Poly(aryl ether) copolymers, their preparation methods and products derived therefrom

Abstract

A capped poly(arylene ether) copolymer comprising reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from an alkyl aryl phenol.

Description

[0001] Citation of relevant applications

[0002] This application claims priority and benefit to European Patent Application No. 201900685, filed August 7, 2020, which claims priority and benefit to U.S. Provisional Patent Application Serial No. 63 / 035,333, filed June 5, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to a capped poly(arylene ether) copolymer, a method for forming the same, a curable thermosetting composition comprising the same, and articles derived therefrom. Background Technology

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

[0005] Therefore, there remains a need in the art for end-capped poly(aryl ether) copolymers having a set of desired properties for use in curable thermosetting compositions. Further advantages would be provided if end-capped poly(aryl ether) copolymers could provide curable thermosetting compositions with improved dielectric constant, dissipation factor, heat resistance, and water absorption. Summary of the Invention

[0006] An end-capped poly(arylene ether) copolymer is provided, comprising reactive end groups, wherein the end-capped poly(arylene ether) copolymer is derived from alkylarylphenol.

[0007] A method for forming a capped poly(arylene ether) copolymer is also provided, the method comprising oxidizing a copolymer of 2-(alkyl)-6-(aryl)phenol and a diphenol in a solvent in the presence of a catalyst composition.

[0008] Further, curable thermosetting compositions comprising end-capped poly(aryl ether) copolymers and articles derived from curable thermosetting compositions are provided, wherein the articles are composite materials, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded parts, prepregs, casings, castings, laminates, or combinations thereof; or wherein the articles are metal foil laminates, electronic composite materials, structural composite materials, or combinations thereof.

[0009] The above-mentioned functions and other features are illustrated through the following specific implementation methods. Detailed Implementation

[0010] The inventors have advantageously discovered that end-capped poly(aryl ether) copolymers comprising repeating units derived from alkylarylphenols can be included in curable thermosetting compositions to achieve improved properties compared to curable thermosetting compositions comprising poly(aryl ether) copolymers without repeating units derived from alkylarylphenols. For example, poly(aryl ether) copolymers comprising repeating units derived from alkylarylphenols can provide an improved combination of properties such as solution viscosity, dissipation factor, resin flow, coefficient of thermal expansion (CTE), and equilibrium water absorption.

[0011] Therefore, one aspect of this disclosure is a capped poly(aryl ether) copolymer containing reactive end groups, wherein the capped poly(aryl ether) copolymer is derived from alkylarylphenol. The alkylarylphenol can be, for example, 2-(alkyl)-6-(aryl)phenol, such as 2-(C 1-12 (primary or secondary alkyl)-6-(unsubstituted C) 6-12 Aryl phenols. For example, alkyl aryl phenols can be 2-(C 1-6 -Primary alkyl)-6-(unsubstituted phenyl)phenol.

[0012] The terminated poly(aryl ether) copolymer contains at least one reactive end group. Exemplary reactive end groups include functional groups such as (meth)acrylates, (meth)acrylonitrile, vinylbenzene, allyl, epoxides (including glycidyl ethers), cyanates, amines, maleimides, carboxylic acids, alkyl carboxylic acids, etc. The terminated poly(aryl ether) copolymer can be a bifunctional oligomer having reactive end groups at both ends of the oligomer chain (i.e., two reactive end groups per oligomer molecule). Bifunctional oligomers with functional groups at both ends of the oligomer chain are also called "distally chelated" oligomers.

[0013] For example, the capped poly(aryl ether) copolymer contains an average of 1.1 to 2, or 1.4 to 2, or 1.8 to 2 reactive end groups per molecule, or contains at least 1.5 to 2, or at least 1.70 to 2, or at least 1.8 to 2, or at least 1.9 to 2, or at least 1.95 to 2 reactive end groups per molecule, or contains at most 1.99 reactive end groups per molecule.

[0014] End-capped poly(arylene ether) copolymers can have formula (1) or formula (2):

[0015]

[0016] Among them, Q 1a and Q 1b Each time it appears, it is independently of halogen and C. 1-12 Hydrocarbon group (provided the hydrocarbon group is not a tertiary hydrocarbon group), C 1-12 Hydroxyl group, C 1-12 Hydroxyl group, or C 2-12 A haloalkoxy group (in which at least two carbon atoms separate the halogen and oxygen atoms); and Q 2 It is independently hydrogen, halogen, unsubstituted or substituted C 1-12 Hydrocarbon group (provided the hydrocarbon group is not a tertiary hydrocarbon group), C 1-12 Hydroxyl group, C 1-12 Hydroxyl group, or C 2-12 Halogenated hydrocarbon oxygen (where at least two carbon atoms separate the halogen and oxygen atoms). For example, Q 1a and Q 1b Each time it appears, it can be C independently. 1-12 Alkyl, C 2-12 Alkenyl or C 2-12 Alkyne group.

[0017] In equation (2), R 1 to R 4 Each is independently hydrogen, halogen, C 1-12 Hydrocarbon group (provided the hydrocarbon group is not a tertiary hydrocarbon group), C 1-12 Hydroxyl group, C 1-12 Hydroxyl group, or C 2-12 Halogenated hydrocarbon oxygen (where at least two carbon atoms separate the halogen and oxygen atoms).

[0018] In equations (1) and (2), R 5a Each time it appears, it is Q independently. 1a or (C) 1-6 (C) 1-6 (Hydrocarbon group) aminomethylene, and R 5b Each time it appears, it is Q independently. 1b or (C) 1-6 (C) 1-6(Hydrocarbonyl)aminomethylene, provided that the end-capped poly(aryl ether) copolymer comprises: at least one repeating unit, wherein Q 1a It is C 1-12 Primary or secondary alkyl groups, and Q 1b It is unreplaced C 6-12 aryl; or at least one terminal unit, wherein R 5a It is C 1-12 Primary or secondary alkyl groups, and R 5b It is unreplaced C 6-12 Aryl groups; or combinations thereof. For example, in one aspect, end-capped poly(aryl ether) copolymers may contain one or more repeating units, wherein Q 1a It is C 1-12 Primary or secondary alkyl groups, and Q 1b It is unreplaced C 6-12 Aryl.

[0019] In equation (1), e is the number of moles of arylene ether units.

[0020] In equation (2), x and y represent the relative molar ratio of arylene ether units, wherein x and y are each independently 0 to 50, or 0 to 30, or 0 to 20, or 0 to 15, or 0 to 10, or 0 to 8, provided that the sum of x and y is at least 2, or at least 3, or at least 4.

[0021] Y in equation (2) 1 It is any one or more of the following divalent linking groups:

[0022]

[0023] Among them, R a R b and R e Each time it appears, it is independently hydrogen or carbon. 1-12 hydrocarbon group or C 1-6 Hydroxyl group, optionally wherein R a and R b Together is C 4-8 Cycloalkylene; R f Each time it appears, it is C independently. 1-6 Hydroxyl group; R g Each time it appears, it is independently hydrogen or carbon. 1-12 hydrocarbon group or C 1-12 Halogenated hydrocarbon group; and n' is 5 to 50.

[0024] In equations (1) and (2), R is independently represented each time it appears. Any one of them, where Y 2 It has a formula One of the divalent linking groups, wherein R is a divalent linker.c and R d Each time it appears, it is independently either hydrogen or carbon. 1-12 Alkyl; R 5a It is a C group containing an epoxide, a cyanate ester, or optionally substituted with one or two carboxylic acid groups. 1-12 hydrocarbon group; R 6 R 7 and R 8 Each time it appears, it is independently hydrogen or carbon. 1-18 hydrocarbon group, C 2-18 Hydroxyl carbonyl, nitrile, formyl, carboxylic acid, imine ester, or thiocarboxylic acid; and R 9 R 10 R 11 R 12 and R 13 Each time it appears, it is independently hydrogen, halogen, or carbon. 1-12 Alkyl, C 2-12 alkenyl, hydroxyl, amino, maleimide, carboxylic acid, or C 2-20 Alkyl esters.

[0025] In specific aspects, Q 1a Each time it appears, it is C independently. 1-12 Primary alkyl or C 1-6 Primary alkyl group; Q 1b Each time it appears, it is C independently. 1-12 Alkyl or C 6-12 aryl, or C 1-6 Alkyl or phenyl; Q 2 It is hydrogen; and R 1 R 2 R 3 and R 4 Each is independently hydrogen, halogen, or C. 1-12 Alkyl, or hydrogen or C 1-6 Alkyl-terminated poly(aryl ether) copolymers comprise at least one repeating unit, wherein Q 1a It is C 1-12 Primary alkyl groups, and Q 1b It is unreplaced C 6-12 Aryl. For example, a capped poly(aryl ether) copolymer may include one or more repeating units of the formula, wherein Q 1a It is C 1-6 Primary alkyl groups, and Q 1b It is an unsubstituted phenyl group.

[0026] In another specific aspect, the end-capped poly(arylene ether) copolymer has formula (2a):

[0027]

[0028] Among them, 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 equations (1) and (2); and R 1a and R 1b Each is hydrogen independently, or R is one of them. 1 and R 2 Each is independently hydrogen or C 1-6 Alkyl groups. For example, end-capped poly(arylene ether) copolymers can be derived from the reaction of diphenols and 2-methyl-6-phenylphenol.

[0029] In another specific aspect, the end-capped poly(arylene ether) copolymer has formula (2b):

[0030]

[0031] Among them, R 1 R 2 R 6 To R 8 R 5a R 5b Q 1a Q 1b Q 2 x and y are defined as in equations (1) and (2).

[0032] The capped poly(aryl ether) copolymer may contain structural units derived from monohydric and dihydric phenols in a molar ratio of 3:1 to 110:1. Within this range, the ratio may 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.

[0033] As disclosed herein, the terminated poly(aryl ether) copolymers are derived from alkylarylphenols, or, for example, the terminated poly(aryl ether) copolymers may be derived from the reaction of a diphenol and a monophenol comprising 2-(alkyl)-6-(aryl)phenol. In one or more aspects, the terminated poly(aryl ether) copolymer can be the product of oxidative copolymerization of a monomer comprising a monophenol or a mixture of monophenols and optionally a diphenol. One aspect provides a method for forming a terminated poly(aryl ether) copolymer, the method comprising oxidative copolymerization in a solvent in the presence of a catalyst at least one of a monophenol and a diphenol. For example, the method for forming a terminated poly(aryl ether) copolymer may comprise oxidative copolymerization in a solvent in the presence of a catalyst composition of a 2-(alkyl)-6-(aryl)phenol monomer, optionally one or more other monophenol monomers and a diphenol monomer.

[0034] Oxidative polymerization can be achieved by continuously adding oxygen to a reaction mixture comprising a monomer, a solvent, and a catalyst composition to provide a hydroxyl-terminated poly(aryl ether) copolymer (i.e., an unterminated copolymer) having a structure of formula (1) or (2), wherein R, R x and R y It is a hydrogen atom. Molecular oxygen (O2) 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 combinations thereof, preferably chromium, manganese, cobalt, copper, or combinations thereof. Exemplary metal salts include cuprous chloride, cuprous chloride, cuprous bromide, cuprous bromide, cuprous iodide, cuprous iodide, cuprous sulfate, copper sulfate, tetraamine cuprous sulfate, tetraamine cuprous sulfate, cuprous acetate, copper acetate, cuprous propionate, copper butyrate, copper laurate, cuprous palmitate, cuprous benzoate, and their corresponding manganese and cobalt salts. Alternatively, a metal or metal oxide and an inorganic acid, organic acid, or an aqueous solution of such an acid can be added and the corresponding metal salt or hydrate can be formed in situ. For example, cuprous oxide and hydrobromic acid can be added to generate cuprous bromide in situ.

