Capped bisphenol polyindane oligomers and compositions, methods of manufacture, and articles made therefrom

Abstract

Formula (1): JPEG2024516417000026.jpg42170(1) [In the formula, R 1 , R 2 and R 3 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and the oxygen atom; R x and R y are as provided herein. Capped polyindane oligomer.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to functionalized polyindanes, and more particularly to end-capped polyindanes, methods of making and their uses. [Background technology]

[0002] Thermoset resins can be used in a wide variety of consumer and industrial products such as protective coatings, adhesives, electronic laminates (such as those used in the fabrication of printed circuit boards), flooring and paving applications, fiberglass reinforced pipe, and automotive parts (including leaf springs, pumps, and electrical components).

[0003] In some cases, thermosetting resin compositions can be prepared to include polymer species having structural repeat units that provide a source of aliphatic carbon content to provide improved dielectric properties in the cured thermosetting product. For example, polyether resins can be prepared from oligomers that are comprehensively versatile and can be combined with thermosetting resins such as epoxy, cyanate ester, maleimide, acrylate, and benzoxazine resins.

[0004] The increasing demand for data storage and data transmission has led to an increasing need for high density and multilayer printed circuit boards for electronics applications. As the complexity of devices such as printed circuit boards increases, so does the demand for high performance materials to accommodate the reduction in free design space caused by miniaturization and the new requirements for signal transmission and bandwidth through them. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there remains a need for materials with lower dielectric constants and dissipation factors. [Means for solving the problem]

[0006] Formula (1): [ka] (1) [In the formula, R 1 , R 2 and R 3 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms; R x and R y are each independently a hydrogen atom, or: [ka] [In the formula, Y 2 is the expression [ka] [In the formula, R c and R d Each occurrence of is independently hydrogen or C 1~12 alkyl], and R 5a is a C optionally substituted with an epoxide-containing group, a cyanate-containing group, or one or two carboxylic acid groups; 1~12 is hydrocarbyl, and R 6 , R 7 and R 8 Each occurrence of is independently hydrogen, C 1~18 Hydrocarbyl, C 2~18 is a hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; R 9 , R 10 , R 11 , R 12 and R 13 Each occurrence of independently represents hydrogen, halogen, C 1~12 Alkyl, C 2~12Alkenyl, hydroxy, amino, maleimide, carboxylic acid or C 2~20 alkyl ester; x and R y at least one of which is not a hydrogen atom; m is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1; and n is an integer from 2 to 20, preferably from 3 to 16. A capped polyindane oligomer of the formula:

[0007] Also provided herein is a method for producing a capped polyindane oligomer, comprising reacting di(isopropenyl)benzene in the presence of an acid catalyst and a cracking product of a dihydric phenol.

[0008] Curable thermoset compositions comprising the capped polyindane oligomers and articles derived from the curable thermoset compositions are also provided herein.

[0009] The above-mentioned and other features are exemplified by the following detailed description, examples, and claims. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure relates to increasing the aliphatic content of aromatic polyether thermoset compositions to improve the dielectric and thermal properties of the corresponding cured thermoset products. The inventors have discovered low molecular weight difunctional polyindane oligomers that achieve improved dielectric performance and have desirable thermal properties. Polyindane oligomers can be obtained, for example, via a polycondensation reaction between di(isopropenyl)benzene and isopropenylphenol, a cracking product of a dihydric phenol, such as bisphenol A (BPA). The phenol end groups of the difunctional polyindane oligomers originate from the monophenol product of the cracking reaction. The inventors have discovered that one or more of the phenol end groups of the difunctional polyindane oligomers can be further modified to include other reactive functional groups.

[0011] Provided herein are capped polyindane oligomers containing one or more reactive end groups, more particularly represented by formula (1): [ka] (1) wherein m is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1; and n is an integer from 2 to 20, preferably from 3 to 16. A capped polyindane oligomer of the formula:

[0012] In formula (1), R 1 , R 2 and R 3 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms. For example, R 1 , R 2 and R 3 Each occurrence of is independently hydrogen, C 1~12 Alkyl, C 2~12 Alkenyl or C 2~12 In particular embodiments, R 1 , R 2 and R 3 Each occurrence of is independently hydrogen or C 1~12 Primary alkyl, preferably hydrogen or C 1~6 In some embodiments, R 3 is hydrogen, C 1~12 Primary or secondary alkyl, or C 6~12 It can be aryl.

[0013] In formula (1), R x and R y are each independently a hydrogen atom, or: [ka] [In the formula, Y 2 is the expression [ka] is a divalent linking group having one of the following formulas: However, R x and R y At least one of the is not a hydrogen atom.

[0014] In formula (1), R c and R d Each occurrence of is independently hydrogen or C 1~12 It is alkyl. R 5a is a C optionally substituted with an epoxide-containing group, a cyanate-containing group, or one or two carboxylic acid groups; 1~12 It is a hydrocarbyl. 6 , R 7 and R 8 Each occurrence of is independently hydrogen, C 1~18 Hydrocarbyl, C 2~18 R is a hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid. 9 , R 10 , R 11 , R 12 and R 13 Each occurrence of independently represents hydrogen, halogen, C 1~12 Alkyl, C 2~12 Alkenyl, hydroxy, amino, maleimide, carboxylic acid or C 2~20 It is an alkyl ester.

[0015] In some embodiments, the capped polyindane oligomer has formula (2): [ka] (2) [In the formula, R 1 From R 3 , R 6 From R8 , m and n are as defined in Equation (1)] It can be an oligomer represented by:

[0016] The capped polyindane oligomer may contain, on average, 1.1 to 2 reactive end groups per molecule. For example, the capped polyindane oligomer may contain, on average, 1.4 to 2 reactive end groups per molecule, or 1.8 to 2 reactive end groups per molecule, or 1.9 to 2 reactive end groups per molecule, about 2 reactive end groups per molecule, or 2 reactive end groups per molecule. As used herein, the term "reactive end group" refers to the R x and R y refers to R x and R y are not hydrogen atoms. x is a hydrogen atom, R x is not considered a reactive end group. y is a hydrogen atom, R y is not considered a reactive end group.

[0017] The capped polyindane oligomers have weight average molecular weights (M) ranging from 450 to 200,000 Daltons (Da) or greater, as determined by gel permeation chromatography (GPC) using polystyrene standards. w Preferably, the M of the capped polyindane oligomer w M may be from 450 to 50,000 Da, more preferably from 450 to 5,000 Da, as determined by GPC using polystyrene standards. w can be from 600 to 2,500 Da as determined by GPC using polystyrene standards.

[0018] The capped polyindane oligomer has a glass transition temperature (T) of 80 to 240°C, preferably 80 to 200°C, and more preferably 80 to 190°C, as determined by differential scanning calorimetry (DSC). g ).

[0019] As disclosed herein, capped polyindane oligomers can be prepared or derived from the polycondensation reaction of di(isopropenyl)benzene with the cracking product of a dihydric phenol, the cracking product comprising an allyl-substituted, more particularly an isopropenyl-substituted, phenol. For example, bisphenol A can be cracked to a mixture of phenol and 2-isopropenylphenol. The resulting mixture of phenol and 2-isopropenylphenol can be directly copolymerized with diisopropenylbenzene under acidic conditions in the presence of an organic solvent to obtain a polyindane containing terminal phenol functionality. As used herein, the term "terminal phenol functionality" refers to a group consisting of R x and / or R y refers to the terminal groups, each of which is a hydrogen atom.

[0020] One embodiment provides a capped polyindane oligomer derived from the polycondensation of di(isopropenyl)benzene in the presence of an acid catalyst and a cracking product of a dihydric phenol. A process for forming the capped polyindane oligomer is also provided, which comprises copolymerizing the cracking product of di(isopropenyl)benzene and the dihydric phenol in the presence of an acid catalyst. For example, a process for forming the capped polyindane oligomer can comprise cracking bisphenol A to form isopropenylphenol and reacting 1,4-diisopropenylbenzene and isopropenylphenol in the presence of triflic acid.

[0021] The di(isopropenyl)benzene can be 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, or a combination thereof. Preferably, the di(isopropenyl)benzene is 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, or a combination thereof. More preferably, the di(isopropenyl)benzene is 1,3-diisopropenylbenzene.

[0022] Dihydric phenols have the formula (4): [ka] (4) [In the formula, R 1 and R 2 is the same as that provided for equation (1); R a and R b are each independently hydrogen, C 1~12 Hydrocarbyl or C 1~6 hydrocarbylene, provided that R a and R b At least one of them is C 1~12- In some embodiments, R a and R b are each independently 1~12 Alkyl, preferably C 1~6 In certain embodiments, R a and R b is methyl.

[0023] For example, dihydric phenols include 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1-bis(3-chloro-4-hydroxyphenyl)ethane, 1,1-bis(3-methyl-4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxy-3,5-dimethylphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)ethane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)ethane, 4,4'-bisphenol A, 2,2'-diallyl-4,4'-bisphenol S, 2,2'-diallyl-4,4'-bisphenol A, 2,2'-diallyl-4,4'-bisphenol S, or a combination thereof.

[0024] The polymerization catalyst can be a Lewis acid or a Bronsted acid. For example, the polymerization catalyst can be trifluoroacetic acid (TFA), SnCl4, BF3, H2SO4, or a combination thereof. Alternatives to acidic polymerization media include strong acids known in the art, such as cationic ion exchange resins, such as the sulfonic acid-functionalized fluoropolymer NAFION (Aldrich Chemical Company, Milwaukee, Wis.). Other alternatives to acidic polymerization media include sulfonic acid-functionalized styrene-divinylbenzene (H) ion exchange resins. Heterogeneous acidic bentonite clays, such as SUPER FILTROL FI0 (Engelhard Corporation, Jackson, Miss.), can be used. Heterogeneous catalysts have the advantage of being easily separated from the reaction mixture by filtration and can be reused repeatedly. Additionally, Ziegler-type complexes can be used to carry out the polymerization reaction. These include, for example, LiBu-TiCl-HCl or Al(Et)Ti(OBu)-HCl, where Bu is butyl and Et is ethyl. In another embodiment, the polymerization reaction can be carried out using two acid steps. The first step can be carried out in a polymerization medium containing TFA. The TFA treatment can then be followed by a post-treatment with sulfuric acid. This two-step process can be useful when the polymerization is carried out at room temperature to avoid products with incomplete indane ring closure and internal olefins along the polymer backbone.

[0025] The reaction is generally carried out in an organic solvent. Suitable polymerization solvents include any solvent known in the art that effectively dissolves the reactants and supports the polymerization reaction. These include, for example, nitrobenzene, benzene, toluene, hexane, 1,2-dichloroethane, tetrachloroethane, tetrachloromethane, etc., or combinations thereof. Preferred polymerization solvents include nitrobenzene and 1,2-dichloroethane.

