Capped poly(phenylene ether)s and curable thermoset compositions containing same - Patents.com

Abstract

Disclosed herein are capped poly(phenylene ethers) having activated ester end groups and structures as further defined herein. The capped poly(phenylene ethers) can be particularly useful in curable compositions, thermoset compositions, and articles formed therefrom.

Description

[Technical field]

[0001] This disclosure relates to capped poly(phenylene ethers), curable thermoset compositions containing same, and articles derived therefrom.

[0002] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of European Patent Application No. 22151118.1, filed January 12, 2022, the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0003] Thermosets are materials that cure to form ultra-hard plastics. These materials can be used in a wide variety of consumer and industrial products. For example, thermosets are used in protective coatings, adhesives, electronic laminates (such as those used in making computer circuit boards), flooring and paving applications, fiberglass reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components).

[0004] Poly(phenylene ethers) can improve the dielectric performance, heat resistance, flame retardancy and moisture absorption of thermoset materials, making them particularly well suited for a variety of applications, especially electronic applications. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, it would be advantageous to provide poly(phenylene ethers) for use in curable thermosetting compositions. [Means for solving the problem]

[0006] The capped poly(phenylene ether) has the structure: [ka] or [ka] In the formula, Z 1 , Z 2 , Z 3 , and Z 4 each independently represents hydrogen, halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C 1-12 Hydrocarbyloxy, and C 2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom, and R 1 is a substituted or unsubstituted phenylene group, R 2 is substituted or unsubstituted C 6-20 an aromatic hydrocarbon group, n is an integer from 4 to 50, x and y are each independently from zero to 50, provided that the sum of x and y is from 2 to 53, and L is a group of the formula: [ka] In the formula, R 3 , R 4 , R 5 , and R 6 Each event is independently hydrogen, halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C 1-12 Hydrocarbyloxy, or C 2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom, z is 0 or 1, and Y has a structure including: [ka] , where R 7 Each event is independently hydrogen and C 1-12 Contains hydrocarbyl, R 8 and R 9 Each event is independently hydrogen, C 1-12 Hydrocarbyl, or C1-6 Hydrocarbylene, where R 8 and R 9 are collectively C 4-12 It forms an alkylene group, or Y has a structure derived from a hydroxyaryl-diterminated polysiloxane.

[0007] The curable thermoset composition comprises a capped poly(phenylene ether).

[0008] A cured thermoset composition comprises the cured product of a curable thermoset composition.

[0009] The article comprises a cured thermoset composition.

[0010] These and other features are illustrated in the following detailed description. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present inventors have discovered that capped poly(phenylene ethers) having activated ester end groups can be prepared and conveniently used to provide curable thermoset compositions having desirable combinations of dielectric properties, flame retardancy, and thermal performance.

[0012] Thus, one aspect of the present disclosure is a capped poly(phenylene ether). The capped poly(phenylene ether) comprises repeat units derived from a substituted or unsubstituted monohydric phenol. The substituted or unsubstituted monohydric phenol can have the structure: [ka] In the formula, Z 1 , Z 2 , Z 3 , and Z 4 each independently represents hydrogen, halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C 1-12 Hydrocarbyloxy, and C2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom. In one embodiment, the substituted or unsubstituted monohydric phenol is a 2,6-(di-C 1-6 In one embodiment, Z 1 and Z 4 are each methyl, and Z 2 and Z 3 are each hydrogen, and the monohydric phenol is 2,6-xylenol (also called 2,6-dimethylphenol or "DMP").

[0013] Thus, the capped poly(phenylene ether) contains repeat units of the formula: [ka] In the formula, Z 1 , Z 2 , Z 3 , and Z 4 can be as described above. In one embodiment, the capped poly(phenylene ether) is a 2,6-(di-C 1-18 alkyl)phenol, or 2,6-diphenylphenol, 2-phenyl-6-(C 1-18 alkyl)phenols, 2-phenyl-6-(cycloalkyl)phenols, 2,6-(dicycloalkyl)phenols, 2-(C 1-18 In one embodiment, the capped poly(phenylene ether) comprises repeat units derived from a monohydric phenol, including 2,6-dimethylphenol, 2,6-dimethylphenyl ...

[0014] The capped poly(phenylene ether) contains at least one activated ester end group of the formula: [ka] In the formula, R 1 is a substituted or unsubstituted phenylene group, R 2 is substituted or unsubstituted C6-20 It is an aromatic hydrocarbon group. * " indicates the point of attachment of the activated ester end group to the poly(phenylene ether).

[0015] In one embodiment, the capped poly(phenylene ether) has the structure: [ka] In the formula, Z 1 , Z 2 , Z 3 , Z 4 , R 1 and R 2 can be as described above, and n is an integer from 4 to 50. In one embodiment, Z 2 and Z 3 are each hydrogen, and Z 1 and Z 4 are each unsubstituted or substituted C 1-12 In one embodiment, Z is a primary hydrocarbyl. 1 and Z 4 are respectively, C 1-6 In one embodiment, R 1 is an unsubstituted phenylene group. 1 is derived from terephthalic acid or isophthalic acid. 2 includes a phenyl group, a methyl-substituted phenyl group, a dimethyl-substituted phenyl group, a phenyl-substituted phenyl group, a benzyl-substituted phenyl group, a cumyl-substituted phenyl group, or a naphthyl group, preferably a phenyl group or a naphthyl group.

[0016] In one embodiment, the capped poly(phenylene ether) can have the structure: [ka] , [ka] , [ka] ,or [ka] , where Z 1 , Z 2 , Z 3 , Z 4 and n can be as described above, where n is an integer from 4 to 50.

[0017] In one embodiment, the capped poly(phenylene ether) can have the structure: [ka] , [ka] , [ka] ,or [ka] where n is an integer from 4 to 50.

[0018] In one embodiment, the capped poly(phenylene ether) has the structure: [ka] In the formula, Z 1 , Z 2 , Z 3 , Z 4 , R 1 and R 2 can be as described above, and x and y are each independently zero to 50, provided that the sum of x and y is 2 to 53. 2 and Z 3 are each hydrogen, and Z 1 and Z 4 are each unsubstituted or substituted C 1-12 In one embodiment, Z is a primary hydrocarbyl. 1and Z 4 are respectively, C 1-6 In one embodiment, R 1 is an unsubstituted phenylene group. 1 is derived from terephthalic acid or isophthalic acid. 2 includes a phenyl group, a methyl-substituted phenyl group, a dimethyl-substituted phenyl group, a phenyl-substituted phenyl group, a benzyl-substituted phenyl group, a cumyl-substituted phenyl group, or a naphthyl group, preferably a phenyl group or a naphthyl group.

[0019] L can be a group of the formula: [ka] In the formula, R 3 , R 4 , R 5 , and R 6 Each event is independently hydrogen, halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C 1-12 Hydrocarbyloxy, or C 2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom, z is 0 or 1, and Y has a structure including: [ka] , where R 7 Each event is independently hydrogen and C 1-12 Contains hydrocarbyl, R 8 and R 9 Each event is independently hydrogen, C 1-12 Hydrocarbyl, or C 1-6 Hydrocarbylene, where R 8 and R 9 are collectively C 4-12 Forms an alkylene group. For example, R 8 and R 9 can collectively form a cyclohexylidene group.

[0020] In one embodiment, L can be a group derived from a hydroxyaryl diterminated polysiloxane. When L is derived from a hydroxyaryl terminated polysiloxane, the poly(phenylene ether) can be referred to as a poly(phenylene ether)-siloxane block copolymer having at least one poly(phenylene ether) block and at least one polysiloxane block.