[0035] Polymerization catalysts may also include amine ligands, such as monoamines, alkylene diamines, or combinations thereof. Monoamines include dialkyl monoamines (such as di-n-butylamine, DBA) and trialkyl monoamines (such as N,N-dimethylbutylamine, DMBA). Diamines include alkylene diamines, such as N,N'-di-tert-butylethylenediamine, DBEDA.

[0036] 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 combinations thereof. Suitable trialkyl monoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, etc., or combinations thereof.

[0037] Exemplary alkylene diamines include those having the following formula:

[0038] (R bb )2N-R aa -N(R bb )2

[0039] Among them, R aa It is a substituted or unsubstituted divalent residue; and each R bb Independently hydrogen or C 1-8 Alkyl groups. In some respects, two or three aliphatic carbon atoms can form a close link between two diamine nitrogen atoms. Specific alkylene diamine ligands include those in which R... aa Those that are dimethylene (-CH2CH2-) or trimethylene (-CH2CH2CH2-). R bb It can be hydrogen, methyl, propyl, isopropyl, butyl, or C independently. 4-8-α-tert-alkyl. Examples of alkylene diamine 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 combinations 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, the polymerization catalyst may include copper ions, bromide ions, and N,N'-di-tert-butylethylenediamine.

[0040] Monohydric phenols can have the structure of formula (3):

[0041]

[0042] Among them, Q 1a and Q 1b As defined in formula (1). Exemplary monohydric phenols include 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, etc., or combinations thereof.

[0043] In addition to monohydric phenols, monomers may include dihydric phenols, wherein the dihydric phenols have the structure of formula (4):

[0044]

[0045] Among them, R 1 to R 4 Y 1 z is defined as in equation (2).

[0046] For example, a diphenol can be 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1-bis(3-chloro-4-hydroxyphenyl)ethane, 1,1-bis(3-methyl-4-hydroxyphenyl)-ethane, 1,2-bis(4-hydroxy-3,5-dimethylphenyl)-1,2-diphenylethane, 1,2-bis(3-methyl-4-hydroxyphenyl)ethane, 2,2'-binaphthol, 2,2'-bisphenol, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2'-bis(3-bromo-4-hydroxyphenyl)propane, 2, 2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(3-chloro-4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3-methyl-4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)pentane, 2,2-bis(3-methyl-4-hydroxyphenyl)-1-phenylpropane, 2,2'-bis(3-methyl-4-hydroxyphenyl)hexane, 2,2-bis(3-methyl-4-hydroxyphenyl)pentane, 2,2'-methylene Bis(4-methylphenol), 2,2'-methylenebis[4-methyl-6-(1-methylcyclohexyl)phenol], 3,3',5,5'-tetramethyl-2,2'-bisphenol, 3,3'-dimethyl-4,4'-bisphenol, bis(2-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)phenylmethane, 2,2',3,3',5,5'-hexamethyl-4,4'-bisphenol, octafluoro -4,4'-bisphenol, 2,3,3',5,5'-pentamethyl-4,4'-bisphenol, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, bis(3-methyl-4-hydroxyphenyl)cyclohexane, tetrabromobisphenol, tetrabromobisphenol A, tetrabromobisphenol A, 2,2'-diallyl-4,4'-bisphenol A, 2,2'-diallyl-4,4'-bisphenol S, 3,3',5,5'-tetramethyl-4,4'-bisphenol sulfide, 3,3'-dimethylbisphenol sulfide, 3,3',5,5'-tetramethyl-4,4'-bisphenol sulfone, or combinations thereof.

[0047] In some respects, the capped poly(arylene ether) copolymer can be a poly(arylene ether)-polysiloxane block copolymer, which is a block copolymer comprising at least one poly(arylene ether) block and at least one polysiloxane block.

[0048] Poly(aryl ether)-polysiloxane block copolymers can be prepared by oxidative copolymerization, including oxidative copolymerization of monomer mixtures comprising monohydric phenol and hydroxyaryl-terminated polysiloxanes. For example, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane, the monomer mixture comprises 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane. The hydroxyaryl-terminated polysiloxane may comprise multiple repeating units having the structure of formula (5):

[0049]

[0050] Among them, R 22 and R 33 Each time it appears, it is independently hydrogen or carbon. 1-12 hydrocarbon group or C 1-12 Halogenated hydrocarbon group; and two terminal units having the structure of formula (5a):

[0051]

[0052] Where M is hydrogen, C 1-12 hydrocarbon group, C 1-12 Hydrocarbon group or halogen, wherein R 44 and R 45 Each time it appears, it is independently hydrogen or carbon. 1-12 hydrocarbon group or C 1-12 Halogenated hydrocarbon group. In a specific aspect, R 8 and R 9 Each time it appears, it is a methyl group, and Y is a methoxy group.

[0053] For example, a monohydric phenol can be 2,6-dimethylphenol, and a hydroxyaryl-terminated polysiloxane has the structure of formula (5b):

[0054]

[0055] Wherein, n is on average 5 to 100, or 5 to 45, or 30 to 60. Therefore, the structural segment of the poly(arylene ether) copolymer with end caps of formula (6) is:

[0056]

[0057] It can have equation (6a):

[0058]

[0059] Where n is 5 to 100, or 5 to 45, or 30 to 60.

[0060] The capped poly(aryl ether) copolymer may also contain 10 to 70 mole percent of copolymer chains comprising terminal units derived from diphenols. For example, when the diphenol is 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, the poly(aryl ether) copolymer may contain 10 to 70 mole percent of copolymer chains comprising terminal units having the structure of formula (7):

[0061]

[0062] Among them, R 1 to R 4 Y 1 And z is as provided in equation (1) or (2), and R is R x Or R y .

[0063] As described above, the capped poly(aryl ether) copolymer is a functionalized aryl ether oligomer having specific end groups, and the method for preparing the functionalized aryl ether oligomer may further include reacting the hydroxyl-capped poly(aryl ether) copolymer with a capping agent. For example, the method for forming the capped poly(aryl ether) copolymer may further include reacting the capping agent with an uncapped poly(aryl ether) copolymer containing phenolic end groups under conditions that effectively provide a reaction mixture comprising the capped poly(aryl ether) copolymer.

[0064] End-capping agents are not particularly limited and can include unsaturated compounds, epoxy resins, benzoxazine, isocyanates, cyanate esters, melamine, cyanophenyl, maleimide, phthalonitrile, cycloalkylphenyl, ethoxylates, carbamates, acid anhydrides, allyl hydroxypropyl, etc., or combinations thereof. Those skilled in the art can determine the end-capping agent based on the desired functionality of the end-capped poly(aryl ether) copolymer. For example, vinyl benzyl ether end groups can be prepared using curing agents of vinyl benzyl halides (e.g., vinyl benzyl chloride), and (meth)acrylic acid end groups can be prepared using curing agents of (meth)acrylic acid halides or (meth)acrylic anhydrides.

[0065] The capping agent and the uncapped poly(aryl ether) copolymer react in a solvent. In some aspects, the uncapped poly(aryl ether) is obtained as a powder, which is subsequently combined with the capping agent and solvent. In other aspects, the uncapped poly(aryl ether) is obtained as a solution from the oxidative polymerization reaction without removing the solvent, and the uncapped poly(aryl ether) is not separated from the solvent solution as a powder. For example, the capping agent can be added directly to a solution of the uncapped poly(aryl ether) copolymer, which is obtained directly by oxidative copolymerization of 2-(alkyl)-6-(aryl)phenol and diphenol in a solvent, wherein the solvent is not removed from the reaction product before reacting with the capping agent.

[0066] On the one hand, the capped polyarylene ether copolymers can have intrinsic viscosities of 0.03 to 0.13 dL / g, or 0.03 to 0.18 dL / g, or 0.04 to 0.15 dL / g in chloroform at 25°C, measured using an Ubbelohde viscometer. The capped poly(arylene ether) copolymers can have weight-average molecular weights (Mn) 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 determined by gel permeation chromatography (GPC) using a polystyrene standard. w The capped poly(aryl ether) copolymers can have a number average molecular weight (Mn) of 500 to 10,000 g / mol, or 750 to 5,000 g / mol, or 500 to 40,000 g / mol as determined by GPC using polystyrene standards. n In some respects, the end-capped poly(arylene ether) copolymer has an M of 1.9 to 3, or at least 2, or up to 2.8, or up to 2.6, or up to 2.4. w With M n The ratio (also known as "polydispersity").

[0067] Also provided are curable thermosetting compositions comprising end-capped poly(aryl ether) copolymers. For example, based on the total weight of the curable thermosetting composition, the end-capped poly(aryl ether) copolymer may be present in the curable thermosetting composition in amounts of 1 to 95 wt%, or 5 to 95 wt%, or 10 to 85 wt%, or 20 to 80 wt%, 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%.

[0068] The curable thermosetting composition may also contain one or more of a crosslinking agent, curing agent, curing catalyst, curing initiator, or combinations thereof. In some aspects, the curable thermosetting composition may also contain one or more of a flame retardant, filler, coupling agent, or combinations thereof. For example, the curable thermosetting composition may contain one or more of a crosslinking agent, curing agent, curing catalyst, curing initiator, or combinations thereof; and may also contain one or more of a flame retardant, filler, coupling agent, or combinations thereof.

[0069] 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, compounds that are thermosetting resins can also be used as crosslinking agents, coupling agents, or both.

[0070] There are no particular limitations on thermosetting resins, and thermosetting resins can be used alone or in combination of two or more thermosetting resins (e.g., including one or more auxiliary thermosetting resins). Exemplary thermosetting resins include epoxy resins, cyanate ester resins, bismaleimide resins, (poly)benzoxazine resins, vinyl resins (e.g., vinyl benzyl ether resins), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers or polymers having curable unsaturation (e.g., vinyl functionality), or combinations thereof.

[0071] Epoxy resins can generally be any epoxy resin suitable for thermosetting. In this context, the term "epoxy resin" refers to a curable composition containing a compound supported by an ethylene oxide carrier, as described, for example, in CA May, Epoxy Resins, 2nd Edition, (New York & Basle: Marcel Dekker Inc.), 1988. Epoxy resins can include bisphenol A type epoxy resins (such as those derived from bisphenol A) and resins obtained by substituting at least one position of the 2, 3, and 5 positions of bisphenol A with a halogen atom, an alkyl group having six or fewer carbon atoms, or a phenyl group; bisphenol F type epoxy resins (such as those derived from bisphenol F) and resins obtained by substituting at least one position of the 2, 3, and 5 positions of bisphenol F with a halogen atom, an alkyl group having six or fewer carbon atoms, or a phenyl group; glycidyl ether compounds derived from divalent, trivalent, or more valent phenols, such as those derived from bisphenol A. Hydroquinone, resorcinol, tri-4-(hydroxyphenyl)methane, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane; phenolic epoxy resins derived from phenolic resins, which are reaction products between phenols (such as phenol and o-cresol, and formaldehyde), including bisphenol A type phenolic epoxy resins and cresol type phenolic resins; alicyclic epoxy compounds, such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)-cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexyl Hexylmethyl-3,4-epoxycyclohexane carboxylate; polyepoxides containing dicyclopentadiene; amine-type epoxy resins derived from 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, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxy-phenyl)propane, and p-phenylenediamine. Epoxy resins include, but are not limited to, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-phenylenediamine, m-phenylenediamine, 1,4-cyclohexane-bis(methylamine), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindene, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindene, etc.; heterocyclic epoxy compounds and glycidyl ester type epoxy compounds, such as those derived from glycidyl esters of aromatic carboxylic acids, such as p-oxobenzoic acid, m-oxobenzoic acid, terephthalic acid, or isophthalic acid. "Epoxy resin" may also include reaction products of compounds containing two or more epoxy groups and aromatic dihydroxy compounds, which may optionally be halogenated and may be used alone or in combination of two or more.