[0026] As disclosed above, a capped polyindan oligomer is a functional oligomer having specific end groups, and a method of making a functionalized polyindan oligomer may further include reacting a hydroxy-terminated polyindan oligomer, such as the oligomer of formula (3), with a capping agent. For example, a process for forming a capped polyindan oligomer may further include reacting a capping agent with an uncapped polyindan oligomer comprising phenol end groups under conditions effective to obtain a reaction mixture comprising the capped polyindan oligomer.

[0027] In some embodiments, the capped polyindane oligomer comprises a capping agent and a polyindane oligomer of formula (3): [ka] (3) [In the formula, R 1 From R 3 , m and n are as defined in Equation (1)] can be prepared by reacting an uncapped polyindane oligomer of the formula:

[0028] The capping agent can be a compound containing, but is not limited to, unsaturated, epoxy, benzoxazine, isocyanate, cyanate ester, melamine, cyanophenyl, maleimide, phthalonitrile, cycloalkylphenyl, ethoxylate, urethane, anhydride, allylhydroxypropyl, or the like, or a combination thereof. Those skilled in the art can determine the capping agent based on the desired functionality of the capped polyindane oligomer. For example, vinylbenzyl ether end groups can be prepared using a curing agent that is a vinylbenzyl halide (e.g., vinylbenzyl chloride), and (meth)acrylic end groups can be prepared using a curing agent that is a (meth)acrylic acid halide or (meth)acrylic anhydride.

[0029] The capping agent and the capped polyindane oligomer are reacted in a solvent. Exemplary solvents include, for example, aromatic hydrocarbons such as toluene or xylene, or chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, or 1,2,4-trichlorobenzene. In some embodiments, the solvent is toluene.

[0030] In some aspects, the uncapped polyindane oligomer is obtained as an isolated product and then combined with a capping agent and a solvent, hi other aspects, the uncapped polyindane oligomer is obtained as a solution from a polymerization reaction without removing the solvent, and the uncapped polyindane oligomer is not isolated from the solvent solution.

[0031] A capping catalyst may be used in the reaction of the uncapped polyindane oligomer with a capping agent. Examples of such compounds include those known in the art that can catalyze the condensation of phenols with the above-mentioned capping agents. Useful materials include basic compounds such as hydroxide salts of basic compounds, such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium hydroxide; tertiary alkylamines, such as tributylamine, triethylamine, dimethylbenzylamine, and dimethylbutylamine; tertiary mixed alkyl-arylamines and their substituted derivatives, such as N,N-dimethylaniline; heterocyclic amines, such as imidazole, pyridine, and their substituted derivatives, such as 2-methylimidazole, 2-vinylimidazole, 4-(dimethylamino)pyridine, 4-(1-pyrrolino)pyridine, 4-(1-piperidino)pyridine, 2-vinylpyridine, 3-vinylpyridine, and 4-vinylpyridine.

[0032] In one embodiment, the capping catalyst is an organic amine catalyst. Preferred organic amine catalysts include, for example, tertiary alkylamines, tertiary mixed alkyl-arylamines, heterocyclic amines, etc. It is understood that the organic amine catalyst comprises an ammonium ion formed by protonation of an organic amine. In one embodiment, the capping catalyst comprises a 4-dialkylaminopyridine, such as 4-dimethylaminopyridine (DMAP).

[0033] Alternatively, the capping catalyst can be a transesterification catalyst. Any suitable transesterification catalyst capable of catalyzing the transesterification of phenol with the above-mentioned capping agent may be used. For example, the capping catalyst can be an alpha catalyst containing a source of alkali or alkaline earth ions. Sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. Other possible sources of alkali and alkaline earth metal ions include carboxylic acids (such as sodium acetate) and the corresponding salts of derivatives of ethylenediaminetetraacetic acid (EDTA) (such as tetrasodium EDTA and magnesium disodium EDTA). Other alpha transesterification catalysts include carbonates such as, for example, CsCO, NaHCO, and NaCO, non-volatile inorganic acids such as, for example, NaHPO, NaHPO, NaHPO, KHPO, CsHPO, CsHPO, or mixed salts of phosphoric acid such as, for example, alkali or alkaline earth metal salts such as NaKHPO, CsNaHPO, CsKHPO. Combinations comprising at least one of any of the foregoing catalysts may be used.

[0034] The capping catalyst may alternatively be a beta transesterification catalyst comprising a quaternary ammonium compound, a quaternary phosphonium compound, or a combination comprising at least one of the foregoing. The quaternary ammonium compound may have the structure (R 14 )4N + X - and each R 14are the same or different, C1 to C 20 Alkyl, C4-C 20 Cycloalkyl or C4-C 20 aryl, and X - is an organic or inorganic anion, such as hydroxide, halide, carboxylate, sulfonate, sulfate, formate, carbonate, or bicarbonate. Examples of organic quaternary ammonium compounds include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium formate, tetrabutylammonium acetate, and combinations comprising at least one of the foregoing. Tetramethylammonium hydroxide is often used. Quaternary phosphonium compounds have the structure (R 15 )4P + X - and each R 15 are the same or different, C1 to C 20 Alkyl, C4-C 20 Cycloalkyl or C4-C 20 aryl, and X - is an organic or inorganic anion, for example, hydroxide, phenoxide, halide, carboxylate such as acetate or formate, sulfonate, sulfate, formate, carbonate or bicarbonate. - It is understood that when R is a polyvalent anion such as carbonate or sulfate, the positive and negative charges in the quaternary ammonium and phosphonium structures are appropriately balanced. For example, R 14 or R 15 are methyl, and X - If is a carbonate, X - is 1 / 2(CO3 -2 ) is understood to represent. Examples of organic quaternary phosphonium compounds include tetramethylphosphonium hydroxide, tetramethylphosphonium acetate, tetramethylphosphonium formate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate (TBPA), tetraphenylphosphonium acetate, tetraphenylphosphonium phenoxide, and combinations comprising at least one of the foregoing. TBPA is often used.

[0035] The process may further include isolating the capped polyindane oligomer from the reaction mixture. Suitable methods include precipitation and total isolation methods. As part of the total isolation, a portion of the solvent is preferably removed to reduce the solvent load on the total isolation equipment. The isolated capped polyindane oligomer may be further dried at elevated temperatures, for example, from 80° C. to 160° C., preferably from 100° C. to 140° C., for 6 to 24 hours, preferably from 8 to 16 hours.

[0036] The capped polyindane oligomer can also be part of a composition that may include a blend of at least two capped polyindane oligomers. Such a blend can be prepared from individually prepared and isolated capped polyindane oligomers. Alternatively, such a blend can be prepared by reacting a single uncapped polyindane oligomer with at least two different capping agents.

[0037] The capped polyindane oligomer may be suitable as a reactive component in a curable composition containing a thermosetting resin. Curable thermosetting compositions containing the capped polyindane oligomer are also provided. For example, the capped polyindane oligomer may be present in the curable thermosetting composition in an amount of 1 to 95 weight percent (wt%), or 5 to 95 wt%, or 10 to 85 wt%, or 20 to 80 wt%, or 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable thermosetting composition.

[0038] The curable thermosetting composition may further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof. In some embodiments, the curable thermosetting composition may further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof. For example, the curable thermosetting composition may further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof, and may further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0039] There is considerable overlap between thermosetting resins, crosslinkers, and coupling agents. As used herein, the term "crosslinker" includes compounds that can be used as thermosetting resins, crosslinkers, coupling agents, or combinations thereof. For example, in some cases, a compound that is a thermosetting resin can also be used as a crosslinker, a coupling agent, or both.

[0040] The thermosetting resin is not particularly limited, and the thermosetting resin may be used alone or in combination of two or more thermosetting resins (e.g., including one or more auxiliary thermosetting resins). Exemplary thermosetting resins include epoxy resins, cyanate ester resins, (bis)maleimide resins, (poly)benzoxazine resins, vinyl resins (e.g., vinylbenzyl ether resins), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers, or polymers having curable unsaturation (e.g., vinyl functional groups), or combinations thereof.

[0041] The epoxy resin may be any epoxy resin suitable for use in thermosetting resins. The term "epoxy resin" in this context refers to a curable composition of oxirane ring-containing compounds, as described, for example, in C.A. May, Epoxy Resins, 2nd Edition, (New York & Basle: Marcel Dekker Inc.), 1988. Epoxy resins include bisphenol A-type epoxy resins, such as those obtained from bisphenol A and resins obtained by substituting at least one of the 2-, 3-, and 5-positions of bisphenol A with a halogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group; bisphenol F-type epoxy resins, such as those obtained from bisphenol F and resins obtained by substituting at least one of the 2-, 3-, and 5-positions of bisphenol F with a halogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group; hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)methane. Glycidyl ether compounds derived from dihydric or trihydric or higher phenols such as bisphenol A novolak epoxy resins and cresol novolak epoxy resins, which are derived from novolak resins that are reaction products between phenols such as o-cresol and formaldehyde; cycloaliphatic epoxy compounds, such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; dicyclopentadiene-containing polyepoxides;Aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2 amine-type epoxy resins derived from, for example, 4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis(methylamine), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane; heterocyclic epoxy compounds; and glycidyl ester-type epoxy compounds, such as those derived from the glycidyl esters of aromatic carboxylic acids, e.g., p-hydroxybenzoic acid, m-hydroxybenzoic acid, terephthalic acid, and isophthalic acid. "Epoxy resin" may also include the reaction product of a compound containing two or more epoxy groups with an aromatic dihydroxy compound, which may optionally be halogen-substituted, either alone or in combination.

[0042] The cyanate ester is not limited, and any resin composed of a cyanate ester monomer that polymerizes to form a polymer containing multiple cyanate ester (-OCN) functional groups can be used. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers or blends of cyanate ester monomers), homopolymers and copolymers, and combinations of these compounds, made using cyanate ester precursors, can be used. For example, cyanate esters can be prepared according to the methods disclosed in "Chemistry and Technology of Cyanate Ester Resins," by Ian Hamerton, Blackie Academic and Professional; U.S. Pat. No. 3,553,244; and Japanese Patent Application Laid-Open No. 7-53497. Exemplary cyanate ester resins include those prepared from 2,2-bis(4-cyanatophenyl)-propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanatophenyl)-m-diisopropyl-benzene, dicyclopentadiene-phenol copolymer, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). Cyanate ester prepolymers can be homopolymers or copolymers incorporating other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical Company, Inc., such as BT2160 and BT2170, which are prepolymers made with cyanate ester and bismaleimide monomers. Other cyanate ester polymers, monomers, prepolymers, and blends of cyanate ester monomers with other non-cyanate ester monomers are disclosed in U.S. Pat. No. 7,393,904, U.S. Pat. No. 7,388,057, U.S. Pat. No. 7,276,563, and U.S. Pat. No. 7,192,651.