[0021] The hydroxyaryl diterminated polysiloxane can include multiple repeat units having the structure: [ka] In the formula, R 10 Each event is independently hydrogen, C 1-12 Hydrocarbyl or C 1-12 The hydroxyaryl diterminated polysiloxane further comprises two terminal units having the following structure: [ka] In the formula, Y is hydrogen, C 1-12 Hydrocarbyl, C 1-12 hydrocarbyloxy, or halogen; R 11 Each event is independently hydrogen, C 1-12 Hydrocarbyl or C 1-12 In one embodiment, R is a halohydrocarbyl. 10 and R 11 Each occurrence of is methyl and Y is methoxy.

[0022] In one embodiment, the hydroxyaryl terminated polysiloxane has the structure: [ka] wherein m is, on average, from 5 to 100, or from 5 to 45, or from 30 to 60.

[0023] In one embodiment, R 3 and R4 is not hydrogen. 3 and R 4 are respectively, C 1-6 is an alkyl group, preferably a methyl group, R 5 and R 6 Each is hydrogen. In certain embodiments, R 3 and R 4 Each event is methyl, and R 5 and R 6 are hydrogen, z is 1, and Y is an isopropylidene group. 3 and R 4 Each event is methyl, and R 5 and R 6 each occurrence of is hydrogen, z is 1, Y is an isopropylidene group, and Z 2 and Z 3 are each hydrogen, and Z 1 and Z 4 are each unsubstituted or substituted C 1-12 It is a primary hydrocarbyl, preferably methyl.

[0024] In one embodiment, the capped poly(phenylene ether) can have the structure: [ka] , [ka] , [ka] ,or [ka] , where Z 1 , Z 2 , Z 3 , Z 4 , L, x and y may be as defined above.

[0025] In one embodiment, the capped poly(phenylene ether) can have the structure: [ka] , [ka] , [ka] ,or [ka] where L, x and y can be as defined above.

[0026] In one embodiment, the capped poly(phenylene ether) can have the structure: [ka] , where x, y, R 1 and R 2 may be as defined above. In one embodiment, R 1 is a divalent phenylene group, R 2 is a phenyl group or a naphthyl group.

[0027] The poly(phenylene ether) can have a number average molecular weight of less than 20,000 grams / mole, or less than 10,000 grams / mole, or less than 7,500 grams / mole. For example, the poly(phenylene ether) can have a number average molecular weight of 500 to 20,000 g / mol, or 500 to 10,000 g / mol, or 500 to 7,500 g / mol. Molecular weights can be determined by gel permeation chromatography (GPC) against polystyrene standards or calculated from the degree of polymerization determined using nuclear magnetic resonance (NMR) spectroscopy.

[0028] The poly(phenylene ether) may have an intrinsic viscosity of 0.15 deciliters per gram or less, preferably from 0.02 to 0.15 deciliters per gram, and more preferably from 0.12 to 0.13 deciliters per gram. Intrinsic viscosity may be determined by Ubbelohde viscometer in chloroform at 25° C.

[0029] Capped poly(phenylene ether)s can be prepared by a process that includes the oxidative polymerization of a monohydric phenol, and optionally a dihydric phenol, in the presence of a catalyst to provide a poly(phenylene ether) having phenolic end groups. The oxidative polymerization can be carried out in the presence of an organic solvent. Suitable organic solvents include alcohols, ketones, aliphatic and aromatic hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, mixed ether-esters, sulfoxides, and the like, provided that they do not interfere with or participate in the oxidation reaction. High molecular weight poly(phenylene ether)s can significantly increase the viscosity of the reaction mixture. Therefore, it is sometimes desirable to use a solvent system that allows low molecular weight polymers to remain in solution until they are precipitated but the high molecular weight polymers form. The organic solvent can include, for example, toluene, benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, trichloroethylene, ethylene dichloride, dichloromethane, chloroform, or a combination thereof. Preferred solvents include aromatic hydrocarbons. In one embodiment, the organic solvent comprises toluene, benzene, xylene, chloroform, chlorobenzene, or a combination thereof, preferably toluene.

[0030] The oxidative polymerization is further carried out in the presence of a copper-amine catalyst. The copper source for the copper-amine catalyst can include salts of cupric or cuprous ions, such as halides, oxides, and carbonates. Alternatively, the copper can be provided in the form of a preformed salt of an alkylenediamine ligand. Preferred copper salts include cuprous halides, cupric halides, and combinations thereof. Cuprous bromide, cupric bromide, and combinations thereof are particularly preferred.

[0031] Preferred copper-amine catalysts contain a secondary alkylenediamine ligand. Suitable secondary alkylenediamine ligands are described in U.S. Patent No. 4,028,341 to Hay and are represented by the formula: R b -NH-R a -NH-R c In the formula, R a is a substituted or unsubstituted divalent residue in which two or three aliphatic carbon atoms form the nearest bond between the two diamine nitrogen atoms, and R b and R c each independently is isopropyl or a substituted or unsubstituted C 4-8 R is a tertiary alkyl group. a Examples of R include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, the various pentylene isomers having 2 to 3 carbon atoms separating the two valences, phenylethylene, tolylethylene, 2-phenyl-1,2-propylene, cyclohexylethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,2-cyclopentylene, and the like. a is ethylene. b and R c Examples of R include isopropyl, t-butyl, 2-methyl-but-2-yl, 2-methyl-pent-2-yl, 3-methyl-pent-3-yl, 2,3-dimethyl-but-2-yl, 2,3-dimethylpent-2-yl, 2,4-dimethyl-pent-2-yl, 1-methylcyclopentyl, 1-methylcyclohexyl, and the like. b and R c A highly preferred example of is t-butyl. An exemplary secondary alkylenediamine ligand is N,N'-di-t-butylethylenediamine (DBEDA). Suitable molar ratios of copper to secondary alkylenediamine are 1:1 to 1:5, preferably 1:1 to 1:3, more preferably 1:1.5 to 1:2.

[0032] Preferred copper-amine catalysts containing a secondary alkylenediamine ligand may further contain a secondary monoamine. Suitable secondary monoamine ligands are described in commonly assigned U.S. Patent No. 4,092,294 to Bennett et al. and are represented by the formula: R d -NH-R e In the formula, R d and R e each independently represents a substituted or unsubstituted C 1-12 Alkyl groups, preferably substituted or unsubstituted C 3-6 It is an alkyl group. Examples of secondary monoamines include di-n-propylamine, di-isopropylamine, di-n-butylamine, di-sec-butylamine, di-t-butylamine, N-isopropyl-t-butylamine, N-sec-butyl-t-butylamine, di-n-pentylamine, bis(1,1-dimethylpropyl)amine, and the like. A highly preferred secondary monoamine is di-n-butylamine (DBA). The preferred molar ratio of copper to secondary monoamine is 1:1 to 1:10, preferably 1:3 to 1:8, more preferably 1:4 to 1:7.

[0033] Preferred copper-amine catalysts containing secondary alkylenediamine ligands can further contain tertiary monoamines. Suitable tertiary monoamine ligands are described in the above-mentioned U.S. Pat. No. 4,028,341 to Hay and U.S. Pat. No. 4,092,294 to Bennett, and include heterocyclic amines and certain trialkylamines, characterized by having an amine nitrogen bonded to at least two groups having a small cross-sectional area. In the case of trialkylamines, at least two of the alkyl groups are methyl and the third alkyl group is a primary C 1-8 Alkyl group or secondary C 3-8It is preferably an alkyl group. It is especially preferred that the third substituent has 4 or less carbon atoms. A highly preferred tertiary amine is dimethylbutylamine (DMBA). The preferred molar ratio of copper to tertiary amine is less than 1:20, preferably less than 1:15, preferably from 1:1 to less than 1:15, more preferably from 1:1 to 1:12.

