):

[0094] A tenth aspect relates to the composition of any preceding aspect, wherein the first inhibitor is pyridine, 3-bromopyridine, or 4-N,N-dimethylaminopyridine.

[0095] An eleventh aspect relates to the composition of any preceding aspect, wherein an amount of the first inhibitor is in about a 10: 1 molar ratio relative to an amount of the catalyst.

[0096] A twelfth aspect relates to the composition of any preceding aspect, wherein the second inhibitor is a trialkyl phosphite, triphenylphosphine, an aminophosphine, an aryl or alkyl phosphoramidite, or a combination thereof.

[0097] A thirteenth aspect relates to the composition of aspect 12, wherein the trialkyl phosphite is trimethyl phosphite, triethyl phosphite, tributyl phosphite, or a combination thereof.

[0098] A fourteenth aspect relates to the composition of any preceding aspect, wherein a molar ratio of an amount of the second inhibitor relative to an amount of the catalyst is at least 1:1.

[0099] A fifteenth aspect relates to the composition of aspect 14, wherein the molar ratio is 100:1.

[0100] A sixteenth aspect relates to the composition of any preceding aspect, wherein the pot life is at least 120 days.

[0101] A seventeenth aspect relates to a method of preparing the composition of any preceding aspect, comprising: adding the catalyst to the functionalized cycloalkene and the first inhibitor to provide a mixture; agitating the mixture to provide a gelled resin; and treating the gelled resin with the second inhibitor to provide the composition, wherein the treating is after a viscosity of the gelled resin increases to a desired viscosity.

[0102] An eighteenth aspect relates to a polymerization mixture comprising the resin composition of aspects 1 to 16 and a second catalyst.

[0103] A nineteenth aspect relates to the polymerization mixture of aspect 18, wherein the second catalyst is G2:

[0104] A twentieth aspect relates to a resin composition, comprising: a functionalized alkene; a catalyst; and an antioxidant; wherein the pot life of the composition is at least 30 days.

[0105] A twenty-first aspect relates to the composition of aspect 20, wherein the functionalized alkene is selected from the group consisting of dicyclopentadiene, 1,5-cyclooctadiene, norbornene, 5-ethylidene-2-norbornene, cyclooctene, cyclooctatetraene, 2,3-dihydrofuran, 2- (4-methoxyphenyl)-2,3-dihydrofuran, 2-(ethoxymethyl)-2,3-dihydrofuran, 3-methyl-2,3- dihydrofuran, 2-phenyl-2,3-dihydrofuran, 1,3-dioxole, 2,5-dihydrofuran, (Z)-2,2-diisopropyl- 5,8-dihydro-4H -1,3,2-dioxasilocine, 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine, (Z)-2- isopropyl-5,8-dihydro-4H -1,3-dioxocine, 2-isopropyl-4,7-dihydro-l,3-dioxepine, norbornenylethyl terminated polydimethylsiloxane, trisilanol phenyl polyhedral oligomeric silsesquioxane, trisilanol vinyl polyhedral oligomeric silsesquioxane, and mixtures thereof.

[0106] A twenty-second aspect relates to the composition of aspect 20 or 21, wherein the catalyst is G2:

[0107] A twenty-third aspect relates to the composition of aspects 20 to 22, wherein an amount of the catalyst is up to a 10"6:l molar ratio relative to an amount of the functionalized cycloalkene.

[0108] A twenty-fourth aspect relates to the composition of aspects 20 to 23, wherein the antioxidant is a phenolic antioxidant derivative.

[0109] A twenty-fifth aspect relates to the composition of aspects 20 to 24, wherein the antioxidant is butylated hydroxytoluene (BHT).

[0110] A twenty-sixth aspect relates to the composition of aspects 20 to 25, wherein the antioxidant is in an amount of up to about 2 mol % relative to an amount of the functionalized cycloalkene.

[0111] A twenty- seventh aspect relates to the composition of aspects 20 to 26, wherein the pot life of the composition is at least 120 days.

[0112] A twenty-eighth aspect relates to the composition of aspects 20 to 27, wherein the functionalized alkene is selected from the group consisting of dicyclopentadiene, 1,5- cyclooctadiene, norbomene, 5-ethylidene-2-norbomene, cyclooctene, cyclooctatetraene, 2,3- dihydrofuran, 2-(4-methoxyphenyl)-2,3-dihydrofuran, 2-(ethoxymethyl)-2,3-dihydrofuran, 3- methyl-2,3-dihydrofuran, 2-phenyl-2,3-dihydrofuran, 1,3-dioxole, 2,5-dihydrofuran, (Z)-2,2- diisopropyl-5 , 8-di hydro-4 / 7- 1 ,3 ,2-dioxasilocine, 2,2-diisopropyl-4,7 -dihydro- 1,3,2- dioxasilepine, (Z)-2-isopropyl-5,8-dihydro-4H -1,3-dioxocine, 2-isopropyl-4,7-dihydro-l,3- dioxepine, norbomenylethyl terminated polydimethylsiloxane, trisilanol phenyl polyhedral oligomeric silsesquioxane, trisilanol vinyl polyhedral oligomeric silsesquioxane, and mixtures thereof.