[0043] Bismaleimide resins can be produced by reaction of a monomeric bismaleimide with a nucleophile such as a diamine, aminophenol or aminobenzhydrazide, or by reaction of a bismaleimide with diallyl bisphenol A.Exemplary bismaleimide resins include 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenylether, 3,3'-bismaleimidodiphenylsulfone, 4,4'-bismaleimidodiphenylsulfone, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6- Bismaleimido-pyridine, 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-bis(citracon-imido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1-phenyl-1,1-bis(4-maleimido-phenyl)ethane, N,N-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-1,2,4-triazole N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexane bismaleimide bismaleimide, N,N'-m-meta-xylene-bismaleimide, N,N'-4,4'-diphenylcyclohexanebismaleimide, and N,N'-methylene-bis(3-chloro-p-phenylene)bismaleimide, and those disclosed in U.S. Pat. Nos. 3,562,223, 4,211,860 and 4,211,861, or prepared by the methods described, for example, in U.S. Pat. No. 3,018,290.

[0044] Benzoxazine compounds have a benzoxazine ring in the molecule. Exemplary benzoxazine monomers can be prepared by the reaction of an aldehyde, a phenol, and a primary amine, with or without a solvent. Phenolic compounds for forming benzoxazines include phenols and polyphenols. The use of polyphenols with two or more hydroxyl groups reactive in forming benzoxazines can result in branched, crosslinked, or a combination of branched and crosslinked products. The group connecting the phenolic group to the phenol can be a branch point or a connecting group in polybenzoxazines.

[0045] Exemplary phenols for use in preparing the benzoxazine monomers are phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynapthalene, 2-(diphenyl-phosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis(2-methyl-phenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol). 4,4'-(1,4-phenylenediisopropylidene)-bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-sulfinyldiphenol, 4,4'-hexafluoroisopropylidene)bisphenol, 4,4'(1-phenylethylidene)-bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, isopropylidene-bis(2-allylphenol), 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi-[indene]5,6'-diol, dihy These include hydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(ortho-cresol), dicyclopentadienylbisphenol, etc.

[0046] The aldehyde used to form the benzoxazine can be any aldehyde, such as an aldehyde having 1 to 10 carbon atoms. For example, the aldehyde can be formaldehyde. The amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic or aromatic-substituted alkylamine. The amine can be a polyamine, for example, to prepare a multifunctional benzoxazine monomer for crosslinking.

[0047] The amines for forming the benzoxazines contain 1 to 40 carbon atoms, and may contain 6 to 40 carbon atoms, provided they do not contain aromatic rings. Di- or polyfunctional amines may be branching points for connecting one polybenzoxazine with another.

[0048] In some cases, thermal polymerization at 150 to 300°C can be used to polymerize the benzoxazine monomers. Polymerization can be carried out in bulk, from solution, or by other methods. Catalysts such as carboxylic acids can be used to reduce the polymerization temperature or accelerate the polymerization rate at the same temperature.

[0049] Vinylbenzyl ether resins can be prepared by the condensation of phenols with vinylbenzyl halides, such as vinylbenzyl chloride. Bisphenol-A and trisphenols and polyphenols are commonly used to produce poly(vinylbenzyl ethers), which can be used to produce crosslinked thermoset resins. Exemplary vinylbenzyl ethers include vinylbenzyl halides, resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2'6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidenediphenol, 4,4'- Isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol A), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidene di-phenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldi-phenol, 4,4'-sulfonylbis(2,6-dimethylphenol) 4,4'-sulfinyl-diphenol, 4,4'-hexafluoroisopropylidene)bisphenol, 4,4'(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloro-ethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(Cyclopentylidene)diphenol, 4,4'-(Cyclohexylidene)diphenol, 4,4'-(Cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)-isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol, dihydroxybenzophenone, tris(4-hydroxyphenyl)- These may include vinyl benzyl ethers thereof produced by reaction with tetrakis(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienyl-bis(2,6-dimethylphenol), dicyclopentadienylbisphenol, and the like.

[0050] Arylcyclobutenes have the structure [ka] wherein B is an organic or inorganic radical of valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidenedialkylsilanyl, arylalkylsilanyl, diarylsilanyl, and C 6~20 each occurrence of X is independently hydroxy or C 1~24hydrocarbyl (including straight and branched chain alkyl and cycloalkyl); each occurrence of Z is independently hydrogen, halogen or C 1~12 n is 1 to 1000, or 1 to 8, or n is 2, 3, or 4. Other exemplary arylcyclobutenes and methods of arylcyclobutene synthesis can be found in U.S. Pat. Nos. 4,743,399, 4,540,763, 4,642,329, 4,661,193, 4,724,260, and 5391,650.

[0051] Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane, followed by zinc-catalyzed reductive elimination to produce ZnFBr and the desired perfluorovinyl ether. By this route, bis-, tris-, and other polyphenols can be used to produce bis-, tris-, and poly(perfluorovinyl ethers). Phenols useful in these syntheses include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynapthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',6,6'-tetramethylbiphenol, and 3,3'-dibromo-2,2'. ,6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1,3-phenylenediisopropylidene)-bisphenol, 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(1,4-phenylenediisopropylidene)-bisphenol, 4,4'-ethylidene diphenol, 4,4'oxydiphenol, 4,4'thiodiphenol, 4,4'thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-hexafluoroisopropylidene)bisphenol, 4,4'(1-phenylethylidene)-bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)-methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(Cyclopentylidene)diphenol, 4,4'-(Cyclohexylidene)diphenol, 4,4'-(Cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)-diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone, These include tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)-phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(2-methylphenol), dicyclopentadienylbisphenol, etc.

[0052] The crosslinking agent, including the auxiliary crosslinking agent, is not particularly limited. The crosslinking agent may be used alone or in combination with two or more different crosslinking agents. Exemplary crosslinking agents and auxiliary crosslinking agents include oligomers or polymers with curable vinyl functionality. Such materials include oligomers and polymers with crosslinkable unsaturation. Examples include styrene butadiene rubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR), which have unsaturated bonds based on butadiene; natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber, which have unsaturated bonds based on isoprene; and ethylene-α-olefin copolymer elastomers (e.g., ethylene-α-olefin copolymers obtained by copolymerizing ethylene, α-olefins, and dienes, such as ethylene-propylene-diene terpolymer (EPDM) and ethylene-butene-diene terpolymer (EBDM)) which have unsaturated bonds based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD). Examples include hydrogenated nitrile rubber, fluorocarbon rubber, such as vinylidene fluoride-hexafluoropropene copolymer and vinylidene fluoride-pentafluoropropene copolymer, epichlorohydrin homopolymer (CO), copolymer rubber prepared from epichlorohydrin and ethylene oxide (ECO), epichlorohydrin allyl glycidyl copolymer, propylene oxide allyl glycidyl ether copolymer, propylene oxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T), and ethylene acrylic rubber. Further examples include various liquid rubbers, such as several types of liquid butadiene rubber, and liquid atactic butadiene rubber, which is a butadiene polymer with 1,2-vinyl connections prepared by anionic living polymerization.It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc., manufactured by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymers, and polynorbornene (such as those sold by Elf Atochem).

[0053] Polybutadiene resins containing increasing levels of 1,2 addition are desirable for thermoset matrices. Examples include functionalized polybutadiene and poly(butadiene-styrene) random copolymers sold under the trade names RICON, RICACRYL, and RICOBOND resins by Ricon Resins, Inc. These include butadienes containing low vinyl contents, such as RICON 130, 131, 134, and 142; polybutadienes containing high vinyl contents, such as RICON 150, 152, 153, 154, 156, 157, and P30D; random copolymers of styrene and butadiene, including RICON 100, 181, and 184; and maleic anhydride-grafted polybutadienes and alcohol condensates derived therefrom, such as RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20, RICON 184MA6, and RICON 156MA17. Polybutadienes that can be used to improve adhesion include RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500; polybutadienes RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene); and (meth)acrylic-functionalized polybutadienes, such as polybutadiene diacrylate and polybutadiene dimethacrylate. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Also included are powder dispersions of functionalized polybutadiene derivatives, including, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 0 1731 HS, and RICOBOND 1756HS.Additional butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those having a molecular weight of 3,000 to 50,000 g / mol, and polybutadiene homopolymers having a molecular weight of 3,000 to 50,000 g / mol. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethylmaleic acid, or hydroxyl functional groups.

[0054] Further examples of curable vinyl-functional oligomers and polymers include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid, and citraconic acid; unsaturated epoxy (meth)acrylate resins containing acryloyl or methacryloyl groups; unsaturated epoxy resins containing vinyl or allyl groups, urethane (meth)acrylate resins, polyether (meth)acrylate resins, polyalcohol (meth)acrylate resins, alkyd acrylate resins, polyester acrylate resins, spiroacetal acrylate resins, diallyl phthalate resins, diallyl tetrabromophthalate resins, diethylene glycol bisallyl carbonate resins, and polyethylene polythiol resins. For example, crosslinking agents. Other exemplary crosslinking agents include multifunctional crosslinking monomers, such as (meth)acrylate monomers having two or more (meth)acrylate moieties per monomer molecule. Exemplary multifunctional monomers include di(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, and the like; Tri(meth)acrylates, for example, trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.; tri(meth)allyls, for example, tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, tri(meth)allyl ester of citric acid, tri(meth)allyl ester of phosphoric acid, pentaerythritol tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; tetra(meth)acrylates, for example, pentaerythritol tetra(meth)acrylate, etc.;Penta(meth)acrylates, for example, dipentaerythritol penta(meth)acrylate; hexa(meth)acrylates, for example, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate; glycidyl compounds, for example, glycidyl (meth)acrylate, (meth)allyl glycidyl ether, 1-chloro-2,3-epoxypropyl (meth)acrylate, 2-bromo-3,4-epoxybutyl (meth)acrylate, 2-(epoxyethyloxy)-ethyl (meth)acrylate, 2-(3,4-epoxybutyloxy)-ethyl (meth)acrylate; polythiol compounds, for example, trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate); silanes, for example and tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloxyimino)silane, vinyltris-(acetoxime)silane, methyltris(methylethyloxyimino)silane, methyltris(acetoxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-t-butoxy-diacetoxysilane, methyltris(ethyllactate)silane, vinyltris(ethyllactate)silane, etc.; carbodiimides, such as N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, etc.; or combinations thereof. The curable thermosetting composition may optionally include a crosslinking catalyst, such as a carboxylate salt.

[0055] When the curable thermoset composition includes a crosslinking agent, the crosslinking agent may be included in an amount of 1 to 60 wt %, or 5 to 50 wt %, or 10 to 40 wt %, based on the total weight of the curable thermoset composition.

