Curable thermoset compositions comprising poly (arylene ether) copolymers

Abstract

To provide a curable thermosetting composition comprising a poly (arylene ether) copolymer having a lower viscosity.SOLUTION: A curable thermoset composition comprising a capped poly(arylene ether) copolymer, wherein the capped poly(arylene ether) copolymer is derived from an alkyl aryl-phenol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of European patent application serial number 201900644, filed August 7, 2020, which in turn claims priority to and the benefit of U.S. provisional patent application serial number 63 / 035,317, filed June 5, 2020, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates to curable thermosetting compositions, including thermosetting compositions, varnish compositions, and articles obtained therefrom. [Background technology]

[0003] 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 in the manufacture of computer circuit boards), flooring and paving applications, fiberglass-reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components). Poly(arylene ether) copolymers generally have good dielectric properties. Due to their wide use in electronic applications, particularly laminates for printed circuit boards, it would be desirable to provide curable thermosetting compositions containing poly(arylene ether) copolymers with lower viscosity while maintaining or improving dielectric constant, dissipation factor, heat resistance, and water absorption. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there remains a need in the art for curable thermosetting compositions comprising poly(arylene ether) copolymers with a desirable set of properties. It would be further advantageous if the curable thermosetting compositions had improved dielectric constant, dissipation factor, heat resistance, and water absorption. [Means for solving the problem]

[0005] A curable thermosetting composition is provided that includes a capped poly(arylene ether) copolymer that includes reactive end groups, where the capped poly(arylene ether) copolymer is derived from an alkyl-aryl-phenol.

[0006] Also provided are cured thermosetting compositions comprising the cured product of the curable thermosetting composition, methods for making the cured thermosetting composition comprising curing the curable thermosetting composition, and articles comprising the cured thermosetting composition of claim 9, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof.

[0007] Another aspect provides a varnish composition comprising a curable thermosetting composition, an article made from the varnish composition, and a method of making the article, the method comprising impregnating the varnish composition into a substrate to form a prepreg and curing the varnish composition. DETAILED DESCRIPTION OF THE INVENTION

[0008] These and other features are exemplified by the following detailed description.

[0009] Detailed Description The present inventors have advantageously discovered that the inclusion of end-capped poly(arylene ether) copolymers containing repeat units derived from alkyl- and aryl-phenols in curable thermosetting compositions can achieve improved properties over curable thermosetting compositions containing poly(arylene ether) copolymers that do not contain repeat units derived from alkyl- and aryl-phenols. For example, poly(arylene ether) copolymers containing repeat units derived from alkyl- and aryl-phenols can provide an improved combination of properties such as solution viscosity, dissipation factor, resin flow, coefficient of thermal expansion (CTE), and equilibrium water absorption.

[0010] Accordingly, one aspect of the present disclosure is a curable thermosetting composition comprising a capped poly(arylene ether) copolymer comprising reactive end-capping, wherein the capped poly(arylene ether) copolymer is derived from an alkyl-aryl-phenol. The alkyl-aryl-phenol may be, for example, a 2-(alkyl)-6-(aryl)phenol, such as 2-(C 1~12 Primary or secondary alkyl)-6-(unsubstituted C 6~12 For example, alkyl-aryl-phenols can be 2-(C 1~6 The compound may be a phenol, such as a phenolic compound, ...

[0011] The capped poly(arylene ether) copolymer contains 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, epoxides including glycidyl ether, cyanate ester, amine, maleimide, carboxylic acid, carboxylic acid alkyl ester, and the like. The capped poly(arylene ether) copolymer can be a difunctional oligomer having reactive end groups at both ends of the oligomeric chain. Difunctional oligomers having functional groups at both ends of the oligomeric chain are also called "telechelic" oligomers.

[0012] For example, a capped poly(arylene ether) copolymer that is a difunctional oligomer may contain, on average, 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 up to 1.99 reactive end groups per molecule, or up to 1.97 hydroxyl groups per molecule.

[0013] The capped poly(arylene ether) copolymers may be represented by formula (1) or formula (2): [ka] (In the formula, Q 1a and Q 1b is, independently in each occurrence, a 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 where at least two carbon atoms separate the halogen atom from the oxygen atom 2~12 halohydrocarbyloxy, and Q 2 are 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 where at least two carbon atoms separate the halogen atom from the oxygen atom 2~12 For example, Q may have a halohydrocarbyloxy group. 1a and Q 1b In each case independently, C 1~12 Alkyl, C 2~12 Alkenyl, or C 2~12 It may be alkynyl.

[0014] In equation (2), R 1 ~R 4 are each independently hydrogen, halogen, or C 1~12hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy, or C where at least two carbon atoms separate the halogen atom from the oxygen atom 2~12 It is a halohydrocarbyloxy.

[0015] In formula (1) and formula (2), R 5a is, in each case independently, Q 1a or (C 1~6 -hydrocarbyl)(C 1~6 -hydrocarbyl)aminomethylene group, and R 5b is, in each case independently, Q 1b or (C 1~6 -hydrocarbyl)(C 1~6 -hydrocarbyl)aminomethylene groups, provided that the capped poly(arylene ether) copolymer is 1a C 1~12 is a primary or secondary alkyl, and Q 1b is unsubstituted C 6~12 at least one repeat unit that is aryl, or R 5a C 1~12 is a primary or secondary alkyl, and R 5b is unsubstituted C 6~12 For example, in one embodiment, the capped poly(arylene ether) copolymer comprises at least one terminal unit that is aryl, Q 1a C 1~12 is a primary or secondary alkyl, and Q 1b is unsubstituted C 6~12 It may contain one or more repeat units that are aryl.

[0016] In formula (1), e is the number of moles of arylene ether units.

[0017] In formula (2), x and y represent the relative molar ratio of arylene ether units, where 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, with the proviso that the sum of x and y is at least 2, or at least 3, or at least 4.

[0018] Y in equation (2) 1 is the expression [ka] (In the formula, R a , R b , and R e is, independently in each occurrence, hydrogen, C 1~12 Hydrocarbyl, or C 1~6 hydrocarbylene, where optionally, R a and R b Together, C 4~8 is a cycloalkylene group, and R f In each case independently, C 1~6 is a hydrocarbylene group, and R g is, independently in each occurrence, hydrogen, C 1~12 Hydrocarbyl, or C 1~12 and n' is 5 to 50. In formula (1) and formula (2), R is independently in each occurrence any one or more divalent linking groups of the formula [ka] wherein Y 2 is the expression [ka] (In the formula, R c and R d is, independently in each occurrence, hydrogen or C 1~12 alkyl), and R 5ais a C optionally substituted with an epoxide-containing group, a cyanate-containing group, or one or two carboxylic acid groups; 1~12 is hydrocarbyl, and R 6 , R 7 , and R 8 is, independently in each occurrence, hydrogen, C 1~18 Hydrocarbyl, C 2~18 is a hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid, and R 9 , R 10 , R 11 , R 12 , and R 13 is, independently in each occurrence, hydrogen, halogen, C 1~12 Alkyl, C 2~12 Alkenyl, hydroxy, amino, maleimide, carboxylic acid, or C 2~20 It is an alkyl ester.

[0019] In certain embodiments, Q 1a In each case independently, C 1~12 Primary alkyl or C 1~6 is a primary alkyl, and Q 1b In each case independently, C 1~12 Alkyl or C 6~12 Aryl, or C 1~6 alkyl or phenyl, and Q 2 is hydrogen and R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, halogen, or C 1~12 Alkyl, or hydrogen or C 1~6 The capped poly(arylene ether) copolymer is 1a C 1~12 is a primary alkyl, and Q 1b is unsubstituted C 6~12 For example, a capped poly(arylene ether) copolymer may contain at least one repeat unit that is Q aryl. 1a C 1~6 is a primary alkyl, and Q1b may contain one or more repeat units in which is unsubstituted phenyl.