[0113] A twenty-ninth aspect relates to the composition of aspects 20 to 27, wherein the functionalized alkene is a compound of formula (I)wherein R3and R4are independently selected from hydrogen, halogen, substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted aryl, (C1-C10)alkylsulfonate, tri(C1- C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; or R3and R4, together with the carbon atoms to which R3and R4are bonded, form a substituted or unsubstituted cyclopentyl or cyclohexyl ring; wherein the substituted (C1-C10)alkyl, substituted aryl, substituted cyclopentyl ring, or substituted cyclohexyl ring is substituted with one or more substituents independently selected from halogen, (C1-C10)alkyl, (C1-C10)alkylsulfonate, tri(C1-C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; provided that the compound of formula (I) comprises only one double bond; and wherein the composition does not comprise a solution of the compound of formula (I) in a solvent.

[0114] A thirtieth aspect relates to the composition of aspect 29, comprising two or more compounds of formula (I).

[0115] A thirty-first aspect relates to the composition of aspect 29 or 30, wherein the compound of formula (I) comprises2,3,3a,4,4a,5,8,8a,9,9a-decahydro-17 / -4,9:5,8-dimethanocyclopenta[6]naphthalene (H2-TCPD).

[0116] A thirty-second aspect relates to the composition of aspects 29 to 31, wherein the compound of formula (I) comprises a compound selected from the group consisting of:1 ,4, 4a, 5, 6, 7, 8, 8a, 9, 9a, 10, 10a-dodecahydro- 1 ,4:9, 10-dimethanoanthracene;1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (NB-CPD;2-methyl- 1 ,2,3,4,4a,5,8,8a-octahydro- 1 ,4:5,8-dimethanonaphthalene;2-ethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2,3-dimethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;wherein each R3aand R3bis independently selected from CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, cyclopentyl, cyclohexyl, or phenyl; and wherein each R4ais independently selected from halogen, OSO2R3a, Si(R3a)2R3b, or OR3a.

[0117] A thirty-third aspect relates to a method of preparing the composition of aspects 20 to 32, comprising: cooling the functionalized cycloalkene to about 0 °C; adding the catalyst and the antioxidant to the functionalized cycloalkene to provide a mixture; heating the mixture to initiate the catalyst; and removing the heat from the mixture to provide the composition.

[0118] A thirty-fourth aspect relates to the method of aspect 33, wherein the heating is to a temperature of about 140 °C.

[0119] A thirty-fifth aspect relates a polymerization mixture comprising the resin composition of aspects 20 to 32 and a second catalyst.

[0120] A thirty-sixth aspect relates to the polymerization mixture of aspect 35, wherein the second catalyst is G2.

[0121] In addition to the features mentioned in each of the independent aspects enumerated above, some examples may show, alone or in combination, the optional features mentioned in the dependent aspects and / or as disclosed in the description above and shown in the figures.

Claims

CLAIMSWhat is claimed is:

1. A resin composition, comprising: a functionalized alkene; a catalyst; a first inhibitor; and a second inhibitor different from the first inhibitor; wherein the pot life of the composition is at least 30 days.

2. The composition of claim 1, wherein the functionalized alkene is a cycloalkene, a heterocyclic alkene, a polymer-functionalized alkene, or a mixture thereof.

3. The composition of claim 1 or 2, wherein the functionalized alkene is selected from the group consisting of dicyclopentadiene, 1,5-cyclooctadiene, norbornene, 5-ethylidene- 2-norbomene, cyclooctene, cyclooctatetraene, 2,3-dihydrofuran, 2-(4-methoxyphenyl)-2,3- dihydrofuran, 2-(ethoxymethyl)-2,3-dihydrofuran, 3-methyl-2,3-dihydrofuran, 2-phenyl-2,3- dihydrofuran, 1,3-dioxole, 2,5-dihydrofuran, (Z)-2,2-diisopropyl-5,8-dihydro-4H - 1,3,2- dioxasilocine, 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine, (Z)-2-isopropyl-5,8-dihydro- 4H -1,3-dioxocine, 2-isopropyl-4,7-dihydro-l,3-dioxepine, norbomenylethyl terminated polydimethylsiloxane, trisilanol phenyl polyhedral oligomeric silsesquioxane, trisilanol vinyl polyhedral oligomeric silsesquioxane, and mixtures thereof.