[0072] Cyanate esters are not limited and any resin composed of cyanate ester monomers can be used, which are polymerized to form polymers containing multiple cyanate ester (-OCN) functional groups. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers or blends of cyanate ester monomers), homopolymers and copolymers prepared using cyanate ester precursors, and combinations of these compounds are acceptable. For example, cyanate esters can be prepared according to methods disclosed in U.S. Patent Nos. 3,553,244 and JP-A-7-53497 of Ian Hamerton, Blackie Academic, and Professional in "Chemistry and Technology of Cyanate Ester Resins". Exemplary cyanate ester resins include 2,2-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)ethane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2-bis(4-cyanophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanophenyl)-m-diisopropylbenzene, cyanate ester resins prepared from dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). Cyanate ester prepolymers can be homopolymers or copolymers incorporating other monomers. Examples of such copolymers include BT resins, such as BT2160 and BT2170, available from Mitsubishi Gas Chemical, which are prepolymers made from cyanate ester monomers and bismaleimide monomers. Other cyanate polymers, monomers, prepolymers, and blends of cyanate monomers with other non-cyanate monomers are disclosed in US 7393904, US7388057, US 7276563, and US 7192651.

[0073] Bismaleimide resins can be prepared by reacting the monomer bismaleimide with a nucleophile (such as a diamine, aminophenol, or aminobenzohydrazine), or by reacting the bismaleimide with diallylbisphenol A. Exemplary bismaleimide resins include 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 1,3-bismaleimide benzene, 1,4-bismaleimide benzene, 2,4-bismaleimide toluene, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide-diphenyl ether, 3,3'-bismaleimide diphenyl sulfone, 4,4'-bismaleimide-diphenyl sulfone, and 4,4'-bismaleimide bicyclic rings. Hexylmethane, 3,5-bis(4-maleimide-phenyl)pyridine, 2,6-bismaleimide-pyridine, 1,3-bis(maleimide-methyl)cyclohexane, 1,3-bis(maleimide-methyl)benzene, 1,1-bis(4-maleimide-phenyl)cyclohexane, 1,3-bis(dichloromaleimide-phenyl)benzene, 4,4'-bis(citronimide-diphenylmethane), 2,2-bis(4-maleimide-phenyl)propane, 1-phenyl-1,1 -Bis(4-maleimide-phenyl)ethane, N,N-bis(4-maleimide-phenyl)toluene, 3,5-bismaleimide-1,2,4-triazole, N,N'-ethylidene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene-bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide Imine, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane-bismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexane-bismaleimide, N,N'-m-xylene-bismaleimide, N,N'-4,4'-diphenylcyclohexane-bismaleimide, and N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, and those disclosed in US 3,562,223, US 4,211,860 and US 4,211,861; or prepared by, for example, the method described in US 3,018,290.

[0074] Benzoxazine compounds have a benzoxazine ring in their molecule. Exemplary benzoxazine monomers can be prepared by reacting aldehydes, phenols, and primary amines with or without a solvent. Phenolic compounds used to form benzoxazines include phenols and polyphenols. Reaction of polyphenols having two or more hydroxyl groups in the formation of benzoxazines can result in branched, cross-linked, or a combination of branched and cross-linked products. The group linking the phenolic group to the phenol can be a branching point or a linking group in the polybenzoxazine.

[0075] Exemplary phenols used for preparing benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydronaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 4,4'-isopropylene biphenol, 4,4'-isopropylene bis(2-methyl-phenol), 4,4'-isopropylene bis(2-allylphenol), 4,4'-(1, 3-Phenylidene diisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidene bis(3-phenylphenol), 4,4'-(1,4-phenylene diisopropylidene)-bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxodiphenol, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethionyl)-bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4- Hydroxyphenyl)methane, 4,4'-(cyclopentyl)diphenol, 4,4'-(cyclohexyl)diphenol, 4,4'-(cyclododecyl)diphenol, 4,4'-(bicyclo[2.2.1]heptyl)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, isopropylidene-bis(2-allylphenol), 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-indene-5 - Alcohols, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi-[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, tetra(4-hydroxyphenyl)ethane, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(o-cresol), dicyclopentadienylbisphenol, etc.

[0076] The aldehyde used to form benzoxazine can be any aldehyde, such as aldehydes having 1 to 10 carbon atoms. For example, the aldehyde can be formaldehyde. The amine used to form benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic amine, or an aromatic-substituted alkyl amine. The amine can be a polyamine, for example, to prepare a polyfunctional benzoxazine monomer for crosslinking.

[0077] The amines used to form benzoxazines have 1 to 40 carbon atoms unless they contain an aromatic ring, and then they can have 6 to 40 carbon atoms. Difunctional or polyfunctional amines can be used as branching points to link one polybenzoxazine to another.

[0078] In some instances, thermal polymerization at temperatures ranging from 150°C to 300°C can be used to polymerize benzoxazine monomers. Polymerization can be carried out in bulk, in solution, or otherwise. Catalysts (such as carboxylic acids) can be used to lower the polymerization temperature or, at the same temperature, to accelerate the polymerization rate.

[0079] Vinyl benzyl ether resins can be prepared by the condensation of phenol with vinyl benzyl halides (such as vinyl benzyl chloride). Bisphenol A, triphenols, and polyphenols are commonly used in the production of poly(vinyl benzyl ether), which can be used to produce crosslinked thermosetting resins.Exemplary vinyl benzyl ethers may comprise vinyl benzyl halides and resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, bis(2,6-dimethylphenol)2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethyl-3,3',5-dibromobiphenol, 4,4'-isopropylidene biphenol, 4,4'-isopropylidene bis(2,6-dihydroxynaphthalene), etc. 4,4'-Isopropylidene bis(2-dibromophenol) (tetramethylbisphenol A), 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis(2-allylphenol), 4,4'-(1,3-phenylene diisopropylidene)bisphenol, 4,4'-isopropylidene bis(3-phenylphenol), 4,4'-(1,4-phenylene diisopropylidene)bisphenol, 4,4'-ethylidene di-phenol, 4,4'-oxodiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfinylbiphenol, 4,4'-hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol , bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylene)biphenol, 4,4'-(cyclohexylene)biphenol, 4,4'-(cyclododecylene)biphenol, 4,4'-(bicyclo[2.2.1]heptylene)biphenol, 4,4'-(9H-fluorene-9,9-diyl)biphenol, 3,3-bis(4-hydroxyphenyl)-isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-indene-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4, Vinyl benzyl ethers produced by the reaction of 6-pentamethyl-2,3-dihydro-1H-indene-5-ol, 3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirodi[indene]-5,6'-diol, dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetras(4-hydroxyphenyl)ethane, tetras(3,5-dimethyl-4-hydroxyphenyl)-ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienyl-bis(2,6-dimethylphenol), dicyclopentadienylbisphenol, etc.

[0080] Arylcyclobutenes include those derived from compounds having the following structures.

[0081]

[0082] Wherein, B is an organic or inorganic group with a valence of n (including carbonyl, sulfonyl, sulfinyl, sulfide, oxygen, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylene, methylene dialkylsilyl, arylalkylsilyl, diarylsilyl, and C). 6-20 (Phenolic compounds); X is an independent hydroxyl group or C each time it appears. 1-24 Hydrocarbon group (including straight-chain and branched alkyl and cycloalkyl groups); and Z is independently hydrogen, halogen, or C each time it appears. 1-12 The alkyl group; 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 US 4,743,399, US 4,540,763, US 4,642,329, US 4,661,193, US 4,724,260, and 5,391,650.

[0083] Perfluorovinyl ethers are typically synthesized from phenol and tetrafluoroethane bromo, followed by zinc-catalyzed reductive elimination, yielding ZnFBr and the desired perfluorovinyl ether. Through this route, bisphenols, triphenols, and other polyphenols can be synthesized into bis-, tri-, and poly(perfluorovinyl ethers). Phenols useful in their synthesis include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3',5-dibromobiphenol, 4,4'-isopropylidene biphenol (bisphenol A), and 4,4'-isopropylidene bis(2,6- Dibromophenol), 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isopropylidene bis(2-allylphenol), 4,4'-(1,3-phenylene diisopropylidene)bisphenol, 4,4'-isopropylidene bis(3-phenylphenol), 4,4'-(1,4-phenylene diisopropylidene)bisphenol, 4,4'-ethylidene biphenol, 4,4'-sulfonyl bis(2,6-dimethylphenol), 4,4'-sulfinyl biphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylene ethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2, 6-Dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentyl)biphenol, 4,4'-(cyclohexyl)biphenol, 4,4'-(cyclododecyl)biphenol, 4,4'-(bicyclo[2.2.1]heptyl)biphenol, 4,4'-(9H-fluorene-9,9-diyl)biphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-indene-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-indene-5-ol, 3, 3',3'-Tetramethyl-2,2',3,3'-Tetrahydro-1,1'-spirodi[indene]-5,6'-diol (spirodiindene), dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetra(4-hydroxyphenyl)ethane, tetra(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)-phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(2-methylphenol), dicyclopentadienylbisphenol, etc.

[0084] There are no particular limitations on crosslinking agents (including auxiliary crosslinking agents). Crosslinking agents can be used alone or in combination of two or more different crosslinking agents. Exemplary crosslinking agents and auxiliary crosslinking agents include oligomers or polymers having curable vinyl functionality. Such materials include oligomers and polymers having crosslinkable unsaturation. Examples include butadiene-based styrene-butadiene rubber (SBR), butadiene rubber (BR), and nitrile rubber (NBR) with unsaturated bonds; isoprene-based natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber with unsaturated bonds; and ethylene-α-olefin copolymer elastomers with unsaturated bonds based on dicyclopentadiene (DCPD), ethylene 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 trimer (EPDM) and ethylene-butene-diene trimer (EBDM)). Examples also include hydrogenated nitrile rubber, fluoroalkane rubbers (such as vinylidene fluoride-hexafluoropropylene copolymers and vinylidene fluoride-pentafluoropropylene copolymers), epichlorohydrin homopolymers (CO), copolymer rubbers (ECO) prepared from epichlorohydrin and ethylene oxide, epichlorohydrin allyl glycidyl copolymers, epichlorohydrin allyl glycidyl ether copolymers, epichlorohydrin epichlorohydrin allyl glycidyl ether trimers, acrylic rubber (ACM), polyurethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T), and ethylene acrylic rubber. Further examples include various liquid rubbers, such as several types of liquid butadiene rubbers and liquid atactic butadiene rubbers of butadiene polymers with 1,2-vinyl linkages prepared by anionic living polymerization. Liquid styrene-butadiene rubber, liquid nitrile-butadiene rubber (CTBN, VTBN, ATBN, etc. of Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymers, and polynorbornene (e.g., sold by Elf Atochem) can also be used.