[0020] In another particular embodiment, the capped poly(arylene ether) copolymer has the formula (2a): [ka] (In the formula, Q 1a , Q 1b , Q 2 , R 1 , R 2 , R 5a , R 5b , R x , R y , x, and y are as defined in formula (1) and formula (2), and R 1a and R 1b are each independently hydrogen or R 1 and R 2 are each independently hydrogen or C 1~6 For example, a capped poly(arylene ether) copolymer can be derived from the reaction of a dihydric phenol with 2-methyl-6-phenylphenol.

[0021] In another particular embodiment, the capped poly(arylene ether) copolymer has the formula (2b): [ka] (In the formula, R 1 , R 2 , R 6 ~R 8 , R 5a , R 5b , Q 1a , Q 1b , Q 2 , x, and y are as defined in formula (1) and formula (2).

[0022] Poly(arylene ether) copolymers are the product of the oxidative copolymerization of monomers including a monohydric phenol or a mixture of a monohydric phenol and, optionally, a dihydric phenol. The monohydric phenol can be represented by formula (3): [ka] (In the formula, Q 1a and Q 1b is as defined for formula (1). Exemplary monohydric phenols 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.

[0023] In addition to monohydric phenols, the monomers can include dihydric phenols, where the dihydric phenols have the formula (4): [ka] (In the formula, R 1 ~R 4 , Y 1 and z is as defined for formula (2).

[0024] For example, dihydric phenols include 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1-bis(3-chloro-4-hydroxyphenyl)ethane, 1,1-bis(3-methyl-4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxy-3,5-dimethylphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)ethane, 2,2'-binaphthol, 2,2'-biphenol, 2,2'-dihydrobenzophenone, 2,2'-dibenzo ... 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)propane phenyl)-1-phenylethane, 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)-1-phenylpropane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)hexane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)pentane, 2,2-bis(3-methyl-4-hydroxynaphthyl)propane, 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-4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 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-(4-hydroxy-3,5-dimethylphenyl)cyclohexylmethane, bis(4-hydroxy-3,5-dimethylphenyl)phenylmethane, bis(3-methyl-4-hydroxyphenyl)cyclohexylmethane, 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'-biphenol, octafluoro-4,4'-biphenol, 2,3,3',5,5'-pentamethyl-4,4'-biphenol, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane The bisphenol A may be 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, bis(3-methyl-4-hydroxyphenyl)cyclohexane, tetrabromobisphenol, tetrabromobisphenol A, tetrabromobisphenol S, 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.

[0025] As disclosed herein, capped poly(arylene ether) copolymers can be derived from alkyl-aryl phenols, or, for example, capped poly(arylene ether) copolymers can be derived from the reaction of a dihydric phenol with a monohydric phenol, including 2-(alkyl)-6-(aryl)phenol. For example, the capped poly(arylene ether) copolymer can be the product of oxidative copolymerization of monomers containing a monohydric phenol, or a mixture of a monohydric phenol and, optionally, a dihydric phenol, in a solvent in the presence of a catalyst. For example, a method for forming a capped poly(arylene ether) copolymer can include oxidatively copolymerizing 2-(alkyl)-6-(aryl)phenol monomers, optionally with another monohydric phenol monomer, and a dihydric phenol monomer in a solvent in the presence of a catalyst composition.

[0026] Oxidative polymerization is carried out by sequentially adding oxygen to a reaction mixture containing monomers, a solvent, and a catalyst composition to form a polymer having the structure of formula (1) or formula (2), wherein R, R x , and R yis a hydrogen atom (i.e., an uncapped copolymer). The molecular oxygen (O) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex containing a transition metal cation. The metal cation can include cations from Groups VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof, preferably chromium, manganese, cobalt, or copper, or a combination thereof. Exemplary metal salts include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous sulfate, cupric sulfate, tetraammine cuprous sulfate, tetraammine cupric sulfate, cuprous acetate, cupric acetate, cuprous propionate, cupric butyrate, cupric laurate, cuprous 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 be added to form the corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be added to form cuprous bromide in situ.

[0027] The polymerization catalyst may further include an amine ligand, such as a monoamine, an alkylenediamine, or a combination 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.

[0028] Exemplary dialkyl monoamines 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)phenylethanolamine, N-(2,6-dimethyl)phenylethanolamine, N-(p-chloro)phenylethanolamine, 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 trialkyl monoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, or a combination thereof.

[0029] Exemplary alkylenediamines include those of the formula: (R bb )2N-R aa -N(R bb )2(wherein, R aa is a substituted or unsubstituted divalent residue, and each R bb are independently hydrogen or C 1~8 In some embodiments, two or three aliphatic carbon atoms may form the nearest link between the two diamine nitrogen atoms. Specific alkylenediamine ligands include those having R aa Examples of alkylenediamine ligands include those in which R is dimethylene (-CH2CH2-) or trimethylene (-CH2CH2CH2-). bb are independently hydrogen, methyl, propyl, isopropyl, butyl, or C 4~8The alkylenediamine ligand may be an α-tertiary alkyl group. 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 the amine ligand. For example, a polymerization catalyst can include copper ions, bromide ions, and N,N'-di-tert-butylethylenediamine.

[0030] The hydroxy-terminated poly(arylene ether) copolymer can be reacted with a capping agent to obtain a capped poly(arylene ether) copolymer. The capping agent is not particularly limited and can be a compound containing unsaturation, an epoxy, a benzoxazine, an isocyanate, a cyanate ester, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an anhydride, an allylhydroxypropyl, or a combination thereof. Those skilled in the art can select a capping agent based on the desired functionality of the capped poly(arylene ether) copolymer. For example, vinylbenzyl ether end groups can be prepared using a curing agent that is a vinylbenzyl halide (e.g., vinylbenzyl chloride), and (meth)acrylic acid end groups can be prepared using a curing agent that is a (meth)acrylic acid halide or (meth)acrylic acid anhydride.

[0031] The capped poly(arylene ether) copolymer can contain structural units derived from a monohydric phenol and structural units derived from 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.

[0032] In some embodiments, the capped poly(arylene ether) copolymer can be a poly(arylene ether)-polysiloxane block copolymer, which, as used herein, refers to a block copolymer comprising at least one poly(arylene ether) block and at least one polysiloxane block.

[0033] The poly(arylene ether)-polysiloxane block copolymers can be prepared by an oxidative copolymerization method comprising oxidatively copolymerizing a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane. For example, the monomer mixture can comprise 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane. The hydroxyaryl-terminated polysiloxane can be represented by the formula (5): [ka] (In the formula, R 22 and R 33 is, independently in each occurrence, hydrogen, C 1~12 Hydrocarbyl, or C 1~12 a plurality of repeating units having the structure of formula (5a): [ka] (Wherein M is hydrogen, C 1~12 Hydrocarbyl, C 1~12 hydrocarbyloxy, or halogen, and R 44 and R 45 is, independently in each occurrence, hydrogen, C 1~12 Hydrocarbyl, or C 1~12 In a specific embodiment, the alkyl group may include two terminal units having the structure R 8 and R 9 is methyl in each instance and Y is methoxy.

[0034] For example, the monohydric phenol can be 2,6-dimethylphenol and the hydroxyaryl-terminated polysiloxane can be of formula (5b): [ka] (wherein n is, on average, 5 to 100, or 5 to 45, or 30 to 60). Thus, the compound has the structure of formula (6): [ka] The structural fragment of the capped poly(arylene ether) copolymer having the formula (6a): [ka] (wherein n is 5 to 100, or 5 to 45, or 30 to 60).