4. The composition of claim 1 or 2, wherein the functionalized alkene is a compound of formula (I)wherein R3and R4are independently selected from hydrogen, halogen, substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted aryl, (C1-C10)alkylsulfonate, tri(C1- C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; or R3and R4, together with the carbon atoms towhich R3and R4are bonded, form a substituted or unsubstituted cyclopentyl or cyclohexyl ring; wherein the substituted (C1-C10)alkyl, substituted aryl, substituted cyclopentyl ring, or substituted cyclohexyl ring is substituted with one or more substituents independently selected from halogen, (C1-C10)alkyl, (C1-C10)alkylsulfonate, tri(C1-C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; provided that the compound of formula (I) comprises only one double bond; and wherein the composition does not comprise a solution of the compound of formula (I) in a solvent.

5. The composition of claim 4, comprising two or more compounds of formula (I).

6. The composition of claim 4 or 5, wherein the compound of formula (I) comprises2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H -4,9:5,8-dimethanocyclopenta[b]naphthalene (H2-TCPD).

7. The composition of claims 4 to 6, wherein the compound of formula (I) comprises a compound selected from the group consisting of:1 ,4, 4a, 5 ,6, 7, 8, 8a, 9, 9a, 10,10a-dodecahydro- 1 ,4 :9,10-dimethanoanthracene; 1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (NB-CPD;2-methyl- 1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2-ethyl- 1 ,2,3,4,4a,5,8,8a-octahydro- 1 ,4:5,8-dimethanonaphthalene;2,3-dimethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;wherein each R3aand R3bis independently selected from CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, cyclopentyl, cyclohexyl, or phenyl; and4ais independently selected from halogen, OSO2R3a, Si(R3a)2R3b, or0R3a.

8. The composition of claims 1 to 7, wherein the catalyst comprises Ru, Ir, Os, Rh,Mo, or W.

9. The composition of claims 1 to 8, wherein the catalyst is third-generationGrubbs’ Catalyst (“GC3-H”):GC3-H.

10. The composition of claims 1 to 9, wherein the first inhibitor is pyridine, 3- bromopyridine, or 4-N,N-dimethylaminopyridine.

11. The composition of claims 1 to 10, wherein an amount of the first inhibitor is in about a 10:1 molar ratio relative to an amount of the catalyst.

12. The composition of claims 1 to 11, wherein the second inhibitor is a trialkyl phosphite, triphenylphosphine, an aminophosphine, an aryl or alkyl phosphoramidite, or a combination thereof.

13. The composition of claim 12, wherein the trialkyl phosphite is trimethyl phosphite, triethyl phosphite, tributyl phosphite, or a combination thereof.

14. The composition of claims 1 to 13, wherein a molar ratio of an amount of the second inhibitor relative to an amount of the catalyst is at least 1:1.

15. The composition of claim 14, wherein the molar ratio is 100:1.

16. The composition of claims 1 to 15, wherein the pot life is at least 120 days.

17. A method of preparing the composition of claims 1 to 16, comprising: adding the catalyst to the functionalized cycloalkene and the first inhibitor to provide a mixture; agitating the mixture to provide a gelled resin; and treating the gelled resin with the second inhibitor to provide the composition,wherein the treating is after a viscosity of the gelled resin increases to a desired viscosity.

18. A polymerization mixture comprising the resin composition of claims 1 to 16 and a second catalyst.

19. The polymerization mixture of claim 18, wherein the second catalyst is G2:

20. A resin composition, comprising: a functionalized alkene; a catalyst; and an antioxidant; wherein the pot life of the composition is at least 30 days.

21. The composition of claim 20, wherein the functionalized alkene is selected from the group consisting of dicyclopentadiene, 1,5-cyclooctadiene, norbornene, 5-ethylidene-2- norbornene, cyclooctene, cyclooctatetraene, 2,3-dihydrofuran, 2-(4-methoxyphenyl)-2,3- dihydrofuran, 2-(ethoxymethyl)-2,3-dihydrofuran, 3-methyl-2,3-dihydrofuran, 2-phenyl-2,3- dihydrofuran, 1,3-dioxole, 2,5-dihydrofuran, (Z)-2,2-diisopropyl-5,8-dihydro-4H - 1,3,2- dioxasilocine, 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine, (Z)-2-isopropyl-5,8-dihydro- 4H -1,3-dioxocine, 2-isopropyl-4,7-dihydro-l,3-dioxepine, norbomenylethyl terminated polydimethylsiloxane, trisilanol phenyl polyhedral oligomeric silsesquioxane, trisilanol vinyl polyhedral oligomeric silsesquioxane, and mixtures thereof.