[0085] Polybutadiene resins containing higher 1,2 addition levels are suitable for thermosetting matrices. Examples include functionalized polybutadiene and poly(butadiene-styrene) random copolymers sold by Ricon Resins Inc. under the trade names RICON, RICACRYL, and RICOBOND Resins. These include butadienes with low vinyl content, such as RICON 130, 131, 134, and 142; polybutadienes with high vinyl content, such as RICON 150, 152, 153, 154, 156, 157, and P30D; and random copolymers of styrene and butadiene, including RICON 100, 181, 184, and maleic anhydride-grafted polybutadiene and alcohol condensates derived therefrom, such as RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20, RICON 184MA6, and RICON 156MA17. Also included are polybutadienes that can be used to improve adhesion, including RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, and RICACRYL 3500; polybutadiene RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene); and (meth)acrylic acid-functionalized polybutadienes, such as polybutadiene diacrylate and polybutadiene dimethacrylate. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. It also includes powder dispersions of functionalized polybutadiene derivatives, including, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 0 1731HS, and RICOBOND 1756HS. Further butadiene resins include polybutadiene-isoprene block copolymers and random copolymers, such as copolymers with a molecular weight of 3,000 to 50,000 g / mol and polybutadiene homopolymers with a molecular weight of 3,000 to 50,000 g / mol. It also includes polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethyl maleic acid, or hydroxylated functional groups.

[0086] Other examples of oligomers and polymers having curable vinyl functional groups include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid, and citraconic acid; unsaturated epoxy (meth)acrylate resins containing acryloyl or methacryloyl groups; unsaturated epoxy resins, urethane (meth)acrylate resins, polyether (meth)acrylate resins, polyol (meth)acrylate resins, alkyd acrylate resins, polyester acrylate resins, spiroacetal acrylate resins, diallyl phthalate resins, tetrabromo-diallyl phthalate resins, diethylene glycol dielyl carbonate resins, and polyethylene polythiol resins. Crosslinking agents, for example, are also included. Other exemplary crosslinking agents include multifunctional crosslinking monomers, such as (meth)acrylate monomers having two or more (meth)acrylate moieties per monomer molecule.Exemplary multifunctional monomers include di(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, etc.; and tri(meth)acrylates, such as trimethylolpropane tri(meth)acrylate, etc. 1,2,4-Butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.; tri(meth)allyl, such as tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, tri(meth)allyl citric acid, tri(meth)allyl phosphoric acid, pentaerythritol tri(meth)acrylate, etc.; penta(meth)acrylate, such as dipentaerythritol penta(meth)acrylate, etc.; hexa(meth)acrylate, such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc. Glycidyl compounds, such as glycidyl (meth)acrylate, (meth)allyl glycidyl ether, 1-chloro-2,3-epoxypropyl (meth)acrylate, 2-(epoxyethyloxy)-ethyl (meth)acrylate, 2-(3,4-epoxybutoxy)ethyl (meth)acrylate, etc.; polythiols, such as trimethylolpropane tris(mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), etc.; silanes, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloxime)silane. Vinyltris(acetone oxime)silane, vinyltris(acetone oxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropoxy)silane, tetraethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-tert-butyldiacetoxysilane, methyltris(ethyl lactate)silane, vinyltris(ethyl lactate)silane, etc.; carbodiimides, such as N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, etc., or combinations thereof. The curable thermosetting composition may optionally include a crosslinking catalyst, such as a carboxylate.

[0087] When a 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.

[0088] Curable thermosetting compositions may contain one or more curing agents. As used herein, the term "curing agent" includes various compounds described as curing agents, hardeners, etc., or both.

[0089] Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, etc. For example, phenolic hardeners include phenolic varnish-type phenolic resins, methyl phenolic resins, cresol phenolic varnish resins, aralkyl 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, bisphenol, triphenylmethane-type phenolic resins, tetraphenylethanol ethane resins, naphthol phenolic varnish resins, naphthol-phenol cocondensed phenolic varnish resins, naphthol-cresol cocondensed phenolic varnish resins, aminotriazine-modified phenolic resins, or combinations thereof. Examples of anhydride curing agents include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymer (SMA), and olefin-maleic anhydride copolymers (such as maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or combinations thereof). Other curing agents and hardeners include compounds such as dicyandiamide, polyamide, amide amine, phenolic amine, Mannich base, anhydride, phenol-formaldehyde resin, amine-formaldehyde resin, phenol-formaldehyde resin, carboxylic acid functional polyester, polysulfide, polythiol, isocyanate, cyanate compound, or any combination thereof. Other exemplary curing agents include tertiary amines, Lewis acids, and oligomers or polymers with unsaturation.

[0090] When a curable thermosetting composition includes a curing agent, the curing agent may be included in an amount of 0.01 to 50 wt%, 0.1 to 30 wt%, or 0.1 to 20 wt%, based on the total weight of the curable thermosetting composition.

[0091] Curable thermosetting compositions may contain a curing catalyst. As used herein, the term "curing catalyst" includes various compounds described as curing accelerators, curing promoters, curing catalysts, and curing co-catalysts.

[0092] Exemplary curing accelerators include heterocyclic accelerators, such as substituted or unsubstituted C-type accelerators containing 1 to 4 cyclic heteroatoms. 3-6Heterocycles, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon or sulfur. Heterocyclic accelerators include benzotriazoles; triazines; piperazines, such as amino-ethylpiperazine, N-(3-aminopropyl)piperazine, etc.; and imidazoles, such as 1-methyl-imidazolium, 2-methylimidazolium, 3-methylimidazolium, 4-methylimidazolium, 5-methylimidazolium, 1-ethylimidazolium, 2-ethylimidazolium, 3-ethylimidazolium, 4-ethylimidazolium, 5-ethylimidazolium, 1-n-propylimidazolium, 2-n-propylimidazolium, 1-isopropylimidazolium, 2-isopropylimidazolium, 1-n-butylimidazolium, 2-n-butylimidazolium, 1-isobutylimidazolium, 2-isobutylimidazolium, 2-undecyl-1H-imidazolium, 2-heptadecanyl-1H-imidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, 2,4-dimethylimidazolium, 2-ethyl-4-methylimidazolium, and 1-phenylimidazolium. 2-Phenylacetazole, 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, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole; cyclic amidines, such as 4-diazabicyclo(2,2,2)-octane, diazabicycloundecene, 2-phenylimidazoline, etc.; N,N-dimethylaminopyridine; aminosulfonates; or combinations thereof.

[0093] Amine curing accelerators include isophorone diamine, triethylenetetramine, diethylenetriamine, 1,2- and 1,3-diaminopropane, 2,2-dimethylpropanediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane, 4-azaheptamethylmethylenediamine, N,N'-bis(3-aminopropyl)butane, 1,4-diamine, dicyandiamide, and diamine. Amide diphenylmethane, diamide diphenylsulfonic acid (amine adduct), 4,4'-methylenediphenylamine, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine-formaldehyde resin, urea-formaldehyde resin, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3'-iminodipropylamine, 2,4-bis(p-aminobenzyl)aniline, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexamethylene-diamine, 1,2- and 1, 3-Diaminocyclohexane, 1,4-Diamino-3,6-Diethylcyclohexane, 1,2-Diamino-4-Ethylcyclohexane, 1,4-Diamino-3,6-Diethylcyclohexane, 1-Cyclohexyl-3,4-Diaminocyclohexane, 4,4'-Diaminodicyclohexylmethane, 4,4'-Diaminodicyclohexylpropane, 2,2-Bis(4-aminocyclohexyl)propane, 3,3'-Dimethyl-4,4'-Diaminodicyclohexylmethane, 3-Amino-1-cyclohexane Alkylaminopropane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, m- and p-phenylenediamine, or diethyltoluenediamine; or a tertiary amine curing accelerator such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tris(N,N-dimethylaminomethyl)phenol; or combinations thereof.

[0094] The curing accelerator can be a potential cationic curing catalyst, including, for example, diaryliodonium salts, phosphonates, sulfonates, carboxylic esters, phosphonites, triarylsulfonium salts, benzylsulfonium salts, aryldiazo salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, etc., or combinations thereof. Diaryliodonium salts can have the structure [(R 10 (R) 11 )I] + X - , where R 10 and R 11 Each is independently C 6-14 Monovalent aromatic groups, optionally surrounded by 1 to 4 atoms selected from C 1-20 Alkyl, C 1-20 The alkoxy, nitro, and chlorine monovalent groups are substituted; and X is wherein - It is anionic. Other curing accelerators can have the structure [(R 10 (R)11 )I] + SbF6 - , where R 10 and R 11 Each is independently C 6-14 Monovalent aromatic hydrocarbons, optionally bound by 1 to 4 carbon atoms 1-20 Alkyl, C 1-20 Alkyl, nitro, or chlorine-substituted; for example, 4-octyloxyphenyliodonium hexafluoroantimonate.

[0095] Curing accelerators can be metal salt complexes, such as copper(II), aluminum(III), zinc, cobalt, or tin salts of aliphatic or aromatic carboxylic acids, selected from copper(II), tin(II), and aluminum(III) salts of acetic acid, stearate, gluconate, citrate, and benzoate, and mixtures thereof. For example, curing accelerators can be copper(II) or aluminum(III) salts of β-diketoic acids; copper(II), iron(II), iron(III), cobalt(II), cobalt(III), or aluminum(III) salts of acetylacetonates; zinc(II), chromium(II), or manganese(II) salts of octanoates; or combinations thereof.

[0096] When a curable thermosetting composition includes a curing catalyst, the curing catalyst may be included in an amount of 0.01 to 5 wt%, 0.05 to 5 wt%, or 0.1 to 5 wt%, based on the total weight of the curable thermosetting composition.

[0097] The curable thermosetting composition may optionally include a curing initiator, such as a peroxide compound. Exemplary peroxide curing initiators may include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, tert-butylbenzene hydroperoxide, tert-butyl peroxyoctanoate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyldioxy)valerate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, di-tert-butyl peroxide, and tert-butylcumyl peroxide. α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, di(tert-butylperoxyisophthalate), tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilylperoxide, etc., or combinations thereof.

[0098] When a curable thermosetting composition includes a curing initiator, the curing agent may be included in an amount of 0.1 to 5 wt%, 0.5 to 5 wt%, or 1 to 5 wt%, based on the total weight of the curable thermosetting composition.

[0099] Flame retardants include, for example, organic compounds containing phosphorus, bromine, or chlorine. For regulatory reasons, non-brominated and non-chlorinated phosphorus-containing flame retardants, such as organophosphates and organic compounds containing phosphorus-nitrogen bonds, may be preferred in certain applications.

[0100] Examples of phosphorus flame retardants include phosphates, phosphazenes, phosphites, phosphine salts, phosphine sulfates, polyphosphates, and phosphonium salts. Phosphate esters include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl)p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, and p-tolyl di(2,5,5'-trimethylhexyl)phosphite. '-Trimethylhexyl' phosphate, 2-ethylhexyl diphenyl phosphate, xylyl-diphenyl phosphate; tolyl-diphenyl phosphate; 1,3-phenylene bis(di-2,6-dimethylyl 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.