[0035] The capped poly(arylene ether) copolymer may also contain 10 mol % to 70 mol % of copolymer chains containing terminal 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 may have the formula (7): [ka] (In the formula, R 1 ~R 4 , Y 1 , and z are as shown in formula (1) or formula (2), and R is R x or R y The copolymer may contain 10 mol % to 70 mol % of copolymer chains containing terminal units having the structure:

[0036] In one embodiment, the capped poly(arylene ether) copolymer can have an intrinsic viscosity of 0.03 deciliters per gram (dL / g) to 0.13 dL / g, or 0.03 dL / g to 0.18 dL / g, or 0.04 dL / g to 0.15 dL / g, using an Ubbelohde viscometer in chloroform at 25° C. The capped poly(arylene ether) copolymer can have a weight average molecular weight (M) of 500 g / mol to 50,000 g / mol, or 1,000 g / mol to 25,000 g / mol, or 1,500 g / mol to 12,500 g / mol, as measured by gel permeation chromatography (GPC) using polystyrene standards. wThe capped poly(arylene ether) copolymer may have a number average molecular weight (M) of 500 grams per mole (g / mol) to 10,000 g / mol, or 750 g / mol to 5,000 g / mol, or 500 g / mol to 4,000 g / mol, as measured by GPC using polystyrene standards. n In some embodiments, the capped poly(arylene ether) copolymer may have an M of 1.9 to 3, or at least 2, or at most 2.8, or at most 2.6, or at most 2.4. w Against M n The ratio of the nuclei to the nuclei is also called "polydispersity."

[0037] The capped poly(arylene ether) copolymer can be present in the curable thermosetting composition in an amount of 1 weight percent (wt%) to 95 wt%, or 5 wt% to 95 wt%, or 10 wt% to 85 wt%, or 20 wt% to 80 wt%, or 30 wt% to 70 wt%, or 5 wt% to 30 wt%, or 5 wt% to 15 wt%, based on the total weight of the curable thermosetting composition.

[0038] The curable thermosetting composition may optionally further comprise one or more crosslinkers, curing agents, curing catalysts, curing initiators, or combinations thereof. In some embodiments, the curable thermosetting composition may further comprise one or more flame retardants, fillers, coupling agents, or combinations thereof. For example, the curable thermosetting composition may comprise one or more crosslinkers, curing agents, curing catalysts, curing initiators, or combinations thereof, and may further comprise one or more flame retardants, fillers, coupling agents, or combinations thereof. For example, the curable thermosetting composition may comprise one or more crosslinkers, curing agents, curing catalysts, curing initiators, or combinations thereof, and may further comprise one or more flame retardants, fillers, coupling agents, or combinations thereof.

[0039] There is considerable overlap between 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.

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

[0041] The epoxy resin may generally be any epoxy resin suitable for use in thermosetting resins. The term "epoxy resin" in this context refers to curable compositions of oxirane ring-containing compounds, such as those described in "Epoxy Resins," 2nd Edition, by CA May (New York & Basel: Marcel Dekker Inc.), 1988. Examples of epoxy resins include bisphenol A epoxy resins, such as epoxy resins obtained from bisphenol A, and resins obtained by substituting at least one of the 2-, 3-, and 5-positions of bisphenol A with a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; bisphenol F epoxy resins, such as epoxy resins obtained from bisphenol F, and resins obtained by substituting at least one of the 2-, 3-, and 5-positions of bisphenol F with a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; glycidyl ether compounds derived from divalent or higher phenols such as hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; bisphenol A novolac epoxy resins; and cresol. novolac-type epoxy resins derived from novolac resins which are reaction products between phenols and formaldehyde, such as phenol and o-cresol, including phenol novolac-type epoxy resins; cycloaliphatic epoxy compounds, such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, dicyclopentadiene-containing polyepoxides, aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene,The epoxy resins may be amine-type epoxy resins derived from 4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)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, or the like; heterocyclic epoxy compounds; and glycidyl ester-type epoxy compounds, for example, epoxy resins derived from the glycidyl esters of aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, or isophthalic acid. The term "epoxy resin" may also include the reaction product of a compound containing two or more epoxy groups with an aromatic dihydroxy compound, which may optionally be halogen-substituted.

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

[0043] Bismaleimide resins can be prepared by reacting a monomeric bismaleimide with a nucleophile such as a diamine, aminophenol, or aminobenzhydrazide, 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'-bismaleimidodiphenyl ether, 3,3'-bismaleimidodiphenyl sulfone, 4,4'-bismaleimidodiphenyl 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'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4, Included are 4'-dimethylenecyclohexane bismaleimide, N,N'-m-meta-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, and N,N'-methylene-bis(3-chloro-p-phenylene) bismaleimide, as well as the maleimide resins disclosed in U.S. Pat. Nos. 3,562,223, 4,211,860, and 4,211,861.Bismaleimide resins can be prepared by methods known in the art, for example, as described in US Pat. No. 3,018,290.

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

[0045] Exemplary phenols used in the preparation of 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'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylenediisopropylidene)bisphenol, bisphenol F), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidenediphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane (bisphenol F), 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, isopropylidenebis(2-allylphenol), 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), Examples include 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, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(ortho-cresol), and dicyclopentadienylbisphenol.

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

[0047] The amines for forming the benzoxazines generally have 1 to 40 carbon atoms, unless they contain an aromatic ring and can have 6 to 40 carbon atoms. Difunctional or polyfunctional amines can be branching points connecting one polybenzoxazine to another.

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

[0049] Vinylbenzyl ether resins can be prepared from the condensation of phenol with vinylbenzyl halides, such as vinylbenzyl chloride. Bisphenol A and trisphenols and polyphenols are commonly used to produce poly(vinylbenzyl ethers), which can be used to produce crosslinked thermoset resins. Exemplary vinylbenzyl ethers include those produced by condensing 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, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidene-diphenol, 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol), 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidene 4,4'-(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidenediphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis( 2,6-dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(Cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)-isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol, dihydroxybenzophenone, tris(4-hydroxyphenyl)-isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol Examples of vinyl benzyl ethers include those produced by reaction with tetrakis(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(ortho-cresol), dicyclopentadienylbisphenol, and the like.

[0050] Arylcyclobutenes include those having the structure [ka] where B is an organic or inorganic group of valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidenedialkylsilanyl, arylalkylsilanyl, diarylsilanyl, and C 6~20 X is independently in each occurrence hydroxy or C 1~24is hydrocarbyl (including linear and branched alkyl and cycloalkyl), and Z is, independently in each occurrence, hydrogen, halogen, or C 1~12 hydrocarbyl and n is 1 to 1000, or 1 to 8, or n is 2, 3, or 4. Other exemplary arylcyclobutenes and methods for synthesizing arylcyclobutenes can be found in U.S. Pat. Nos. 4,743,399, 4,540,763, 4,642,329, 4,661,193, 4,724,260, and 5,391,650.

[0051] Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane, followed by reductive elimination catalyzed by ZnFBr and zinc to produce the desired perfluorovinyl ether. By this route, bisphenols, trisphenols, and other polyphenols can produce bis(perfluorovinyl ethers), tris(perfluorovinyl ethers), 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-dibromobiphenol, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol) (tetramethylphenol A), 4 ,4'-Isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidenediphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2,6-Dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3' -tetrahydro-1,1'-spirobi[indene]-5,6'-diol, 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, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(2-methylphenol), etc.

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

[0053] Polybutadiene resins containing elevated levels of 1,2 addition are desirable for thermosetting matrices. Examples include functionalized polybutadiene and poly(butadiene-styrene) random copolymers sold by Ricon Resins under the trade names RICON resin, RICACRYL resin, and RICOBOND resin. These resins include butadienes with low vinyl content such as RICON 130, RICON 131, RICON 134, RICON 142, polybutadienes with high vinyl content such as RICON 150, RICON 152, RICON 153, RICON 154, RICON 156, RICON 157, and RICON P30D, random copolymers of styrene and butadiene including RICON 100, RICON 181, RICON 184, and maleic anhydride grafted polybutadienes and alcohol condensates derived therefrom, e.g., 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-functionalized polybutadienes such as polybutadiene diacrylate and polybutadiene dimethacrylate. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801.Also included are powder dispersions of functionalized polybutadiene derivatives, including, for example, RICON 150D, RICON 152D, RICON 153D, RICON 154D, RICON P30D, RICOBOND 01731HS, and RICOBOND 1756HS. Additional butadiene resins include poly(butadiene-isoprene) block and random copolymers, e.g., copolymers having a molecular weight of 3,000 g / mol to 50,000 g / mol, and polybutadiene homopolymers having a molecular weight of 3,000 g / mol to 50,000 g / mol. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride functionality, 2-hydroxyethyl maleic acid functionality, or hydroxylated functionality.