[0056] Curable thermoset compositions may include one or more curing agents. As used herein, the term "curing agent" includes compounds variously described as curing agents, hardeners, etc., or both.

[0057] Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, etc. For example, phenolic hardeners include novolac-type phenolic resins, resole-type phenolic resins, cresol novolac resins, aralkyl-type phenolic resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene-type phenolic resins, terpene-modified phenolic resins, biphenyl-type phenolic resins, biphenyl-modified phenol aralkyl resins, bisphenols, triphenylmethane-type phenolic resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, aminotriazine-modified phenolic resins, or combinations thereof. Examples of anhydride hardeners include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymer (SMA), and olefin-maleic anhydride copolymers, such as maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or combinations thereof. Other hardeners and hardeners include compounds such as dicyandiamide, polyamides, amidoamines, phenalkamines, Mannich bases, anhydrides, phenol-formaldehyde resins, amine-formaldehyde resins, phenol-formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate ester compounds, or any combination thereof. Other exemplary hardeners include tertiary amines, Lewis acids, and oligomers or polymers with unsaturation.

[0058] When the curable thermoset composition includes a curing agent, the curing agent may be included in an amount of 0.01 to 50 wt %, or 0.1 to 30 wt %, or 0.1 to 20 wt %, based on the total weight of the curable thermoset composition.

[0059] Curable thermosetting compositions may include a curing catalyst. As used herein, the term "curing catalyst" includes compounds variously described as cure accelerators, cure promoters, cure catalysts, and cure cocatalysts.

[0060] Exemplary cure accelerators include substituted or unsubstituted C 3~6Heterocyclic accelerators include heterocyclic accelerators such as heterocycles, where each heteroatom is independently the same or different and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocyclic accelerators include benzotriazoles, triazines, piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, and the like; imidazoles such as 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1- n-Propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole Imidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole midazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole; cyclic amidines, such as 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenylimidazoline, and the like; N,N-dimethylaminopyridine; sulfamidate; or combinations thereof.

[0061] Amine cure accelerators include isophoronediamine, triethylenetetraamine, diethylenetriamine, 1,2- and 1,3-diaminopropane, 2,2-dimethylpropylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane, 4-azaheptamethylenediamine, N,N'-bis(3-aminopropyl)butane- 1,4-diamine, dicyanamide, diamidodiphenylmethane, diamidodiphenylsulfonic acid (amine adduct), 4,4'-methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine formaldehyde resin, urea formaldehyde resin, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3'-iminobispropylamine, 2,4-bis(p-aminobenzyl)amine diamine, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,2- and 1,3-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1,2-diamino-4-ethylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1-cyclohexyl-3,4-diminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, 2,2-bis(4-aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-1-cyclohexaneaminopropane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, m- and p-xylylenediamine, or diethyltoluenediamine; or a tertiary amine hardening accelerator accelerators), including, for example, triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tri(N,N-dimethylaminomethyl)phenol; or combinations thereof.

[0062] The cure accelerator can be a latent cationic cure catalyst including, for example, diaryliodonium salts, phosphonate esters, sulfonate esters, carboxylic acid esters, phosphonic acid ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, and the like, or combinations thereof. Diaryliodonium salts are compounds having the structure [(R 10 )(R 11 )I] + X - R 10 and R 11 are each independently 1~20 Alkyl, C 1~20 C optionally substituted with one to four monovalent radicals selected from alkoxy, nitro, and chloro; 6~14 is a monovalent aromatic hydrocarbon radical; and X- is an anion. Additional cure accelerators include those having the structure [(R 10 )(R 11 )I] + SbF6 - R 10 and R 11 are each independently 1 to 4 C 1~20 Alkyl, C 1~20 C optionally substituted with alkoxy, nitro or chloro 6~14 Monovalent aromatic hydrocarbons; for example, 4-octyloxyphenyl phenyl iodonium hexafluoroantimonate.

[0063] The cure accelerator may be a metal salt complex such as a copper(II), aluminum(III), zinc, cobalt, or tin salt of an aliphatic or aromatic carboxylic acid selected from copper(II), tin(II), and aluminum(III) salts of acetate, stearate, gluconate, citrate, or benzoate, and mixtures thereof. For example, the cure accelerator may be a copper(II) or aluminum(III) salt of a β-diketonate; a copper(II), iron(II), iron(III), cobalt(II), cobalt(III), or aluminum(III) salt of an acetylacetonate; a zinc(II), chromium(II), or manganese(II) salt of an octoate; or a combination thereof.

[0064] When the curable thermoset composition includes a curing catalyst, the curing catalyst may be included in an amount of 0.01 to 5 wt %, or 0.05 to 5 wt %, or 0.1 to 5 wt %, based on the total weight of the curable thermoset composition.

[0065] The curable thermosetting composition may optionally include a cure initiator such as a peroxide compound. Exemplary peroxide cure initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butylbenzene hydroperoxide, t-butyl peroctoate, t-butyl peroxybenzoate, t-butylperoxy 2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyldioxy)valerate, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butyl peroxide, and t-butylcumyl. peroxides, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di(t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilylperoxide, and the like, or combinations thereof.

[0066] When the curable thermoset composition includes a curing initiator, the curing initiator may be included in an amount of 0.1 to 5 wt %, or 0.5 to 5 wt %, or 1 to 5 wt %, based on the total weight of the curable thermoset composition.

[0067] Flame retardants include, for example, organic compounds containing phosphorus, bromine, or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds, may be preferred in certain applications for regulatory reasons.

[0068] Examples of phosphorus flame retardants include phosphates, phosphazenes, phosphites, phosphines, phosphinates, polyphosphates, and phosphonium salts. Phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenylbis(dodecyl)phosphate, phenylbis(neopentyl)phosphate, phenylbis(3,5,5'-trimethylhexyl)phosphate, ethyldiphenylphosphate, 2-ethylhexyldi(p-tolyl)phosphate, bis(2-ethylhexyl)p-tolylphosphate, tritolyl phosphate, bis(2-ethylhexyl)phenylphosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolylphosphate, dibutylphenylphosphate, 2-chloroethyldiphenylphosphate, p-tolylbis(2,5,5'-trimethylhexyl), and the like. cresyl-diphenyl phosphate; 1,3-phenylenebis(di-2,6-xylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetraphenyl diphosphate (RDP), condensed phosphate compounds, for example, aromatic condensed phosphate compounds; and cyclic phosphate ester compounds, bis(diphenyl)phosphate of hydroquinone, bis(diphenyl)phosphate of bisphenol A, etc., or their oligomeric or polymeric counterparts, or combinations thereof.

[0069] Examples of phosphazene compounds include cyclic and linear phosphazene compounds. Cyclic phosphazene compounds (cyclophosphazenes) have a ring structure in which a phosphorus-nitrogen double bond exists in the molecule. Examples of phosphinate compounds include aluminum dialkylphosphinate, aluminum tris-(diethylphosphinate), aluminum tris-(methylethylphosphinate), aluminum tris-(diphenylphosphinate), zinc bis-(diethylphosphinate), zinc bis-(methylphosphinate), zinc bis-(diphenylphosphinate), titanyl bis-(diethylphosphinate), titanyl bis-(methylethylphosphinate), and titanyl bis-(diphenylphosphinate). Examples of polyphosphate compounds include melamine polyphosphate, melam polyphosphate, and melem polyphosphate. Examples of phosphonium salt compounds include tetraphenylphosphonium tetraphenylborate. Examples of phosphite ester compounds include trimethyl phosphite and triethyl phosphite. Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphoric ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide.

[0070] Halogenated materials, such as bisphenols, for example, 2,2-bis-(3,5-dichlorophenyl)-propane, bis-(2-chlorophenyl)-methane, bis(2,6-dibromophenyl)-methane, 1,1-bis-(4-iodophenyl)-ethane, 1,2-bis-(2,6-dichlorophenyl)-ethane, 1,1-bis-(2-chloro-4-iodophenyl)ethane, 1,1-bis-(2-chloro-4-iodophenyl)ethane, Also usable as flame retardants are 2,2-bis-(3-bromo-4-hydroxyphenyl)-ethane, 1,1-bis-(3,5-dichlorophenyl)-ethane, 2,2-bis-(3-phenyl-4-bromophenyl)-ethane, 2,6-bis-(4,6-dichloronaphthyl)-propane, and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl, as well as decabromobiphenyl ether, decabromodiphenylethane, and oligomeric and polymeric halogenated aromatic compounds such as brominated styrene, 4,4-dibromobiphenyl, ethylene-bis(tetrabromophthalimide), or copolycarbonate of bisphenol A and tetrabromobisphenol A, and carbonate precursors such as phosgene. Metal synergists, such as antimony oxide, can also be used with the flame retardant.

[0071] Inorganic flame retardants, such as, for example, potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate. 1~16Salts of alkylsulfonates; such as Na2CO3, K2CO3, MgCO3, CaCO3 and BaCO3, or fluoro-anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6 or Na3AlF6 may also be used.

[0072] When the curable thermoset composition includes a flame retardant, the flame retardant may be included in an amount greater than 1 wt %, or from 1 to 20 wt %, or from 5 to 15 wt %, based on the total weight of the curable thermoset composition.

[0073] The curable thermoset composition may further include inorganic or organic fillers, such as particulate fillers, fibrous fillers, and the like, or combinations thereof. Any inorganic and organic fillers may be used, including but not limited to, those known in the art.

[0074] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; alumina, thiourea, glass powder, B- or Sn-based fillers, such as zinc borate, zinc stannate, and zinc hydroxystannate; metal oxides, such as zinc oxide and tin oxide, alumina, silica (including fused silica, fumed silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fibers (chopped, milled, or cloth), glass mat, small glass spheres, hollow glass microspheres, aramid fiber, quartz, and the like, or combinations thereof. Other exemplary inorganic fillers include powdered titanium ceramics, such as any one of titanates of barium, lead, strontium, calcium, bismuth, magnesium, and the like. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolites, and hydrotalcites, hi some embodiments, the filler may be treated with a coupling agent as disclosed herein.

[0075] Glass fibers include E, A, C, ECR, R, S, D, and NE glass, as well as quartz-based ones. The glass fibers can have any suitable diameter, such as 2 to 30 micrometers (μm), or 5 to 25 μm, or 5 to 15 μm. The length of the glass fibers before compounding is not limited and can be 2 to 7 millimeters (mm), or 1.5 to 5 mm. Alternatively, longer or continuous glass fibers can be used. Suitable glass fibers are commercially available from suppliers such as Owens Corning, Nippon Electric Glass Co., Ltd., PPG, and Johns Manville.