[0101] Examples of phosphazene compounds include cyclic phosphazene compounds and chain phosphazene compounds. Cyclic phosphazene compounds (cyclophosphazenes) have a cyclic structure in which a phosphorus-nitrogen double bond is present in the molecule. Examples of phosphonates include aluminum dialkylphosphonates, aluminum tri-(diethylphosphonate), aluminum tri-(methylethylphosphonate), aluminum tri-(diphenylphosphonate), zinc bis-(diethylphosphonate), zinc bis-(methylphosphonate), zinc bis-(diphenylphosphonate), titanoxy bis-(diethylphosphonate), titanoxy bis-(methylethylphosphonate), and titanoxy bis-(diphenylphosphonate). Examples of polyphosphates include melamine polyphosphate, melamine polyphosphate, and melamine polyphosphate. Examples of phosphonium salts include tetraphenylphosphonium tetraphenylborate. Examples of phosphites include trimethyl phosphite and triethyl phosphite. Flame retardant compounds containing phosphorus-nitrogen bonds include phosphazene chloride, phosphamide, phosphoramide, phosphonamide, hypophosphonamide, and tri(aziridinyl)phosphine oxide.

[0102] Halogenated materials can also be used as flame retardants, such as bisphenols like 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane; 1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane; 1,1-bis-(2-chloro-4-iodophenyl)-ethane; 1,1-bis-(2-chloro-4-methylphenyl)-ethane; 1,1-bis-(3,5-dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane; 2,6-bis-(4,6-dichloronaphthyl)-propane; and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane; 2,2-bis-(3-bromo-4-hydroxyphenyl)-propane. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl and 2,4'-dichlorobiphenyl, as well as decabromodiphenyl ether, decabromodiphenyl ethane, and oligomeric and polymerized halogenated aromatic compounds such as brominated styrene, 4,4-dibromobiphenyl, ethylene-bis(tetrabromophthalimide), or copolycarbonates of bisphenol A and tetrabromobisphenol A with carbonate precursors (e.g., phosgene). Metal synergists, such as antimony oxide, can also be used with flame retardants.

[0103] Inorganic flame retardants, such as C, can also be used. 1-16 Salts of alkyl sulfonates, such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenyl sulfone sulfonate; salts, such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoride anion complexes, such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6.

[0104] When a curable thermosetting composition includes a flame retardant, the flame retardant may be included in an amount greater than 1 wt%, or 1 to 20 wt%, or 5 to 20 wt%, based on the total weight of the curable thermosetting composition.

[0105] Curable thermosetting compositions may also include inorganic or organic fillers, such as particulate fillers, fibrous fillers, or combinations thereof. Any inorganic and organic fillers, including those known in the art, may be used without limitation.

[0106] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; alumina, thiourea, glass powder, B or Sn-based fillers such as zinc borate, zinc stannate, and zinc hydroxystannate; metal oxides such as zinc oxide and tin oxide; alumina, silica (including fused silica, fumed silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesium oxide, magnesium silicate, antimony trioxide, glass fibers (chopped, ground, or cloth), glass mat, glass bulb, hollow glass microspheres, aromatic polyamide fibers, quartz, etc., or combinations thereof. Other exemplary inorganic fillers include powdered titanium ceramics, such as any one of the titanates of barium, lead, strontium, calcium, bismuth, magnesium, etc. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolite, and hydrotalcite. In some aspects, the fillers can be treated with coupling agents disclosed herein.

[0107] Glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as those based on quartz. Glass fibers can have any suitable diameter, such as from 2 to 30 micrometers (μm), or 5 to 25 μm, or 5 to 15 μm. The length of the glass fibers before lamination is not limited and can be from 2 to 7 millimeters (mm), or 1.5 to 5 mm. Longer glass fibers or continuous glass fibers can be used alternatively. Suitable glass fibers are commercially available from suppliers such as Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.

[0108] Organic fillers can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, and poly(ether sulfone) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, or combinations thereof.

[0109] Fillers can be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, Al2O3, BN, AlN, or combinations thereof can be used for electronic modules with high thermal conductivity. For example, MgO can be used to increase both thermal conductivity and CTE. For example, SiO2 (e.g., amorphous SiO2) can be used for lightweight modules with low CTE and small dielectric constant.

[0110] When a curable thermosetting composition includes fillers, the fillers may be included in an amount greater than 1 wt%, or 1 to 50 wt%, or 1 to 30 wt%, or 10 to 30 wt%, based on the total weight of the curable thermosetting composition.

[0111] Coupling agents, also known as adhesion promoters, include chromium complexes, silanes, titanates, zircon aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, etc. Exemplary olefin-maleic anhydride copolymers may include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or combinations thereof. Exemplary silanes may include epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0112] Examples of aminosilane coupling agents are γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyl-dimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, and N-β(aminoethyl)γ-aminopropyltriethoxysilane. Illustrative epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of methacryloyloxysilane coupling agents include γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane.

[0113] 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-dimethylthiocarbamoyltetrasulfide, and 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide. -Dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxysilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthio-carbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, etc., or combinations thereof. The silane coupling agent can be a polysulfide silane coupling agent having 2 to 4 sulfur atoms forming polysulfide bridges. For example, the coupling agent can be a bis(3-triethoxysilylpropyl) disulfide, trisulfide, or tetrasulfide.

[0114] When a curable thermosetting composition includes a coupling agent, the coupling agent may be included in an amount of 0.01 to 5 wt%, 0.05 to 5 wt%, or 0.1 to 5 wt%, based on the total weight of the curable thermosetting composition.

[0115] The curable thermosetting composition may optionally include a solvent. The solvent may be, for example, C. 3-8 Ketones, C 3-8 N,N-dialkylamide, C 4-16 Dialkyl ethers, C 6-12 Aromatics, C 1-3 Chlorinated hydrocarbons, C 3-6 Alkyl esters of alkyl alkanoates, C 2-6 Alkyl cyanides, or combinations thereof. Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. Specific C 4-8-N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. Aromatic hydrocarbon solvents can be non-halogenated. Specific C 3-6 Alkyl alkyl esters include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. Specific C 2-6 Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. Specific C 2-6 Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. For example, solvents may be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolium ketone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, γ-caprolactone, dimethyl sulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone. Ketones, cyclohexanone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, N,N-dimethylethyl urea, N,N-dimethylpropyl urea, tetramethyl urea, propylene glycol phenyl ether, anisole, veratrum ether, o-dichlorobenzene, chlorobenzene, trichloroethane, dichloromethane, chloroform, pyridine, methylpyridine, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, ionic liquids, or combinations thereof.

[0116] When using a solvent, the curable thermosetting composition may contain 2 to 99 wt% solvent based on the total weight of the curable thermosetting composition. For example, the amount of solvent may be 5 to 80 wt%, 10 to 60 wt%, or 20 to 50 wt% based on the total weight of the curable thermosetting composition. The solvent can be partially selected to adjust the viscosity of the curable thermosetting composition. Therefore, the amount of solvent may depend on variables including the type and amount of the end-capped poly(aryl ether), the type and amount of other components (such as curing additives), the type and amount of any auxiliary thermosetting resin, and the processing temperature for any subsequent processing of the curable thermosetting composition, such as impregnating a reinforcing structure with the curable thermosetting composition to prepare a composite material. The solvent may be anhydrous. For example, based on the total weight of the solvent, the solvent may include less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water.

[0117] Curable thermosetting compositions may also include curable unsaturated monomer compositions, which may include, for example, monofunctional styrene compounds (e.g., styrene), monofunctional (meth)acrylate compounds, or combinations thereof. For example, the curable unsaturated monomer composition may be an olefin-containing monomer or an alkynyl-containing monomer. Exemplary olefin- and alkynyl-containing monomers include (meth)acrylates, (meth)acrylamide, N-vinylpyrrolidone, and vinyl sulpholactone as described in U.S. Patent No. 6,627,704 to Yeager et al., and (meth)acrylates, (meth)acrylamide, N-vinylpyrrolidone, and vinyl sulpholactone as described in U.S. Patent No. 4,304,705 to Heilman et al. Exemplary monofunctional monomers include mono(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isooctyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid, n-hexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, etc., or combinations thereof.

[0118] The curable thermosetting composition may optionally include one or more additional additives. Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow modifiers, anti-drip agents, anti-sticking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, release agents, toughening agents, low profile additives, stress-relieving additives, etc., or combinations thereof. When present, additional additives may be included in any effective amount, such as 0.01 to 20 wt%, or 0.01 to 10 wt%, or 0.01 to 5 wt%, or 0.01 to 1 wt%, based on the total weight of the curable thermosetting composition.

[0119] Curable thermosetting compositions can be prepared by using any suitable method to combine end-capped poly(arylene ether) copolymers and other optional components disclosed herein.

[0120] A curable thermosetting composition is also provided, comprising a cured product of a 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, by heat curing or by using irradiation techniques (including UV irradiation or electron beam irradiation). For example, a cured product can be obtained by heating the curable thermosetting composition as defined herein to a time and temperature sufficient to evaporate the solvent and achieve curing. When using heat curing, the temperature can be from 30°C to 400°C, or from 50°C to 250°C, or from 100°C to 250°C. Heating can be from 1 minute to 24 hours, or from 1 minute to 6 hours, or from 3 hours to 5 hours. Curing can be staged to produce a partially cured and generally non-sticky resin, which is then fully cured by heating for a longer period or temperature within the aforementioned range. As used herein, the term "cured" encompasses both partially cured and fully cured products.

[0121] Curing thermosetting compositions 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.

[0122] The disclosed curable thermosetting compositions and curing compositions can be used in a wide variety of applications and uses, including any application using conventional thermosetting compositions. For example, useful articles comprising curable thermosetting compositions or curing thermosetting compositions can be in the form of composite materials, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded parts, prepregs, housings, laminates, metal foil laminates, electronic composite materials, structural composite materials, 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; glues; and composite materials, such as those using carbon fiber and glass fiber reinforcement. When used as coatings, the disclosed compounds and compositions can be deposited on a variety of substrates. For example, the compositions can be deposited on surfaces of metals, plastics, glass, fiber adhesives, ceramics, stone, wood, or any combination thereof. The disclosed compositions can be used as coatings on the surfaces of metal containers (e.g., aluminum or steel), such as those commonly used in the paint and surface covering industry for packaging and containment. Curable thermosetting compositions and curable thermosetting compositions derived therefrom are also particularly suitable for forming electrical and computer components.

[0123] Methods of forming composite materials may include impregnating a reinforcing structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and laminating multiple prepregs. The reinforcing structure may be a porous substrate material, such as a fiber preform or substrate, or other porous materials comprising ceramics, polymers, glass, carbon, or combinations thereof. For example, the porous substrate material may be woven or nonwoven glass fabric, glass fiber fabric, or carbon fiber. When the article includes a fiber preform, methods of manufacturing the article may include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fiber preform may optionally be formed before or after solvent removal. In some aspects, the curable thermosetting composition layer may also include woven or nonwoven glass fabric. For example, the curable layer may be prepared by impregnating the glass fabric with the curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described in Anonymous (Hexcel Corporation), “Prepreg Technology,” March 2005, Publication No. FGU017b; Anonymous (Hexcel Corporation), “Advanced Fibre Reinforced Matrix Products for Direct Processes,” June 2005, Publication No. ITA272; and Bob Griffiths, “Farnborough Airshow Report 2006,” Composites World.com, September 2006. The weight and thickness of the reinforcing structure are selected according to standards well known to those skilled in the art of fiber-reinforced resin composites, based on the intended use of the composite material. The reinforcing structure may contain various finishes suitable for thermosetting components in curable thermosetting compositions.