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

[0055] When the curable thermosetting composition includes a crosslinking agent, the crosslinking agent 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.

[0056] Curable thermosetting compositions may include one or more curing agents, including compounds that may be described as curing agents, hardeners, or both.

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

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

[0059] Curable thermosetting compositions may contain curing catalysts, including compounds also described as cure accelerators, cure promoters, cure catalysts, and cure cocatalysts.

[0060] Exemplary cure accelerators include heterocyclic accelerators, such as substituted or unsubstituted C 12 alkyl acrylates containing 1 to 4 ring heteroatoms, each heteroatom being independently the same or different and being nitrogen, oxygen, phosphorus, silicon, or sulfur. 3~6Heterocyclic accelerators include benzotriazoles, triazines, piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, and the like, imidazoles such as 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methyl ... propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole Imidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, cyclic amidines such as 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenylimidazoline, N,N-dimethylaminopyridine, sulfamidate, or combinations thereof.

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

[0062] The cure accelerator can be, for example, a latent cationic cure catalyst including a diaryliodonium salt, a phosphonate ester, a sulfonate ester, a carboxylic acid ester, a phosphonic acid ylide, a triarylsulfonium salt, a benzylsulfonium salt, an aryldiazonium salt, a benzylpyridinium salt, a benzylammonium salt, an isoxazolium salt, or a combination thereof. Diaryliodonium salts are compounds having the structure [(R 10 )(R 11 )I] + X - (In the formula, R 10 and R 11 are each independently 1~20 Alkyl, C 1~20 C optionally substituted with 1 to 4 monovalent groups selected from alkoxy, nitro, and chloro 6~14 a monovalent aromatic hydrocarbon group, and X - is an anion). Additional cure accelerators may have the structure [(R 10 )(R 11 )I] + SbF6 - (In the formula, R 10 and R 11 are each independently 1 to 4 C 1~20 Alkyl, C 1~20 C optionally substituted with alkoxy, nitro, or chloro 6~14 monovalent aromatic hydrocarbon), such as 4-octyloxyphenylphenyliodonium hexafluoroantimonate.

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

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

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

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

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

[0068] Examples of phosphorus-based flame retardants include phosphates, phosphazenes, phosphites, phosphite esters, phosphines, phosphinates, polyphosphates, and phosphonium salts. Phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenylbis(dodecyl)phosphate, phenylbis(neopentyl)phosphate, phenylbis(3,5,5'-trimethylhexyl)phosphate, ethyldiphenylphosphate, 2-ethylhexyldi(p-tolyl)phosphate, bis(2-ethylhexyl)p-tolylphosphate, tritolylphosphate, bis(2-ethylhexyl)phenylphosphate, tri(nonylphenyl)phosphate, bis(dodecyl)p-tolylphosphate, dibutylphenyl phosphate, 2-chloroethyldiphenylphosphate, p-tolylbisulfite, and methyltrimethylbis(trimethylhexyl). bis(2,5,5'-trimethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylenebis(di-2,6-xylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetraphenyl diphosphate (RDP), condensed phosphate compounds 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.

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

[0070] Flame retardants can also be used, such as halogenated materials, for example, bisphenols such as 2,2-bis(3,5-dichlorophenyl)propane, bis(2-chlorophenyl)methane, bis(2,6-dibromophenyl)methane, 1,1-bis(4-iodophenyl)ethane, 1,2-bis(2,6-dichlorophenyl)ethane, 1,1-bis(2-chloro-4-iodophenyl)ethane, 1,1-bis(2-chloro-4-methylphenyl)ethane, 1,1-bis(3,5-dichlorophenyl)ethane, 2,2-bis(3-phenyl-4-bromophenyl)ethane, 2,6-bis(4,6-dichloronaphthyl)propane, and 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane. 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-diphenoxybenzenes, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl, as well as decabromobiphenyl ether, decabromodiphenylethane, and oligomeric and polymeric halogenated aromatic compounds such as brominated styrene, 4,4-dibromobiphenyl, ethylene-bis(tetrabromophthalimide), or bisphenol A copolycarbonate, and tetrabromobisphenol A and carbonate precursors such as phosgene. Metal synergists, such as antimony oxide, may be present.

[0071] Inorganic flame retardants, such as C 1~16 Salts of alkylsulfonates, such as potassium perfluorobutanesulfonate (Rimar's salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate, salts such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoroanion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6, can also be used.

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

[0073] The curable thermosetting composition may further comprise an inorganic or organic filler, such as a particulate filler, a fibrous filler, or a combination thereof. Any inorganic or organic filler, including fillers known in the art, may be used without limitation.

[0074] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate, alumina, thiourea, glass powder, B-based fillers or Sn-based fillers such as zinc borate, zinc stannate, and zinc hydroxystannate, metal oxides such as zinc oxide and tin oxide, alumina, silica (including fused silica, fumed silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fiber (chopped, milled, or cloth), glass mat, glass bubbles, hollow glass microspheres, aramid fiber, quartz, or a combination thereof. Other exemplary inorganic fillers include powdered titanium ceramics, such as any one of 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 embodiments, the fillers may be coated or surface treated with the coupling agents disclosed herein.

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

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

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

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

[0079] Coupling agents, also referred to as adhesion promoters, include chromium complexes, silanes, titanates, zircon-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.

[0080] Examples of aminosilane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-beta(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-beta(aminoethyl)γ-aminopropyltrimethoxysilane, N-beta(aminoethyl)γ-aminopropyltriethoxysilane, and combinations of two or more of the above. Exemplary epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and combinations of two or more of the above. Exemplary methacryloxysilane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, or combinations thereof.

[0081] 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-triethoxy ... Examples of suitable silane coupling agents include N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxydimethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, or combinations thereof. The silane coupling agent may be a polysulfide silane coupling agent having two to four sulfur atoms to form a polysulfide bridge. For example, the coupling agent can be bis(3-triethoxysilylpropyl) disulfide, bis(3-triethoxysilylpropyl) trisulfide, or bis(3-triethoxysilylpropyl) tetrasulfide.

[0082] When the curable thermosetting composition includes a coupling agent, the coupling agent may be included in an amount of 0.01 wt % to 5 wt %, or 0.05 wt % to 5 wt %, or 0.1 wt % to 5 wt %, based on the total weight of the curable thermosetting composition.

[0083] The curable thermosetting composition may optionally contain a solvent. 3~8 Ketone, C 3~8 N,N-dialkylamide, C 4~16 Dialkyl ether, C 6~12 Aromatic hydrocarbons, C 1~3 Chlorinated hydrocarbons, C 3~6 Alkyl alkanoates, C 2~6 The ketone solvent may be, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof. 4~8 Examples of N,N-dialkylamide solvents include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or a combination thereof. Examples of dialkyl ether solvents include tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or a combination thereof. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, styrene, divinylbenzene, or a combination thereof. The aromatic hydrocarbon solvent may be non-halogenated. Examples of C 3~6 Alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. 2~6 Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. 2~6Examples of alkyl cyanides include acetonitrile, propionitrile, butyronitrile, or a combination thereof. For example, the solvent may be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, γ-caprolactone, dimethyl sulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexyl methyl ketone, methyl ... The solvent may be xanone, diglyme, triglyme, tetraglyme, N,N-dimethylethyleneurea, N,N-dimethylpropyleneurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, picoline, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, an ionic liquid, or a combination thereof.

[0084] When a solvent is utilized, the curable thermosetting composition may comprise 2% to 99% by weight of the solvent, based on the total weight of the curable thermosetting composition. For example, the amount of solvent may be 5% to 80%, or 10% to 60%, or 20% to 50% by weight, based on the total weight of the curable thermosetting composition. The solvent may be selected, in part, to adjust the viscosity of the curable thermosetting composition. Thus, the amount of solvent may depend on variables including the type and amount of capped poly(arylene ether) copolymer, the type and amount of other ingredients such as curing additives, the type and amount of auxiliary thermosetting resin(s), and any subsequent processing of the curable thermosetting composition, such as the processing temperature used to impregnate the curable thermosetting composition into a structure to be reinforced to prepare a composite. The solvent may be anhydrous. For example, the solvent may contain less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water, based on the total weight of the solvent.