[0076] The organic filler can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, and poly(ether sulfone) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, and the like, or a combination thereof.

[0077] The filler may be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, Al2O3, BN, AlN, or a combination thereof may be used for electronic modules with high thermal conductivity. For example, MgO may be used for increased thermal conductivity and increased CTE. For example, SiO2 (e.g., amorphous SiO2) may be used for lightweight modules with low CTE and small dielectric constant.

[0078] When the curable thermoset composition includes a filler, the filler can be present in an amount greater than 1 wt %, or from 1 to 50 wt %, or from 1 to 30 wt %, or from 10 to 30 wt %, based on the total weight of the curable thermoset composition.

[0079] Coupling agents, also referred to as adhesion promoters, include chromium complexes, silanes, titanates, zircon-aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, and the like. Exemplary olefin-maleic anhydride copolymers may include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or combinations thereof. Exemplary silanes may include epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0080] When the curable thermoset composition includes a coupling agent, the coupling agent may be included in an amount of 0.01 to 5 wt %, or 0.05 to 5 wt %, or 0.1 to 5 wt %, based on the total weight of the curable thermoset composition.

[0081] The curable thermosetting composition may optionally contain a solvent. 3~8 Ketone, C 3~8 N,N-Dialkylamide, C 4~16 Dialkyl ether, C 6~12 Aromatic hydrocarbons, C 1~3 Chlorinated hydrocarbons, C 3~6 Alkyl alkanoates, C 2~6 Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. 4~8 N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or a combination thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or a combination thereof. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or a combination thereof. The aromatic hydrocarbon solvent may be non-halogenated. Specific C 3~6Alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. 2~6 Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. 2~6 The alkyl cyanide includes, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. For example, the solvent can be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, γ-caprolactone, dimethyl sulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl methyl ketone, methyl ... The solvent may be sanon, diglyme, triglyme, tetraglyme, N,N-dimethylethyleneurea, N,N-dimethylpropyleneurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, picoline, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, an ionic liquid, or a combination thereof.

[0082] When a solvent is utilized, the curable thermoset composition can contain 2 to 99 wt% of the solvent, based on the total weight of the curable thermoset composition. For example, the amount of solvent can be 5 to 80 wt%, or 10 to 70 wt%, or 20 to 60 wt%, based on the total weight of the curable thermoset composition. The solvent can be selected, in part, to adjust the viscosity of the curable thermoset composition. Thus, the amount of solvent can depend on variables including the type and amount of capped poly(arylene ether) copolymer, the type and amount of other ingredients such as curing additives, the type and amount of any supplemental thermoset resin, and the processing temperature used for any subsequent processing of the curable thermoset composition, such as impregnation of a reinforcing structure with the curable thermoset composition to prepare a composite. The solvent can be anhydrous. For example, the solvent can contain less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water, based on the total weight of the solvent.

[0083] The curable thermosetting composition can further include a curable unsaturated monomer composition, which can include, for example, a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, or the like, or a combination thereof. For example, the curable unsaturated monomer composition can be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene- and alkyne-containing monomers include those described in U.S. Pat. No. 6,627,704 to Yeager et al., and (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidones, and vinylazalactones as disclosed in U.S. Pat. No. 4,304,705 to Heilman et al. Exemplary monofunctional monomers include mono(meth)acrylates, such as methyl(meth)acrylate, ethyl(meth)acrylate, isopropyl(meth)acrylate, isooctyl(meth)acrylate, isobornyl(meth)acrylate, (meth)acrylic acid, n-hexyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, and the like, or combinations thereof.

[0084] The curable thermoset composition may optionally further comprise one or more additional additives. Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, antifoaming agents, lubricants, dispersants, flow improvers, anti-drip agents, anti-blocking agents, anti-static agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low-shrinkage additives, stress relief additives, and the like, or combinations thereof. When present, the additional additives may be included in any effective amount, for example, from 0.01 to 20 wt %, or from 0.01 to 10 wt %, or from 0.01 to 5 wt %, or from 0.01 to 1 wt %, based on the total weight of the curable thermoset composition.

[0085] The curable thermoset composition may be prepared by combining the capped polyindane oligomer and other optional ingredients disclosed herein using any suitable method.

[0086] Cured thermosetting compositions, including the cured product of a curable thermosetting composition, are also provided. There are no limitations on the method by which a curable thermosetting composition can be cured. The curable composition can be cured, for example, thermally or by using irradiation techniques, including UV or electron beam irradiation. For example, a cured product can be obtained by heating a curable thermosetting composition as defined herein for a time and temperature sufficient to evaporate the solvent and achieve curing. If heat curing is used, the temperature can be 30 to 400°C, or 50 to 250°C, or 100 to 250°C. Heating can range from 1 minute to 24 hours, or 1 minute to 6 hours, or 3 to 5 hours. Curing can be staged to produce a partially cured and often tack-free resin, which can then be fully cured by heating for a longer period of time or at a temperature within the aforementioned range. As used herein, the term "cured" encompasses partially cured or fully cured products.

[0087] The cured thermoset composition may exhibit one or more desirable properties, such as improved viscosity, gel time, glass transition temperature (T g ), coefficient of thermal expansion (CTE), dielectric constant (Dk), dissipation factor (Df), equilibrium water absorption, etc., or a combination thereof.

[0088] The disclosed curable thermoset compositions and cured compositions can be used in a variety of applications, including any application in which conventional thermoset compositions are used. For example, useful articles comprising the curable thermoset compositions or cured thermoset compositions can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, cast components, prepregs, casings, laminates, metal-clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary uses and applications include coatings such as protective coatings, sealants, weather-resistant coatings, scratch-resistant coatings, and electrically insulating coatings; adhesives; binders; glues; and composites such as those using carbon fiber and glass fiber reinforcement. When utilized as coatings, the disclosed compounds and compositions can be deposited on the surface of a variety of underlying substrates. For example, the compositions can be deposited on the surface of metal, plastic, glass, fiber sizing, ceramic, stone, wood, or any combination thereof. The disclosed compositions can be used as coatings on the surface of metal containers (e.g., aluminum or steel), such as those commonly used for packaging and storage in the paint and surface coating industries. Curable thermoset compositions and cured thermoset compositions derived therefrom may also be particularly well suited for use in forming electrical and computer components.

[0089] A method for forming a composite can include impregnating a reinforcing structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and laminating multiple prepregs. The reinforcing structure can be a porous substrate, such as a fiber preform or substrate, or other porous material including ceramic, polymer, glass, carbon, or a combination thereof. For example, the porous substrate can be a woven or nonwoven glass fabric, a glass fiber fabric, or a carbon fiber. When the article includes a fiber preform, a method for manufacturing the article can include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fiber preform can optionally be shaped before or after removing the solvent. In some embodiments, the curable thermosetting composition layer can further include a woven or nonwoven glass fabric. For example, the curable layer can be prepared by impregnating a glass fabric with the curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), "Prepreg Technology," March 2005, Publication No. FGU 017b; Anonymous (Hexcel Corporation), "Advanced Fiber Reinforced Matrix Products for Direct Processes," June 2005, Publication No. ITA 272; and Bob Griffiths, "Farnborough Airshow Report 2006," CompositesWorld.com, September 2006. The weight and thickness of the reinforcing structure are selected according to the intended use of the composite, using criteria well known to those skilled in the art of producing fiber-reinforced resin composites. The reinforcing structure can contain various finishes suitable for the thermoset component of the curable thermoset composition.

[0090] Methods for producing articles from curable thermosetting compositions can include partially curing the curable thermosetting composition to form a prepreg or fully curing the curable thermosetting composition to form a composite article. References herein to the property of a "cured composition" refer to a composition that is substantially fully cured. For example, the resin in a laminate formed from a prepreg is typically substantially fully cured. One skilled in the art of thermosetting can determine whether a sample is partially cured or substantially fully cured without undue experimentation. Curing can occur before or after removal of the solvent from the curable composition. Additionally, the article can be further shaped, for example, by thermoforming, before or after solvent removal, before curing, after partial curing, or after full curing. In some embodiments, the article is formed and the solvent is removed; the article is partially cured (B-staged); optionally shaped; and then further cured.

[0091] Commercial-scale methods for forming composites are known in the art, and the curable thermosetting compositions described herein are easily adaptable to existing processes and equipment. For example, prepregs are often produced in a treater. The main components of a treater include a feeder roller, a resin impregnation tank, a treater oven, and a receiver roller. A reinforcing structure (e.g., E-glass) is typically wound onto a large spool. The spool is then placed on a feeder roller, which rotates and slowly rolls the reinforcing structure. The reinforcing structure then travels through a resin impregnation tank containing the curable thermosetting composition. The curable composition impregnates the reinforcing structure. After emerging from the tank, the coated reinforcing structure travels upward through a vertical treater oven, typically at temperatures of 175 to 200°C, where the solvent evaporates. The resin begins to polymerize at this point. When the composite emerges from the tower, it is sufficiently cured so that the web is neither wet nor sticky. However, the curing process is stopped short to allow additional curing to occur as the laminate is made. The web then wraps the prepreg around a receiver roll.

[0092] Electrical and electronic articles comprising or derived from the curable thermoset compositions are also provided. Articles include those comprising printed circuits, such as those used in the medical or aerospace industries. Other articles include antennas and similar articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic memo pads, and similar devices, or office automation equipment. For example, electrical components can be mounted on printed circuit boards, including laminates. Other exemplary articles prepared from the curable compositions for various applications can include copper-clad laminates (CCLs), e.g., metal-core copper-clad laminates (MCCCLs), composite articles, and coated articles, e.g., multilayer articles.

[0093] The dielectric layer can be prepared from a curable thermosetting composition and can be useful in circuit assemblies, e.g., metal-clad laminates such as copper-clad laminates. For example, the laminate can include a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally, a heat-dissipating metal matrix layer disposed on the dielectric layer opposite the conductive metal layer. The dielectric layer can optionally include a fiber preform (e.g., a cloth layer). For example, the dielectric layer can further include a glass cloth layer.

[0094] The conductive metal layer can be in the form of a circuit and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, etc., or combinations thereof. Other metals include copper-molybdenum alloys, nickel-cobalt-iron alloys such as KOVAR available from Carpenter Technology Corporation, nickel-iron alloys such as INVAR available from National Electronic Alloys, Inc., bimetals, trimetals, trimetals derived from two layers of copper and one layer of INVAR, and trimetals derived from two layers of copper and one layer of molybdenum. Exemplary metal layers include copper or copper alloys. Alternatively, rolled copper foil can be used. The conductive metal layer can have a thickness of 2 to 200 μm, or 5 to 50 μm, or 5 to 40 μm.