22. The composition of claim 20 or 21, wherein the catalyst is G2:G2.

23. The composition of claims 20 to 22, wherein an amount of the catalyst is up to a 10"6:l molar ratio relative to an amount of the functionalized alkene.

24. The composition of claims 20 to 23, wherein the antioxidant is a phenolic antioxidant derivative.

25. The composition of claims 20 to 24, wherein the antioxidant is butylated hydroxy toluene (BHT).

26. The composition of claims 20 to 25, wherein the antioxidant is in an amount of up to about 2 mol % relative to an amount of the functionalized alkene.

27. The composition of claims 20 to 26, wherein the pot life of the composition is at least 120 days.

28. The composition of claims 20 to 27, wherein the functionalized alkene is selected from the group consisting of dicyclopentadiene, 1,5 -cyclooctadiene, norbomene, 5- ethylidene-2-norbomene, cyclooctene, cyclooctatetraene, 2,3-dihydrofuran, 2-(4- methoxyphenyl)-2,3-dihydrofuran, 2-(ethoxymethyl)-2,3-dihydrofuran, 3-methyl-2,3- dihydrofuran, 2-phenyl-2,3-dihydrofuran, 1,3-dioxole, 2,5-dihydrofuran, (Z)-2,2-diisopropyl- 5,8-dihydro-4H -1,3,2-dioxasilocine, 2,2-diisopropyl-4,7-dihydro-l,3,2-dioxasilepine, (Z)-2- isopropyl-5,8-dihydro-4H -1,3-dioxocine, 2-isopropyl-4,7-dihydro-l,3-dioxepine, norbornenylethyl terminated polydimethylsiloxane, trisilanol phenyl polyhedral oligomeric silsesquioxane, trisilanol vinyl polyhedral oligomeric silsesquioxane, and mixtures thereof.

29. The composition of claims 20 to 27, wherein the functionalized alkene is a compound of formula (I)wherein R3and R4are independently selected from hydrogen, halogen, substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted aryl, (C1-C10)alkylsulfonate, tri(C1- C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; or R3and R4, together with the carbon atoms to which R3and R4are bonded, form a substituted or unsubstituted cyclopentyl or cyclohexyl ring; wherein the substituted (C1-C10)alkyl, substituted aryl, substituted cyclopentyl ring, or substituted cyclohexyl ring is substituted with one or more substituents independently selected from halogen, (C1-C10)alkyl, (C1-C10)alkylsulfonate, tri(C1-C10)alkylsilyl, (C1-C10)alkoxy, or aryloxy; provided that the compound of formula (I) comprises only one double bond; and wherein the composition does not comprise a solution of the compound of formula (I) in a solvent.

30. The composition of claim 29, comprising two or more compounds of formula(I).

31. The composition of claim 29 or 30, wherein the compound of formula (I) comprises2,3,3a,4,4a,5,8,8a,9,9a-decahydro-1H -4,9:5,8-dimethanocyclopenta[6]naphthalene (H2-TCPD).

32. The composition of claims 29 to 31, wherein the compound of formula (I) comprises a compound selected from the group consisting of:1 ,4, 4a, 5 ,6, 7, 8, 8a, 9, 9a, 10,10a-dodecahydro- 1 ,4 :9, 10-dimethanoanthracene;1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene (NB-CPD;2-methyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2-ethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;2,3-dimethyl-1 ,2,3,4,4a,5,8,8a-octahydro-l,4:5,8-dimethanonaphthalene;wherein each R3aand R3bis independently selected from CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH(CH3)2, CH(CH3)CH2CH3, C(CH3)3, cyclopentyl, cyclohexyl, or phenyl; and wherein each R4ais independently selected from halogen, OSO2R3a, Si(R3a)2R3b, or OR3a.

33. A method of preparing the composition of claims 20 to 32, comprising: cooling the functionalized alkene to about 0 °C;adding the catalyst and the antioxidant to the functionalized alkene to provide a mixture; heating the mixture to initiate the catalyst; and removing the heat from the mixture to provide the composition.

34. The method of claim 33, wherein the heating is to a temperature of about 140°C.

35. A polymerization mixture comprising the resin composition of claims 20 to 32 and a second catalyst.

36. The polymerization mixture of claim 35, wherein the second catalyst is G2.