[0085] The curable thermosetting composition may further comprise a curable unsaturated monomer composition, which may comprise, for example, a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, or a combination thereof. For example, the curable unsaturated monomer composition may be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene-containing and alkyne-containing monomers include those described in U.S. Pat. No. 6,627,704, and the (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidones, and vinylazalactones disclosed in U.S. Pat. No. 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, and the like, or combinations thereof.

[0086] The curable thermosetting composition may optionally further comprise one or more additional additives, such as dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow improvers, drip retardants, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low-shrinkage additives, stress relief additives, or combinations thereof. When present, the additional additives may be included in any effective amount, such as, for example, from 0.01% to 20% by weight, or from 0.01% to 10% by weight, or from 0.01% to 5% by weight, or from 0.01% to 1% by weight, based on the total weight of the curable thermosetting composition.

[0087] The curable thermosetting composition can be prepared by combining the capped poly(arylene ether) copolymer and any other components disclosed herein using any suitable method.

[0088] Also provided are cured thermosetting compositions, including the cured product of the curable thermosetting composition. There are no particular limitations 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 or electron beam irradiation. For example, a cured product can be obtained by heating the curable thermosetting composition defined herein for a time and temperature sufficient to evaporate the solvent and effect curing. When thermal curing is used, the temperature can be 30°C to 400°C, or 50°C to 250°C, or 100°C to 250°C. Heating can range from 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, often tack-free, resin, which is then fully cured by heating for a longer time or temperature within the aforementioned ranges. As used herein, the term "cured" encompasses partially cured or fully cured products.

[0089] 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 a combination thereof.

[0090] The disclosed curable thermosetting compositions and cured compositions can be used in a variety of applications and uses, including any application in which conventional thermosetting compositions are used. For example, useful articles comprising the curable thermosetting compositions or cured thermosetting compositions can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded components, prepregs, casings, laminates, metal-clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary uses and applications include coatings such as protective coatings, sealants, weather-resistant coatings, scratch-resistant coatings, and electrically insulating coatings; adhesives, binders, glues; and composites such as composites using carbon fiber and fiberglass reinforcement. When used as coatings, the disclosed compounds and compositions can be deposited on the surface of various underlying substrates. For example, the compositions can be deposited on the surface of metal, plastic, glass, fiber siding, ceramic, stone, wood, or any combination thereof. The disclosed compositions can be used as coatings on the surface of metal containers (e.g., aluminum or steel), such as those commonly used for packaging and storage in the paint and surface coating industries. The curable thermosetting compositions and the resulting cured thermosetting compositions may also be particularly well suited for use in forming electrical and computer components.

[0091] A method for forming a composite may include impregnating a structure to be reinforced with a curable thermosetting composition, partially curing the curable thermosetting composition to form a prepreg, and laminating multiple prepregs. The structure to be reinforced may be a porous base material such as a fiber preform or fiber substrate, or other porous materials including ceramic, polymer, glass, carbon, or combinations thereof. For example, the porous base material may be woven or nonwoven glass fabric, fiberglass fabric, or carbon fiber. When the article includes a fibrous preform, a method for manufacturing the article may include forming the article from the curable thermosetting composition by coating or impregnating the preform with a varnish. The impregnated fiber preform may optionally be shaped before or after solvent removal. In some embodiments, the curable thermosetting composition layer may further include a woven or nonwoven glass fabric. For example, the curable layer may be prepared by impregnating a glass fabric with the curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), "Prepreg Technology," March 2005, Publication No. FGU 017b; Anonymous (Hexcel Corporation), "Advanced Fiber Reinforced Matrix Products for Direct Processes," June 2005, Publication No. ITA 272; and Bob Griffiths, "Farnborough Airshow Report 2006," CompositesWorld.com, September 2006. The weight and thickness of the reinforcing structure are selected according to the intended use of the composite using criteria familiar to those skilled in the art of fiber-reinforced resin composite manufacturing. The reinforced structure may include various finishes appropriate for the thermosetting component of the curable thermosetting composition.

[0092] Methods for producing articles from curable thermosetting compositions can include partially curing the curable thermosetting composition to form a prepreg or fully curing the curable thermosetting composition to form a composite article. References herein to the property of a "cured composition" apply to a substantially fully cured composition. For example, the resin in a laminate formed from a prepreg is typically substantially fully cured. One skilled in the art of thermosetting materials can determine whether a sample is partially cured or substantially fully cured without undue experimentation. Curing can occur before or after removing the solvent from the curable composition. Furthermore, the article can be further shaped, for example, by thermoforming, before or after solvent removal, before curing, after partial curing, or after full curing. In one embodiment, an article is formed, the solvent is removed, the article is partially cured (B-staged), and optionally shaped, followed by further curing.

[0093] Commercial-scale methods for forming composites are known in the art, and the curable thermosetting compositions described herein can be easily adapted to existing methods and equipment. For example, prepregs are often produced in an impregnation dryer. The main components of an impregnation dryer include a feed roller, a resin impregnation tank, an impregnation dryer oven, and a receiving roller. The structure to be reinforced (e.g., E-glass) is typically wound onto a large spool. The spool is then placed on a feed roller, which rotates the structure to be reinforced and slowly unwinds it. The structure to be reinforced then passes through a resin impregnation tank containing the curable thermosetting composition. The curable composition impregnates the structure to be reinforced. After exiting the tank, the coated reinforcing structure is moved upward through a vertical impregnation dryer oven, typically at temperatures between 175°C and 200°C, to evaporate the solvent. The resin begins to polymerize at this point. When the composite exits the tower, it is sufficiently cured so that the web is neither wet nor tacky. However, the curing process is stopped before completion so that additional curing can occur when the laminate is made. A web then wraps the prepreg onto a receiving roll.

[0094] Electrical and electronic articles containing or obtained from the curable thermosetting composition are also provided. Examples of such articles include those containing printed circuits used in the medical or aerospace industries. Other examples include antennas and similar articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic memo pads, and similar devices, or office automation equipment. For example, electrical components can be mounted on printed circuit boards containing laminates. Other exemplary articles prepared from the varnish compositions for various applications include copper clad laminates (CCLs), such as metal-core copper clad laminates (MCCCLs), composite articles, and coated articles, such as multilayer articles.

[0095] Dielectric layers prepared from the curable thermosetting compositions can be useful in circuit assemblies, such as 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 matrix layer disposed on the dielectric layer opposite the conductive metal layer. The dielectric layer can optionally include a fibrous preform (e.g., a fabric layer). For example, the dielectric layer can further include a glass cloth layer.

[0096] The conductive metal layer may be in the form of a circuit and may 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, rolled copper foil may be used. The conductive metal layer may have a thickness of 2 micrometers (μm) to 200 μm, or 5 μm to 50 μm, or 5 μm to 40 μm.

[0097] The heat-dissipating metal matrix layer can be a thermally conductive metal, such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or a combination thereof. Thermally conductive, electrically conductive metals can be used provided that the metal is electrically insulated from the metal circuit layer. Preferred supporting metal matrix layers can have a thickness of 0.1 millimeters (mm) to 20 mm, or 0.5 mm to 10 mm, or 0.8 mm to 2 mm.

[0098] The conductive metal layer and the supporting metal matrix layer can be pretreated to have a high surface roughness to enhance adhesion to the dielectric layer. Treatment methods include, for example, cleaning, flame treatment, plasma discharge, corona discharge, etc. to enhance the adhesion of the metal layer. The dielectric layer can be firmly adhered to the conductive metal layer or heat dissipation layer without the use of an adhesive, or an adhesive can be used to improve the adhesion of the dielectric layer to the conductive metal layer or heat dissipation layer. Exemplary adhesives used to bond the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxies, or combinations thereof.