[0095] The heat-dissipating metal matrix layer can be a thermally conductive metal, such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like, or a combination thereof. Any thermally conductive, electrically conductive metal can be used, provided that the metal is electrically insulated from the metal circuit layer. Preferred supporting metal matrix layers can have a thickness of 0.1 to 20 mm, or 0.5 to 10 mm, or 0.8 to 2 mm.

[0096] The conductive metal layer and the supporting metal matrix layer can be pretreated to have a high surface roughness to enhance adhesion to the dielectric layer. Treatment methods include, for example, cleaning, flame treatment, plasma discharge, corona discharge, etc. to enhance adhesion of the metal layer. The dielectric layer can be firmly bonded to the conductive metal layer or heat dissipation layer without the use of an adhesive, or an adhesive can be used to improve adhesion of the dielectric layer to the conductive metal layer or heat dissipation layer. Exemplary adhesives used to bond the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxies, etc., or combinations thereof.

[0097] Copper-clad laminates can be produced by thermal lamination of one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer under pressure without the use of a thermosetting adhesive. The dielectric layer can be prepared from a curable thermosetting composition and can be prepared by a solvent casting process to form the layer before the thermal lamination step. For example, a dielectric layer, a conductive metal layer, and a heat-dissipating layer can be thermally laminated together by an adhesive-free process under pressure to form a laminate. The conductive metal layer can optionally be in the form of a circuit before lamination, or the conductive metal layer can optionally be etched after lamination to form an electrical circuit. Lamination can be by hot pressing or roll calendaring, for example, a roll-to-roll process. The conductive metal layer in the copper-clad laminate can be further patterned to obtain a printed circuit board. Furthermore, the copper-clad laminate can be shaped to obtain a circuit board having a sheet, tube, or rod shape.

[0098] Alternatively, laminates for circuit assemblies can be made by solution casting, in which a curable thermosetting composition is cast directly onto a conductive metal layer, followed by lamination to a heat-dissipating metal matrix layer. For example, a curable thermosetting composition can be cast directly onto a heat-dissipating metal matrix layer, followed by lamination to a conductive metal layer.

[0099] Multilayer laminates containing additional layers can also be prepared by thermal lamination in one step or two or more consecutive steps by processes such as hot pressing or roll calendering. For example, there can be up to seven layers, or up to 16 layers, in a laminate. In one embodiment, a laminate can be formed in one step or two or more consecutive steps with sequential layers of fabric-thermoset-metal-thermoset-fabric-thermoset-metal foil, or subcombinations thereof with fewer layers, with the laminate including a layer of thermoset film between any layer of metal foil and any layer of fabric. In another embodiment, a first laminate can be formed in one step or two or more consecutive steps with a layer of fabric between two layers of thermoset, e.g., a layer of woven glass fabric between two layers of thermoset. A second laminate can then be prepared by laminating metal foil to the thermoset side of the first laminate.

[0100] Printed circuit boards prepared from the curable thermosetting compositions can have a total thickness of 0.1 to 20 mm, specifically 0.5 to 10 mm, where the total thickness refers to the assembly including the dielectric layer, conductive metal layer, and supporting metal matrix layer. The circuit assembly can have a total thickness of 0.5 to 2 mm, specifically 0.5 to 1.5 mm. There is no limit to the thickness of the dielectric layer, which can be 5 to 1500 μm, or 5 to 750 μm, or 10 to 150 μm, or 10 to 100 μm. For example, the printed circuit board can be a metal-core printed circuit board (MCPCB) for use in light-emitting diode (LED) applications.

[0101] The curable thermoset composition can be used as a coating, for example, in preparing multilayer articles. A method of making a coating can include combining the curable thermoset composition and optionally a fluoropolymer, and forming a coating on a substrate. For example, a multilayer article can be produced by forming a layer comprising a curable thermoset composition, removing solvent from the layer and optionally curing to obtain a primer layer, forming a second layer over the primer layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, YO3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, BC, TiC, Si3N4, TiN, BN, AlN, TiB, ZrB2, etc.), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, etc.), or a combination thereof to obtain a multilayer article, and optionally thermally treating the multilayer article to cure the curable thermoset composition. In some embodiments, the second layer can further comprise a curable thermoset composition.

[0102] Additional uses for the curable thermoset compositions include, for example, acid bath vessels; neutralization tanks; aircraft components; bridge girders; bridge decks; electrolytic cells; exhaust stacks; scrubbers; athletic equipment; stairs; walkways; automotive skin panels such as hoods and trunk lids; floor pans; air intakes; pipes and ducts, including heater ducts; industrial fans, fan housings and blowers; industrial mixers; ship hulls and decks; fenders for marine terminals; tiles and coatings; building panels; business machine housings; trays, including cable trays; concrete modifiers; dishwashers and refrigeration. Warehouse components; electrical encapsulants; electrical panels; tanks and tank linings, including electrolytic refining tanks, water softener tanks, fuel tanks, and various filament-wound tanks; furniture; garage doors; gratings; protective body gear; luggage; outdoor vehicles; pressure tanks; optical waveguides; radomes; handrails; railroad components such as tank cars; hopper car covers; car doors; truck bed liners; satellite dishes; signage; solar energy panels; telephone switch housings; tractor components; transformer covers; truck components such as fenders, hoods, bodies, cabs, and berths; connections Insulation for rotating machines, including ground, turn and phase isolation insulators; commutators; conductor insulation and cord and lacing tape; drive shaft couplings; propeller blades; missile components; rocket motor cases; wing sections; sucker rods; fuselage sections; wing skins and flaring; engine nacelles; cargo doors; tennis rackets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; lateral leaf springs; pumps, such as automotive smog pumps; electrical components, such as power cable joints, embedded and tooling wire wound and densely packed multi-element assemblies; electromechanical device encapsulations; battery cases; resistors; fuses and thermal cut-off devices; coatings for printed wiring boards; casting items such as capacitors, transformers, crankcase heaters, etc.; miniature molded electronic components including coils, capacitors, resistors and semiconductors; as steel replacement in chemical processing, pulp and paper, power generation and wastewater treatment; scrubbers; pultruded parts for structural applications including structural members, gratings and safety rails; swimming pools, swimming pool slides, hot tubs and saunas;Drive shafts for under-hood applications; dry toner resins for copiers; marine tooling and composites; heat shields; submarine hulls; prototype production; experimental model development; laminate trim; drilling jigs; joining jigs; inspection fixtures; industrial metal forming dies; aircraft stretch block and hammer formwork; vacuum molding tools; flooring, including flooring for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, coolers, and outdoor loading docks; conductive compositions for antistatic applications; decorative flooring; expansion joints for bridges; injectable mortars for patching and repairing cracks in structural concrete; tile grouting; machine rails; metal dowels; bolts and supports; oil and fuel storage tank repair, and numerous other uses.

[0103] Useful processes for preparing articles and materials include those generally known in the art for processing thermoset resins, as described in, for example, Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987, Cyril A. Dostal, Senior Ed., pp. 105-168 and 497-533, and "Polyesters and Their Applications" by Bjorksten Research Laboratories, Johan Bjorksten (pres.), Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), and James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing techniques include resin transfer molding, sheet molding, bulk molding, pultrusion, injection molding, including reaction injection molding (RIM), atmospheric pressure molding (APM), casting, including centrifugal and static casting, open mold casting, lamination, including wet or dry layup and spray layup, contact molding, including cylindrical contact molding, compression molding, including vacuum-assisted resin transfer molding and chemically-assisted resin transfer molding, conformal tool molding, autoclave curing, heat curing in air, vacuum bagging, pultrusion, Seeman's Composite Resin Infusion Manufacturing Processing (SCRIMP), open molding, sequential combination of resin and glass, and filament winding, including cylindrical filament winding. For example, articles can be prepared by a resin transfer molding process.

[0104] In some embodiments, an article is provided that is derived from the curable thermosetting composition, and the article is a composite, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded component, prepreg, casing, cast article, laminate, or combination thereof; alternatively, the article is a metal-clad laminate, electronic composite, structural composite, or combination thereof. The article can be manufactured as disclosed herein, for example, by casting, molding, extruding, etc., and removing the solvent from the formed article. In some embodiments, the article can be a layer and can be formed by casting the curable composition on a substrate to form a cast layer. The solvent can be removed by any number of means, including heating the cast layer, heating the cast layer under heat and pressure, for example, by laminating the cast layer to another substrate. In some embodiments, the article prepared by the above-described methods can include an adhesive, packaging material, capacitor film, or circuit board layer. In some embodiments, the article prepared from the curable composition can be a dielectric layer or a coating disposed on a substrate, such as a wire or cable coating. For example, the article can be a dielectric layer in a circuit material, such as a printed circuit board, used, for example, in lighting or communication applications. Another exemplary article prepared from the curable composition can be one or more coating layers. The curable composition can be used to prepare articles as disclosed herein for other curable thermoset compositions. [Example]

[0105] The present disclosure is further illustrated by the following non-limiting examples.

[0106] The ingredients used in the examples are summarized in Table 1.

[0107] [Table 1]

[0108] Weight average molecular weight (Mw ) was measured by gel permeation chromatography (GPC). n ) is a proton nuclear magnetic resonance ( 1 The average degree of functionality was measured by H-NMR spectroscopy and by GPC using polystyrene standards. 1 The glass transition temperature (T g The viscosity of the oligomers was measured by differential scanning calorimetry (DSC) from 25 to 300°C at a heating rate of 20°C / min. Solution viscosity was measured at 25°C (Brookfield viscometer; spindle 00) using 50 wt% solutions of the oligomers in either MEK or toluene. Viscosity measurements were performed under nitrogen using a 25 mm parallel plate with a 1 mm target gap. Oscillatory temperature ramping was used at a starting temperature of 80°C and a heating ramp rate of 3°C / min, at a constant strain of 1% and an angular frequency of 10 Rad / s. Gel time was measured under nitrogen using a 25 mm parallel plate with a 1 mm target gap. Oscillatory temperature ramping was used at a starting temperature of 80°C and a heating ramp rate of 5°C / min, at a constant strain of 30% and an angular frequency of 10 Rad / s. Dielectric measurements were performed at 10 GHz using an Agilent Technologies E5071C network analyzer equipped with a split-post resonator, SPDR, and fixture. A Keysight E4991B impedance analyzer equipped with a Hewlett Packard 16453A parallel plate fixture was used for Dk and Df measurements from 100 MHz to 10 GHz.