[0034] Suitable molar ratios of copper-amine catalyst (measured as moles of metal) to poly(phenylene ether) starting material are from 1:50 to 1:400, preferably from 1:100 to 1:200, more preferably from 1:100 to 1:180.

[0035] The reaction carried out in the presence of a copper-amine catalyst can optionally be carried out in the presence of bromide ions. It has already been mentioned that bromide ions can be provided as cuprous bromide or cupric bromide salts. Bromide ions can also be provided by the addition of 4-bromophenols such as 2,6-dimethyl-4-bromophenol. Additional bromide ions can be provided in the form of hydrobromic acid, alkali metal bromides, or alkaline earth metal bromides. Sodium bromide and hydrobromic acid are highly preferred sources of bromide. The preferred ratio of bromide ions to copper ions is 2 to 20, preferably 3 to 20, more preferably 4 to 7.

[0036] In one embodiment, each of the above components of the copper-amine catalyst are added simultaneously to the oxidative polymerization reaction.

[0037] The oxidative polymerization can optionally be carried out in the presence of one or more additional components, such as a lower alkanol or glycol, a small amount of water, or a phase transfer agent. Generally, it is not necessary to remove the reaction by-product water during the reaction.

[0038] In one embodiment, a phase transfer agent is present. Suitable phase transfer agents include, for example, quaternary ammonium compounds, quaternary phosphonium compounds, tertiary sulfonium compounds, or combinations thereof. Preferably, the phase transfer agent is a compound represented by the formula (R 3 )4Q +X, where R 3 are the same or different, C 1-10 alkyl, Q is a nitrogen or phosphorus atom, and X is a halogen atom or C 1-8 Alkoxy or C 6-18 Exemplary phase transfer catalysts include (CH(CH))NX, (CH(CH)PX, (CH(CH))NX, (CH(CH))NX, (CH(CH))NX, (CH(CH))NX, CH(CH(CH))NX, and CH(CH(CH)NX), where X is Cl. - , Br - , C 1-8 Alkoxy or C 6-18 aryloxy. An effective amount of the phase transfer agent can be 0.1 to 10 wt%, or 0.5 to 2 wt%, each based on the weight of the reaction mixture. In one embodiment, the phase transfer agent is present and comprises N,N,N'N'-didecyldimethylammonium chloride.

[0039] The oxidative polymerization can be carried out at a temperature of from 20 to 70° C., preferably from 30 to 60° C., more preferably from 45 to 55° C. Depending on the exact reaction conditions selected, the total polymerization reaction time - i.e., the time elapsed between the initiation of the oxidative polymerization and the termination of the oxidative polymerization - can vary, but is typically from 100 to 250 minutes, particularly from 145 to 210 minutes.

[0040] The method further includes terminating the oxidative polymerization to form a terminated reaction mixture. The reaction is terminated when the flow of oxygen to the reactor is stopped. Residual oxygen in the reactor headspace is removed by flushing with an oxygen-free gas, such as nitrogen.

[0041] After the polymerization reaction is terminated, the copper ions of the polymerization catalyst are separated from the reaction mixture. This is accomplished by combining a chelating agent with the terminated reaction mixture to form a chelated mixture. The chelating agent comprises an alkali metal salt of an aminopolycarboxylic acid, preferably an alkali metal salt of aminoacetic acid, more preferably an alkali metal salt of nitrilotriacetic acid, ethylenediaminetetraacetic acid, or a combination thereof, even more preferably a sodium salt of nitrilotriacetic acid, a sodium salt of ethylenediaminetetraacetic acid, or a combination thereof. In one embodiment, the chelating agent comprises an alkali metal salt of nitrilotriacetic acid. In one embodiment, the chelating agent is a sodium or potassium salt of nitrilotriacetic acid, specifically trisodium nitrilotriacetate. After stirring the chelated mixture, the mixture comprises an aqueous phase containing chelated copper ions and an organic phase containing dissolved poly(phenylene ether). The chelating mixture can exclude the dihydric phenols required by Cooper et al., U.S. Pat. No. 4,110,311, the aromatic amines required by Cooper et al., U.S. Pat. No. 4,116,939, and the mild reducing agents of Cooper et al., U.S. Pat. No. 4,110,311, including sulfur dioxide, sulfurous acid, sodium bisulfite, sodium thionite, tin(II) chloride, iron(II) sulfate, chromium(II) sulfate, titanium(III) chloride, hydroxylamine and their salts, phosphates, glucose, and mixtures thereof. The chelating mixture is maintained at a temperature of 40 to 55° C., specifically 45 to 50° C., for a period of 5 to 100 minutes, specifically 10 to 60 minutes, and more specifically 15 to 30 minutes. This combination of temperature and time is effective for copper sequestration while minimizing molecular weight degradation of the poly(phenylene ether). The chelation process includes (and is completed by) separating the aqueous and organic phases of the chelation mixture. This separation step can be carried out at a temperature of 40 to 55° C., specifically 45 to 50° C. The 5 to 100 minute time interval for maintaining the chelation mixture at 40-55° C. is measured from the time the terminated reaction mixture is first combined with the chelating agent to the time separation of the aqueous and organic phases is complete.

[0042] The method further includes reacting the poly(phenylene ether) with a capping agent under conditions effective to provide a capped poly(phenylene ether). Suitable capping agents can be selected without undue experimentation and guided by the present disclosure to provide the desired capped poly(phenylene ether). Exemplary methods for making capped poly(phenylene ether)s are provided in the Examples below.

[0043] Also provided are curable thermoset compositions comprising the capped poly(phenylene ether). For example, the capped poly(phenylene ether) can be present in the curable thermoset 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%, 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable thermoset composition.

[0044] 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 one embodiment, 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 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.

[0045] There is considerable overlap between thermosetting resins, crosslinkers, and coupling agents. As used herein, the term "crosslinker" includes compounds that can be used as a thermosetting resin, a crosslinker, a coupling agent, or a combination thereof. For example, in some cases, a compound that is a thermosetting resin could also be used as a crosslinker, a coupling agent, or both.

[0046] The thermosetting resin is not particularly limited, and the thermosetting resin can 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), and the like, or combinations thereof.

[0047] In one embodiment, the curable thermosetting composition comprises a capped poly(phenylene ether) and an epoxy resin.

[0048] The epoxy resin can generally 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, for example, as described in CA May, Epoxy Resins, Second Supplementary Edition, (New York & Basle: Marcel Dekker Inc.), 1988. Examples of epoxy resins include bisphenol A type epoxy resins, such as those obtained from bisphenol A and those 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 less carbon atoms, or a phenyl group; bisphenol F type epoxy resins, such as those obtained from bisphenol F and those 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 less carbon atoms, or a phenyl group; glycidyl ether compounds derived from divalent, trivalent or higher hydric phenols, such as hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; glycidyl ether compounds derived from phenol and formaldehyde, such as phenol and o-cresol; novolac-type epoxy resins derived from novolac resins which are reaction products between aldehydes, such as bisphenol A novolac-type epoxy resins and cresol novolac-type epoxy resins, cycloaliphatic epoxy compounds such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, dicyclopentadiene-containing polyepoxides, aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenyl-ethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene,Amine-type epoxy resins derived from 4-bis(3-aminophenoxy)-benzene, 1,3-bis(4-aminophenoxy)-benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-amino-phenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylene-diamine, m-xylylenediamine, 1,4-cyclohexane-bis(methylamine), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethyl-indane, etc., heterocyclic epoxy compounds, and glycidyl ester-type epoxy compounds, for example, those derived from the glycidyl esters of aromatic carboxylic acids, such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid. "Epoxy resin" can also include the reaction product of a compound containing two or more epoxy groups and an aromatic dihydroxy compound, which can be optionally halogen-substituted and can be used alone or in combination of two or more.

