Curable thermosetting composition comprising a poly(arylene ether) copolymer

Abstract

A curable thermosetting composition comprising a capped poly(arylene ether) copolymer having reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from an alkylaryl phenol.

Description

[0001] Citation of Related Applications

[0002] This application claims the priority and benefit of European Patent Application No. 201900644, filed on August 7, 2020, which claims the priority and benefit of U.S. Provisional Patent Application Serial No. 63 / 035,317, filed on June 5, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to curable thermosetting compositions, which include curable thermosetting compositions, thermosetting compositions, varnish compositions, and articles derived therefrom. Background Art

[0004] Thermosetting resins are materials that cure to form extremely hard plastics. These materials can be used in a wide variety of consumer and industrial products. For example, thermosetting materials are used in protective coatings, adhesives, electronic laminates (such as those used to manufacture computer circuit boards), flooring and paving applications, fiberglass-reinforced tubes, and automotive components (including leaf springs, pumps, and electrical components). Poly(arylene ether) copolymers generally have good dielectric properties. Due to their wide range of uses, especially in electronic applications (such as laminates for printed circuit boards), it is desirable to provide curable thermosetting compositions containing poly(arylene ether) copolymers that have a lower viscosity while maintaining or improving the dielectric constant, dissipation factor, heat resistance, and water absorption.

[0005] Accordingly, there is still a need in the art for curable thermosetting compositions, including poly(arylene ether) copolymers having a set of desired properties. It would be a further advantage if the curable thermosetting compositions had improved dielectric constant, dissipation factor, heat resistance, and water absorption. Summary of the Invention

[0006] The present invention provides a curable thermosetting composition comprising a capped poly(arylene ether) copolymer having reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from an alkyl,aryl-phenol.

[0007] The present invention also provides a cured thermosetting composition comprising a cured product of the curable thermosetting composition; a method for manufacturing the cured thermosetting composition, which comprises curing the curable thermosetting composition; and an article comprising the cured thermosetting composition, wherein the article is a composite material, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded part, prepreg, housing, cast article, laminate, or a combination thereof.

[0008] On the other hand, there is provided a varnish composition comprising a curable thermosetting composition; an article made from the varnish composition; and a method for manufacturing an article, wherein the method comprises impregnating the varnish composition into a substrate to form a prepreg; and curing the varnish composition.

[0009] The above functions and other features are exemplified by the following specific embodiments. Specific Embodiments

[0010] The present inventors have advantageously found that a capped poly(arylene ether) copolymer comprising repeating units derived from an alkylaryl phenol can be included in a curable thermosetting composition to achieve improved properties over a curable thermosetting composition comprising a poly(arylene ether) copolymer having no repeating units derived from an alkylaryl phenol. For example, a poly(arylene ether) copolymer comprising repeating units derived from an alkylaryl phenol can provide an improved combination of properties such as solution viscosity, dissipation factor, resin flow, coefficient of thermal expansion (CTE), and equilibrium water absorption.

[0011] Accordingly, one aspect of the present disclosure is a curable thermosetting composition comprising a capped poly(arylene ether) copolymer having reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from an alkylaryl phenol. The alkylaryl phenol can be, for example, 2-(alkyl)-6-(aryl) phenol, such as 2-(C 1-12 primary or secondary alkyl)-6-(unsubstituted C 6-12 aryl) phenol. For example, the alkylaryl phenol can be 2-(C 1-6 -primary alkyl)-6-(unsubstituted phenyl) phenol.

[0012] The capped poly(arylene ether) copolymer comprises at least one reactive end group. Exemplary reactive end groups include, but are not limited to, functional groups such as (meth)acrylate, (meth)acrylonitrile, vinylbenzene, allyl, epoxide (including glycidyl ether), cyanate ester, amine, maleimide, carboxylic acid, carboxylic acid alkyl ester, etc. The capped poly(arylene ether) copolymer can be a bifunctional oligomer having reactive end groups at both ends of the oligomer chain. A bifunctional oligomer having functional groups at both ends of the oligomer chain is also referred to as a "telechelic" oligomer.

[0013] For example, the capped poly(arylene ether) copolymer as a bifunctional oligomer can include an average of 1.8 to 2 reactive end groups per molecule, or at least 1.85 reactive end groups per molecule, or at least 1.90 reactive end groups per molecule, or at most 1.99 reactive end groups per molecule, or at most 1.97 hydroxyl groups per molecule.

[0014] The capped poly(arylene ether) copolymer can have the formula (1) or formula (2):

[0015]

[0016]

[0017] wherein, Q 1a and Q 1b are each independently halogen, C 1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy (wherein at least two carbon atoms separate the halogen and the oxygen atom); and Q 2 is independently hydrogen, halogen, unsubstituted or substituted C 1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy (wherein at least two carbon atoms separate the halogen and the oxygen atom). For example, Q 1a and Q 1b can each independently be C 1-12 alkyl, C 2-12 alkenyl or C 2-12 alkynyl.

[0018] In formula (2), R 1 to R 4 are each independently hydrogen, halogen, C 1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy (wherein at least two carbon atoms separate the halogen and the oxygen atom).

[0019] In formula (1) and formula (2), R 5a is each independently Q 1a or (C 1-6 hydrocarbyl)(C 1-6 hydrocarbyl)aminomethylene, and R 5b is each independently Q 1b or (C 1-6 hydrocarbyl)(C 1-6 hydrocarbyl)aminomethylene, provided that the capped poly(arylene ether) copolymer contains: at least one repeating unit wherein, Q 1a is C 1-12 primary or secondary alkyl, and Q 1b is unsubstituted C 6-12an aryl; or at least one end unit, wherein R 5a is a C 1-12 primary or secondary alkyl, and R 5b is an unsubstituted C 6-12 aryl; or a combination thereof. For example, in one aspect, the capped poly(arylene ether) copolymer can comprise one or more repeating units, wherein Q 1a is a C 1-12 primary or secondary alkyl, and Q 1b is an unsubstituted C 6-12 aryl.

[0020] In formula (1), e is the number of moles of arylene ether units.

[0021] In formula (2), x and y represent the relative molar ratio of arylene ether units, wherein x and y are each independently 0 to 50, or 0 to 30, or 0 to 20, or 0 to 15, or 0 to 10, or 0 to 8, provided that the sum of x and y is at least 2, or at least 3, or at least 4.

[0022] Y in formula (2) 1 is a divalent linking group of any one or more of the following formulas:

[0023]

[0024] wherein R a , R b and R e are each independently hydrogen, a C 1-12 hydrocarbyl or a C 1-6 subhydrocarbyl, optionally wherein R a and R b together are a C 4-8 subcycloalkyl; R f is each independently a C 1-6 subhydrocarbyl; R g is each independently hydrogen, a C 1-12 hydrocarbyl or a C 1-12 halohydrocarbyl; and n' is 5 to 50.

[0025] In formulas (1) and (2), R is each independently any one of the formula wherein Y 2 is a divalent linking group having one of the formulas

[0026] wherein R c and R d are each independently hydrogen or a C 1-12 alkyl; R 5ais an epoxide-containing group, a cyanate-containing group, or a C 1-12 Hydrocarbon; R 6 , R 7 and R 8 Each occurrence is independently hydrogen, C 1-18 Hydrocarbon, C 2-18 alkyloxycarbonyl, nitrile, formyl, carboxylic acid, imidoester or thiocarboxylic acid; and R 9 , R 10 , R 11 , R 12 and R 13 Each occurrence is independently hydrogen, halogen, C 1-12 Alkyl, C 2-12 Alkenyl, hydroxyl, amino, maleimide, carboxylic acid or C 2-20 Alkyl esters.

[0027] In a specific aspect, Q 1a Each occurrence is independently C 1-12 Primary alkyl or C 1-6 Primary alkyl; Q 1b Each occurrence is independently C 1-12 Alkyl or C 6-12 Aryl, or C 1-6 Alkyl or phenyl; Q 2 is hydrogen; and R 1 , R 2 , R 3 and R 4 are independently hydrogen, halogen or C 1-12 Alkyl, or hydrogen or C 1-6 The capped poly(arylene ether) copolymer comprises at least one repeating unit wherein Q 1a It is C 1-12 primary alkyl, and Q 1b is unsubstituted C 6-12 For example, the capped poly(arylene ether) copolymer may include one or more repeating units wherein Q 1a It is C 1-6 primary alkyl, and Q 1b It is an unsubstituted phenyl group.

[0028] In another specific aspect, the capped poly(arylene ether) copolymer has formula (2a):

[0029]

[0030] Among them, Q 1a , Q 1b , Q 2 , R 1 , R2 , R 5a , R 5b , R x , R y , x and y are defined as in formulas (1) and (2); and R 1a and R 1b are each independently hydrogen, or wherein, R 1 and R 2 are each independently hydrogen or C 1-6 alkyl. For example, the end-capped poly(arylene ether) copolymer can be derived from the reaction of a diphenol and 2-methyl-6-phenylphenol.

[0031] In another specific aspect, the end-capped poly(arylene ether) copolymer has formula (2b):

[0032]

[0033] wherein, R 1 , R 2 , R 6 to R 8 , R 5a , R 5b , Q 1a , Q 1b , Q 2 , x and y are defined as in formulas (1) and (2).

[0034] The poly(arylene ether) copolymer is the product of oxidative copolymerization of monomers comprising a monophenol or a mixture of monophenols and optionally a diphenol. The monophenol can have formula (3):

[0035]

[0036] wherein, Q 1a and Q 1b are defined as in formula (1). Exemplary monophenols include, but are not limited to, 2-methylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2,6-diallylphenol, 2,3,6-trimethylphenol, 2,6-dimethyl-3-allylphenol, 2-methyl-6-phenylphenol, 2-ethyl-6-phenylphenol, 2-allyl-6-methylphenol, 2,6-diphenylphenol, or combinations thereof.

[0037] In addition to the monophenol, the monomers can include a diphenol, wherein the diphenol has the structure of formula (4):

[0038]

[0039] wherein, R 1 to R 4 , Y 1Y and Z are as defined in formula (2).