[0109] Example 1 [Synthesis of uncapped polyindane oligomer (BPA-DIPB)] 74.5 grams (g) of BPA and 1.3 g of NaOH pellets were placed in a three-neck round-bottom flask. 2The flask was placed in a heating mantle with a thermocouple directly into the contents, with the temperature controlled via a Thermo-O-Watch controller. A vacuum distillation attachment was connected to the remaining neck of the flask and equipped with a one-neck round-bottom collection flask charged with 0.1 g of sodium bicarbonate. The collection flask was placed in an ice-water bath (0 °C). The contents of both flasks were drained under reduced pressure. The BPA and sodium hydroxide mixture was then slowly heated to melting (approximately 130-145 °C) and stirred with a magnetic stir bar. The yellow distillate was collected and formed a solid upon cooling in an ice bath. After distillation was complete, a small amount of residue remained in the original three-neck flask. The distillate was collected, dissolved in 100 milliliters (mL) of methylene chloride, and added to the first addition funnel. In a separate second addition funnel, 100 g of DIPB was added along with 100 mL of methylene chloride. In a three-necked round-bottom flask equipped with a magnetic stir bar, 10 mL of TFA was added to 100 mL of methylene chloride. Two addition funnels were attached to the remaining necks of the flask. The TFA-methylene chloride solution was stirred vigorously while the distillate solution and DIPB solution were added to the flask at a rate of 4 drops per minute. Once the addition was complete, the monomer and end-cap were added to the flask, and 3 drops of triflic acid were added, and the solution was stirred overnight. A white powder was precipitated from the solution using a mixture of methanol (600 mL) and distilled water (200 mL). The powder was collected via vacuum filtration and then washed in water (100 °C) for 4 hours to remove excess catalyst. The resulting product was obtained as a powder and dried in a vacuum oven under reduced pressure.

[0110] <Example 2> [Synthesis of uncapped polyindane oligomer (BPA-pDIPB)] This example was prepared following the same procedure as in Example 1, using the same amounts and types of reagents, except that 100 g of pDIPB was used instead of 100 g of DIPB.

[0111] Example 3 [Synthesis of uncapped polyindane oligomer (BPA-DIPB)] 301.01 g of BPA and 1.22 g of NaOH pellets were placed in a three-neck round-bottom flask. 2 The flask was placed in a heating mantle with a thermocouple directly into the contents, with the temperature controlled via a Thermo-O-Watch controller. A vacuum distillation attachment was connected to the remaining neck of the flask and equipped with a collection flask. The distillation column was equipped with another three-neck round-bottom flask, which was charged with dichloroethane (300 mL) and 5 mL of TFA. This flask was also equipped with a magnetic stir bar and an addition funnel, and charged with 246.8 g of DIPB and 300 mL of dichloroethane. The BPA and sodium hydroxide mixture was slowly heated to melt (approximately 140-145 °C) and stirred with a magnetic stir bar while both flasks were under vacuum. Once the distillate began to evolve, the addition funnel containing DIPB was opened to match the rate of distillate addition. The reaction flask containing the dichloroethane and TFA was vigorously stirred while the monomer and end cap were added. Once the distillation was complete and all the DIPB had been added, the flask was returned to atmospheric pressure and allowed to stir for 16 hours. A mixture of 600 mL of methanol and 200 mL of distilled water was added to the product to precipitate a white powder. The resulting powder was then pulverized using a blender and washed in methanol and water (three times each). The product was then washed in water (100°C) until a neutral pH was obtained. The powder was dried under reduced pressure. GPC: Mw = 1339 g / mol, Mn = 836 g / mol (polycarbonate standard).

[0112] Example 4 [Synthesis of uncapped polyindane oligomer (TMBPA-DIPB)] 81.3 g of TMBPA and 0.8 g of NaOH pellets were placed in a three-neck round-bottom flask. 2The flask was placed in a heating mantle with a thermocouple directly into the contents, with the temperature controlled via a R THERMO-O-WATCH controller. A vacuum distillation attachment was connected to the remaining neck of the flask and equipped with a single-neck round-bottom collection flask charged with 0.1 g of sodium bicarbonate. The collection flask was placed in an ice-water bath. Both flasks were under vacuum while the BPA and sodium hydroxide mixture was slowly heated to melt (approximately 200 °C) and stirred with a magnetic stir bar. The yellow distillate was collected and cooled in an ice bath to form a solid. Upon completion of the distillation, a small amount of residue remained in the original three-neck flask. The distillate was collected, dissolved in 75 mL of methylene chloride, and added to an addition funnel. In a separate addition funnel, 58.87 g of DIPB was added along with 75 mL of methylene chloride. In a three-neck round-bottom flask, 3 mL of TFA acid was added to 150 mL of methylene chloride and equipped with a magnetic stir bar. Two addition funnels were attached to the remaining neck of the flask. The TFA-methylene chloride solution was vigorously stirred while the distillate solution and DIPB solution were added to the flask at a rate of 4 drops per minute. The reaction was monitored by GPC and found to be complete in 4 hours. A white powder was precipitated from the solution using a mixture of methanol (600 mL) and distilled water (200 mL). The powder was isolated via vacuum filtration and then washed in boiling water for 4 hours to remove excess catalyst. The resulting product was obtained as a powder and dried in a vacuum oven under reduced pressure. GPC: Mw = 1956 g / mol, Mn = 1003 g / mol (polycarbonate standard).

[0113] <Example 5> [Synthesis of methacrylate-capped polyindane oligomer (BPA-DIPB-2MA)] The BPA-DIPB oligomer (50 g) from Example 3 was dissolved in 89 g of toluene in a 250 mL three-neck round-bottom flask equipped with a heating mantle, Dean-Stark condenser, stirrer, and thermocouple. Azeotropic distillation was performed to ensure water removal at 120°C. After water removal, the reaction mixture was cooled to 85°C, and DMAP (0.5 g) was added to it. After complete dissolution of DMAP, MAA (13.31 grams) was slowly added to the mixture using an addition funnel over 15 minutes. The reaction temperature was increased to 110°C for gentle reflux. The reaction was maintained at reflux with stirring for 4 hours and then allowed to cool. The BPA-DIPB-2MA product was isolated as a powder by precipitation into methanol. The product was further dried under vacuum and nitrogen at 110°C for 16 hours. Tg = 184°C (DSC).

[0114] Example 6 [Synthesis of methacrylate-capped polyindane oligomer (TMBPA-DIPB-2MA)] The TMBPA-DIPB oligomer (50 g) from Example 4 was dissolved in 89 g of toluene in a 250 mL three-neck round-bottom flask equipped with a heating mantle, Dean-Stark condenser, stirrer, and thermocouple. Azeotropic distillation was performed to ensure water removal at 120°C. After water removal, the reaction mixture was cooled to 85°C, and DMAP (0.5 g) was added to it. After complete dissolution of DMAP, MAA (12.15 g) was slowly added to the mixture using an addition funnel over 15 minutes. The reaction temperature was increased to 110°C for gentle reflux. The reaction was maintained at reflux with stirring for 4 hours and then allowed to cool. The toluene solution was washed twice with 30 g of deionized water. The toluene phase was separated, and TMBPA-DIPB-2MA was isolated by precipitation into methanol. The powder was further dried under vacuum and nitrogen at 110°C for 16 hours.

[0115] Curable compositions were prepared by dissolving and dispersing the ingredients listed in Table 2 in chloroform. The chloroform was removed under reduced pressure and nitrogen until a dry powder was obtained. The obtained dry powder was used for chemorheology and further cured during casting for performance evaluation. Casting preparation was as follows: the composition was partially cured until its gel time. The partially cured composition was transferred to a 40 mm diameter mold, and the mold was placed under a hot mold press. The sample was cured by ramping the temperature to 150°C under pressure (1 ton). Once at that temperature, the sample was cooled to 70°C, and the mold was transferred to a vacuum oven, where the sample was cured at 200°C for 120 minutes under vacuum.

[0116] Table 2 shows the formulations and properties of thermosetting formulations A and B. The properties are gel time (seconds, s), viscosity (Pascal seconds, Pa s), dielectric constant (Dk) and dissipation factor (Df).

[0117] [Table 2]

[0118] The results demonstrate that the examples can simultaneously achieve beneficial combinations of properties including dissipation factor, dielectric constant, viscosity, and gel time. Thus, curable thermoset compositions can provide desirable performance attributes for resins used in electronic materials.

[0119] Aspect 1. Formula (1): [ka] (1) [In the formula, R 1 , R 2 and R 3 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms; R x and R y are each independently a hydrogen atom, or: [ka] [In the formula, Y 2 is the expression [ka] [In the formula, R c and R d Each occurrence of is independently hydrogen or C 1~12 alkyl], and R 5a is a C optionally substituted with an epoxide-containing group, a cyanate-containing group, or one or two carboxylic acid groups; 1~12 is hydrocarbyl, and R 6 , R 7 and R 8 Each occurrence of is independently hydrogen, C 1~18 Hydrocarbyl, C 2~18 is a hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; R 9 , R 10 , R 11 , R 12 and R 13 Each occurrence of independently represents hydrogen, halogen, C 1~12 Alkyl, C 2~12 Alkenyl, hydroxy, amino, maleimide, carboxylic acid or C 2~20 alkyl ester; x and R y at least one of which is not a hydrogen atom; m is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1; and n is an integer from 2 to 20, preferably from 3 to 16. Capped polyindane oligomer.

[0120] Embodiment 2. The capped polyindane oligomer of embodiment 1, wherein the capped polyindane oligomer has Formula (2): [ka] (2) [In the formula, R 1 , R 2 and R 3 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms; R 6 , R 7 and R 8 Each occurrence of is independently hydrogen, C 1~18 Hydrocarbyl, C 2~18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; m is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1; and n is an integer from 2 to 20, preferably from 3 to 16. A capped polyindane oligomer comprising:

[0121] Embodiment 3. The capped polyindane oligomer of embodiment 1 or 2, wherein the capped polyindane oligomer has an average of 1.1 to 2 reactive end groups per molecule, or 1.4 to 2 reactive end groups per molecule, or 1.8 to 2 reactive end groups per molecule.

[0122] Embodiment 4. The capped polyindane oligomer of any one of Embodiments 1 to 3, wherein the capped polyindane oligomer comprises a capping agent and a compound of Formula (3): [ka] (3) [In the formula, R1 , R 2 and R 3 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms; m is an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1; and n is an integer from 2 to 20, preferably from 3 to 16. A capped polyindane oligomer prepared by reacting an uncapped polyindane oligomer of

[0123] Embodiment 5. The capped polyindane oligomer of any one of embodiments 1 to 4, wherein R 1 and R 2 are each independently hydrogen or C 1~12 primary alkyl; or hydrogen or C 1~6 is a primary alkyl; preferably, R 1 and R 2 A capped polyindane oligomer in which

[0124] Embodiment 6. The capped polyindane oligomer of any one of Embodiments 1 through 5, wherein m is 0.

[0125] Embodiment 7. The capped polyindane oligomer of any one of embodiments 1 to 6, wherein the capped polyindane oligomer is derived from the polycondensation of di(isopropenyl)benzene in the presence of an acid catalyst and a cracking product of a dihydric phenol.