[0099] Copper-clad laminates can be made by thermally laminating one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer under pressure without the use of a thermosetting adhesive. The dielectric layer can be prepared from a curable thermosetting composition, and can be prepared by forming the layers by a solution casting method before the thermal lamination step. For example, a dielectric layer, a conductive metal layer, and a heat-dissipating layer can be thermally laminated together under pressure using an adhesive-free method 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 be optionally etched after lamination to form an electrical circuit. Lamination can be performed by hot pressing or roll calendering, for example, a roll-to-roll process. The conductive metal layer in the copper-clad laminate can be further patterned to form a printed circuit board. Furthermore, the copper-clad laminate can be molded to form a circuit board in the shape of a sheet, tube, or rod.

[0100] Alternatively, laminates for circuit assemblies can be made by solution casting, where the curable thermosetting composition is cast directly onto a conductive metal layer, followed by lamination to an exothermic metal matrix layer. For example, the curable thermosetting composition can be cast directly onto a heat-dissipating metal matrix layer, followed by lamination to an electrically conductive metal layer.

[0101] Multilayer laminates containing additional layers can also be prepared by thermal lamination, in one or more sequential steps, by methods such as hot pressing or roll calendering. For example, there can be up to seven layers, or up to 16 layers, in a laminate. In one embodiment, a laminate can be formed in one or more sequential steps with a fabric-thermoset-metal-thermoset-fabric-thermoset-metal foil sequence or a subcombination thereof having fewer layers, with the laminate including a layer of thermoset film between any layer of metal foil and any layer of fabric. In another embodiment, a first laminate can be formed in one or more sequential steps with a layer of fabric between two layers of thermoset, such as a layer of woven glass fabric between two layers of thermoset. A second laminate can then be prepared by laminating a metal foil to the thermoset side of the first laminate.

[0102] Printed circuit boards prepared from the curable thermosetting compositions can have a total thickness of 0.1 mm to 20 mm, specifically 0.5 mm to 10 mm, where the total thickness refers to the assembly including the dielectric layer, conductive metal layer, and supporting metal matrix layer. The circuit assembly can have a total thickness of 0.5 mm to 2 mm, specifically 0.5 mm to 1.5 mm. The thickness of the dielectric layer is not particularly limited and 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) used in light-emitting diode (LED) applications.

[0103] The curable thermosetting composition can be used as a coating, for example, in preparing multi-layer articles. A method of making a coating can include combining the curable thermosetting composition and, optionally, a fluoropolymer, and forming the coating on a substrate. For example, a multilayer article can be made by forming a layer comprising a curable thermosetting composition, removing solvent from the layer, and optionally curing to obtain a primer layer, forming a second layer over the primer layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, YO3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, BC, TiC, Si3N4, TiN, BN, AlN, TiB, ZrB2, etc.), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, etc.), or a combination thereof, to obtain a multilayer article, and optionally heat treating the multilayer article to cure the curable thermosetting composition. In some embodiments, the second layer may further comprise a curable thermosetting composition.

[0104] Additional uses for the curable thermosetting compositions include, for example, acid bath vessels, neutralization tanks, aircraft components, bridge beams, bridge decks, electrolytic cells, exhaust stacks, scrubbers, sporting goods, stairs, walkways, automotive exterior panels such as hoods and trunk lids, floor pans, air scoops, pipes and ducts including heater ducts, industrial fans, fan housings, and blowers, industrial mixers, boat hulls and decks, marine terminal fenders, tiles and coatings, siding, business machine housings, trays including cable trays, concrete modifiers, and the like. lumber, dishwasher and refrigerator parts, electrical seals, electrical panels, tanks and tank linings including electrorefining tanks, water softening tanks, fuel tanks, and various filament wound tanks, furniture, garage doors, gratings, protective body gear, luggage, outdoor motor vehicles, pressure tanks, optical waveguides, radomes, handrails, railroad parts such as tank cars, hopper car covers, car doors, truck bed liners, satellite antennas, signs, solar energy panels, telephone switch housings, tractor parts, transformer covers, fenders, hoods truck parts such as bodies, cabs, and beds; rotating machinery insulation including ground insulation, turn insulation, and phase isolation insulation; commutators, conductor insulation and cord and lacing tape; drive shaft couplings; propeller blades; missile components; rocket motor cases; wings, sucker rods, fuselage sections, wing skins and flaring; engine nacelles; cargo doors; tennis rackets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; lateral leaf springs; pumps such as automotive smog pumps; electrical components Components, embedding materials, and tools such as electrical cable joints, windings and high-density multi-element assemblies, sealants for electromechanical devices, battery cases, resistors, fuses and thermal cut-off devices, coatings for printed wiring boards, castings such as capacitors, transformers, crankcase heaters, small molded electronic components including coils, capacitors, resistors, and semiconductors, steel replacement in chemical processing, pulp and paper, power generation, and wastewater treatment, pultruded parts for structural applications including washing towers, structural elements, gratings, and safety rails, swimming pools,Applications include swimming pool slides, hot tubs, and saunas, drive shafts for under-the-hood applications, dry toner resins for copiers, marine tools and composites, heat shields, submarine hulls, prototyping, experimental model development, laminate trim, drill fixtures, joining jigs, inspection fixtures, industrial metal forming dies, aircraft stretch blocks and hammer forms, vacuum forming tools, flooring including flooring for manufacturing and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking garages, freezers, coolers, and outdoor loading docks, conductive compositions for anti-static applications, decorative flooring, bridge expansion joints, injectable mortar for repairing and repairing cracks in structural concrete, tile grouting, machine rails, metal dowels, bolts and supports, repair of oil and fuel storage tanks, and many other applications.

[0105] Useful methods for preparing the articles and materials include methods commonly known to those skilled in the art of processing thermoset resins. Such methods are described, for example, in Engineered Materials Handbook, Vol. 1, Composites, ASM International, Metals Park, Ohio, Copyright 1987, Cyril A. Dostal, Editor, pp. 105-168 and 497-533, and in "Polyesters and Their Applications," by Johan Bjorksten (pres.), Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), and James Henning (Ad. Ass.), Bjorksten Research Laboratories, 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), centrifugal and static casting, casting, including open mold casting, lamination, including wet or dry layup and spray layup, contact molding, including cylindrical contact molding, compression molding, including vacuum-assisted resin transfer molding and chemical-assisted resin transfer molding, conformal tool molding, autoclave curing, thermal curing in air, vacuum bagging, pultrusion, Seeman's Composite Resin Infusion Manufacturing Processes (SCRIMP), open molding, continuous combination of resin and glass, and filament winding, including cylindrical filament winding. For example, articles can be prepared by resin transfer molding methods.

[0106] Also provided is a varnish composition comprising the curable thermosetting composition disclosed herein and a solvent. The solvent of the varnish composition can be the same as the solvent disclosed herein for the curable thermosetting composition.

[0107] The varnish composition can be prepared by combining the capped poly(arylene ether) copolymer, the solvent, and any optional ingredients with stirring until a viscous solution is formed. For example, a method for producing the varnish composition can include combining the components of the varnish composition and heating the components with stirring, agitation, or both at a temperature and for a period of time effective to dissolve the components in the solvent or below the boiling point of the solvent. The temperature is not particularly limited and can be 50°C or less, or 30°C or less, or 25°C or less.

[0108] The varnish composition can be used in the manufacture of articles useful in a wide variety of applications, including those disclosed herein. Articles can be produced from the varnish composition, for example, by forming the article from the varnish composition, for example, by casting, molding, extruding, and removing the solvent from the formed article. Exemplary articles can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, cast articles, molded components, prepregs, casings, laminates, metal-clad laminates, electronic composites, structural composites, or combinations thereof. In some embodiments, the article can be a layer formed by casting the varnish composition onto a substrate to form a cast layer. The solvent can be removed by any number of means, including heating the cast layer, heating the cast layer under heat and pressure, for example, by laminating the cast layer to another substrate. In some embodiments, the article prepared by the above method can include an adhesive, packaging material, capacitor film, or circuit board layer. In some embodiments, the article prepared from the varnish composition can be a dielectric layer or a coating disposed on a substrate, such as a wire coating or a cable coating. For example, the article can be a dielectric layer in a circuit material, such as a printed circuit board, used in, for example, lighting or communication applications. Another exemplary article prepared from the varnish composition can be one or more coating layers. The varnish composition can be used to prepare articles disclosed herein for other curable thermosetting compositions.