[0040] For example, the diphenol may be 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1-bis(3-chloro-4-hydroxyphenyl)ethane, 1,1-bis(3-methyl-4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxy-3,5-dimethylphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)ethane, 2,2'-binaphthol, 2,2'-bisphenol, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2'-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(3-chloro-4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3-methyl-4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)pentane, 2,2-bis(3-methyl-4-hydroxyphenyl)-1-phenylpropane, 2,2'-bis(3-methyl-4-hydroxyphenyl)hexane, 2,2-bis(3-methyl-4-hydroxyphenyl)pentane, 2,2'-methylenebis(4-methylphenol), 2,2'-methylenebis[4-methyl-6-(1-methylcyclohexyl)phenol], 3,3',5,5'-tetramethyl-2,2'-bisphenol, 3,3'-dimethyl-4,4'-bisphenol, bis(2-hydroxyphenyl)-methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)phenylmethane, 2,2',3,3',5,5'-hexamethyl-4,4'-bisphenol, octafluoro-4,4'-bisphenol, 2,3,3',5,5'-pentamethyl-4,4'-bisphenol, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, bis(3-methyl-4-hydroxyphenyl)cyclohexane, tetrabromobisphenol, tetrabromobisphenol A, tetrabromobisphenol A, 2,2'-diallyl-4,4'-bisphenol A, 2,2'-diallyl-4,4'-bisphenol S, 3,3',5,5'-tetramethyl-4,4'-bisphenol sulfide, 3,3'-dimethylbisphenol sulfide, 3,3',5,5'-tetramethyl-4,4'-bisphenol sulfone, or a combination thereof.

[0041] As disclosed herein, the capped poly(arylene ether) copolymer is derived from an alkylaryl phenol, or for example, the capped poly(arylene ether) copolymer can be derived from the reaction of a diphenol and a monophenol comprising 2-(alkyl)-6-(aryl) phenol. For example, the capped poly(arylene ether) copolymer can be the product of the oxidative copolymerization of a monophenol or a mixture of monophenols and optionally a diphenol monomer in a solvent in the presence of a catalyst. For example, a method for forming a capped poly(arylene ether) copolymer can include the oxidative copolymerization of 2-(alkyl)-6-(aryl) phenol monomers, optionally one or more other monophenol monomers, and diphenol monomers in a solvent in the presence of a catalyst composition.

[0042] The oxidative polymerization can be carried out by continuously adding oxygen to a reaction mixture comprising monomers, a solvent, and a catalyst composition to provide a hydroxyl-terminated poly(arylene ether) copolymer (i.e., an uncapped copolymer) having the structure of formula (1) or formula (2), and wherein, R, R x and R y are hydrogen atoms. Molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex comprising a transition metal cation. The metal cation can include cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or combinations thereof, preferably chromium, manganese, cobalt, copper, or combinations thereof. Exemplary metal salts include cuprous chloride, copper chloride, cuprous bromide, copper bromide, cuprous iodide, copper iodide, cuprous sulfate, copper sulfate, cuprous tetraamine sulfate, copper tetraamine sulfate, cuprous acetate, copper acetate, cuprous propionate, copper butyrate, copper laurate, copper palmitate, cuprous benzoate, and the corresponding manganese and cobalt salts. Alternatively, a metal or metal oxide and an inorganic acid, an organic acid, or an aqueous solution of such an acid can also be added and the corresponding metal salt or hydrate can be formed in situ. For example, cuprous oxide and hydrobromic acid can be added to generate cuprous bromide in situ.

[0043] The polymerization catalyst can also include amine ligands, such as monoamines, alkylenediamines, or combinations thereof. Monoamines include dialkylmonoamines (such as di-n-butylamine, DBA) and trialkylmonoamines (such as N,N-dimethylbutylamine, DMBA). Diamines include alkylenediamines, such as N,N'-di-tert-butylethylenediamine, DBEDA.

[0044] Exemplary dialkylmonoamines include dimethylamine, di-n-propylamine, di-n-butylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine, dihexylamine, dioctylamine, didecylamine, dibenzylamine, methylethylamine, methylbutylamine, dicyclohexylamine, N-phenylethanolamine, N-(p-methyl)phenyl ethanolamine, N-(2,6-dimethyl)phenyl ethanolamine, N-(p-chloro)phenyl ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, etc., or a combination comprising at least one of the foregoing. Suitable trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenethylamine, or a combination thereof.

[0045] Exemplary alkylenediamines include those of the formula: (R bb )2N-R aa -N(R bb )2, where R aa is a substituted or unsubstituted divalent residue; and each R bb is independently hydrogen or a C 1-8 alkyl. In some aspects, two or three aliphatic carbon atoms can form the nearest connection between the two diamine nitrogen atoms. Specific alkylenediamine ligands include those in which R aa is dimethylene (-CH2CH2-) or trimethylene (-CH2CH2CH2-). R bb can independently be hydrogen, methyl, propyl, isopropyl, butyl, or a C 4-8 -α-tert-alkyl. Examples of alkylenediamine ligands include N,N,N',N'-tetramethylethylenediamine (TMED), N,N'-di-tert-butylethylenediamine (DBEDA), N,N,N',N'-tetramethyl-1,3-diaminopropane (TMPD), N-methyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N,N,N'-dimethyl-1,3-diaminopropane, N-ethyl-1,3-diaminopropane, N-methyl-1,4-diaminobutane, N,N'-trimethyl-1,4-diaminobutane, N,N,N'-trimethyl-1,4-diaminobutane, N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetramethyl-1,5-diaminopentane, or a combination comprising at least one of the foregoing. In some embodiments, the amine ligand is di-n-butylamine (DBA), N,N-dimethylbutylamine (DMBA), N,N'-di-tert-butylethylenediamine (DBEDA), or a combination thereof. The catalyst can be prepared in situ by mixing a metal ion source (e.g., cuprous oxide and hydrobromic acid) and an amine ligand. For example, the polymerization catalyst can include copper ions, bromide ions, and N,N'-di-tert-butylethylenediamine.

[0046] Hydroxyl-terminated poly(arylene ether) copolymers can react with a capping agent to provide a capped poly(arylene ether) copolymer. The capping agent is not particularly limited and can be a compound including unsaturation, an epoxy resin, a benzoxazine, an isocyanate, a cyanate ester, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an acid anhydride, an allyl hydroxypropyl, or a combination thereof. One skilled in the art can select the capping agent based on the desired functionality of the capped poly(arylene ether) copolymer. For example, vinyl benzyl ether end groups can be prepared using a curing agent of vinyl benzyl halide (e.g., vinyl benzyl chloride), and (meth)acrylic end groups can be prepared using a curing agent of (meth)acrylic halide or (meth)acrylic anhydride.

[0047] The capped poly(arylene ether) copolymer can contain structural units derived from a monohydric phenol and a dihydric phenol in a molar ratio of 3:1 to 110:1. Within this range, the ratio can be at least 3.5:1, or at least 5:1, or at least 7:1, or up to 50:1, or up to 25:1.

[0048] In some aspects, the capped poly(arylene ether) copolymer can be a poly(arylene ether)-polysiloxane block copolymer, as used herein, which refers to a block copolymer containing at least one poly(arylene ether) block and at least one polysiloxane block.

[0049] The poly(arylene ether)-polysiloxane block copolymer can be prepared by an oxidative copolymerization method, including oxidative copolymerization of a monomer mixture containing a monohydric phenol and a hydroxyaryl-terminated polysiloxane. For example, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane, the monomer mixture contains 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane. The hydroxyaryl-terminated polysiloxane can contain a plurality of repeating units having the structure of formula (5):

[0050]

[0051] wherein, R 22 and R 33 are each independently hydrogen, a C 1-12 hydrocarbon group or a C 1-12 halohydrocarbon group; and two end units having the structure of formula (5a):

[0052]

[0053] wherein, M is hydrogen, a C 1-12 hydrocarbon group, a C 1-12 hydrocarbon group or a halogen, wherein, R 44 and R 45 are each independently hydrogen, a C 1-11Hydrocarbyl or C 1-12 halohydrocarbyl. In a specific aspect, R 8 and R 9 are each methyl and Y is methoxy each time they appear.

[0054] For example, the monohydric phenol can be 2,6-dimethylphenol, and the hydroxyaryl-terminated polysiloxane has the structure of formula (5b):

[0055]

[0056] wherein, n is on average 5 to 100, or 5 to 45, or 30 to 60. Thus, the structural fragment of the capped poly(arylene ether) copolymer having formula (6):

[0057]

[0058] can have formula (6a):

[0059]

[0060] wherein, n is 5 - 100, or 5 - 45, or 30 - 60.

[0061] The capped poly(arylene ether) copolymer can also contain 10 to 70 mole percent of copolymer chains that contain end units derived from a dihydric phenol. For example, when the dihydric phenol is 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, the poly(arylene ether) copolymer can contain 10 to 70 mole percent of copolymer chains that contain end units having the structure of formula (7):

[0062]

[0063] wherein, R 1 to R 4 , Y 1 and z are as provided in formula (1) or (2), and R is R x or R y .

[0064] In one aspect, the capped polyarylether copolymer can have an intrinsic viscosity of 0.03 to 0.13 deciliters per gram (dL / g), or 0.03 to 0.28 dL / g, or 0.04 to 0.15 dL / g in chloroform at 25 °C using an Ubbelohde viscometer. The capped poly(arylene ether) copolymer can have a weight-average molecular weight (M w)。The capped poly(arylene ether) copolymer may have a number average molecular weight (M n ) determined by GPC using polystyrene standards of 500 to 10,000 grams per mole (g / mol), or 750 to 5,000 g / mol, or 500 to 40,00 g / mol. w In some aspects, the capped poly(arylene ether) copolymer has a ratio of M n to M

[0065] (also referred to as the "polydispersity") of 1.9 to 3, or at least 2, or up to 2.8, or up to 2.6, or up to 2.4.

[0066] Based on the total weight of the curable thermosetting composition, the capped poly(arylene ether) copolymer may be present in the curable thermosetting composition in an amount of 1 to 95 weight percent (wt%), or 5 to 95 wt%, or 10 to 85 wt%, or 20 to 80 wt%, 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%.