[0049] The cyanate ester is not limited, and any resin composed of cyanate ester monomers that polymerize 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 made using cyanate ester precursors, and combinations of these compounds. 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 JP-A-7-53497. Exemplary cyanate ester resins include 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, cyanate ester resins prepared from dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). Cyanate ester prepolymers can be homopolymers or can be copolymers incorporating other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical, such as BT2160 and BT2170, which are prepolymers made of 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 US7393904, US7388057, US7276563, and US7192651.

[0050] Bismaleimide resins can be formed by reaction of monomeric bismaleimides with nucleophiles such as diamines, aminophenols, or aminobenzhydrazides, or by reaction of bismaleimides with diallyl bisphenol A.Exemplary bismaleimide resins include 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimido-benzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimido-diphenylether, 3,3'-bismaleimidodiphenylsulfone, 4,4'-bismaleimido-diphenylsulfone, 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)propane, midophenyl)toluene, 3,5-bismaleimide-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, N,N'-m-meta-xylene-bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, and N,N'-methylene-bis(3-chloro-p-phenylene) bismaleimide, and those disclosed in US 3,562,223, US 4,211,860, and US 4,211,861 or prepared by the method described, for example, in US 3,018,290.

[0051] Benzoxazine compounds have a benzoxazine ring in the molecule. Exemplary benzoxazine monomers can be prepared from the reaction of aldehydes, phenols, and primary amines with or without solvent. Phenolic compounds for forming benzoxazines include phenols and polyphenols. By using polyphenols with two or more reactive hydroxyl groups in forming benzoxazines, branched products, crosslinked products, or combinations of branched and crosslinked products can be obtained. The group that links the phenol group in the phenol can be the branch point or linking group in the polybenzoxazine.

[0052] Exemplary phenols for use in preparing the benzoxazine monomers include: phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 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 hydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxy-phenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, dicyclopentadienyl bis(2,6-dimethylphenol), dicyclopentadienyl bis(ortho-cresol), dicyclopentadienyl bisphenol, etc. .

[0053] 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 an aromatic-substituted alkyl amine. The amine can be a polyamine, for example, to prepare a multifunctional benzoxazine monomer for crosslinking.

[0054] The amines for forming the benzoxazines have from 1 to 40 carbon atoms as long as they do not contain aromatic rings, and then they can have from 6 to 40 carbon atoms. Di- or polyfunctional amines can serve as branching points for linking one polybenzoxazine to another.

[0055] In some embodiments, thermal polymerization at 150 to 300° C. can be used to polymerize the benzoxazine monomers. The polymerization can be carried out in bulk, from solution, or otherwise. A catalyst, such as a carboxylic acid, can be used to reduce the polymerization temperature or to accelerate the polymerization rate at the same temperature.

[0056] Vinylbenzyl ether resins can be prepared from 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 thermosetting resins. Exemplary vinylbenzyl ethers include those produced from the reaction of vinylbenzyl halides with: resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',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)(tetramethylphenol) tetramethylbisphenol 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 diphenol, 4,4'-oxydiphenol, 4, 4'-Thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 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)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), dicyclopentadienyl bisphenol, etc.,

[0057] Arylcyclobutenes include those derived from compounds of the structure: [ka] where 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 phenolic compounds), each occurrence of X is independently hydroxy or C1-24 is hydrocarbyl (including straight chain and branched alkyl and cycloalkyl), and each occurrence of Z is independently hydrogen, halogen, or C 1-12 hydrocarbyl, and 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 US 4,743,399, US 4,540,763, US 4,642,329, US 4,661,193, US 4,724,260, and 5391,650.

[0058] Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane, followed by zinc-catalyzed reductive elimination to produce ZnFBr and the desired perfluorovinyl ether. Bis-, tris-, and other polyphenols can be used to produce bis-, tris-, and poly(perfluorovinyl ethers) by this route. Phenols useful in their synthesis include: resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)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'-tetra ... 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 (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol), 4,4'-isopropylidenebis(2-methylfuran) phenol), 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 (spirobiindan), dihydroxybenzophenone, 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, dicyclopentadienyl bis(2,6-dimethylphenol), dicyclopentadienyl bis(2-methylphenol), dicyclopentadienyl bisphenol, etc. ,

[0059] The crosslinking agent (including the auxiliary crosslinking agent) is not particularly limited. The crosslinking agent can be used alone or in combination of two or more different crosslinking agents. Exemplary crosslinking agents and auxiliary crosslinking agents include oligomers or polymers with vinyl functional groups that can be cured. Such materials include oligomers and polymers with crosslinkable unsaturation. Examples include styrene butadiene rubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR) (having unsaturated bonds based on butadiene), natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber (having unsaturated bonds based on isoprene), ethylene-α-olefin copolymer elastomers having unsaturated bonds based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD) (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)). Examples also 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 some types of liquid butadiene rubber, and liquid atactic butadiene rubber, which is a butadiene polymer with 1,2-vinyl linkages prepared by anionic living polymerization.It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc., from Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene type hydrocarbon polymers, and polynorbornene (sold, for example, by Elf Atochem).

[0060] Polybutadiene resins with increased levels of 1,2 addition are desirable for thermosetting matrices. Examples include functionalized polybutadienes and poly(butadiene-styrene) random copolymers sold under the trade names RICON, RICACRYL, and RICOBOND resins by Ricon Resins, Inc. These include butadienes containing both low vinyl contents, such as RICON 130, 131, 134, 142, polybutadienes containing high vinyl contents, such as RICON 150, 152, 153, 154, 156, 157, and P30D, random copolymers of styrene and butadiene, such as RICON 100, 181, 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. Also included are polybutadienes that can be used to improve adhesion, such as RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500, polybutadiene RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene), (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. Powder dispersions of functional polybutadiene derivatives are also included, such as 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 polybutadienes, polyisoprenes, and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethylmaleic acid, or hydroxylated functional groups.

[0061] 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 further 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, such as trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.; tri(meth)allyls, such as 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, such as pentaerythritol tetra(meth)acrylate, etc.; penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate, etc.; hexa(meth)acrylates, such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc.; glycidyl compounds, such as 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, etc.; polythiol compounds, for example, trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc.; silanes, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloximine)silane, vinyltris-(acetoxime)silane, methyltris(methylethyloximine)silane, methyltris(acetoxime)silane, etc. silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxy-silane, 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 can optionally include a crosslinking catalyst, such as a carboxylate.

[0062] When the curable thermosetting composition includes a crosslinking agent, the crosslinking agent may be included in an amount of 1 to 60 wt%, or 5 to 45 wt%, or 10 to 30 wt%, based on the total weight of the curable thermosetting composition.