[0124] Methods for manufacturing articles from curable thermosetting compositions may include partially curing the curable thermosetting composition to form a prepreg, or fully curing the curable thermosetting composition to form a composite article. The characteristic of a “cured composition” as used herein refers to a substantially fully cured composition. For example, the resin in a laminate formed from a prepreg is typically substantially fully cured. Those skilled in the art of thermosetting can determine whether a sample is partially cured or substantially fully cured without extensive experimentation. Curing may occur before or after the removal of the solvent from the curable composition. Furthermore, the article may be further shaped, for example, by thermoforming, before or after solvent removal, before curing, after partial curing, or after full curing. In one approach, the article is formed, and the solvent is removed; the article is partially cured (B-stage); optionally shaped; and then further cured.

[0125] Methods for producing composite materials on a commercial scale are known in the art, and the curable thermosetting compositions described herein are readily adaptable to existing processes and equipment. For example, prepregs are typically produced on a processor. The main components of a processor include a feed roller, a resin impregnation tank, a processing furnace, and a receiving roller. The reinforcing structure (e.g., E-glass) is typically wound into a large spool. The spool is then placed on the feed roller, which rotates and slowly rolls the reinforcing structure out. The reinforcing structure then moves through a resin impregnation tank containing the curable thermosetting composition. The curable composition impregnates the reinforcing structure. After exiting the tank, the coated reinforcing structure moves upward through a vertical processing furnace, typically at a temperature of 175°C to 200°C, and the solvent evaporates. The resin then begins to polymerize. When the composite material exits the tower, it is fully cured, such that the web is neither wet nor sticky. However, the curing process is stopped before completion to allow for additional curing during the fabrication of the laminate. The web then rolls the prepreg onto the receiving roller.

[0126] Electrical and electronic articles comprising or derived from curable thermosetting compositions are also provided. Articles include those comprising printed circuits used in industries such as medical or aerospace. Other articles include antennas and similar articles. Articles (such as printed circuit boards) are used in, for example, lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic notebooks and similar devices, or office automation equipment. For example, electrical components may be mounted on a printed circuit board including a laminate. Other exemplary articles prepared from curable compositions for various applications may include copper-clad laminates (CCLs) (e.g., metal-core copper-clad laminates (MCCCLs)), composite articles, and coated articles (e.g., multilayer articles).

[0127] Dielectric layers that can be prepared from curable thermosetting compositions can be used in circuit assemblies, such as metal foil laminates like copper-clad laminates. For example, a laminate may include a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally a heat-dissipating metal substrate layer disposed on the dielectric layer on a side opposite the conductive metal layer. The dielectric layer may optionally include a fiber preform (e.g., a fabric layer). For example, the dielectric layer may also include a glass fabric layer.

[0128] The conductive metal layer can be in the form of a circuit and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, or combinations thereof. Other metals include copper-molybdenum alloys, nickel-cobalt-iron alloys such as KOVAR available from Carpenter Technology Corporation, nickel-iron alloys such as INVAR available from National Electronic Alloys, Inc., bimetallic, trimetallic, trimetallic derived from two layers of copper and one layer of INVAR, and trimetallic derived from two layers of copper and one layer of molybdenum. Exemplary metal layers include copper or copper alloys. Alternatively, forged copper foil can be used. The conductive metal layer can have a thickness of 2 to 200 micrometers (μm), or 5 to 50 μm, or 5 to 40 μm.

[0129] The heat-dissipating metal substrate layer can be a thermally conductive metal, such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or a combination thereof. Thermally and electrically conductive metals can be used, provided that the metal is electrically isolated from the metal circuit layer. Preferred supporting metal substrate layers may have a thickness of 0.1 to 20 mm, or 0.5 to 10 mm, or 0.8 to 2 mm.

[0130] The conductive metal layer and the supporting metal substrate layer can be pretreated to have a high surface roughness to enhance adhesion to the dielectric layer. Treatment methods include, for example, washing, flame treatment, plasma discharge, corona discharge, etc., to enhance the adhesion of the metal layer. The dielectric layer can be firmly adhered to the conductive metal layer or heat dissipation layer without the use of adhesives, or adhesives can be used to improve the adhesion of the dielectric layer to the conductive metal layer or heat dissipation layer. Exemplary adhesives for bonding composite sheets to metals include polyimide adhesives, acrylic adhesives, epoxy resins, etc., or combinations thereof.

[0131] Copper-clad laminates can be prepared by thermally laminating one or more dielectric layers, one or more conductive metal layers, and a supporting metal substrate layer under pressure without the use of thermosetting adhesives. The dielectric layers can be prepared from a curable thermosetting composition and can be formed into layers by a solvent casting process prior to the thermal lamination step. For example, the dielectric layer, conductive metal layer, and heat-dissipating layer can be thermally laminated together under pressure using an adhesive-free process to form a laminate. The conductive metal layer can optionally be in the form of a circuit prior to lamination, or the conductive metal layer can optionally be etched to form a circuit after lamination. Lamination can be performed by hot pressing or roll forming methods, such as roll-to-roll methods. The conductive metal layers in the copper-clad laminate can be further patterned to provide a printed circuit board. Furthermore, the copper-clad laminate can be shaped to provide a circuit board with sheet, tube, or rod shapes.

[0132] Alternatively, the laminate for the circuit assembly can be manufactured using a solution casting method, in which a curable thermosetting composition is cast directly onto a conductive metal layer and then laminated onto a heat-dissipating metal substrate layer. For example, the curable thermosetting composition can be cast directly onto a heat-dissipating metal substrate layer and then laminated onto a conductive metal layer.

[0133] Multilayer laminates including additional layers can also be prepared by thermal lamination in one step or two or more consecutive steps using methods such as hot pressing or roll calendering. For example, seven or fewer layers, or sixteen or fewer layers, can be present in the laminate. On one hand, the laminate can be formed in one or two or more consecutive steps using a continuous fabric-thermoset-metal-thermoset-fabric-thermoset-metal foil layer or a sub-combination having fewer layers, such that the laminate includes a thermosetting film layer between any metal foil layer and any fabric layer. On the other hand, a first laminate can be formed in one step or two or more consecutive steps, wherein a fabric layer, such as a woven glass fabric layer, is located between two thermosetting layers. A second laminate can then be prepared by laminating a metal foil onto the thermosetting side of the first laminate.

[0134] Printed circuit boards prepared from curable thermosetting compositions can have a total thickness of 0.1 mm to 20 mm, and specifically 0.5 mm to 10 mm, wherein the total thickness refers to the assembly including each of the dielectric layer, conductive metal layer, and supporting metal substrate layer. Circuit components can have a total thickness of 0.5 mm to 2 mm, and specifically 0.5 mm to 1.5 mm. There is no specific limitation on the thickness of the dielectric layer, and it can be 5 to 1500 μm, or 5 to 750 μm, or 10 to 150 μm, or 10 to 100 μm. For example, the printed circuit board can be a metal-core printed circuit board (MCPCB) for light-emitting diode (LED) applications.

[0135] Curable thermosetting compositions can be used as coatings, for example, in the preparation of multilayer articles. Methods of manufacturing a coating may include combining a curable thermosetting composition with an optional fluoropolymer and forming the coating on a substrate. For example, a multilayer article can be manufactured by forming a layer comprising a curable thermosetting composition, removing a solvent from the layer and optionally curing it to provide a primer layer, forming a second layer on the primer layer comprising ceramics (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, Y2O3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, B4C, TiC, Si3N4, TiN, BN, AlN, TiB, ZrB2, etc.), thermoplastic polymers, fluoropolymers (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, etc.) or combinations thereof to provide a multilayer article, and optionally heat-treating the multilayer article to cure the curable thermosetting composition. In some aspects, the second layer may also comprise a curable thermosetting composition.

[0136] Other applications of curable thermosetting compositions include, for example, acid bath containers; neutralization tanks; aircraft parts; bridging beams; bridging covers; electrolytic cells; exhaust stacks; scrubbers; sports equipment; stair boxes; walkways; automotive exterior panels, such as covers and trunk lids; floor chassis; vent hoods; pipes and conduits, including heater conduits; industrial fans, fan housings, and blowers; industrial mixers; ship hulls and decks; marine dock fenders; tiles and coatings; building panels; commercial machine housings; cable trays, including cable ducts; concrete modifiers; dishwasher and refrigerator components; electrical sealants; electrical panels; tanks, including electrolytic refining tanks, soft water tanks, fuel tanks, and various filament-wound tanks and tank liners; furniture; garage doors; grilles; furniture garage doors; grilles; vehicle body protection. Devices; luggage; outdoor motor vehicles; pressure tanks; optical waveguides; radomes; railings; railway components such as tank cars; hopper car covers; car doors; truck bed liners; satellite antennas; signs; solar panels; telephone switch housings; tractor components; transformer covers; truck components such as fenders, covers, bodies, cabs, and beds; insulators for rotating machinery, including grounding insulation, turn-to-turn insulation, and phase insulation; steering gears; core insulation and cables and straps; drive shaft couplings; propeller blades; missile components; rocket engine housings; wing sections; sucker rods; fuselage sections; wing skins and winglets; engine vents; cargo doors; tennis rackets; golf club shafts; fishing rods; skis and ski clubs; bicycle components; transverse leaf springs; pumps, such as automotive smoke pumps. Pumps; electrical components, inserts, and tools such as cable connectors; winding and densely packed multi-element assemblies; seals for electromechanical devices; battery housings; resistors; fuses and slide bars; bicycle parts; leaf springs; pumps such as automotive smoke pumps; electrical components, inserts, and tools such as cable connectors; wire windings and densely packed multi-element assemblies; seals for electromechanical devices; battery boxes; resistors; fuses and thermal cut-off devices; printed circuit board coatings; casting projects such as capacitors, transformers, crankcase heaters; small molded electronic components, including coils, capacitors, resistors, and semiconductors; as alternatives in chemical processing of steel, pulp and paper, power generation, and wastewater treatment; scrubbing towers; washing towers; pultruded parts for structural applications, including structural members, grids, etc. Fences and safety railings; swimming pools, pool slides, hot tubs and saunas; pultruded components for structural applications, including structural members, gratings and safety rails; swimming pools, pool slides, hot tubs and saunas; drive shafts for engine hood applications; dry toner resins for copiers; marine tools and composites; heat shields; submarine hulls; prototyping; experimental model development; laminated trims; drilling jigs; adhesive jigs; inspection jigs; industrial metal forming dies; aircraft stretch blocks and hammer forms; vacuum molding tools; flooring, including flooring for production and assembly areas; flooring for cleanrooms, machine shops, control rooms, laboratories, parking garages, freezers, laboratories and outdoor loading docks; conductive compositions for antistatic applications;Applications include: decorative flooring; expansion joints for bridges; injectable mortar for repairing and reinforcing cracks in structural concrete; grouting for tiles; machine tracks; metal pins; bolts and posts; repair of oil and fuel storage tanks; and many other applications.