[0067] There is a significant overlap among thermosetting resins, crosslinking agents, and coupling agents. As used herein, the term "crosslinking agent" includes compounds that can be used as thermosetting resins, crosslinking agents, coupling agents, or combinations thereof. For example, in some cases, a compound that is a thermosetting resin can also be used as a crosslinking agent, a coupling agent, or both.

[0068] The thermosetting resin is not particularly limited, and the thermosetting resin can be used alone or in combination of two or more thermosetting resins. Exemplary thermosetting resins include, but are not limited to, epoxy resins, cyanate ester resins, bismaleimide resins, polybenzoxazine resins, vinyl resins (e.g., vinyl benzyl ether resins), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers, or polymers having curable unsaturation (e.g., vinyl functionality), or combinations thereof.

[0069] The epoxy resin can generally be any epoxy resin suitable for thermosetting resins. In this context, the term "epoxy resin" refers to a curable composition of a compound containing an ethylene oxide carrier, as described, for example, in C.A. May, Epoxy Resins, 2nd Edition, (New York & Basle: Marcel Dekker Inc.), 1988. The epoxy resin can be, for example, a bisphenol A type epoxy resin (such as those obtained from bisphenol A), and resins obtained by substituting at least one of the 2-position, 3-position, and 5-position of bisphenol A with a halogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group; bisphenol F type epoxy resins (such as those obtained from bisphenol F) and resins obtained by substituting at least one of the 2-position, 3-position, and 5-position of bisphenol F with a halogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group; glycidyl ether compounds derived from divalent or trivalent or higher-valent phenols, such as hydroquinone, resorcinol, tri-4-(hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; phenolic type epoxy resins derived from phenolic resins, which are reaction products between phenols (such as phenol and o-cresol and formaldehyde), including bisphenol A type phenolic epoxy resins and cresol type phenolic resins; alicyclic 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; polyepoxides containing dicyclopentadiene; amine type epoxy resins, derived from aniline, p-aminophenol, m-aminophenol, 4-aminom-cresol, 6-aminom-cresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxy-phenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexane-bis(methylamine), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, etc.; heterocyclic epoxy compounds and glycidyl ester type epoxy compounds, for example, those derived from glycidyl esters of aromatic carboxylic acids, such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, or isophthalic acid. The term "epoxy resin" can also include reaction products of compounds containing two or more epoxy groups and aromatic dihydroxy compounds, which may be optionally halogen-substituted.

[0070] The cyanate esters are not limited, and any resin composed of cyanate ester monomers can be used, and these monomers polymerize to form a polymer containing a plurality of cyanate (-OCN) functional groups. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers or blends of cyanate ester monomers), homopolymers and copolymers prepared using cyanate ester precursors, and combinations of these compounds. For example, the cyanate esters can be prepared according to the methods disclosed in "Chemistry and Technology of Cyanate Ester Resins" such as U.S. Patent No. 3,553,244 by Ian Hamerton, Blackie Academic and Professional and JP-A-7-53497. Exemplary cyanate ester resins include but are not limited to 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-diisopropylbenzene, cyanate ester resins prepared from dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). The cyanate ester prepolymer can be a homopolymer or can be a copolymer incorporating other monomers. Examples of such copolymers include the BT resins available from Mitsubishi Gas Chemical, such as BT 2160 and BT 2170, which are prepolymers made from cyanate ester monomers and bismaleimide monomers. Other examples of cyanate ester polymers, monomers, prepolymers, and blends of cyanate ester monomers with other non-cyanate ester monomers include those disclosed in, for example, US 7,393,904, US 7,388,057, US 7,276,563, and US 7,192,651.

[0071] Bismaleimide resins can be prepared by reacting a monomeric bismaleimide with a nucleophile (such as a diamine, an aminophenol, or an aminobenzohydrazide), or by reacting a bismaleimide with diallyl bisphenol A. Exemplary bismaleimide resins include 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimido-diphenyl ether, 3,3'-bismaleimidodiphenyl sulfone, 4,4'-bismaleimido-diphenyl sulfone, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6-bismaleimidopyridine, 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-bis(citraconimido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1-phenyl-1,1-bis(4-maleimidophenyl)ethane, N,N-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-1,2,4-triazole, N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-4,4'-diphenylmethanebismaleimide, N,N'-4,4'-diphenyletherbismaleimide, N,N'-4,4'-diphenylsulfonebismaleimide, N,N'-4,4'-dicyclohexylmethane-bismaleimide, N,N'-α,α'-4,4'-dimethylene cyclohexane-bismaleimide, N,N'-m-xylenebismaleimide, N,N,-4,4'-diphenylcyclohexanebismaleimide, and N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, and the maleimide resins disclosed in US 3,562,223, US 4,211,860, and US 4,211,861. Bismaleimide resins can be prepared by methods known in the art, as described, for example, in US 3018290.

[0072] Benzoxazine compounds have a benzoxazine ring in the molecule. Exemplary benzoxazine monomers can be prepared by reacting an aldehyde, a phenol, and a primary amine with or without a solvent. Phenolic compounds used to form benzoxazine include phenol and polyphenols. Reacting with polyphenols having two or more hydroxyl groups during the formation of benzoxazine can result in branched, crosslinked, or a combination of branched and crosslinked products. The group connecting the phenolic groups into a phenol can be a branching point or a linking group in the polybenzoxazine.

[0073] Exemplary phenols for preparing benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, 2,2'-biphenol, 4,4'-biphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane (bisphenol F), 4,4-(cyclopentyl)biphenol, 4,4-(cyclohexyl)diphenol, 4,4-(cyclododecyl)biphenol, 4,4-(bicyclo[2.2.1]heptylidene)biphenol, 4,4-(9H-fluorene-9,9-diyl)biphenol, isopropylidene bis(2-allylphenol), 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-indene-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane dicyclopentadienyl bis(2,6-dimethylphenol), dicyclopentadienyl bis(o-cresol), dicyclopentadienyl bisphenol, etc.

[0074] The aldehyde used to form 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 benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic, or an aromatic-substituted alkylamine. The amine can be a polyamine, for example, to prepare a polyfunctional benzoxazine monomer for crosslinking.

[0075] The amine used to form benzoxazine generally has 1 to 40 carbon atoms, unless they contain an aromatic ring, then they can have 6 to 40 carbon atoms. A difunctional or polyfunctional amine can be used as a branching point to link one polybenzoxazine to another polybenzoxazine.

[0076] In some instances, thermal polymerization at 150 °C to 300 °C can be used to polymerize 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 lower the polymerization temperature or increase the polymerization rate at the same temperature.

[0077] Vinyl benzyl ether resins can be prepared by the condensation of phenol with vinyl benzyl halides (such as vinyl benzyl chloride). Bisphenol A and tri- and polyphenols are commonly used in the production of poly(vinyl benzyl ether), which can be used to produce crosslinked thermosetting resins.Exemplary vinyl benzyl ethers can include those vinyl benzyl ethers produced by the reaction of vinyl halides with resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol) 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3',5-dibromobiphenol, 4,4'-isopropylidene biphenol, 4,4'-isopropylidene bis(2,6-dibromophenol), 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis(2-allylphenol), 4,4'-(1,3-phenylene diisopropylidene)bisphenol, 4,4'-isopropylidene bis(3-phenylphenol), 4,4'-(1,4-phenylene diisopropylidene)bisphenol, 4,4'-ethylenebiphenol, 4,4'-oxybiphenol, 4,4'-thiobiphenol, 4,4'-thio bis(2,6-dimethylphenol), 4,4'-sulfonylbiphenol, 4,4'-sulfonyl bis(2,6-dimethyl-phenol), 4,4'-sulfinylbiphenol, 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-indene-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-indene-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 bis(o-cresol), dicyclopentadienyl bisphenol, etc.

[0078] Arylcyclobutenes include those derived from compounds having the following structure

[0079]

[0080] wherein B is an organic or inorganic group having a valence of n (including carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isopropylidene, cycloalkylidene, arylalkylidene, diarylmethylene, methylenedialkylsilyl, arylalkylsilyl, diarylsilyl, and C 6-20 phenolic compounds); X is independently a hydroxyl group or C 1-24 hydrocarbyl (including straight-chain and branched-chain alkyls and cycloalkyls) each time it appears; and Z is independently hydrogen, halogen, or C 1-12 hydrocarbyl each time it appears; and n is from 1 to 1000, or from 1 to 8, or n is 2, 3, or 4. Other exemplary arylcyclobutenes and methods for synthesizing arylcyclobutenes 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 US 5,391,650.

[0081] Perfluorovinyl ethers are typically synthesized from phenols and bromotetrafluoroethane followed by zinc-catalyzed reductive elimination, producing ZnFBr and the desired perfluorovinyl ether. By this route, bisphenols, triphenols, and other polyphenols can produce bis-, tris-, and poly(perfluorovinyl ethers).Phenols useful in their synthesis include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol) 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3',5-dibromobisphenol, 4,4'-isopropylidenediphenol, 4,4'-isopropylidene bis(2,6-dibromophenol), 4,4'-isopropylidene bis(2,6-dimethylphenol) (tetramethyl bisphenol A), 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)diphenol, 4,4'-isopropylidene bis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)diphenol, 4,4'-ethylenediphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thio bis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonyl bis(2,6-dimethylphenol), 4,4'-sulfinyl diphenol, 4,4'-(hexafluoroisopropylidene)biphenol, 4,4'-(1-phenylethylidene)diphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)biphenol, 4,4'-(cyclohexylidene)biphenol, 4,4'-(cyclododecylidene)-biphenol, 4,4'-(bicyclo[2.2.1]heptylidene)biphenol, 4,4'-(9H-fluorene-9,9-diyl)biphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-indene-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-indene-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 bis(2-methylphenol), etc.