[0063] Curable thermosetting compositions can include one or more curing agents. As used herein, the term "curing agent" includes compounds variously described as curing agents, hardeners, etc., or both.

[0064] 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.

[0065] When the curable thermosetting 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 thermosetting composition.

[0066] The curable thermosetting composition 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.

[0067] Exemplary cure accelerators include heterocyclic accelerators, such as substituted or unsubstituted C 3-6Heterocycles include heterocycles, where each heteroatom is independently the same or different and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocycle accelerators include benzotriazoles, triazines, piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, etc., 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, 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-Fu phenylimidazole, 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, etc., N,N-dimethylaminopyridine, sulfamidate, or combinations thereof.

[0068] Amine cure accelerators include: isophorone diamine, 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, diphenylmethane, diaminodi ... Midodiphenylsulfonic 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)aniline, 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-Diaminocyclohexane, 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, such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tri(N,N-dimethylaminomethyl)phenol, or a combination thereof.

[0069] The cure accelerator can be a latent cationic cure catalyst, such as diaryliodonium salts, phosphonate esters, sulfonate esters, carboxylate esters, phosphonate ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, and the like, or combinations thereof. Diaryliodonium salts have the structure [(R 10 )(R 11 )I] + X - wherein R 10 and R 11 each independently optionally represents C 1-20 Alkyl, C 1-20 C 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 have the structure [(R 10 )(R 11 )I] + SbF6 - wherein R 10 and R 11 each independently represents, optionally, 1 to 4 C 1-20 Alkyl, C 1-20 Alkoxy, nitro, or chloro substituted C 6-14 It is a monovalent aromatic hydrocarbon, for example, 4-octyloxyphenylphenyliodonium hexafluoroantimonate.

[0070] The cure accelerator may be a metal salt complex, such as a copper(II), aluminum(III), zinc, cobalt, tin salt of an aliphatic or aromatic carboxylic acid selected from copper(II), tin(II), and aluminum(III) salts of acetate, stearate, gluconate, citrate, 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.

[0071] When the curable thermosetting 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 thermosetting composition.

[0072] 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-butyl benzene hydroperoxide, t-butyl peroctoate, t-butyl peroxybenzoate, t-butyl peroxy 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, ... -butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di(t-butylperoxy)isophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilylperoxide, and the like, or combinations thereof.

[0073] When the curable thermosetting 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 thermosetting composition.

[0074] Flame retardants include, for example, organic compounds containing phosphorus, bromine, or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred in certain applications for regulatory reasons, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0075] Examples of phosphorus flame retardants include phosphates, phosphazenes, phosphites, phosphines, phosphinates, polyphosphates, and phosphonium salts. Phosphates include the following: triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl)phosphate, phenyl bis(neopentyl)phosphate, phenyl bis(3,5,5'-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl)phosphate, bis(2-ethylhexyl)p-tolylphosphate, tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolylphosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl phosphate, dibutyl ... aryl bis(2,5,5'-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, xylenyl-diphenyl phosphate, cresyl-diphenyl phosphate, 1,3-phenylene bis(di-2,6-xylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetraphenyl diphosphate (RDP), condensed phosphate compounds such as aromatic condensed phosphate compounds, and cyclic phosphate compounds, bis(diphenyl)phosphate of hydroquinone, bis(diphenyl)phosphate of bisphenol A, etc., or their oligomeric or polymeric counterparts, or combinations thereof.

[0076] Examples of phosphazene compounds include cyclic and linear phosphazene compounds. Cyclic phosphazene compounds (cyclophosphazenes) have a cyclic structure, where a phosphorus-nitrogen double bond is present 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 compounds include trimethyl phosphite and triethyl phosphite. Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide.

[0077] Halogenated materials can also be used as flame retardants, for example bisphenols such as 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-methylphenyl)-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 2,2 bis-(3-bromo-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 decabromodiphenyl ether, decabromodiphenylethane, and oligomeric and polymeric halogenated aromatic compounds such as brominated styrene, 4,4-dibromobiphenyl, ethylene-bis(tetrabromophthalimide), or copolycarbonates and carbonate precursors of bisphenol A and tetrabromobisphenol A, such as phosgene. Metal synergists such as antimony oxide can also be used with the flame retardants.

[0078] Inorganic flame retardants may also be used, such as: 1-16Salts of alkylsulfonates, such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate, salts of Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoro-anion complexes, such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6.

[0079] When the curable thermosetting 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 20 wt%, based on the total weight of the curable thermosetting composition.

[0080] The curable thermosetting composition can further include inorganic or organic fillers, such as particulate fillers, fibrous fillers, etc., or combinations thereof. Any inorganic and organic fillers, including those known in the art, can be used without limitation.

[0081] 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 quartz, 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, crushed, cloth), glass mat, 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 the 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. In one aspect, the fillers can be treated with the coupling agents disclosed herein.

[0082] Glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz. The glass fibers can have any suitable diameter, for example, 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 glass fibers or continuous glass fibers can be used. Suitable glass fibers are commercially available from sources such as Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.

[0083] 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 combinations thereof.

[0084] Fillers can be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, Al2O3, BN, AlN, or combinations thereof can be used for electronics modules with high thermal conductivity. For example, MgO can be used for increased thermal conductivity and increased CTE. For example, SiO2 (e.g., amorphous SiO2) can be used for lightweight modules with low CTE and small dielectric constant.

[0085] When the curable thermosetting composition includes a filler, the filler may be included in an amount of 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 thermosetting composition.

[0086] 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 include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or combinations thereof. Exemplary silanes include epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0087] Examples of aminosilane coupling agents are: γ-aminopropyltrimethoxy-silane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyl-dimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, and N-β(aminoethyl)γ-aminopropyltriethoxysilane. Exemplary epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of methacryloxysilane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0088] Other exemplary silane coupling agents include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl triethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl -N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethyl silane, dimethoxymethylsilylpropyl-N,N-dimethylthio-carbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, etc., or combinations thereof. The silane coupling agent can be a polysulfide silane coupling agent having 2 to 4 sulfur atoms forming a polysulfide bridge. For example, the coupling agent can be bis(3-triethoxysilylpropyl) di-, tri-, or tetrasulfide.

[0089] When the curable thermosetting 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 thermosetting composition.

[0090] The curable thermosetting composition can optionally include a solvent. The solvent can be, for example, C 3-8 Ketone, C 3-8 N,N-Dialkylamides, C 4-16 Dialkyl ether, C 6-12 Aromatic Hydrocarbons, C 1-3 Chlorinated hydrocarbons, C 3-6 Alkyl alkanoates, C 2-6 The specific ketone solvent may be, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof. 4-8 N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Particular dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Particular aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. The aromatic hydrocarbon solvent can be non-halogenated. Particular C 3-6 Alkyl 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. 2-6The alkyl cyanide can be, 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, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexafluoropropane, methyl ethyl ketone ... non, 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, and ionic liquids, or combinations thereof.

[0091] If a solvent is used, the curable thermosetting composition can include 2 to 99 wt% of the solvent based on the total weight of the curable thermosetting composition. For example, the amount of solvent can be 5 to 80 wt%, or 10 to 60 wt%, or 20 to 50 wt%, based on the total weight of the curable thermosetting composition. The solvent can be selected, in part, to adjust the viscosity of the curable thermosetting composition. Thus, the amount of solvent can depend on variables including the type and amount of the linear block copolymer, the type and amount of other ingredients such as hardening additives, the type and amount of any supplemental thermosetting resin(s), and the processing temperature used for any subsequent processing of the curable thermosetting composition, such as impregnation of a reinforcing structure with the curable thermosetting composition for preparation of a composite. The solvent can be anhydrous. For example, the solvent can include 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.