[0137] Methods that can be used to prepare articles and materials include those commonly known in the art for processing thermosetting resins. Such methods have been described, for example, in Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal Senior Ed, pp. 105-168 and 497-533, and in “Polyesters and Their Applications” by Bjorksten Research Laboratories, Johan Bjorksten (pres.), Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), and James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing technologies include resin transfer molding; sheet molding; bulk molding; pultrusion; injection molding, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting; 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; tooling molding; autoclave curing; thermosetting in air; vacuum bagging; pultrusion; SCRIMP composite resin injection manufacturing process; open-face molding, continuous combination of resin and glass; and filament winding, including cylindrical filament winding. For example, articles can be prepared by resin transfer molding.

[0138] In one aspect, articles derived from curable thermosetting compositions are also provided, wherein the article is a composite material, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded part, prepreg, housing, cast article, laminate, or combination thereof; or wherein the article is a metal foil laminate, electronic composite material, structural composite material, or combination thereof. The article can be manufactured as disclosed herein, for example by casting, molding, extrusion, etc., and solvents are removed from the formed article. In some aspects, the article can be a layer and can be formed by casting the curable composition onto a substrate to form a cast layer. Solvents can be removed by a variety of methods, including by heating the cast layer, heating the cast layer under heat and pressure, for example by laminating the cast layer onto another substrate. In some aspects, articles prepared by the above methods can include adhesives, encapsulation materials, capacitor films, or circuit board layers. In some aspects, articles prepared from curable compositions can be dielectric layers or coatings disposed on a substrate, such as wire or cable coatings. For example, the article can be a dielectric layer in a circuit material (e.g., a printed circuit board) for use in applications such as lighting or communications. Other exemplary articles prepared from the curable composition can be one or more coating layers. The curable composition can be used to prepare articles disclosed herein for use with other curable thermosetting compositions.

[0139] This disclosure is further illustrated by the following examples, which are not limiting.

[0140] Example

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

[0142] Table 1

[0143]

[0144] Weight-average molecular weight (M w The number-average molecular weight (Mn) was determined using a polystyrene standard via gel permeation chromatography (GPC). n ) via proton nuclear magnetic resonance ( 1 H-NMR spectra were measured at 600 MHz using a polystyrene standard via GPC. 1 H-NMR spectroscopy determines the average functionality. gThe solutions were measured by differential scanning calorimetry (DSC) at a heating rate of 20 °C / min from 25 °C to 300 °C. Solution viscosity was measured at 25 °C (Brønsted viscometer; rotor 00) using a 50 wt% solution of the oligomer in MEK or toluene. The solubility of the oligomer in MEK and toluene is reported as the amount of oligomer soluble in the solvent, expressed as a weight percentage (wt%) based on the total weight of the oligomer and solvent.

[0145] Example 1. Synthesis of PPE-MPP oligomers (in the presence of DBA)

[0146] Toluene (216 g), 102.64 g MPP, 14 g TMBPA, 2.17 g DMBA, 1.17 g DBA, 0.18 g DBEDA, 0.09 g MAQUAT, and 0.33 g toluene were fed into a 500 mL bubbling polymerization vessel and stirred under nitrogen. Next, 0.87 g of a catalyst solution containing 0.06 g Cu₂O and 0.8 g HBr (48%) were added to the reaction mixture. After the catalyst solution was added, an oxygen flow was started. The temperature was increased from 25 °C to 32 °C over 15 minutes, maintained at 32 °C for 100 minutes, and then increased to 49 °C. The oxygen flow was maintained for another 35 minutes, at which point the oxygen flow was stopped, and 0.46 g NTA and 5.68 g water were added to the reaction mixture. The resulting mixture was stirred at 60 °C for 2 hours. The layers were separated by centrifugation, and the lighter phase was separated by removing toluene. Powdered PPE-MPP oligomers were obtained by drying in a vacuum oven at 110°C for 12 hours. Separation temperatures can be as high as 300°C. Depending on the separation temperature and time, the amount of the dibutylamine structural moiety can range from 0 to 1 wt%.

[0147] Example 2. Synthesis of PPE-MPP (in the absence of DBA)

[0148] PPE-MPP was prepared in the same manner as in Example 1, except that 0.18 g of DBEDA was not used. The amount of the dibutylamine structural moiety can be from 0 to 1 wt%, depending on the separation temperature and time.

[0149] Example 3. Synthesis of PPE-MPP-2MA oligomers (from separated PPE-MPP powder)

[0150] 150 g of PPE-MPP oligomer powder was prepared using the same method as in Example 1. This oligomer powder was dissolved in toluene (40 wt) and transferred to a 500 mL three-necked round-bottom flask equipped with a heating mantle, Dean-Stark condenser, stirrer, and thermocouple. The solution was then azeotropically distilled at 120 °C to remove water. After water removal, the reaction mixture was cooled to 85 °C and 0.64 g of DMAP was added. After the added DMAP was completely dissolved, 9.20 g of MAA was slowly added over 15 minutes using a feeding funnel. The reaction temperature was raised to 110 °C to achieve gentle reflux. The reaction was maintained at this temperature with stirring for 4 hours. The PPE-MPP-2MA oligomer product was separated by cooling the reaction mixture and precipitating the product in methanol. The product was further dried under vacuum at 110 °C for 12 hours. The structure of the PPE-MPP-2MA oligomer is shown below:

[0151]

[0152] Example 4. Synthesis of PPE-MPP-oligomers

[0153] The PPE-MPP oligomers were prepared in the same manner as in Example 1, except that the lighter phase was not separated by removing toluene. Instead, without separating the PPE-MPP oligomers into powder, a toluene solution of the PPE-MPP oligomers was used for the subsequent reaction with the capping agent, and then the PPE-MPP oligomers were redissolved in toluene for the subsequent reaction with the capping agent.

[0154] Table 2 shows the performance of the PPE-MPP-2MA oligomers of Examples 1 to 4, wherein the amounts are listed in the range including the working examples.

[0155] Table 2

[0156] Performance (units) physical form powder Average functionality 1.98-2.00 Tg(℃) 128-151 Mn, measured by NMR (number average molecular weight in g / mol). 2,300-4,000 Mn, determined by the number-average molecular weight (g / mol) of GPC. 2,200-3,110 Mw, the weight-average molecular weight (g / mol) of GPC. 4,100-4,880 Dibutylamine substituents (wt%) 0-0.91 Biphenyl (wt%) 0-1.0 Solubility of toluene (wt%) >50 Solubility of methyl ethyl ketone (wt%) >50 <![CDATA[Viscosity, 50 wt% toluene solution at 25 °C (cP) * > 107 <![CDATA[Viscosity, 50 wt% MEK at 25 °C (cP) * > 36

[0157] *Use M with 2800 g / mol n The molecular weight was measured in PPE-MPP-2MA oligomers. The molecular weight can be altered based on the amount of diphenol involved in the oxidative coupling reaction.

[0158] Furthermore, based on the total weight of the PPE-MPP-2MA oligomers prepared by the methods in Examples 3 and 4, respectively, by 1 H-NMR spectra showed trace amounts of the substance at or below 1 wt%. The observed trace amounts (A) and (B) have the following structures:

[0159]

[0160] Without being constrained by theory, the amount of biphenyl-containing oligomer (A) can be varied based on factors such as temperature, the amount of amine catalyst, and the monomer concentration during oxidative coupling polymerization to form the PPE-MPP-2MA oligomer. The amount of amine-substituted oligomer (B) (also known as Mannich amine-substituted oligomer) can be varied by the amount of DBA used during oxidative coupling polymerization to form the PPE-MPP-2MA oligomer and by post-treatment conditions, including the temperature used during the separation of the PPE-MPP-2MA oligomer.

[0161] The present invention further covers the following aspects.

[0162] Aspect 1. A capped poly(arylene ether) copolymer comprising reactive end groups, wherein the capped poly(arylene ether) copolymer is derived from alkylarylphenol.

[0163] Aspect 2. The end-capped poly(arylene ether) copolymer according to aspect 1, wherein the end-capped poly(arylene ether) copolymer has an average of 1.1 to 2 reactive end groups per molecule; or 1.4 to 2 reactive end groups per molecule; or 1.8 to 2 reactive end groups per molecule.

[0164] Aspect 3. The end-capped poly(aryl ether) copolymer according to aspect 1 or 2, wherein the end-capped poly(aryl ether) copolymer is derived from the reaction of a diphenol and a monophenol comprising 2-(alkyl)-6-(aryl)phenol; or wherein the monophenol is 2-(C 1-12 (primary or secondary alkyl)-6-(unsubstituted C) 6-12 (Aryl)phenol.

[0165] Aspect 4. A terminated poly(arylene ether) copolymer according to any of the preceding aspects, wherein, in the presence of a catalyst composition, the terminated poly(arylene ether) copolymer is derived from the oxidative polymerization of a diphenol and a monophenol comprising 2-(alkyl)-6-(aryl)phenol.

[0166] Aspect 5. A terminated poly(arylene ether) copolymer according to any of the preceding aspects, wherein the terminated poly(arylene ether) copolymer has a formula (1) or formula (2) as provided herein.

[0167] Aspect 6. The end-capped poly(arylene ether) copolymer according to aspect 5, wherein Q 1a Each time it appears, it is C independently. 1-12 Primary alkyl or C 1-6 Primary alkyl group; Q 1b Each time it appears, it is C independently. 1-12 Alkyl or C 6-12 aryl, or C 1-6 Alkyl or phenyl; Q 2It is hydrogen; and R 1 R 2 R 3 and R 4 Each is independently hydrogen, halogen, or C. 1-12 Alkyl, or hydrogen or C 1-6 alkyl.

[0168] Aspect 7. A capped poly(aryl ether) copolymer according to any one of Aspects 5 or 6, wherein at least one repeating unit is derived from a monohydric phenol of formula (3), wherein Q 1a It is C 1-6 Primary alkyl group, Q 1b It is an unsubstituted phenyl group, and Q 2 For example, in aspect 5 or 6.

[0169] Aspect 8. A capped poly(aryl ether) copolymer according to any one of Aspects 5 to 7, wherein the capped poly(aryl ether) copolymer has formula (2a), wherein 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 aspect 5 or 6; or where R 1 and R 2 Each is independently hydrogen or C 1-6 alkyl.

[0170] Aspect 9. A terminated poly(aryl ether) copolymer according to any one of Aspects 5 to 8, wherein the terminated poly(aryl ether) copolymer has formula (2b), wherein R 1 R 2 R 6 to R 8 R 5a R 5b Q 1a Q 1b Q 2 x and y are defined as in any of aspects 5 to 8.

[0171] Aspect 10. A method for forming a capped poly(arylene ether) copolymer according to any one of aspects 1 to 9, the method comprising oxidizing a copolymer of 2-(alkyl)-6-(aryl)phenol and a diphenol in a solvent in the presence of a catalyst composition.

[0172] Aspect 11. The method according to aspect 10 further includes reacting the capping agent with an uncapped poly(aryl ether) copolymer containing phenolic end groups, provided that a reaction mixture comprising the capped poly(aryl ether) copolymer is effectively provided.

[0173] Aspect 12. The method according to aspect 10 or 11 further includes oxidizing the copolymerization of 2-(alkyl)-6-(aryl)phenol and diphenol in a solvent in the presence of a catalyst composition to provide a reaction product comprising an uncapped poly(aryl ether) copolymer, wherein the solvent is not removed from the reaction product prior to reaction with a capping agent.

[0174] Aspect 13. The method according to any of the preceding aspects, wherein an additional monohydric phenol other than 2-(alkyl)-6-(aryl)phenol is present during the oxidative copolymerization process.