[0109] The present disclosure is further illustrated by the following non-limiting examples. [Example]

[0110] The ingredients used in the examples are summarized in Table 1.

[0111] [Table 1]

[0112] Weight average molecular weight (M w ) was measured by gel permeation chromatography (GPC). The viscosity of the solution was measured at 25°C using a Brookfield viscometer with spindle S00. The gel time was measured under nitrogen using 25 millimeter (mm) parallel plates with a target gap of 1 mm between the plates. An oscillatory temperature ramping profile was used (ARES G2 rheometer, TA Instruments) from a starting temperature of 80°C and a ramp rate of 5°C / min, at a constant strain of 30%, and at an angular frequency of 10 radians per second (Rad / s). The viscosity was measured under nitrogen using 25 mm parallel plates with a target gap of 1 mm between the plates. An oscillatory temperature ramping profile was used (ARES G2 rheometer, TA Instruments) from a starting temperature of 80°C and a ramp rate of 3°C / min, at a constant strain of 1%, and at an angular frequency of 10 Rad / s. g The thermal expansion coefficient (CTE) was measured by thermomechanical analysis (TMA) at a rate of 10°C / min from 25°C to 300°C (TA Instruments). The exotherm and extent of cure were measured at a rate of 10°C / min from 25°C to 300°C (TA Instruments). The onset thermal decomposition temperature was measured by thermogravimetric analysis (TGA) at a rate of 10°C / min from 25°C to 800°C (TA Instruments). The coefficient of thermal expansion (CTE) was measured by thermomechanical analysis (TMA) at a rate of 10°C / min from 25°C to 300°C (TA Instruments). The dielectric constant and dissipation factor were measured using a network analyzer equipped with a split post resonator (SPDR) (Agilent Technologies E5071C) after conditioning the castings at 50% relative humidity for 24 hours. Moisture absorption was measured by placing the sample in a water bath at 85° C. The sample was removed from the bath, allowed to dry, and weighed after 24 hours.

[0113] Curable compositions were prepared by combining the ingredients shown in Table 2, where the amounts are weight percent based on the total weight of the curable thermoset composition.

[0114] [Table 2]

[0115] The curable thermosetting composition was dissolved and dispersed in chloroform, placed on a plate, and the chloroform was removed under vacuum and nitrogen to obtain a dry powder, which was used for chemorheology after partially curing the composition by heating until a gel was obtained.

[0116] The properties of the partially cured composition (gel) are shown in Table 3.

[0117] [Table 3]

[0118] The partially cured composition was transferred to a 40 mm diameter die and heated under 1 ton of pressure to 150° C. The sample was then cooled to 70° C. and the die was transferred to an oven where the sample was cured at 200° C. under vacuum for 120 minutes.

[0119] The properties of the cured compositions are shown in Table 4.

[0120] [Table 4]

[0121] As shown in Tables 3 and 4, the dielectric performance, resin flow after partial curing, thermal expansion coefficient, and water absorption of the Examples are improved compared to the Comparative Examples. Furthermore, the onset decomposition temperature and dielectric constant were similar for the Examples and Comparative Examples. These results are surprising because the 2-(C 1~12 Primary or secondary alkyl)-6-(unsubstituted C 6~12It was not expected that the properties shown in Tables 3 and 4 could be improved simultaneously by introducing repeating units derived from a (aryl)phenol, such as 2-methyl-6-phenylphenol.

[0122] The figure is a spider chart showing that the Examples have a smaller total area than the Comparative Examples based on several properties. These results show that the Examples have a lower total area than the Comparative Examples, such as dissipation factor, viscosity, T g These results demonstrate that a combination of improved thermal conductivity, CTE, and water absorption can be simultaneously achieved. Thus, curable thermosetting compositions can provide desirable performance attributes for resins used in electronic materials, particularly prepregs, laminates, and metal-clad laminates for printed circuit boards.

[0123] The present disclosure further encompasses the following aspects.

[0124] Aspect 1. A curable thermosetting composition comprising a capped poly(arylene ether) copolymer comprising reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from an alkyl-aryl-phenol.

[0125] Embodiment 2. The capped poly(arylene ether) copolymer is derived from the reaction of a dihydric phenol with a monohydric phenol, including a 2-(alkyl)-6-(aryl)phenol, or the monohydric phenol is a 2-(C 1~12 Primary or secondary alkyl)-6-(unsubstituted C 6~12 2. The curable thermosetting composition of embodiment 1, wherein the aryl is a (aryl)phenol.

[0126] Embodiment 3. The curable thermosetting composition of any one of the preceding embodiments, wherein the capped poly(arylene ether) copolymer is a copolymer of Formula (1) or Formula (2) shown herein.

[0127] Aspect 4.Q 1a In each case independently, C 1~12 Primary alkyl or C 1~6is a primary alkyl, and Q 1b In each case independently, C 1~12 Alkyl or C 6~12 Aryl, or C 1~6 alkyl or phenyl, and Q 2 is hydrogen and R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, halogen, or C 1~12 Alkyl, or hydrogen or C 1~6 alkyl, wherein the optionally capped poly(arylene ether) copolymer is 1a C 1~12 is a primary alkyl, and Q 1b is unsubstituted C 6~12 The poly(arylene ether) copolymers containing at least one repeat unit that is aryl or capped may be 1a C 1~6 is a primary alkyl, and Q 1b The curable thermosetting composition of embodiment 3, comprising at least one repeat unit wherein is unsubstituted phenyl.

[0128] Embodiment 5. The curable thermosetting composition of any one of Embodiments 3 or 4, wherein the capped poly(arylene ether) copolymer is a copolymer of Formula (2a) shown herein.

[0129] Embodiment 6. The curable thermosetting composition of any one of Embodiments 3-5, wherein the capped poly(arylene ether) copolymer is a copolymer of formula (2b) shown herein.

[0130] Embodiment 7. The curable thermosetting composition of any one of the preceding embodiments, further comprising one or more of a crosslinker, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

[0131] Embodiment 8. The curable thermosetting composition of any one of the preceding embodiments, further comprising one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0132] Embodiment 9. A cured thermosetting composition comprising the cured product of the curable thermosetting composition of any one of the preceding embodiments.

[0133] Embodiment 10. A method of making the cured thermosetting composition of Embodiment 9, comprising curing the curable thermosetting composition at a temperature of from 50°C to 250°C.

[0134] Embodiment 11. An article comprising the cured thermosetting composition of embodiment 9, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof, or the article is a metal-clad laminate, an electronics composite, a structural composite, or a combination thereof.

[0135] Aspect 12. A varnish composition comprising the curable thermosetting composition of any one of Aspects 1 to 8 and a solvent.

[0136] Embodiment 13. An article made from the varnish composition of embodiment 12, wherein the article is a fiber, a layer, a coating, a cast article, a prepreg, a composite, or a laminate, or the article is a metal-clad laminate.

[0137] Embodiment 14. A method of making the article of embodiment 13, comprising impregnating a varnish composition into a substrate to form a prepreg, and curing the varnish composition.

[0138] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of any suitable materials, steps, or ingredients disclosed herein. The compositions, methods, and articles can additionally or alternatively be formulated to be devoid of, or substantially free of, any materials (or species), steps, or ingredients that are not necessary to achieve the function or purpose of the compositions, methods, and articles.

