WO2008036454A1

WO2008036454A1 - Poly (arylene ether) copolymer

Info

Publication number: WO2008036454A1
Application number: PCT/US2007/073560
Authority: WO
Inventors: Gary William Yeager; Joshua Stone
Original assignee: Sabic Innovative Plastics Ip B.V.
Priority date: 2006-09-21
Filing date: 2007-07-16
Publication date: 2008-03-27

Abstract

A poly(arylene ether) copolymer is formed by oxidative copolymerization of monomers including 2,6-dimethylphenol and a phenyl-substituted monohydric phenol having a particular structure. In some instances, the monomers also include 2- methylphenol and/or 2,2-bis(3,5-dimethyl-4-hydroxy)propane. The poly(arylene ether) copolymer is much more soluble than a homopolymer of 2,6-dimethylphenol, and it can be dissolved at room temperature in a wide variety of solvents. The resulting solutions can be used to conveniently add the poly(arylene ether) copolymer to a thermoset composition.

Description

POLY(ARYLENE ETHER) COPOLYMER

BACKGROUND OF THE INVENTION

Thermoset resins are materials that cure to form very hard plastics. These materials that can be used in a wide variety of consumer and industrial products. For example, thermosets are used in protective coatings, adhesives, electronic laminates (such as those used in the fabrication of computer circuit boards), flooring and paving applications, glass fiber-reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components). Relative to other types of plastics, cured thermosets are typically brittle. It would therefore be desirable to retain the good properties of thermosets and also reduce their brittleness.

Poly(arylene ether) resins, sometimes called polyphenylene ethers, have been disclosed as additives to reduce the brittleness (improve the toughness) of cured thermosets. For example, it is known to combine certain poly(arylene ether) resins with thermosets resins such as epoxies, cyanate esters, maleimides, acrylates, and benzoxazine resins. These poly(arylene ether)-containing compositions are often processed in solvents to reduce the viscosity of the curable composition and to enhance impregnation of the curable composition into fillers and/or reinforcements. When a solvent is used, it would be preferable to use a non-chlorinated hydrocarbon solvent. However, non-chlorinated hydrocarbon solvents such as

JV-methyl-2-pyrrolidone (NMP), toluene, and xylene are not ideal for this purpose because they produce phase-separated mixtures with poly(2,6-dimethyl-l,4-phenylene ether) at room temperature. Improvements in the miscibility of poly(arylene ether)s and solvents have been obtained by processing curable compositions containing them at elevated temperatures as described, for example, in Japanese Patent Application Publication No. JP 06-220226 A of Katayose et al. However, it would be desirable to avoid the use of elevated temperatures because they are associated with increased solvent flammability, increased solvent emissions, and increased energy costs. Another method of improving the miscibility of poly(arylene ether)s and solvents has been to reduce the molecular weight of the poly(arylene ether). However, reducing the poly(arylene ether) molecular weight reduces the heat resistance and toughness of the ultimate cured composition. There is therefore a need to develop materials and methods providing homogeneous poly(arylene ether) solutions in non-halogenated solvents such as NMP, toluene, and xylene at room temperature.

BRIEF DESCRIPTION OF THE INVENTION

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising: 2,6-dimethylphenol; and a phenyl- substituted monohydric phenol having the structure

wherein q is 0 or 1, and R¹² and R¹³ are independently hydrogen or Ci-C₆ alkyl; wherein when q is 0, the monomers further comprise 2-methylphenol, 2,2-bis(3,5- dimethyl-4-hydroxy)propane, or a mixture thereof.

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 90 weight percent of 2,6- dimethylphenol and about 10 to about 99 weight percent of 2-methyl-6-( 1 -phenylethyl)phenol.

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 90 weight percent of 2,6-dimethylphenol and about 10 to about 99 weight percent of 2-methyl-6-( 1 -phenylethyl)phenol.

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 89 weight percent of 2,6- dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 89 weight percent of 2-methylphenol. One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 89 weight percent of 2-methylphenol.

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 89 weight percent of 2,6- dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 20 weight percent of 2,2-bis(3,5- dimethyl-4-hydroxypheny)propane.