[0175] Aspect 14. A curable thermosetting composition comprising a poly(arylene ether) copolymer with end caps according to any one of aspects 1 to 9.

[0176] Aspect 15. An article of a curable thermosetting composition derived from aspect 14, wherein the article is a composite material, foam, fiber, layer, coating, encapsulant, adhesive, sealant, molded part, prepreg, shell, casting, laminate, or combination thereof; or wherein the article is a metal foil laminate, electronic composite material, structural composite material, or combination thereof.

[0177] Compositions, methods, and articles may alternatively include, constitute, or substantially constitute any suitable materials, steps, or components disclosed herein. Compositions, methods, and articles may additionally, or alternatively, be formulated to contain no or substantially contain any materials (or kinds), steps, or components that would otherwise be unnecessary for achieving the function or purpose of the composition, method, and article.

[0178] All scopes disclosed herein include endpoints, and endpoints may be combined independently of each other. "Combination" includes blends, mixtures, alloys, reaction products, etc. Unless otherwise indicated herein or clearly contradicted by the context, the terms "a," "an," and "the" do not indicate a limitation of quantity but are to be interpreted to cover both singular and plural. Unless otherwise expressly stated, "or" means "and / or." Throughout the specification, references to "some aspects," "an aspect," etc., mean that a particular element described in that aspect is included in at least one aspect described herein and may or may not be present in other aspects. Furthermore, it should be understood that the described elements may be combined in any suitable manner in each aspect. "Combination of them" is open-ended and includes any combination that comprises at least one of the listed components or properties (optionally together with similar or equivalent components or properties not listed).

[0179] Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application contradicts or conflicts with terminology in an incorporated reference, the terminology from this application shall take precedence over the conflicting terminology from the incorporated reference. Unless otherwise specified herein, all test standards are the most recent standards effective from the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0180] Unless otherwise stated, compounds are described using standard terminology. The terms “hydrocarbon” and “hydrocarbon group” refer to any compound, group, or substituent containing carbon and hydrogen. Residues can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. They can also contain combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbon group residue is described as substituted, it may optionally contain heteroatoms above and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, a hydrocarbon group residue may also contain one or more carbonyl, amino, hydroxyl, etc. As used herein, the term “heterohydrocarbon group” refers to a hydrocarbon group containing one or more heteroatoms within the backbone of the hydrocarbon group residue. "Aliphatic" refers to a non-aromatic hydrocarbon group; "aryl" refers to a monocyclic or polycyclic aromatic hydrocarbon group in which all ring members are carbon; "arylene" refers to a divalent aryl group; "alkylaryl" refers to an aryl group substituted with an alkyl group; and "aralkyl" refers to an alkyl group substituted with an aryl group. The prefix "hetero" means that a compound or group includes at least one ring member containing heteroatoms (e.g., 1, 2, or 3 heteroatoms), wherein each heteroatom is independently N, O, S, Si, or P.

[0181] In the chemical formulas shown by the structure, it should be understood that any position not substituted by the shown group has a valence filled by the shown bond or hydrogen atom. Unless otherwise specifically stated, each of the above groups may be unsubstituted or substituted, provided that substitution does not significantly and adversely affect the synthesis, stability, or use of the compound. “Substitution” means that a compound, group, or atom is substituted by at least one (e.g., 1, 2, 3, or 4) substituent, which may each independently be nitro (-NO2), cyano (-CN), hydroxyl (-OH), halogen, mercapto (-SH), thiocyanate (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 Aryl, C 7-13 Aryl alkyl (e.g., benzyl), C 7-12 Alkyl (e.g., toluenemethyl), C 4-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl) or toluenesulfonyl (CH3C6H4SO2-), instead of hydrogen, provided that the valence of the substituted atom does not exceed the normal valence. The number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0182] While specific aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents may arise that are currently unforeseeable or unforeseeable by the applicant or others skilled in the art. Therefore, the appended claims, as filed and as they may be modified, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A capped poly(aryl ether) copolymer comprising reactive end groups, wherein, The terminated poly(arylene ether) copolymer is of formula (1) or formula (2): in, Q 1a and Q 1b Each time it appears, it is an independent halogen; C 1-12 Hydrocarbon group, provided that the hydrocarbon group is not a tertiary hydrocarbon group; C 1-12 Hydrothiolated group; C 1-12 Hydroxyl group; or C 2-12 Haloalkoxy group, wherein at least two carbon atoms separate the halogen and oxygen atoms; Q 2 Each time it appears independently, it is hydrogen; halogen; unsubstituted or substituted C. 1-12 Hydrocarbon group, provided that the hydrocarbon group is not a tertiary hydrocarbon group; C 1-12 Hydrothiolated group; C 1-12 Hydroxyl group; or C 2-12 Haloalkoxy group, wherein at least two carbon atoms separate the halogen and oxygen atoms; R 1 R 2 R 3 and R 4 Each time it appears independently, it is hydrogen; halogen; C. 1-12 Hydrocarbon group, provided that the hydrocarbon group is not a tertiary hydrocarbon group; C 1-12 Hydrothiolated group; C 1-12 Hydroxyl group; or C 2-12 Haloalkoxy group, wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y represent the relative molar ratio of aryl ether units, where x and y are each independently from 0 to 50, provided that the sum of x and y is at least 2; and e is the number of moles of aryl ether units. R 5a Each time it appears, it is Q independently. 1a or (C) 1-6 (Hydrocarbon group)(C) 1-6 (Hydrocarbon group) aminomethylene; R 5b Each time it appears, it is Q independently. 1b or (C) 1-6 (Hydrocarbon group)(C) 1-6 (Hydrocarbon group) aminomethylene; The condition is that the terminated poly(arylene ether) copolymer comprises: At least one repeating unit, where Q 1a It is C 1-12 Primary or secondary alkyl groups, and Q 1b It is unreplaced C 6-12 Aryl, At least one end unit, wherein R 5a It is C 1-12 Primary or secondary alkyl groups, and R 5b It is unreplaced C 6-12 Aryl, or Their combination; Y 1 It is any one or more of the following divalent linking groups: in, R a R b and R e Each time it appears, it is independently hydrogen or carbon. 1-12 hydrocarbon group or C 1-6 Hydroxyl group, optionally wherein R a and R b Together is C 4-8 Cycloalkylene R f Each time it appears, it is C independently. 1-6 Hydroxyl group, R g Each time it appears, it is independently hydrogen or carbon. 1-12 hydrocarbon group or C 1-12 Halogenated hydrocarbon groups, and n′ is between 5 and 50; z is 0 or 1; and R is independent each time it appears. -Y 2 -R 5 、 in, Y 2 It is a divalent linker having one of the following formulas. in, R c and R d Each time it appears, it is independently either hydrogen or carbon. 1-12 alkyl, R 5 It is a C group containing an epoxide, a cyanate ester, or optionally substituted with one or two carboxylic acid groups. 1-12 hydrocarbon group, R 6 R 7 and R 8 Each time it appears, it is independently hydrogen or carbon. 1-18 hydrocarbon group, C 2-18 Hydroxyl carbonyl, nitrile, formyl, carboxylic acid, imine ester or thiocarboxylic acid, and R 9 R 10 R 11 R 12 and R 13 Each time it appears, it is independently hydrogen, halogen, or carbon. 1-12 Alkyl, C 2-12 alkenyl, hydroxyl, amino, maleimide, carboxylic acid, or C 2-20 Alkyl esters; and R x and R y Each is independently either an R or a hydrogen atom, provided that R is an R. x and R y At least one of them is not a hydrogen atom.

2. The end-capped poly(arylene ether) copolymer according to claim 1, wherein, The terminated poly(arylene ether) copolymer has an average of 1.1 to 2 reactive end groups per molecule.

3. The end-capped poly(arylene ether) copolymer according to claim 1 or 2, wherein the end-capped poly(arylene ether) copolymer is derived from the reaction of a dihydric phenol and a monohydric phenol, wherein the monohydric phenol comprises 2-(alkyl)-6-(aryl)phenol.

4. The end-capped poly(arylene ether) copolymer according to claim 1 or 2, wherein, In the presence of a catalyst composition, the terminated poly(arylene ether) copolymer is derived from the oxidative polymerization of a diphenol and a monophenol comprising 2-(alkyl)-6-(aryl)phenol.

5. The end-capped poly(aryl ether) copolymer according to claim 1, wherein, Q 1a Each time it appears, it is C independently. 1-12 Primary alkyl groups; Q 1b Each time it appears, it is C independently. 1-12 Alkyl or C 6-12 Aryl; Q 2 It is hydrogen; and R 1 R 2 R 3 and R 4 Each is independently hydrogen, halogen, or C. 1-12 Alkyl; or hydrogen or C 1-6 alkyl.

6. The end-capped poly(aryl ether) copolymer according to claim 1 or 2, wherein, At least one repeating unit is derived from a monohydric phenol of the following formula: Among them, Q 1a It is C 1-6 Primary alkyl group, Q 1b It is an unsubstituted phenyl group, and Q 2 As defined in claim 1.

7. The end-capped poly(aryl ether) copolymer according to claim 1 or 2, wherein, The terminated poly(arylene ether) copolymer is of formula (2a): Among them, Q 1a Q 1b Q 2 R 1 R 2 R 5a R 5b R x R y x and y are as defined in claim 1; And among them, R 1 and R 2 Each is independently hydrogen or C 1-6 alkyl.

8. The end-capped poly(aryl ether) copolymer according to claim 1 or 2, wherein, The terminated poly(arylene ether) copolymer is of formula (2b): Among them, R 1 R 2 R 6 To R 8 R 5a R 5b Q 1a Q 1b Q 2 x and y are as defined in claim 1.

9. The end-capped poly(arylene ether) copolymer according to claim 8, wherein, The terminated poly(arylene ether) copolymer is derived from: copolymerization of tetramethylbisphenol A and 2-methyl-6-phenylphenol to form an unterminated poly(arylene ether) copolymer, and then terminating the unterminated poly(arylene ether) copolymer with methacrylic anhydride to form the terminated poly(arylene ether) copolymer.

10. A method for forming a capped poly(arylene ether) copolymer according to any one of claims 1 to 9, the method comprising oxidizing a copolymer of 2-(alkyl)-6-(aryl)phenol and a diphenol in a solvent in the presence of a catalyst composition.

11. The method of claim 10, further comprising reacting the capping agent with an uncapped poly(aryl ether) copolymer containing phenolic end groups, provided that a reaction mixture comprising the capped poly(aryl ether) copolymer is effectively provided.

12. The method according to claim 10 or 11, further comprising oxidizing the copolymerization of the 2-(alkyl)-6-(aryl)phenol and the diphenol in the solvent in the presence of the catalyst composition to provide a reaction product comprising an uncapped poly(aryl ether) copolymer, wherein, The solvent was not removed from the reaction product before reacting with the capping agent.

13. The method according to claim 10 or 11, wherein, During the oxidative copolymerization process, there is another monohydric phenol that is different from the 2-(alkyl)-6-(aryl)phenol.

14. A curable thermosetting composition comprising a capped poly(arylene ether) copolymer according to claim 1 or 2.

15. An article derived from the curable thermosetting composition of claim 14, wherein, The article is a composite material, foam, fiber, layer, encapsulant, adhesive, sealant, molded part, prepreg, shell, casting, laminate, or combination thereof.

16. An article derived from the curable thermosetting composition of claim 14, wherein the article is a metal foil laminate, an electronic composite material, a structural composite material, or a combination thereof.

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