[0082] There is no particular limitation on the crosslinking agent including the auxiliary crosslinking agent. 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 having curable vinyl functionality. Such materials include oligomers and polymers having crosslinkable unsaturation. Examples include styrene-butadiene rubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR) based on butadiene with unsaturated bonds; natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber based on isoprene with unsaturated bonds; ethylene-α-olefin copolymer elastomers having unsaturated bonds based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-hexadiene (1,4-HD) (e.g., ethylene-α-olefin copolymers obtained by copolymerizing ethylene, α-olefin, and diene, such as ethylene-propylene-diene terpolymer (EPDM) and ethylene-butene-diene terpolymer (EBDM)). Examples also include hydrogenated nitrile butadiene rubber, fluoroelastomers (such as vinylidene fluoride-hexafluoropropylene copolymer and vinylidene fluoride-pentafluoropropylene copolymer), epichlorohydrin homopolymer (CO), copolymer rubber (ECO) prepared from epichlorohydrin and ethylene oxide, epichlorohydrin allyl glycidyl copolymer, propylene oxide allyl glycidyl ether copolymer, propylene oxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber (ACM), polyurethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T), and ethylene acrylic rubber. Further examples include various liquid rubbers, such as several types of liquid butadiene rubber and liquid random butadiene rubber of butadiene polymers having 1,2-vinyl linkages prepared by anionic living polymerization. Liquid styrene-butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. of Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymer, and polynorbornene can also be used.

[0083] Polybutadiene resins with relatively high 1,2-addition levels are suitable for thermosetting matrices. Examples include functionalized polybutadienes and poly(butadiene-styrene) random copolymers sold by Ricon Resins Inc under the trade names RICON, RICACRYL, and RICOBOND resins. These include butadienes with low vinyl content, such as RICON 130, 131, 134, 142; polybutadienes with high vinyl content, such as RICON 150, 152, 153, 154, 156, 157, and P30D; random copolymers of styrene and butadiene, including RIC0N 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, including 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 acid-functionalized polybutadienes, such as polybutadiene diacrylate and polybutadiene dimethacrylate. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Also included are powder dispersions of functional polybutadiene derivatives, including, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 01731HS, and RICOBOND 1756HS. Further butadiene resins include polybutadiene-isoprene block copolymers and random copolymers, such as copolymers with molecular weights from 3,000 to 5,0000 g / mol and polybutadiene homopolymers with molecular weights from 3,000 to 50000 g / mol. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride functional groups, 2-hydroxyethyl maleic acid functional groups, or hydroxylated functional groups.

[0084] Other examples of oligomers and polymers having curable vinyl functional groups 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, urethane (meth)acrylate resins, polyether (meth)acrylate resins, polyol (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 polythiols. For example, crosslinking agents. Other exemplary crosslinking agents include multifunctional crosslinking monomers such as (meth)acrylic monomers in which each monomer molecule has two or more (meth)acrylate moieties.Exemplary polyfunctional 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, etc.; 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 citrate, tri(meth)allyl phosphate, pentaerythritol tri(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 - (epoxyethyloxy)ethyl (meth)acrylate, 2 - (3,4 - epoxybutoxy)ethyl (meth)acrylate, etc.; polythiol compounds such as trimethylolpropane tris(mercaptoacetate), pentaerythritol tetra(3 - mercaptopropionate), etc.; silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra - n - butoxysilane, vinyltris(methylethylketoxime)silane, vinyltris(acetoneoxime)silane, vinyltris(acetoneoxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenyloxy)silane, tetraethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di - tert - butyldiacetoxysilane, methyltris(ethyl lactate)silane, vinyltris(ethyl lactate)silane, etc.; carbodiimides such as N-(3 - dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide or combinations thereof. The curable thermosetting composition may optionally include a cross - linking catalyst such as carboxylate salts.

[0085] When the curable thermosetting composition includes a cross - linker, the cross - linker may be included in an amount of 1 wt% to 60 wt%, or 5 wt% to 45 wt%, or 10 wt% to 30 wt% based on the total weight of the curable thermosetting composition.

[0086] The curable thermosetting composition may include one or more curing agents, and the curing agents include compounds that can be described as curing agents, hardeners, or both.

[0087] 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, tetraphenylol ethane 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 acid 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 curing agents and hardeners include compounds such as dicyandiamide, polyamides, amidoamines, phenolic amines, Mannich bases, acid anhydrides, phenol formaldehyde resins, amine formaldehyde resins, phenol-formaldehyde resins, carboxylic acid-functional polyesters, polysulfides, polythiols, isocyanates, cyanate ester compounds, or any combination thereof. Other exemplary curing agents include tertiary amines, Lewis acids, and oligomers or polymers having unsaturation.

[0088] When the curable thermosetting composition includes a curing agent, the curing agent can be included in an amount of 0.01 to 50 wt%, 0.1 to 30 wt%, or 0.1 to 20 wt% based on the total weight of the curable thermosetting composition.

[0089] The curable thermosetting composition can include a curing catalyst, including compounds also described as curing accelerators, curing promoters, curing catalysts, and curing co-catalysts.

[0090] Exemplary curing promoters include heterocyclic promoters such as substituted or unsubstituted C containing 1 to 4 ring heteroatoms 3-6Heterocycles, wherein each heteroatom is independently the same or different and is nitrogen, oxygen, phosphorus, silicon or sulfur. Heterocyclic accelerators include benzotriazoles; triazines; piperazines such as amino-ethylpiperazine, N-(3-aminopropyl)piperazine, etc.; imidazoles such as 1-methyl-imidazole, 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-butyl-imidazole, 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-methyl-imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-cyanoethyl-2-phenyl-4,5-bis(2-cyanoethoxy)methylimidazole; cyclic amidines such as 4-diazabicyclo(2,2,2)-octane, diazabicycloundecene, 2-phenylimidazoline, etc.; N,N-dimethylaminopyridine; sulfamate; or combinations thereof.

[0091] Amine curing accelerators include isophorone diamine, triethylenetetramine, 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, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfonic acid (amine adduct), 4,4'-methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine formaldehyde resin, urea formaldehyde resin, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3'-iminodipropylamine, 2,4-bis(p-aminobenzyl)aniline, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexamethylene-diamine, 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'-diaminodicyclopropylmethane, 2,2-bis(4-aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-1-cyclohexylaminopropane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, m- and p-xylenediamine, or diethyltoluenediamine; or a tertiary amine curing accelerator such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tris(N,N-dimethylaminomethyl)phenol; or a combination thereof.

[0092] The curing accelerator can be a latent cationic curing catalyst, including, for example, diaryliodonium salts, phosphonates, sulfonates, carboxylates, phosphinites, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, or a combination thereof. The diaryliodonium salt can have the structure [(R 10 )(R 11 )I] + X - wherein R 10 and R 11 are each independently a C 6-14 monovalent aryl group, optionally substituted with 1 to 4 monovalent groups selected from C 1-20 alkyl, C 1-20 alkoxy, nitro, and chlorine; and wherein X - is an anion. Another curing accelerator can have the structure [(R 10 )(R11 )I] + SbF6 - , wherein R 10 and R 11 are each independently a C 6-14 monovalent arene, optionally substituted with 1 to 4 C 1-20 alkyl, C 1-20 alkoxy, nitro or chlorine; for example, 4-octyloxyphenyl iodonium hexafluorostibate.

[0093] The curing accelerator can be a metal salt complex, such as copper(II), aluminum(III), zinc, cobalt, tin salts of aliphatic or aromatic carboxylic acids, or copper(III), tin(II) and aluminum(III) salts of acetic acid, stearic acid, gluconic acid, citric acid, benzoic acid. For example, the curing accelerator can be a copper(II) or aluminum(III) salt of β-diketo acid; a copper(II), iron(II), iron(III), cobalt(II), cobalt(III), or aluminum(III) salt of acetylacetonate; a zinc(II), chromium(II), or manganese(II) salt of octanoate; or a combination thereof.

[0094] When the curable thermosetting composition includes a curing catalyst, the curing catalyst can 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.

[0095] The curable thermosetting composition can optionally include a curing initiator, such as a peroxide. Exemplary peroxide curing initiators can include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, tert-butylbenzene hydroperoxide, tert-butyl peroxy-2-ethylhexyl carbonate, tert-butyl peroxybenzoate, 2,4-dichlorobenzoyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyl-dioxy)valerate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-hex-3-yne, di-tert-butyl peroxide, tert-butyl cumyl peroxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, dicumyl peroxide, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, bis(trimethylsilyl)peroxide, trimethylsilyl phenyl triphenylsilyl peroxide, or a combination thereof.

[0096] When the curable thermosetting composition includes a curing initiator, the curing agent 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.

[0097] The flame retardant includes, for example, organic compounds containing phosphorus, bromine or chlorine. For regulatory reasons, in certain applications, non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred, such as, for example, organophosphates and organic compounds containing phosphorus-nitrogen bonds.

[0098] Examples of phosphorus flame retardants include phosphates, phosphonitriles, phosphites, phosphines, phosphinates, polyphosphates and phosphonium salts. Phosphoric acid esters include triphenyl phosphate, tricresyl phosphate, isopropylphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl bis(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tris(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, xylenyl-diphenyl phosphate; tolyl-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, or their oligomeric or polymeric counterparts, or combinations thereof.

[0099] Examples of phosphonitrile compounds include cyclic phosphonitrile compounds and chain phosphonitrile compounds. Cyclic phosphonitrile compounds (cyclophosphazenes) have a cyclic structure in which phosphorus-nitrogen double bonds are present in the molecule. Examples of phosphinate compounds include aluminum dialkylphosphinates, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylphosphinate), zinc bis(diphenylphosphinate), titanium oxybis(diethylphosphinate), titanium oxybis(methylethylphosphinate), and titanium oxybis(diphenyl-phosphinate). Examples of polyphosphate compounds include melamine polyphosphate, melem polyphosphate and melam 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 chlorophosphonitrile, phosphoester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide.

[0100] Halogenated materials can also be used as flame retardants, such as bisphenols like 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-dichloro-naphthyl)-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 of bisphenol A and tetrabromobisphenol A with a carbonate precursor (e.g., phosgene). Metal synergists, such as antimony oxide, may be present.