[0092] The curable thermosetting composition can further include a curable unsaturated monomer composition, such as 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 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.

[0093] The curable thermosetting composition can optionally further comprise one or more additional additives. Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow modifiers, anti-drip agents, anti-blocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low profile additives, stress relief additives, and the like, or combinations thereof. If present, the additional additives can be included in any effective amount, for example, in an amount of 0.01 to 20 wt%, or 0.01 to 10 wt%, or 0.01 to 5 wt%, or 0.01 to 1 wt%, based on the total weight of the curable thermosetting composition.

[0094] The curable thermosetting composition can be prepared by combining the capped poly(phenylene ether) and other optional ingredients disclosed herein using any suitable method.

[0095] Cured thermosetting compositions are also provided, including the cured product of the curable thermosetting composition. There is no particular restriction on the manner in which the curable thermosetting composition can be cured. The curable composition can be cured, for example, thermally or by using irradiation techniques, such as UV irradiation or electron beam irradiation. For example, the cured product can be obtained by heating the curable thermosetting composition as defined herein for a time and temperature sufficient to evaporate the solvent and effect curing. If thermal curing is used, the temperature can be 30 to 400°C, or 50 to 250°C, or 100 to 250°C. Heating can be between 1 minute and 24 hours, or 1 minute and 6 hours, or 3 hours and 5 hours. Curing can be stepwise, producing a partially cured, often tack-free, resin, which is then fully cured by heating for a longer period or temperature within the ranges. As used herein, the term "cured" encompasses partially cured or fully cured products.

[0096] The cured thermoset composition can have one or more desirable properties. For example, the thermoset composition can have a glass transition temperature of 165° C. or more, preferably 170° C. or more, more preferably 165 to 180° C. The thermoset composition can also advantageously exhibit a low dielectric constant (Dk), a low dissipation factor (Df), and reduced moisture absorption. For example, the thermoset composition can have a dielectric constant of less than 3.0, preferably less than 2.75, more preferably less than 2.6 at a frequency of 10 GHz. The thermoset composition can have a dissipation factor of less than 0.01, or less than 0.005 at a frequency of 10 GHz. Thus, the thermoset composition including the linear block copolymer of the present disclosure can be particularly well suited for use in electronics applications.

[0097] The curable thermosetting composition and the cured thermosetting composition can be used in a variety of applications and uses, for example, in any application where conventional thermosetting compositions are used. For example, useful articles comprising the curable thermosetting composition or the cured thermosetting composition can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, moldings, prepregs, casings, laminates, metal clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary applications and uses include coatings, such as protective coatings, sealants, weather resistant coatings, scratch resistant coatings, and electrically insulating coatings, adhesives, binders, glues, composites, such as those using carbon fiber and fiberglass reinforcement. When used as coatings, the disclosed compounds and compositions can be deposited on the surface of various underlying substrates. For example, the compositions can be deposited on the surface of metal, plastic, glass, fiber siding, ceramic, stone, wood, or any combination thereof. The disclosed compositions can be used as coatings on the surfaces of metal containers (e.g., aluminum or steel), such as those commonly used for packaging and containment in the paint and surface coating industries. The curable thermosetting compositions and cured thermosetting compositions derived therefrom can be particularly well suited for use in forming electrical devices and computer components.

[0098] The method of 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 stacking a plurality of prepregs. The reinforcing structure can be a porous base material, such as a fibrous preform or substrate, or other porous material including ceramic, polymer, glass, carbon, or combinations thereof. For example, the porous base material can be a woven or nonwoven glass cloth, fiberglass cloth, or carbon fiber. When the article includes a fibrous preform, the method of making the article can include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fibrous preform can optionally be molded before or after removing the solvent. In some aspects, the curable thermosetting composition layer can further include a woven or nonwoven glass cloth. For example, the curable layer can be prepared by impregnating a glass cloth with the curable composition and removing the solvent from the impregnated glass cloth. Exemplary reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), "Prepreg Technology", March 2005, Publication No. FGU017b, Anonymous (Hexcel Corporation), "Advanced Fibre Reinforced Matrix Products for Direct Processes", June 2005, Publication No. IT272, and Bob Griffiths, "Farnborough Airshow Report 2006", CompositesWorld.com, September 2006. The weight and thickness of the reinforcing structure is 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 include a variety of finishes suitable for the thermosetting component of the curable thermosetting composition.

[0099] A method of making an article from a curable thermosetting composition 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 substantially fully cured composition. For example, the resin in a laminate formed from a prepreg is typically substantially fully cured. Those skilled in the art of thermosetting can determine whether an article is partially cured or substantially fully cured without undue experimentation. Curing can be before or after removal of the solvent from the curable composition. In addition, the article can be further molded, for example, by thermoforming, before or after removal of the solvent, before curing, after partial curing, or after full curing. In one embodiment, an article is formed and the solvent is removed, the article is partially cured (B-staged), optionally molded, and then further cured.

[0100] 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 on a treater. The main components of a treater include a feeder roller, a resin impregnation tank, a treater oven, and a receiver roller. The reinforcing structure (e.g., E-glass) is usually wound onto a large spool. The spool is then placed on a feeder roller, which rotates and gradually unwinds 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 exiting the tank, the coated reinforcing structure travels upward through a vertical treater oven, which is typically at a temperature of 175 to 200° C., and the solvent is evaporated. The resin begins to polymerize at this point. When the composite emerges from the tower, it is fully cured, so that the web is neither wet nor sticky. However, the curing process is stopped short of completion, so that additional curing can occur if a laminate is made. The web then winds the prepreg onto a receiver roll.

[0101] The curable thermosetting composition can be used as a coating, for example, in the preparation of multi-layer articles. A method of making a coating can include combining the curable thermosetting composition and, optionally, a fluoropolymer, and forming a coating on a substrate. For example, a multilayer article can be made by forming a layer comprising a curable thermosetting composition, removing the solvent from the layer, optionally curing, providing a primer layer, forming a second layer on the primer layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, YO3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, B4C, 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, providing a multilayer article, and optionally heat treating the multilayer article to cure the curable thermosetting composition. In some embodiments, the second layer can further comprise a curable thermosetting composition.