[0139] All ranges disclosed in this disclosure are inclusive of the endpoints, and the endpoints are independently combinable with each other. "Combinations" include blends, mixtures, alloys, reaction products, and the like. "A," "an," and "the" do not denote limitations of quantity and should be construed to include both the singular and the plural unless otherwise stated or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. It should be understood that the listed elements can be combined in any suitable manner in the various embodiments. "Combinations thereof" are open-ended and include all combinations that include at least one of the listed elements or properties together with similar or equivalent, if any, unlisted elements or properties.

[0140] Unless otherwise specified, technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application pertains.All cited patents, patent applications, and other references are incorporated herein by reference in their entirety.However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term from this application shall take precedence over the conflicting term from the incorporated reference.Unless otherwise specified herein, all test standards are the most recent standards in effect as of the filing date of this application, or, if priority is claimed, as of the filing date of the earliest priority application in which the test standard appears.

[0141] Unless otherwise specified, compounds are described using standard nomenclature. The terms "hydrocarbon" and "hydrocarbyl" refer to any compound, group, or substituent containing carbon and hydrogen. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. The residue may also contain a combination of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as substituted, the hydrocarbyl residue may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc. As used herein, the term "heterohydrocarbyl" refers to a hydrocarbyl containing one or more heteroatoms within the main chain of the hydrocarbyl residue. "Aliphatic" means a non-aromatic hydrocarbon group, "aryl" means a monocyclic or polycyclic aromatic hydrocarbon group in which all ring members are carbon, "alkylaryl" means an aryl group substituted with an alkyl group, and "arylalkyl" means an alkyl group substituted with an aryl group. The prefix "hetero" means that the compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where each heteroatom(s) is independently N, O, S, Si, or P.

[0142] In the chemical formula depicted by the structure, any position not replaced by a depicted group should be understood to have a valency filled by the depicted bond or by a hydrogen atom. Unless a substituent is specifically indicated otherwise, each of the above groups may be unsubstituted or substituted, provided that the substitution does not significantly adversely affect the synthesis, stability, or use of the compound. "Substituted" refers to a compound, group, or atom that, in place of hydrogen, has, each independently, nitro (-NO), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C, or the like, provided that the normal valency of the substituted atom is not exceeded.1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 6~12 Aryl, C 7~13 Arylalkyl (e.g., benzyl), C 7~12 Alkylaryl (e.g., toluyl), C 4~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 This means that the group is substituted with at least one (e.g., 1, 2, 3, or 4) substituent, which may be arylsulfonyl (-S(=O)-aryl), or tosyl (CHCHSO-). The number of carbon atoms indicated in the group is exclusive of any substituents. For example, -CHCHCN is a C alkyl group substituted with a nitrile.

[0143] The appended claims, as filed and as they may be amended, are intended to embrace alternatives, modifications, improvements, and substantial equivalents that are presently foreseen or can be foreseen, or that may occur to applicant or those skilled in the art.

Claims

1. 1. A curable thermosetting composition comprising a capped poly(arylene ether) copolymer, the capped poly(arylene ether) copolymer being derived from an alkyl-aryl-phenol; The capped poly(arylene ether) copolymer has Formula (1) or Formula (2): 【Chemistry 1】 (In the formula, R ｘ and R ｙ are each independently a reactive end group comprising a (meth)acrylate, vinylbenzene, allyl, maleimide, or combinations thereof; Q １ａ is, independently in each case, C １～１２ primary alkyl, or C １～６ is a primary alkyl, Q １ｂ is, independently in each case, 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 each independently hydrogen, halogen, or C １～１２ Alkyl, or hydrogen or C １～６ is alkyl, wherein optionally the capped poly(arylene ether) copolymer comprises Q １ａ is C １～１２ is a primary alkyl, and Q １ｂ is unsubstituted C ６～１２ or the capped poly(arylene ether) copolymer comprises at least one repeat unit that is aryl, Q １ａ is C １～６ is a primary alkyl, and Q １ｂ at least one repeat unit in which is unsubstituted phenyl; x and y represent the relative molar ratio of arylene ether units, where x and y are each independently 0 to 50, or 0 to 30, with the proviso that the sum of x and y is at least 2, or e is the number of moles of said arylene ether units; R ５ａ is, independently in each case, Q １ａ or (C １～６ -hydrocarbyl) (C １～６ -hydrocarbyl)aminomethylene group, R ５ｂ is, independently in each case, Q １ｂ or (C １～６ -hydrocarbyl) (C １～６ -hydrocarbyl)aminomethylene group, wherein the capped poly(arylene ether) copolymer is Q １ａ is C １～１２ is a primary or secondary alkyl, and Q １ｂ is unsubstituted C ６～１２ at least one repeat unit which is aryl; R ５ａ is C １～１２ is a primary or secondary alkyl, and R ５ｂ is unsubstituted C ６～１２ at least one terminal unit that is aryl, or combinations of these, Including, Y １ is the expression 【Chemistry 2】 and any one or more divalent linking groups of the formula: R ａ , R ｂ , and R ｅ is independently in each occurrence hydrogen, C １～１２ Hydrocarbyl, or C １～６ hydrocarbylene, where optionally, R ａ and R ｂ Together, C ４～８ is a cycloalkylene group, R ｆ is, independently in each case, C １～６ is a hydrocarbylene group, R ｇ is independently in each occurrence hydrogen, C １～１２ Hydrocarbyl, or C １～１２ is a halohydrocarbyl, and n' is 5 to 50; z is 0 or 1, and R is in each case 【Transformation 3】 wherein: Y ２ is the expression 【Chemistry 4】 is a divalent linking group of the formula R ｃ and R ｄ is independently in each occurrence hydrogen or C １～１２ is alkyl, R ５ａ is an epoxide-containing group or a C substituted with one or two carboxylic acid groups １～１２ is a hydrocarbyl, R ６ , R ７ , and R ８ is independently in each occurrence hydrogen, C １～１８ Hydrocarbyl, C ２～１８ is a hydrocarbyloxycarbonyl or carboxylic acid, and R ９ , R １０ , R １１ , R １２ , and R １３ is independently in each occurrence hydrogen, halogen, C １～１２ Alkyl, C ２～１２ Alkenyl, hydroxy, maleimide, carboxylic acid, or C ２～２０ A curable thermosetting composition comprising a copolymer of (a) a carboxylic acid ester of (a) a carboxylic acid ester of (b) a carboxylic acid ester of (c) a carboxylic acid ester of (d) a carboxylic acid ester of (e) a carboxylic acid ester of (f) a carboxylic acid ester of (f) a carboxylic acid ester of (c) a carboxylic acid ester of (f ...

2. Q １ａ is, independently in each case, C １～１２ Primary alkyl or C １～６ is a primary alkyl, Q １ｂ is, independently in each case, 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 each independently hydrogen, halogen, or C １～１２ Alkyl, or hydrogen or C １～６ is alkyl, wherein optionally the capped poly(arylene ether) copolymer comprises Q １ａ is C １～１２ is a primary alkyl, and Q １ｂ is unsubstituted C ６～１２ or the capped poly(arylene ether) copolymer comprises at least one repeat unit that is aryl, Q １ａ is C １～６ is a primary alkyl, and Q １ｂ The curable thermosetting composition of claim 1 , comprising at least one repeat unit where is unsubstituted phenyl.

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

4. A cured thermosetting composition comprising the cured product of the curable thermosetting composition of any one of claims 1 to 3.

5. 5. A method for producing the cured thermosetting composition of claim 4, comprising curing the curable thermosetting composition at a temperature of from 50°C to 250°C.

6. 5. An article comprising the cured thermosetting composition of claim 4, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof, or the article is a metal clad laminate, an electronics composite, a structural composite, or a combination thereof.

7. A varnish composition comprising the curable thermosetting composition according to any one of claims 1 to 3 and a solvent.

8. 10. An article made from the varnish composition of claim 7, wherein the article is a fiber, a layer, a coating, a cast article, a prepreg, a composite, or a laminate, or the article is a metal clad laminate.

9. 10. A method of manufacturing the article of claim 8, comprising impregnating the varnish composition into a substrate to form a prepreg and curing the varnish composition.

Images