[0101] Inorganic flame retardants can also be used, such as C 1-16 Salts of alkyl sulfonates, such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfone sulfonate; salts such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoride anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6.

[0102] When the curable thermosetting composition includes a flame retardant, the flame retardant can be included in an amount greater than 1 wt%, or 1 to 20 wt%, or 5 to 20 wt% based on the total weight of the curable thermosetting composition.

[0103] The curable thermosetting composition can also include inorganic or organic fillers, such as particulate fillers, fibrous fillers, or combinations thereof. Any inorganic and organic fillers, including those known in the art, can be used without limitation.

[0104] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; alumina, thiourea, glass powder, B- or Sn-based fillers such as zinc borate, zinc stannate, and zinc hydroxystannate; metal oxides such as zinc oxide and tin oxide; alumina, silica (including fused silica, fumed silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesium oxide, magnesium silicate, antimony trioxide, glass fibers (chopped, milled, or cloth), glass mats, glass bubbles, hollow glass microspheres, aramid fibers, quartz, or combinations thereof. Other exemplary inorganic fillers include powdered titanium ceramics such as any of the titanates of barium, lead, strontium, calcium, bismuth, magnesium, etc. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolites, and hydrotalcites. In some aspects, the fillers can be coated or surface-treated with the coupling agents disclosed herein.

[0105] Glass fibers include those based on E, A, C, ECR, R, S, D, and NE glass, as well as quartz. The glass fibers can have any suitable diameter, such as from 2 to 30 micrometers (μm), or 5 to 25 μm, or 5 to 15 μm. The length of the glass fibers prior to 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 suppliers such as Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.

[0106] Organic fillers can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, and poly(ether sulfone) powder, poly(phenylene oxide) powder, polystyrene, divinylbenzene resin, or combinations thereof.

[0107] The 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 in electronic 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 in lightweight modules with low CTE and small dielectric constant.

[0108] When the curable thermosetting composition includes fillers, the fillers can be included in an amount greater than 1 wt%, or 1 to 50 wt%, or 1 to 30 wt%, or 10 to 30 wt% based on the total weight of the curable thermosetting composition.

[0109] Coupling agents, also known as adhesion promoters, include chromium complexes, silanes, titanates, zirconium aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, etc. Exemplary olefin-maleic anhydride copolymers can include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or combinations thereof. Exemplary silanes can include epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0110] Exemplary examples of amino silane coupling agents include γ-aminopropyl-trimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyl-dimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, and combinations of two or more of the above. Illustrative epoxy silane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxy-propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and combinations of two or more of the above. Illustrative methacryloxy silane coupling agents include γ-methacryloxypropyl-methyl dimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl-diethoxysilane, γ-methacryloxypropyltriethoxysilane, or combinations thereof.

[0111] 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-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl phenyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxysilylpropyl)tetrasulfide, 3-mercaptopropyl dimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, 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.

[0112] When the curable thermosetting composition includes a coupling agent, the coupling agent can be included in an amount of 0.01 to 5 wt%, 0.05 to 5 wt%, or 0.1 to 5 wt% based on the total weight of the curable thermosetting composition.

[0113] The curable thermosetting composition can optionally include a solvent. The solvent can be, for example, a C 3-8 ketone, a C 3-8 N,N-dialkylamide, a C 4-16 dialkyl ether, an C 6-12 aromatic hydrocarbon, a C 1-3 chlorinated hydrocarbon, a C 3-6 alkyl ester of a fatty acid, a C 2-6 alkyl cyanide, or combinations thereof. Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. Specific C 4-8-N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. The aromatic hydrocarbon solvents can be non-halogenated. Specific C 3-6 alkyl chain alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. Specific C 2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. Specific C 2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. For example, the solvent can be dimethylformamide, dimethylacetamide, diethylacetamide, dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, γ-caprolactone, dimethyl sulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, N,N-dimethylethylurea, N,N-dimethylpropylurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, dichloromethane, chloroform, pyridine, methylpyridine, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, ionic liquids, or combinations thereof.

[0114] When a solvent is used, based on the total weight of the curable thermosetting composition, the curable thermosetting composition can contain 2 to 99 wt% of the solvent. For example, based on the total weight of the curable thermosetting composition, the amount of the solvent can be 5 to 80 wt%, or 10 to 60 wt%, or 20 to 50 wt%. The solvent can be partially selected to adjust the viscosity of the curable thermosetting composition. Thus, the amount of the solvent can depend on variables including the type and amount of the end-capped poly(arylene ether), the type and amount of other components such as curing additives, the type and amount of the auxiliary thermosetting resin, and the processing temperature for any subsequent processing of the curable thermosetting composition, for example, impregnating a reinforcing structure with the curable thermosetting composition to prepare a composite material. The solvent can be anhydrous. For example, based on the total weight of the solvent, the solvent can include less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water.

[0115] The curable thermosetting composition may further comprise a curable unsaturated monomer composition, which may include, for example, monofunctional styrenic compounds (e.g., styrene), monofunctional (meth)acrylic compounds, or combinations thereof. For example, the curable unsaturated monomer composition may be an olefin-containing monomer or an alkyne-containing monomer. Exemplary olefin- and alkyne-containing monomers include those described in US 6,627,704 and include (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidone, and vinyl z-lactone as disclosed in US 4,304,705. 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, etc., or combinations thereof.

[0116] The curable thermosetting composition may also optionally include 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, release agents, toughening agents, low-profile additives, stress relief additives, or combinations thereof. When present, the additional additives may 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.

[0117] The curable thermosetting composition can be prepared by combining the capped poly(arylene ether) copolymer and the other optional components disclosed herein using any suitable method.

[0118] There is also provided a cured thermosetting composition comprising a cured product of a curable thermosetting composition. There is no particular limitation on the method by which the curable thermosetting composition can be cured. The curable composition can be cured, for example, thermally or by using irradiation techniques (including 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. When using thermal curing, the temperature can be from 30°C to 400°C, or from 50°C to 250°C, or from 100°C to 250°C. The heating can be for 1 minute to 24 hours, or 1 minute to 6 hours, or 3 hours to 5 hours. Curing can be carried out in stages to produce a partially cured and generally tack-free resin, and then the resin can be fully cured by heating for a longer period or at a temperature within the above ranges. As used herein, the term "curing" encompasses partially cured or fully cured products.

[0119] The cured thermosetting composition can achieve one or more desired properties, such as improved viscosity, coefficient of thermal expansion (CTE), dissipation factor, equilibrium water absorption, or combinations thereof.

[0120] The disclosed curable thermosetting compositions and cured compositions can be used in a variety of applications and uses, including any application using conventional thermosetting compositions. For example, useful articles comprising a curable thermosetting composition or a cured thermosetting composition can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded parts, prepregs, housings, laminates, metal-clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary uses and applications include coatings, such as protective coatings, sealants, weather-resistant coatings, scratch-resistant coatings, and electrical insulation coatings; adhesives; adhesives; glues; composites, such as those using carbon fiber and glass fiber reinforcements. When used as a coating, the disclosed compounds and compositions can be deposited on the surface of a variety of underlying substrates. For example, the composition can be deposited on the surface of metals, plastics, glass, fiber sizing, ceramics, stone, wood, or any combination thereof. The disclosed compositions can be used as a coating on the surface of metal containers (e.g., aluminum or steel), such as those commonly used in the paint and surface coating industries for packaging and containment. The curable thermosetting compositions and cured thermosetting compositions derived therefrom can also be particularly suitable for forming electrical components and computer components.

[0121] A method of forming a composite material can include impregnating a reinforcement structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and laminating a plurality of prepregs. The reinforcement structure can be a porous substrate material, such as a fiber preform or substrate, or other porous material comprising ceramics, polymers, glass, carbon, or combinations thereof. For example, the porous substrate material can be a woven or non-woven glass fabric, glass fiber fabric, or carbon fiber. When the article includes a fiber preform, the method of manufacturing the article can include forming the article from the curable thermosetting composition by coating or impregnating the preform with a varnish. The impregnated fiber preform can optionally be shaped before or after removal of the solvent. In some aspects, the curable thermosetting composition layer can also include a woven or non-woven glass fabric. For example, the curable layer can be prepared by impregnating a glass fabric with the curable composition and removing the solvent from the impregnated glass fabric. For example, exemplary reinforcement structures are described 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. ITA 272; and Bob Griffiths, “Farnborough Airshow Report 2006”, Composites World.com, September 2006. The weight and thickness of the reinforcement structure are selected according to the intended use of the composite material using standards well known to those skilled in the art of fiber reinforced resin composites. The reinforcement structure can contain various finishes suitable for the thermosetting component of the curable thermosetting composition.

[0122] A method of manufacturing 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. As used herein, the term “cured composition” refers to a composition that is substantially fully cured. For example, the resin in a laminate formed from a prepreg is typically substantially fully cured. A person skilled in the thermosetting art can determine whether a sample 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 shaped, for example by thermoforming, before removal of the solvent, before curing, after partial curing, or after full curing. In one aspect, the article is formed and the solvent is removed; the article is partially cured (B-stage); optionally shaped; and then further cured.

[0123] Methods for forming composites on a commercial scale are known in the art, and the curable thermosetting compositions described herein are readily adaptable to existing processes and equipment. For example, prepregs are typically produced on a processor. The main components of the processor include feed rolls, a resin impregnation tank, a processing oven, and take-up rolls. Reinforcing structures (e.g., E-glass) are typically wound into large spools. The spools are then placed on the feed rolls, which rotate and slowly unwind the reinforcing structure. The reinforcing structure then moves 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 moves up through a vertical processing oven, which is typically at a temperature of 175 °C to 200 °C, and the solvent is evaporated. The resin begins to polymerize at this time. When the composite exits the tower, it is fully cured such that the web is not wet or tacky. However, the curing process is stopped before completion in order to allow for additional curing when making laminates. The web then rolls the prepreg onto the take-up rolls.