[0102] Additional uses for the curable thermosetting compositions include, for example, acid bath vessels, neutralization tanks, aircraft components, bridge girders, bridge decks, electrolytic cells, exhaust stacks, scrubbers, sporting goods, stairs, walkways, automotive exterior panels, such as hoods and trunk lids, floor pans, air scoops, pipes and ducts, such as heater ducts, industrial fans, fan housings, and blowers, industrial mixers, ship hulls and decks, marine terminal fenders, tiles and coatings, siding, business machine housings, trays, such as cable trays, concrete modifiers, dishwasher and refrigerator parts, electrical sealants, electrical panels, tanks, such as electrorefining tanks, water softener tanks, fuel tanks, and various filament wound tanks, and and tank linings, furniture, garage doors, grilles, protective gear, luggage, outdoor motor vehicles, pressurized tanks, optical waveguides, radomes, handrails, railway components such as tank cars, hopper car covers, vehicle doors, truck bed liners, satellite television antennas, signs, solar energy panels, telephone switchgear housings, tractor components, transformer covers, truck components such as fenders, hoods, bodies, cabs, and beds, insulation for rotating machinery such as ground insulation, turn insulation, and phase isolation insulation, commutators, core insulation and cords, racing tape, drive shaft couplings, propeller blades, vehicle structural components, rocket motor cases, airfoils, sucker rods, fuselage sections, wing skins and flares, engine nuclei.narcelle), cargo hatches, tennis racquets, golf club shafts, fishing rods, skis and ski poles, bicycle parts, lateral leaf springs, pumps such as automotive smog pumps, electrical components, fittings, and tools such as electrical cable joints, wire windings and high density multi-element assemblies, sealing of electromechanical devices, battery cases, resistors, fuses and thermal cut-off devices, coatings for printed wiring boards, castings such as capacitors, transformers, crankcase heaters, miniaturized molded electronic components such as coils, capacitors, resistors, and semiconductors, as a replacement for steel in chemical processing, pulp and paper, power generation, and wastewater treatment, scrub towers, pultruded parts for structural applications such as structural members, grates, and guard rails, swimming Pools, swimming pool slides, hot tubs, and saunas, drive shafts under the hood applications, dry toner resins for copiers, marine tools and composites, heat shields, submarine hulls, prototyping, development of experimental models, laminate trim, drilling fixtures, bonding fixtures, inspection fixtures, industrial metal forming dies, stretch block and hammer forms for aircraft, vacuum forming dies, floors such as floors for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, chillers, outside loading docks, conductive compositions for antistatic applications, decorative floors, expansion joints for bridges, injection mortars for patching and repairing cracks in structural concrete, grout for tiles, machine rails, metal dowels, bolts and columns, repair of oil and fuel storage tanks, and many other uses.

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

[0104] Also provided are articles derived from the curable thermosetting compositions, the articles being composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, moldings, prepregs, casings, castings, laminates, or combinations thereof, or the articles being metal clad laminates, electronic composites, structural composites, or combinations thereof. The articles can be manufactured, for example, by casting, molding, extrusion, or the like, as disclosed herein, and removing the solvent from the formed article. In one aspect, the article can be a single layer, formed by casting the curable composition onto a substrate and forming 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, laminating the cast layer to another substrate. In one aspect, the articles prepared by the above methods include adhesives, packaging materials, capacitor films, or circuit board layers. In one aspect, the articles prepared from the curable compositions 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, for example, in a printed circuit board, for example, in a circuit material used in lighting or communication applications. Another exemplary article prepared from the curable composition can be one or more painted layers. The curable composition can be used to prepare articles disclosed herein for other curable thermosetting compositions. EXAMPLES

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

[0106] Prophetic Example 1: Preparation of Capped Poly(phenylene ether) In a round bottom flask fitted with a thermocouple, addition funnel, condenser and overhead stirrer, isophthalic or terephthalic acid chloride and toluene are added under nitrogen. Once the acid chloride is dissolved, naphthol and the difunctional hydroxy-terminated poly(phenylene ether) are added, followed by tetrabutylammonium bromide under nitrogen. The temperature is raised to 50-60°C and aqueous sodium hydroxide is added dropwise over several hours. After the addition is complete, the reaction is monitored for completion. Deionized water is added and the reaction mixture is stirred for 15-30 minutes. The organic layer is separated and the activated ester-capped poly(phenylene ether) is isolated by removal of the toluene. Alternatively, the activated ester-capped poly(phenylene ether) can be precipitated into a suitable non-solvent, such as methanol. The product is dried under vacuum and nitrogen. The structure of the activated ester-capped poly(phenylene ether) can be confirmed, for example, using nuclear magnetic resonance (NMR) spectroscopy. The molecular weight of the activated ester-capped poly(phenylene ether) can be determined using gel permeation chromatography (GPC) versus polystyrene standards. Alternatively, or in addition, the number average molecular weight can be calculated from the degree of polymerization determined using nuclear magnetic resonance spectroscopy.

[0107] The disclosure further includes the following aspects.

[0108] Embodiment 1: A capped poly(phenylene ether) having the structure: [ka] or [ka] In the formula, Z 1 , Z 2 , Z 3 , and Z 4 each independently represents hydrogen, halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C1-12 Hydrocarbyloxy, and C 2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom, and R 1 is a substituted or unsubstituted phenylene group, R 2 is substituted or unsubstituted C 6-20 an aromatic hydrocarbon group, n is an integer from 4 to 50, x and y are each independently from zero to 50, provided that the sum of x and y is from 2 to 53, and L is a group of the formula: [ka] In the formula, R 3 , R 4 , R 5 , and R 6 Each event is independently hydrogen, halogen, unsubstituted or substituted C 1-12 Primary or secondary hydrocarbyl, C 1-12 Hydrocarbylthio, C 1-12 Hydrocarbyloxy, or C 2-12 halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom, z is 0 or 1, and Y has a structure including: [ka] , where R 7 Each event is independently hydrogen and C 1-12 Contains hydrocarbyl, R 8 and R 9 Each event is independently hydrogen, C 1-12 Hydrocarbyl, or C 1-6 Hydrocarbylene, where R 8 and R 9 are collectively C 4-12 A capped poly(phenylene ether) which forms an alkylene group or Y has a structure derived from a hydroxyaryl-diterminated polysiloxane.

[0109] Embodiment 2: The capped poly(phenylene ether) of embodiment 1, wherein the capped poly(phenylene ether) comprises repeat units derived from 2,6-dimethylphenol.

[0110] Aspect 3: R 3 and R 4 Each event is methyl, and R 5 and R 6 is hydrogen, z is 1, and Y is an isopropylidene group.

[0111] Aspect 4: Z 2 and Z 3 are each hydrogen, and Z 1 and Z 4 are each unsubstituted or substituted C 1-12 The capped poly(phenylene ether) of any of embodiments 1 through 3, wherein the primary hydrocarbyl is preferably methyl.

[0112] Aspect 5: R 1 The capped poly(phenylene ether) of any of embodiments 1 to 4, wherein:

[0113] Aspect 6: R 1 The capped poly(phenylene ether) of embodiment 5, which is derived from terephthalic acid or isophthalic acid.

[0114] Aspect 7: R 2 The capped poly(phenylene ether) of any of the preceding embodiments, wherein R comprises a phenyl group, a methyl-substituted phenyl group, a dimethyl-substituted phenyl group, a phenyl-substituted phenyl group, a benzyl-substituted phenyl group, a cumyl-substituted phenyl group, or a naphthyl group.

[0115] Aspect 8: R 2 The capped poly(phenylene ether) of any of the preceding embodiments, wherein R comprises a phenyl group, or a naphthyl group.

[0116] Embodiment 9: The capped poly(phenylene ether) of embodiment 1 has the structure: [ka] .

[0117] Aspect 10: R 1 is a divalent phenylene group, and R 2 The capped poly(phenylene ether) of embodiment 9, wherein is a phenyl or naphthyl group.

[0118] Example 11: The capped poly(phenylene ether) of any of Examples 1 to 10, wherein the capped poly(phenylene ether) has a number average molecular weight of from 500 to 20,000 g / mol, or from 500 to 10,000 g / mol, or from 500 to 7,500 g / mol, as determined by gel permeation chromatography (GPC) versus polystyrene standards.

[0119] Embodiment 12: A method for making the capped poly(phenylene ether) of any of embodiments 1 to 11, comprising oxidatively polymerizing a monohydric phenol, and optionally a dihydric phenol, in the presence of a catalyst to provide a poly(phenylene ether) having phenol end groups, and reacting the poly(phenylene ether) with a capping agent under conditions effective to provide the capped poly(phenylene ether).