[0126] Embodiment 8. The capped polyindane oligomer of embodiment 7, wherein the dihydric phenol is a dihydric phenol represented by formula (4): [ka] (4) [In the formula, R 1 and R 2 are each independently hydrogen, halogen, or C 1~12 hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy or C 2~12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen and oxygen atoms; R a and R b are each independently hydrogen, C 1~12 Hydrocarbyl or C 1~6 hydrocarbylene, provided that R a and R b At least one of the 1~12- alkyl] A capped polyindane oligomer comprising the compound:

[0127] Embodiment 9. The capped polyindane oligomer of embodiment 7 or 8, wherein the di(isopropenyl)benzene is 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, or a combination thereof; preferably 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, or a combination thereof; more preferably 1,3-diisopropenylbenzene.

[0128] Embodiment 10. A method of making the capped polyindane oligomer of any one of embodiments 1 to 9, comprising reacting di(isopropenyl)benzene in the presence of an acid catalyst and a cracking product of a dihydric phenol.

[0129] Embodiment 11. The method of embodiment 10, wherein the acid catalyst is a Lewis acid or a Bronsted acid; preferably, the acid catalyst is trifluoroacetic acid, SnCl4, BF3, H2SO4, or a combination thereof.

[0130] Embodiment 12. The method of embodiment 10 or 11, further comprising reacting a capping agent with an uncapped polyindane oligomer comprising phenolic end groups under conditions effective to provide a reaction mixture comprising the capped polyindane oligomer.

[0131] Embodiment 13. A curable thermoset composition comprising the capped polyindane oligomer of any one of Embodiments 1 to 9.

[0132] Embodiment 14. An article derived from the curable thermoset composition of embodiment 13.

[0133] Embodiment 15. The article of embodiment 14, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; preferably, the article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

[0134] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of any suitable material, step, or ingredient disclosed herein. The compositions, methods, and articles can additionally or alternatively be formulated to be devoid of, or substantially free of, any material (or species), step, or ingredient that is not otherwise necessary to achieve the function or purpose of the compositions, methods, and articles.

[0135] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., a range of "up to 25 wt%, or more specifically, 5 wt% to 20 wt%" includes the endpoints of the range, such as "5 wt% to 25 wt%," and all intermediate values). The disclosure of a narrower range or more specific group in addition to a broader range does not negate the broader range or larger group.

[0136] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "Combination" is inclusive of admixtures, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. "Or" means "and / or" unless expressly stated otherwise. References to "embodiments" throughout the specification mean that the particular element described in connection with that embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. In addition, it is understood that the described elements may be combined in any suitable manner in various embodiments. "Combinations thereof" is open and includes any combination that includes at least one of the listed components or properties, optionally together with a similar or equivalent component or property that is not listed.

[0137] Unless otherwise specified herein, all test standards are the latest standards in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears. Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term from this application shall take precedence over the conflicting term from the incorporated reference.

[0138] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency satisfied by the bond or hydrogen atom as indicated. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

[0139] The term "hydrocarbyl" refers to a univalent group containing carbon and hydrogen. Hydrocarbyl can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkylaryl, or arylalkyl, as defined below. The term "hydrocarbylene" refers to a divalent group containing carbon and hydrogen. Hydrocarbylene can be alkylene, cycloalkylene, arylene, alkylarylene, or arylalkylene, as defined below. The term "alkyl" refers to a branched or straight-chain, unsaturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" refers to a straight- or branched-chain, monovalent hydrocarbon group having at least one carbon-carbon double bond, such as ethenyl (-HC=CH). "Alkoxy" refers to an alkyl group linked through oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a straight- or branched-chain, saturated, divalent aliphatic hydrocarbon group, such as methylene (-CH-) or propylene (-(CH)-). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-xwhere x is the number of hydrogens replaced by the cyclization. "Cycloalkenyl" means a monovalent radical having one or more rings and one or more carbon-carbon double bonds in the ring, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon radical containing the specified number of carbon atoms, e.g., phenyl, tropone, indanyl, or naphthyl. "Arylene" means a divalent aryl radical. "Alkylaryl" means an aryl group substituted with an alkyl group. "Arylalkyl" means an alkyl group substituted with an aryl group (e.g., benzyl). "Aryloxy" means an aryl group having the indicated number of carbon atoms attached through an oxygen bridge (-O-). "Alkylester" means a radical of the formula -C(O)OR, where R is an alkyl group. "Amino" means a monovalent radical of the formula -NRR', where R and R' are independently hydrogen or C 1~30 Hydrocarbyl, e.g., C 1~20 Alkyl group or C 6~30 It is an aryl group. "Halogen" or "halogen atom" means a fluorine, chlorine, bromine, or iodine atom. The prefix "halo" refers to a group or compound that contains one or more fluoro, chloro, bromo, or iodo substituents. Combinations of different halo groups (e.g., bromo and fluoro), or only chloro groups, can be present. The prefix "hetero" refers to a compound or group that contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), each of which is independently N, O, S, Si, or P.

[0140] Unless a substituent is specifically indicated otherwise, each of the foregoing groups may be unsubstituted or substituted, provided that the substitution does not significantly adversely affect either the synthesis, stability, or use of the compound. "Substituted" means that the compound, group, or atom is substituted in place of hydrogen with at least one (e.g., 1, 2, 3, or 4) substituents, each of which is independently selected from the group consisting of nitro (-NO), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 6~12 Aryl, C 7~13 Arylalkyl (e.g., benzyl), C 7~12 Alkylaryl (e.g., toluyl), C 4~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 arylsulfonyl (-S(=O)-aryl) or tosyl (CHCHSO-), provided that the normal valence of the substituted atom is not exceeded and the substitution does not significantly adversely affect either the preparation, stability, or desired properties of the compound. When a compound is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the compound or group, including those of any substituents.

[0141] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not presently foreseen or may not be foreseen may become apparent to applicants or others skilled in the art. Accordingly, the appended claims are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents as filed and as they may be amended.

Claims

1. Formula (1): 【Chemistry 1】 （１） [In the formula, R １ , R ２ and R ３ are each independently hydrogen, halogen, or C １～１２ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; １～１２ Hydrocarbylthio, C １～１２ Hydrocarbyloxy or C ２～１２ halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms in said C2-12 halohydrocarbyloxy; R ｘ and R ｙ are each independently a hydrogen atom, or: 【Chemistry 2】 [In the formula, Y ２ is the expression 【Transformation 3】 [In the formula, R ｃ and R ｄ Each occurrence of is independently hydrogen or C １～１２ is an alkyl; R ５ａ is a C optionally substituted with an epoxide-containing group, a cyanate-containing group, or one or two carboxylic acid groups; １～１２ is a hydrocarbyl, R ６ , R ７ and R ８ Each occurrence of is independently hydrogen, C １～１８ Hydrocarbyl, C ２～１８ is a hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; R ９ , R １０ , R １１ , R １２ and R １３ Each occurrence of is independently hydrogen, halogen, C １～１２ Alkyl, C ２～１２ Alkenyl, hydroxy, amino, maleimide, carboxylic acid or C ２～２０ is an alkyl ester; However, R ｘ and R ｙ at least one of which is not a hydrogen atom; m is an integer from 0 to 3; n is an integer from 2 to 20. A capped polyindane oligomer characterized by:

2. 10. The capped polyindane oligomer of claim 1, wherein the capped polyindane oligomer has the formula (2): 【Chemistry 4】 （２） [In the formula, R １ , R ２ and R ３ are each independently hydrogen, halogen, or C １～１２ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; １～１２ Hydrocarbylthio, C １～１２ Hydrocarbyloxy or C ２～１２ halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms in said C2-12 halohydrocarbyloxy; R ６ , R ７ and R ８ Each occurrence of is independently hydrogen, C １～１８ Hydrocarbyl, C ２～１８ is a hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; m is an integer from 0 to 3; n is an integer from 2 to 20.

1. A capped polyindane oligomer comprising:

3. 10. The capped polyindane oligomer of claim 1, wherein the capped polyindane oligomer has an average of 1.1 to 2 reactive end groups per molecule.

4. 10. The capped polyindane oligomer of claim 1, comprising a capping agent and a polyindane oligomer of formula (3): 【Transformation 5】 （３） [In the formula, R １ , R ２ and R ３ are each independently hydrogen, halogen, or C １～１２ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; １～１２ Hydrocarbylthio, C １～１２ Hydrocarbyloxy or C ２～１２ halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms in said C2-12 halohydrocarbyloxy; m is an integer from 0 to 3; n is an integer from 2 to 20.

1. A capped polyindane oligomer prepared by reacting an uncapped polyindane oligomer of the formula:

5. 2. The capped polyindane oligomer of claim 1, wherein R １ and R ２ are each independently hydrogen or C １～１２ primary alkyl; or hydrogen or C １～６ A capped polyindane oligomer characterized by being a primary alkyl.

6. 2. The capped polyindane oligomer of claim 1, wherein m is 0.

7. 10. The capped polyindane oligomer of claim 1, wherein the capped polyindane oligomer is derived from the polycondensation of di(isopropenyl)benzene in the presence of an acid catalyst and a cracking product of a dihydric phenol.

8. 8. The capped polyindane oligomer of claim 7, wherein the dihydric phenol is represented by formula (4): 【Transformation 6】 （４） [In the formula, R １ and R ２ are each independently hydrogen, halogen, or C １～１２ hydrocarbyl, provided that the hydrocarbyl group is not a tertiary hydrocarbyl; １～１２ Hydrocarbylthio, C １～１２ Hydrocarbyloxy or C ２～１２ halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms in said C2-12 halohydrocarbyloxy; R ａ and R ｂ are each independently hydrogen, C １～１２ Hydrocarbyl or C １～６ is hydrocarbylene, However, R ａ and R ｂ At least one of １～１２－ alkyl] A capped polyindane oligomer comprising the compound:

9. 8. The capped polyindane oligomer of claim 7, wherein the di(isopropenyl)benzene is 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, or a combination thereof.

10. 10. A method for producing the capped polyindane oligomer of any one of claims 1 to 9, comprising reacting di(isopropenyl)benzene in the presence of an acid catalyst and a cracking product of a dihydric phenol.

11. 11. The method of claim 10, wherein the acid catalyst is a Lewis acid or a Bronsted acid.

12. 11. The method of claim 10, further comprising reacting a capping agent with an uncapped polyindane oligomer comprising phenolic end groups under conditions effective to provide a reaction mixture comprising the capped polyindane oligomer.

13. A curable thermosetting composition comprising the capped polyindane oligomer of any one of claims 1 to 9.

14. 14. An article derived from the curable thermoset composition of claim 13.

15. 15. The article of claim 14, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof.

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