[0124] Electrical and electronic articles comprising or derived from the curable thermosetting compositions are also provided. Articles include those containing printed circuits such as used in the medical or aerospace industries. Other articles include antennas and the like. Articles (such as printed circuit boards) are used in, for example, lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic notepads and similar devices, or office automation equipment. For example, electrical components can be mounted on a printed circuit board comprising a laminate. Other exemplary articles prepared from varnish compositions for various applications can include copper-clad laminates (CCLs) (e.g., metal core copper-clad laminates (MCCCLs)), composite articles, and coated articles (e.g., multi-layer articles).

[0125] Dielectric layers that can be prepared from the curable thermosetting compositions can be used in circuit components, such as in metal-clad laminates such as copper-clad laminates. For example, a laminate can include a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally a heat dissipating metal substrate layer disposed on the dielectric layer on the side opposite the conductive metal layer. The dielectric layer can optionally include a fiber preform (e.g., a fabric layer). For example, the dielectric layer can also include a glass fabric layer.

[0126] The conductive metal layer can be in the form of a circuit and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, or a combination thereof. Other metals include copper-molybdenum alloys, nickel-cobalt-iron alloys such as KOVAR available from Carpenter Technology Corporation, nickel-iron alloys such as INVAR available from National Electronic Alloys, Inc, bimetals, trimetals, trimetals derived from two layers of copper and one layer of INVAR, and trimetals derived from two layers of copper and one layer of molybdenum. Exemplary metal layers include copper or copper alloys. Alternatively, a forged copper foil can be used. The conductive metal layer can have a thickness of 2 to 200 micrometers (μm), or 5 μm to 50 μm, or 5 μm to 40 μm.

[0127] The heat-dissipating metal substrate layer can be a heat-conductive metal, such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or a combination thereof. A heat-conductive and conductive metal can be used provided that the metal is electrically isolated from the metal circuit layer. The preferred support metal substrate layer can have a thickness of 0.1 to 20 millimeters (mm), or 0.5 mm to 10 mm, or 0.8 mm to 2 mm.

[0128] The conductive metal layer and the support metal substrate layer can be pretreated to have a high surface roughness for enhancing adhesion to the dielectric layer. Treatment methods include, for example, washing, flame treatment, plasma discharge, corona discharge, etc., to enhance the adhesion of the metal layer. The dielectric layer can adhere firmly to the conductive metal layer or the heat-dissipating layer without using an adhesive, or an adhesive can be used to improve the adhesion of the dielectric layer to the conductive metal layer or the heat-dissipating layer. Exemplary adhesives for bonding the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxy resins, or a combination thereof.

[0129] The copper-clad laminate can be prepared by thermally laminating one or more dielectric layers, one or more conductive metal layers, and the support metal substrate layer under pressure without using a thermosetting adhesive. The dielectric layer can be prepared from a curable thermosetting composition and can be prepared by a solvent casting process to form a layer before the thermal lamination step. For example, the dielectric layer, the conductive metal layer, and the heat-dissipating layer can be thermally laminated together under pressure by an adhesive-free process to form a laminate. The conductive metal layer can optionally be in the form of a circuit before lamination, or the conductive metal layer can optionally be etched after lamination to form a circuit. Lamination can be by a hot pressing or roll calendering method, such as a roll-to-roll method. The conductive metal layer in the copper-clad laminate can be further patterned to provide a printed circuit board. In addition, the copper-clad laminate can be shaped to provide a circuit board having a sheet, tube, or rod shape.

[0130] Alternatively, the laminate for the circuit component can be made by solution casting method, in which the curable thermosetting composition is directly cast onto the conductive metal layer and then laminated onto the heat-dissipating metal substrate layer. For example, the curable thermosetting composition can be directly cast onto the heat-dissipating metal substrate layer and then laminated onto the conductive metal layer.

[0131] The multi-layer laminate including additional layers can also be prepared by hot lamination in one step or in two or more consecutive steps by methods such as hot pressing or roll calendering methods. For example, there can be seven or fewer layers, or sixteen or fewer layers in the laminate. In one aspect, the laminate can be formed in one step or in two or more consecutive steps with a continuous fabric-thermosetting-metal-thermosetting-fabric-thermosetting-metal foil layer or its sub-combination with fewer layers, such that the laminate includes a thermosetting film layer between any metal foil layer and any fabric layer. In another aspect, a first laminate can be formed in one step or in two or more consecutive steps, where the fabric layer is located between two thermosetting layers, such as a woven glass fabric layer located between two thermosetting layers. Then the second laminate can be prepared by laminating the metal foil onto the thermosetting side of the first laminate.

[0132] The printed circuit board prepared from the curable thermosetting composition can have a total thickness of 0.1 mm to 20 mm, and specifically 0.5 mm to 10 mm, where the total thickness refers to the component including each layer of the dielectric layer, the conductive metal layer, and the supporting metal substrate layer. The circuit component can have a total thickness of 0.5 mm to 2 mm, and specifically 0.5 to 1.5. There is no specific limitation on the thickness of the dielectric layer and it can be 5 μm to 1500 μm, or 5 μm to 750 μm, or 10 μm to 150 μm, or 10 μm to 100 μm. For example, the printed circuit board can be a metal core printed circuit board (MCPCB) for light emitting diode (LED) applications.

[0133] The curable thermosetting composition can be used as a coating, for example, in the preparation of multi-layer articles. The method of making a coating can include combining the curable thermosetting composition with an optional fluoropolymer and forming a coating on a substrate. For example, a multi-layer article can be made by forming a layer comprising the curable thermosetting composition, removing the solvent from the layer and optionally curing to provide a primer layer, forming a second layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, Y2O3, 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, poly(chlorotrifluoroethylene), tetrafluoroethylene-ethylene copolymer, poly(vinylidene fluoride), etc.) or a combination thereof on the primer layer to provide a multi-layer article, and optionally heat treating the multi-layer article to cure the curable thermosetting composition. In some aspects, the second layer can also include the curable thermosetting composition.

[0134] Additional applications of the curable thermosetting composition include, for example, acid bath containers; neutralization tanks; aircraft components; bridging beams; bridging covers; electrolytic cells; exhaust stacks; scrubbers; sports equipment; stairwells; walkways; automotive exterior panels such as hoods and trunk lids; floor pans; air deflectors; pipes and ducts, including heater ducts; industrial fans, fan housings, and blowers; industrial mixers; hulls and decks; marine dock fenders; tiles and coatings; building panels; commercial machine housings; cable troughs, including cable trays; concrete modifiers; dishwasher and refrigerator components; electrical sealants; electrical panels; tanks, including electrolytic refining tanks, water softener tanks, fuel tanks, and various filament wound tanks and tank liners; furniture; garage doors; grilles; furniture garage doors; grilles; body protection devices; luggage; outdoor motor vehicles; pressure tanks; optical waveguides; radomes; railings; railway components such as tank cars; hopper car covers; vehicle doors; truck bed liners; satellite antennas; signs; solar panels; telephone switchgear housings; tractor components; transformer covers; truck components such as fenders, hoods, bodies, cabs, and beds; insulators for rotating machinery, including ground insulation, interturn insulation, and phase separation insulation; steering gears; core insulation and cables and ties; drive shaft couplings; propeller blades; missile components; rocket engine housings; wing sections; sucker rods; fuselage sections; wing skins and flaps; engine vents; cargo doors; tennis rackets; golf club shafts; fishing rods; skis and ski poles; bicycle components; transverse leaf springs; pumps, such as automotive fume pumps; electrical components, inserts, and tools such as cable connectors; wire windings and densely packed multi-component assemblies; seals for electromechanical devices; battery cases; resistors; fuses and skid bars; bicycle components; transverse leaf springs; pumps, such as automotive fume pumps; electrical components, embedded parts, and tools such as cable connectors; wire windings and densely packed multi-component assemblies; seals for electromechanical devices; battery boxes; resistors; fuses and thermal cut-off devices; printed circuit board coatings; casting items such as capacitors, transformers, crankcase heaters; small molded electronic components, including coils, capacitors, resistors, and semiconductors; as alternatives in chemical processing, steel, pulp and paper, power generation, and wastewater treatment; scrubbing towers; washing towers; pultruded parts for structural applications, including structural members, grilles, and safety railings; swimming pools, pool slides, hot tubs, and saunas; pultruded components for structural applications, including structural members, grilles, and safety rails; swimming pools, pool slides, hot tubs, and saunas; drive shafts for engine hood applications; dry toner resins for copiers; marine tools and composites; heat shields; submarine hulls; prototype generation; development of experimental models; laminated trim; drilling jigs; bonding jigs; inspection jigs; industrial metal forming dies; aircraft stretch blocks and hammer forms; vacuum molding tools; floors, including floors for production and assembly areas; floors for clean rooms, machine shops, control rooms, laboratories, parking garages, freezers, laboratories, and outdoor loading docks; conductive compositions for antistatic applications;For decorating floors; expansion joints for bridges; injectable mortar for repairing and fixing cracks in structural concrete; grouting for tiles; mechanical tracks; metal pins; bolts and columns; repair of oil and fuel storage tanks; and many other applications;

[0135] Methods for preparing articles and materials can include those commonly known in the art for processing thermosetting resins. Such methods have been described, for example, in Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal Senior Ed, pp. 105 - 168 and 497 - 533, and in "Polyesters and Their Applications" by 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, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting open mold casting; lamination, including wet or dry lay-up and spray lay-up; also including contact molding, including cylindrical contact molding; compression molding; including vacuum assisted resin transfer molding and chemically assisted resin transfer molding; matched tool molding; autoclave curing; thermal curing in air; vacuum bagging; pultrusion; Seemann composite resin infusion manufacturing process (SCRIMP); open mold molding, continuous combination of resin and glass; and filament winding, including cylindrical filament winding. For example, an article can be prepared by a resin transfer molding method.

[0136] Varnish compositions are also provided, comprising the curable thermosetting compositions disclosed herein and a solvent. The solvent of the varnish composition can be the same as those disclosed herein for the curable thermosetting compositions.

[0137] The varnish composition can be prepared by stirring to mix the blocked poly(arylene ether) copolymer, the solvent, and any optional components until a viscous solution is formed. For example, the method of making the varnish composition can include combining the components of the varnish composition and heating the components with agitation, stirring, or both at a temperature and for a period of time effective to dissolve the components in the solvent, or at a temperature below the boiling point of the solvent. The temperature is not particularly limited and can be below 50°C, or below 30°C, or below 25°C.