[0120] Example 13: A curable thermosetting composition comprising the capped poly(phenylene ether) of any of Examples 1 to 11.

[0121] Example 14: A cured thermoset composition comprising the cured product of the curable thermoset composition of Example 13.

[0122] Example 15: An article comprising the cured thermoset composition of example 14, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molding, a prepreg, a casing, a casting, a laminate, or a combination thereof, or the article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

[0123] The compositions, methods, and articles may optionally comprise, consist of, or consist essentially of any suitable materials, steps, or components disclosed herein. The compositions, methods, and articles may additionally, or alternatively, be formulated to be devoid of, or substantially free of, any materials (or species), steps, or components that are not otherwise required for the function or achievement of the purpose of the compositions, methods, and articles.

[0124] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. "Combinations" include blends, mixtures, alloys, reaction products, and the like. The terms "first," "second," and the like do not denote an order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a," "an," or "the" do not denote a limitation of quantity, and should be construed to encompass both the singular and the plural, unless otherwise stated herein or clearly contradicted by context. "Or" means "and / or," unless expressly stated otherwise. Throughout the specification, reference to "an embodiment" means that a particular element described in connection with an embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. The term "combinations thereof," as used herein, includes one or more of the listed elements and is not limited, allowing for the presence of one or more similar elements not named. In addition, it should be understood that the elements described can be combined in any suitable manner in the various embodiments.

[0125] Unless specified to the contrary 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.

[0126] Unless otherwise specified, technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs. 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 in this application shall take precedence over the conflicting term in the incorporated reference.

[0127] Compounds are described using standard nomenclature. For example, any position that is not substituted by any indicated group is understood to have its valence filled by the indicated bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment for a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

[0128] As used herein, the term "hydrocarbyl", whether used by itself or as a prefix, subscript, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain a combination of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituted residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" refers to branched or straight-chain, saturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond, such as ethenyl (-HC=CH2). "Alkoxy" means an alkyl group linked through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group, such as methylene (-CH2-) or propylene (-(CH2)3-). "Cycloalkylene" means a divalent cyclic alkylene group, -C n H 2n-xwhere x is the number of hydrogens replaced by the cyclization(s). "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds within the rings, all ring members being carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, e.g., phenyl, tropone, indanyl, or naphthyl. "Arylene" means a divalent aryl group. "Alkylarylene" means an arylene group substituted with an alkyl group. "Arylalkylene" means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. A combination of different halo atoms (e.g., bromo and fluoro) or only chloro atoms can be present. The prefix "hetero" means that the compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where the heteroatom(s) are each independently N, O, S, Si, or P. "Substituted" means that the compound or group contains, each independently, C, H, or C, in place of a hydrogen. 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Aryl alkylene, C 4-12 Heterocycloalkyl, and C 3-12 It means substituted with at least one (e.g., 1, 2, 3, or 4) substituents, which may be heteroaryl, provided that the standard valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group excludes any substituents. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0129] While particular embodiments have been described, presently unanticipated or unforeseen alternatives, modifications, variations, improvements, and substantial equivalents may occur to the applicant or those skilled in the art, and it is therefore intended that the appended claims, as filed and as they may be amended, shall cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A capped poly(phenylene ether) having the structure: 【Chemical 1】 or 【Chemistry 2】 During the ceremony, Z １ , Z ２ , Z ３ , and Z ４ are each independently hydrogen, halogen, unsubstituted or substituted C １－１２ Primary or secondary hydrocarbyl, C １－１２ Hydrocarbylthio, C １－１２ hydrocarbyloxy, and C ２－１２ halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom; R １ is a substituted or unsubstituted phenylene group, R ２ is substituted or unsubstituted C ６－２０ is an aromatic hydrocarbon group, n is an integer from 4 to 50; x and y are each independently from zero to 50, provided that the sum of x and y is from 2 to 53; and L is a group of the formula: 【Chemistry 3】 During the ceremony, R ３ , R ４ , R ５ , and R ６ Each occurrence is independently hydrogen, halogen, unsubstituted or substituted C １－１２ Primary or secondary hydrocarbyl, C １－１２ Hydrocarbylthio, C １－１２ hydrocarbyloxy, or C ２－１２ halohydrocarbyloxy, where at least two carbon atoms separate the halogen atom and the oxygen atom; z is 0 or 1, and Y has a structure including: 【Chemistry 4】 、 During the ceremony, R ７ Each event is independently hydrogen and C １－１２ Contains hydrocarbyl, R ８ and R ９ Each event is independently hydrogen, C １－１２ Hydrocarbyl, or C １－６ hydrocarbylene, where R ８ and R ９ are collectively C ４－１２ forming an alkylene group, or Y is a capped poly(phenylene ether) having a structure derived from a hydroxyaryl di-terminated polysiloxane.

2. 10. The capped poly(phenylene ether) of claim 1, wherein said capped poly(phenylene ether) comprises repeat units derived from 2,6-dimethylphenol.

3. R ３ and R ４ Each occurrence of R is methyl, ５ and R ６ 2. The capped poly(phenylene ether) of claim 1, wherein each occurrence of is hydrogen, z is 1, and Y is an isopropylidene group.

4. Z ２ and Z ３ are each hydrogen, and Z １ and Z ４ are each unsubstituted or substituted C １－１２ 2. The capped poly(phenylene ether) of claim 1, wherein the primary hydrocarbyl is preferably methyl.

5. R １ The capped poly(phenylene ether) of claim 1 , wherein is an unsubstituted phenylene group.

6. R １ The capped poly(phenylene ether) of claim 5 wherein is derived from terephthalic acid or isophthalic acid.

7. R ２ 5. The capped poly(phenylene ether) of claim 1 , wherein R 1 is a phenyl group, a methyl-substituted phenyl group, a dimethyl-substituted phenyl group, a phenyl-substituted phenyl group, a benzyl-substituted phenyl group, a cumyl-substituted phenyl group, or a naphthyl group.

8. R ２ The capped poly(phenylene ether) of claim 1 , wherein comprises a phenyl group or a naphthyl group.

9. 5. The capped poly(phenylene ether) of claim 1, wherein the capped poly(phenylene ether) has the structure: 【Chemistry 5】

10. R １ is a divalent phenylene group, and R ２ The capped poly(phenylene ether) of claim 9 , wherein is a phenyl or naphthyl group.

11. 5. The capped poly(phenylene ether) of claim 1, wherein the capped poly(phenylene ether) has a number average molecular weight of from 500 to 20,000 g / mol, or from 500 to 10,000 g / mol, or from 500 to 7,500 g / mol, as determined by gel permeation chromatography (GPC) against polystyrene standards.

12. 5. A process for producing the capped poly(phenylene ether) of any one of claims 1 to 4, comprising: oxidatively polymerizing the monohydric phenol, and optionally a dihydric phenol, in the presence of a catalyst to provide a poly(phenylene ether) having phenol end groups; and reacting said poly(phenylene ether) with a capping agent under conditions effective to provide said capped poly(phenylene ether). A method comprising:

13. A curable thermosetting composition comprising the capped poly(phenylene ether) of any one of claims 1 to 4.

14. A cured thermoset composition comprising the cured product of the curable thermoset composition of claim 13.

15. 15. An article comprising the cured thermoset composition of claim 14, wherein the article is a composite, a foam, a fiber, a layer, a coating, a sealant, an adhesive, a sealant, a molding, a prepreg, a casing, a casting, a laminate, or a combination thereof; or The article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

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