[0138] The varnish composition can be used to make articles useful for a variety of applications, including those disclosed herein. The articles can be made from the varnish composition, for example, by forming the article from the varnish composition, such as by casting, molding, extrusion, and removing the solvent from the formed article. Exemplary articles can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, seal layers, castings, molded parts, prepregs, housings, laminates, metal-clad laminates, electronic composites, structural composites, or combinations thereof. In some aspects, the article can be a layer and can be formed by casting the varnish composition onto a substrate to form a cast layer. The solvent can be removed by a number of methods, including by heating the cast layer, heating the cast layer under heat and pressure, such as by laminating the cast layer to another substrate. In some aspects, the articles prepared by the above methods can include adhesives, encapsulating materials, capacitor films, or circuit board layers. In some aspects, the articles prepared from the varnish composition can be dielectric layers or coatings disposed on a substrate, such as wire or cable coatings. For example, the article can be a dielectric layer in a circuit material (such as a printed circuit board) for use in, for example, lighting or communication applications. Other exemplary articles prepared from the varnish composition can be one or more painted layers. The varnish composition can be used to prepare the articles disclosed herein for other curable thermosetting compositions.

[0139] The present disclosure is further illustrated by the following examples, which are non-limiting.

[0140] Examples

[0141] The components used in the examples are summarized in Table 1.

[0142] Table 1

[0143]

[0144] Weight average molecular weight (M w)Measured by gel permeation chromatography (GPC). The solution viscosity was measured using a Brookfield viscometer with rotor S00 at 25 °C. The gelation time was measured using a 25 millimeter (mm) parallel plate under nitrogen with a target gap of 1 mm between the plates. The oscillatory temperature sweep curve was used under the conditions of an initial temperature of 80 °C, a ramp rate of 5 °C / min, a constant strain of 30%, and an angular frequency of 10 radians per second (Rad / s) (ARES G2 rheometer, TA Instruments). The viscosity was measured using a 25 mm parallel plate under nitrogen with a target gap of 1 mm between the plates. The oscillatory temperature sweep curve was used under the conditions of an initial temperature of 80 °C, a ramp rate of 3 °C / min, a constant strain of 1%, and an angular frequency of 10 Rad / s (ARES G2 rheometer, TA Instruments). The glass transition temperature (T g )(DSC, TA Instruments) was measured by differential scanning calorimetry (DSC) from 25 °C to 300 °C at a rate of 20 °C / min. The exothermic heat and degree of cure were measured from 25 to 300 °C at a rate of 10 °C / min (DSC, TA Instruments). The onset thermal decomposition temperature was measured by thermogravimetric analysis (TGA) from 25 °C to 800 °C at a rate of 10 °C / min (TGA, TA Instruments). The coefficient of thermal expansion (CTE) was measured by thermomechanical analysis (TMA) from 25 °C to 300 °C at a rate of 10 °C / min (TMA, TA Instruments). After the casting was conditioned at 50% relative humidity for 24 hours, a network analyzer (Agilent Technologies E5071C) equipped with a split post resonator (SPDR) was used to measure the dielectric constant and dissipation factor. The hygroscopicity was measured by placing the sample in a water bath at 85 °C. The sample was removed from the bath, wetted and dried, and weighed after 24 hours.

[0145] The curable composition was prepared by combining the components shown in Table 2, where the amounts are in weight percentages based on the total weight of the curable thermosetting composition.

[0146] Table 2

[0147] Component Comparative Example Example PPE 49 -- PPE-MPP -- 49 TAIC 21 21 Accelerator 2 2 Flame Retardant 8 8 Filler 20 20 Silane Coupling Agent 0.3 0.3

[0148] The curable thermosetting composition was dissolved and dispersed in chloroform, set on a plate, and the chloroform was removed under vacuum and nitrogen to obtain a dry powder. After the composition was partially cured by heating until a gel was obtained, the dry powder was used for chemical rheology.

[0149] The properties of the partially cured composition (gel) are shown in Table 3.

[0150] Table 3

[0151] Property Unit Comparative Example Example <![CDATA[M n > g / mol 2300 2800 Viscosity in Toluene, 50 wt% cP 298 107 Viscosity in MEK, 50 wt% cP 160 36 Heat of Exotherm J / g 204 211 Initial Exothermic Temperature (DSC) ℃ 127 129 Peak Exothermic Temperature (DSC) ℃ 160 157 Gel Time Second 446 468 Resin Flow (Before B-Stage) Pa·s 253 151 Resin Flow (After B-Stage) Pa·s 15664 8327 Degree of Cure (After B-Stage, DSC) ％ 10 13.4

[0152] Transfer a portion of the partially cured composition into a 40 mm diameter die head and heat it to 150 °C under a pressure of 1 ton. Then cool the sample to 70 °C and transfer the die head to an oven where the sample is dried under vacuum at 200 °C for 120 minutes.

[0153] The properties of the cured composition are shown in Table 4.

[0154] Table 4

[0155] Property Unit Comparative Example Example Glass Transition Temperature (DSC) ℃ 228 180 Initial Decomposition Temperature (TGA) ℃ 400 405 Glass Transition Temperature (TMA) ℃ 251 231 <![CDATA[Coefficient of thermal expansion (>T g )(TMA) * > ppm℃ 253 205 Dielectric Constant (10 GHz) -- 2.83±0.03 2.85±0.01 Dissipation Factor (10 GHz) <![CDATA[x 10 -3 > 5.75±0.083 3.85±0.06 Equilibrium Water Absorption (85℃) wt% 0.79 0.44

[0156] * The coefficient of thermal expansion is measured at a temperature higher than T g .

[0157] As shown in Tables 3 and 4, compared with the comparative examples, the dielectric properties, resin flow after partial curing, coefficient of thermal expansion, and water absorption of the examples are improved. In addition, for the examples and comparative examples, the onset decomposition temperature and dielectric constant are similar. These results are unexpected because unexpectedly, the incorporation of repeating units derived from 2-(C 1-12 primary or secondary alkyl)-6-(unsubstituted C 6-12 -aryl)phenols (such as 2-methyl-6-phenylphenol) in the poly(arylene ether) copolymer can simultaneously improve the properties mentioned in Tables 3 and 4.

[0158] The results show that the examples can simultaneously achieve an improved combination of dissipation factor, viscosity, T g , CTE, and water absorption. Therefore, the curable thermosetting composition can provide the performance attributes required for resins used in electronic materials, particularly prepregs, laminates, and metal-clad laminates for printed circuit boards.

[0159] The present invention further encompasses the following aspects.

[0160] Aspect 1. A curable thermosetting composition comprising a capped poly(arylene ether) copolymer having reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from an alkylaryl phenol.

[0161] Aspect 2. The curable thermosetting composition according to Aspect 1, wherein the capped poly(arylene ether) copolymer is derived from the reaction of a diphenol and a monophenol comprising 2-(alkyl)-6-(aryl)phenol; or wherein the monophenol is 2-(C 1-12 primary or secondary alkyl)-6-(unsubstituted C 6-12 aryl)phenol.

[0162] Aspect 3. The curable thermosetting composition according to any one of the preceding aspects, wherein the capped poly(arylene ether) copolymer has the formula (1) or formula (2) as provided herein.

[0163] Aspect 4. The curable thermosetting composition according to Aspect 3, wherein Q 1a is independently, each time it appears, a C 1-12 primary alkyl group or a C 1-6 primary alkyl group; Q 1b is independently, each time it appears, a C 1-12 alkyl group or a C 6-12 aryl group; or a C 1-6 alkyl group or a phenyl group; Q 2 is hydrogen; and R 1 , R 2 , R 3 and R 4 are each independently hydrogen, a halogen, or a C 1-12 alkyl group; or hydrogen or a C 1-6 alkyl group, optionally wherein the end-capped poly(arylene ether) copolymer comprises at least one repeating unit, wherein Q 1a is a C 1-12 primary alkyl group, and Q 1b is an unsubstituted C 6-12 aryl group; or wherein the end-capped poly(arylene ether) copolymer comprises at least one repeating unit, wherein Q 1a is a C 1-6 primary alkyl group, and Q 1b is an unsubstituted phenyl group.

[0164] Aspect 5. The curable thermosetting composition according to any one of Aspects 3 or 4, wherein the end-capped poly(arylene ether) copolymer has the formula (2a) as provided herein.

[0165] Aspect 6. The curable thermosetting composition according to any one of Aspects 3 to 5, wherein the end-capped poly(arylene ether) copolymer has the formula (2b) as provided herein.

[0166] Aspect 7. The curable thermosetting composition according to any one of the foregoing aspects, further comprising one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

[0167] Aspect 8. The curable thermosetting composition according to any one of the foregoing aspects, further comprising one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0168] Aspect 9. A cured thermosetting composition comprising a cured product of the curable thermosetting composition according to any one of the foregoing aspects.

[0169] Aspect 10. A method for manufacturing the cured thermosetting composition according to Aspect 9, the method comprising curing the thermosetting composition at a temperature of 50°C to 250°C.

[0170] Aspect 11. An article comprising a cured thermosetting composition according to Aspect 9, wherein the article is a composite material, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded part, prepreg, housing, cast article, laminate, or a combination thereof; or wherein the article is a metal-clad laminate, electronic composite material, structural composite material, or a combination thereof.

[0171] Aspect 12. A varnish composition comprising: a curable thermosetting composition according to any one of Aspects 1 to 8; and a solvent.

[0172] Aspect 13. An article made from the varnish composition according to Aspect 12, or wherein the article is a fiber, layer, coating, cast article, prepreg, composite material, or laminate; or wherein the article is a metal-clad laminate.

[0173] Aspect 14. A method for manufacturing an article according to Aspect 13, comprising: impregnating a substrate with the varnish composition to form a prepreg; and curing the varnish composition.

[0174] The compositions, methods, and articles may alternatively 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 so as to be free or substantially free of any materials (or types), steps, or components that would otherwise be unnecessary for the function or purpose of the compositions, methods, and articles.

[0175] All ranges disclosed herein include the endpoints, and the endpoints can be combined independently of each other. "Combination" includes blends, mixtures, alloys, reaction products, etc. Unless otherwise indicated herein or clearly contradicted by the context, the terms "a" and "an" and "the" do not denote a limitation of quantity, but are to be construed as covering the singular and the plural. Unless otherwise expressly stated, "or" means "and / or". It should be understood that the described elements can be combined in a suitable manner in various aspects. "Their combination" is open-ended and includes any combination that includes at least one of the listed components or properties (optionally together with similar or equivalent components or properties not listed).

[0176] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All patents, patent applications, and other references cited are incorporated herein by reference in their entirety. However, if a term in this application conflicts or contradicts a term in a incorporated reference, the term from this application prevails over the conflicting term from the incorporated reference. Unless otherwise specified herein, all test standards are the latest standards in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0177] Unless otherwise indicated, compounds are described using standard terminology. The terms "hydrocarbon" and "hydrocarbyl" refer to any compound, group, or substituent containing carbon and hydrogen. Residues can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. They can also contain combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as substituted, it can optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, a hydrocarbyl residue can also contain one or more carbonyl, amino, hydroxy, etc. As used herein, the term "heterohydrocarbyl" refers to a hydrocarbyl containing one or more heteroatoms within the backbone of the hydrocarbyl residue. "Aliphatic" refers to a non-aromatic hydrocarbyl; "aryl" refers to a monocyclic or polycyclic aromatic hydrocarbyl in which all ring members are carbon; "alkaryl" refers to an aryl substituted with an alkyl; "aralkyl" refers to an alkyl substituted with an aryl. The prefix "hetero" refers to a compound or group in which at least one ring member includes a heteroatom (e.g., 1, 2, or 3 heteroatoms), where the heteroatoms are each independently N, O, S, Si, or P.

[0178] In chemical formulas shown by structures, it should be understood that any position not shown as being substituted by the indicated group has a valence filled by the indicated bond or a hydrogen atom. Unless otherwise specifically stated, each of the above groups can be unsubstituted or substituted, provided that the substitution does not significantly and adversely affect the synthesis, stability, or use of the compound. "Substituted" means that a compound, group, or atom is substituted by at least one (e.g., 1, 2, 3, or 4) substituent, which can each independently be nitro (-NO2), cyano (-CN), hydroxy (-OH), halogen, mercapto (-SH), thiocyanato (-SCN), C 1-6 alkyl, C2-6 alkenyl, C 2-6 alkynyl, C 1-6 haloalkyl, C 1-9 alkoxy, C 1-6 haloalkoxy, C 3-12 cycloalkyl, C 5-18 cycloalkenyl, C6-12 aryl, C 7-13 aralkyl (e.g., benzyl), C 7-12 alkaryl (e.g., toluoyl), C 4-12 heterocycloalkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (—S(═O)2-alkyl), C 6-12 arylsulfonyl (—S(═O)2-aryl) or tosyl (CH3C6H4SO2-), rather than hydrogen, provided that the normal valences of the substituted atoms are not exceeded. The number of carbon atoms indicated in the group does not include any substituents. For example, —CH2CH2CN is a C2 alkyl substituted with a nitrile group.

[0179] The appended claims, as filed and as they may be amended, are intended to cover alternatives, modifications, improvements, and substantial equivalents that are now unforeseen or may be unforeseen or that may arise to the applicant or other persons skilled in the art.

Claims

1. A curable thermosetting composition comprising a capped poly(arylene ether) copolymer having reactive end groups, wherein, The capped poly(arylene ether) copolymer is derived from an alkyl aryl phenol; wherein the capped poly(arylene ether) copolymer is of formula (1): wherein, Q 1a and Q 1b is independently, each time it appears, halogen, C 1-12 The alkyl group condition is that the alkyl group is not a tertiary alkyl group, C 1-12 alkylthio, C 1-12 alkoxy, or C 2-12 haloalkoxy in which at least two carbon atoms separate the halogen and the oxygen atom; Q 2 Each occurrence is independently hydrogen, halogen, unsubstituted or substituted C 1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and the oxygen atom; R 5a is independently Q each time it appears 1a or (C 1-6 hydrocarbyl)(C 1-6 hydrocarbyl)aminomethylene; R 5b is independently Q each time it appears 1b or (C 1-6 hydrocarbyl)(C 1-6 hydrocarbyl)aminomethylene; e is the number of moles of arylene ether units; provided that the capped poly(arylene ether) copolymer comprises: At least one repeating unit, wherein Q 1a is C 1-12 primary or secondary alkyl, and Q 1b is unsubstituted C 6-12 aryl, At least one terminal unit, wherein R 5a is C 1-12 primary or secondary alkyl, and R 5b is unsubstituted C 6-12 aryl, or their combination; R is independently, each occurrence, wherein, Y 2 is a divalent linking group having one of the following formulas wherein, R 6 、R 7 and R 8 is, each time it appears independently, hydrogen, a C 1-18 hydrocarbyl group, a C 2-18 hydroxycarbonyl group, a nitrile group, a formyl group, a carboxyl group, an iminoester group or a thiocarboxyl group.

2. The curable thermosetting composition according to claim 1, wherein, the capped poly(arylene ether) copolymer is derived from the reaction of a dihydric phenol and a monohydric phenol, the monohydric phenol comprising 2-(alkyl)-6-(aryl) phenol; Or wherein, the monohydric phenol is 2-(C 1-12 primary or secondary alkyl)-6-(unsubstituted C 6-12 aryl)phenol.

3. The curable thermosetting composition according to claim 1, wherein, the capped poly(arylene ether) copolymer is of formula (2): wherein, R 1 、R 2 、R 3 and R 4 is independently, each time it appears, hydrogen, halogen, C 1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy in which at least two carbon atoms separate the halogen and the oxygen atom; x and y represent the relative molar ratios of arylene ether units, wherein x and y are each independently from 0 to 50, provided that the sum of x and y is at least 2; R 5a each occurrence independently is Q 1a or (C 1-6 hydrocarbyl)(C 1-6 hydrocarbyl)aminomethylene; R 5b each occurrence independently is Q 1b or (C 1-6 hydrocarbyl)(C 1-6 hydrocarbyl)aminomethylene; provided that the capped poly(arylene ether) copolymer comprises: At least one repeating unit, wherein Q 1a is a C 1-12 primary or secondary alkyl group, and Q 1b is an unsubstituted C 6-12 aryl group At least one terminal unit, wherein R 5a is C 1-12 primary or secondary alkyl, and R 5b is an unsubstituted C 6-12 aryl, or their combination; Y 1 is a divalent linking group that is any one or more of the following formulas: wherein, R a , R b and R e Each occurrence is independently hydrogen, C 1-12 Hydrocarbon or C 1-6 alkylene, optionally wherein R a and R b Together is C 4-8 Cycloalkylene, R f is independently C each time it appears 1-6 a divalent hydrocarbon radical R g is independently, each time it appears, hydrogen, C 1-12 hydrocarbyl or C 1-12 halohydrocarbyl, and n′ is from 5 to 50; z is 0 or 1; and R x and R y each independently when it appears wherein, Y 2 is a divalent linking group having one of the following formulas wherein, R 6 、R 7 and R 8 each independently is hydrogen, C 1-18 hydrocarbyl, C 2-18 hydroxycarbonyl, nitrile, formyl, carboxyl, iminoester or thiocarboxyl each time it appears.

4. The curable thermosetting composition according to claim 3, wherein, Q 1a is independently C each time it appears 1-12 a primary alkyl group or C 1-6 a primary alkyl group; Q 1b is independently C each time it appears 1-12 alkyl or C 6-12 aryl; or C 1-6 alkyl or phenyl; Q 2 is hydrogen; and R 1 、R 2 、R 3 and R 4 each independently is hydrogen, halogen or C 1-12 alkyl; or hydrogen or C 1-6 alkyl, Optionally, wherein the capped poly(arylene ether) copolymer comprises at least one repeating unit, wherein Q 1a is C 1-12 a primary alkyl group, and Q 1b is an unsubstituted C 6-12 aryl group; or wherein the capped poly(arylene ether) copolymer comprises at least one repeating unit, wherein Q 1a is C 1-6 a primary alkyl group, and Q 1b is an unsubstituted phenyl group.

5. The curable thermosetting composition according to claim 3, wherein, the capped poly(arylene ether) copolymer has formula (2a): Among them, Q 1a 、Q 1b 、Q 2 、R 1 、R 2 、R 5a 、R 5b 、R x 、R y 、x and y are defined in claim 3 or claim 4; Or wherein, R 1 and R 2 are each independently hydrogen or C 1-6 alkyl.

6. The curable thermosetting composition according to claim 3, wherein, the capped poly(arylene ether) copolymer has formula (2b): wherein, R 1 , R 2 , R 6 to R 8 , R 5a , R 5b , Q 1a , Q 1b , Q 2 , x and y are as defined in claim 3.

7. The curable thermosetting composition according to any one of claims 1 to 6 further comprises one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

8. The curable thermosetting composition according to any one of claims 1 to 6 further comprises one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

9. A cured thermosetting composition comprising a cured product of the curable thermosetting composition according to any one of claims 1 to 6.

10. A method for manufacturing the cured thermosetting composition according to claim 9, comprising curing the curable thermosetting composition at a temperature of 50°C to 250°C.

11. An article comprising the cured thermosetting composition of claim 9, wherein the article is a composite material, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded part, prepreg, housing, casting, laminate, or a combination thereof; or wherein, The article is a metal-clad laminate, an electronic composite material, a structural composite material, or a combination thereof.

12. A varnish composition comprising the curable thermosetting composition of any one of claims 1 to 6; and a solvent.

13. An article made from the varnish composition of claim 12, wherein, The article is a fiber, a layer, a coating, a casting, a prepreg, a composite material, or a laminate; or wherein the article is a metal-clad laminate.

14. A method for manufacturing the article of claim 13, comprising: Impregnating the varnish composition into a substrate to form a prepreg; and curing the varnish composition.

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