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 20 weight percent of 2,2-bis(3,5- dimethyl-4-hydroxypheny)propane.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent selected from the group consisting of C₃-Cs ketones, C₄-Cs N,N-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C1-C3 chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C₃-Cs ketone; wherein the poly(arylene ether) has a solubility in acetone of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and acetone.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C₄-Cg Λ/,jV-dialkylamide; wherein the poly(arylene ether) has a solubility in N,N- dimethylformamide of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and Λ/,N-dimethylformamide.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C₄-Ci₆ dialkyl ether; wherein the poly(arylene ether) has a solubility in ethylene glycol monomethyl ether of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethylene glycol monomethyl ether.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C₆-Ci₂ aromatic hydrocarbon; wherein the poly(arylene ether) has a solubility in toluene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and toluene.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C1-C3 chlorinated hydrocarbon; wherein the poly(arylene ether) has a solubility in trichloroethylene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and trichloroethylene.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C₃-C₆ alkyl alkanoate; wherein the poly(arylene ether) has a solubility in ethyl acetate of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethyl acetate.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent comprising a C₂-C₆ alkyl cyanide; wherein the poly(arylene ether) has a solubility in acetonitrile of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and acetonitrile.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent selected from the group consisting of C₃-Cg ketones, C₄-Cg Λ/,iV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 10 to about 700 grams per kilogram of composition at 25⁰C. One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; wherein the monomers are free of ethylenic unsaturation; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from the group consisting of acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof, and optionally, a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; wherein the monomers are free of ethylenic unsaturation; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and a solvent selected from the group consisting of acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C. One embodiment is a composition, comprising: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl- 6-phenylphenol, and mixtures thereof; wherein the monomers are free of ethylenic unsaturation; wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; about 20 to about 80 weight percent of a solvent selected from the group consisting of acetone, methyl ethyl ketone, JV-methyl-2- pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, consisting of: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl- 6-phenylphenol, and mixtures thereof, and optionally, about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof; wherein the monomers are free of ethylenic unsaturation; wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; about 20 to about 80 weight percent of a solvent selected from the group consisting of acetone, methyl ethyl ketone, N-methyl-2- pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, comprising: adjusting the temperature of a solvent to a temperature in a range from about 3O⁰C to the atmospheric boiling point of the solvent; wherein the solvent is selected from the group consisting of C₃-Cs ketones, C₄-Cg Λ/,jV-dialkylamides, C₄-C ₁₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof; combining the temperature-adjusted solvent with a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and agitating the combined solvent and poly(arylene ether) to form the poly(arylene ether) composition; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent selected from the group consisting of C₃-Cg ketones, C₄-Cg Λ/,JV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, Ci-C₃ chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C₃-Cs ketone; wherein the poly(arylene ether) has a solubility in methyl ethyl ketone of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and methyl ethyl ketone.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C₄-Cs Λ/,jV-dialkylamide; wherein the poly(arylene ether) has a solubility in JV-methyl-2- pyrrolidone of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and JV-methyl-2-pyrrolidone.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C₄-Ci₆ dialkyl ether; wherein the poly(arylene ether) has a solubility in ethylene glycol monomethyl ether of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethylene glycol monomethyl ether.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C₆-Ci₂ aromatic hydrocarbon; wherein the poly(arylene ether) has a solubility in toluene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and toluene. One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C1-C3 chlorinated hydrocarbon; wherein the poly(arylene ether) has a solubility in trichloroethylene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and trichloroethylene.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C₃-C₆ alkyl alkanoate; wherein the poly(arylene ether) has a solubility in ethyl acetate of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethyl acetate.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent comprising a C₂-C₆ alkyl cyanide; wherein the poly(arylene ether) has a solubility in acetonitrile of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and acetonitrile.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent selected from the group consisting of C3-C8 ketones, C₄-Cs N,N-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C₁-C₃ chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 10 to about 700 grams per kilogram of composition at 25⁰C.

One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6-allylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from the group consisting of methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6-allylphenol, and mixtures thereof, and optionally, about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6- dimethylphenyl)propane, 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4- bis(4-hydroxyphenyl)pentanoic acid, 2,2 ' 6,6 ' -tetramethyl-3 ,3 '5,5' -tetrabromo-4,4 ' - biphenol, 2,2'5,5'-tetramethyl-4,4'-biphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from the group consisting of methyl ethyl ketone, Λ/-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, comprising: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 96 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 2 to about 30 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6- allylphenol, and mixtures thereof, and about 2 to about 68 weight percent of a third monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl- 6-phenylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol, the second monohydric phenol, and third monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and about 20 to about 80 weight percent of a solvent selected from the group consisting of methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, consisting of: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 96 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 2 to about 30 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6- allylphenol, and mixtures thereof, about 2 to about 68 weight percent of a third monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl- 6-phenylphenol, and mixtures thereof, and optionally, about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol, the second monohydric phenol, and third monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and about 20 to about 80 weight percent of a solvent selected from the group consisting of methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

A method of preparing a poly(arylene ether) composition, comprising: adjusting the temperature of a solvent to a temperature in a range from about 3O⁰C to the atmospheric boiling point of the solvent; wherein the solvent is selected from the group consisting of C₃-Cs ketones, C₄-Cs Λ/,Λ/-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof; combining the temperature- adjusted solvent with a poly(arylene ether) that is the product of oxidative polymerization of monomers a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and agitating the combined solvent and poly(arylene ether) to form the poly(arylene ether) composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C.

Other embodiments are described in detail below.

DETAILED DESCRIPTION OF THE INVENTION

In the course of research on poly(arylene ether) copolymers and their solubility properties, the present inventors have discovered that particular poly(arylene ether) copolymers exhibit markedly improved solubility in non-halogenated solvents compared to poly(2,6-dimethyl-l,4-phenylene ether)s of comparable molecular weight. In particular, these particular poly(arylene ether) copolymers enable the preparation of concentrated solutions at room temperature in non-halogenated solvents. These poly(arylene ether) copolymers also eliminate the need to handle solutions at elevated temperature. Furthermore, these solutions eliminate the need to reduce the molecular weight of the poly(arylene ether) - and thereby sacrifice physical and thermal properties - in order to improve solubility.

The poly(arylene ether) exhibiting improved solubility may comprise ethylenic unsaturation, or it may be free of ethylenic unsaturation. Both types of poly(arylene ether) compositions are useful in the preparation of thermoset compositions. In the embodiment in which the poly(arylene ether) is free of ethylenic unsaturation, the composition comprises a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent selected from the group consisting of C₃-Cs ketones, C₄-Cg Λ/,JV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C₃-C₆ chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C. In the embodiments in which the poly(arylene ether) comprises ethylenic unsaturation, the composition comprises a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent selected from the group consisting of C₃-C₈ ketones, C₄-C₈ Λ/,JV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C₃-C₆ chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C. In some embodiments, the solvent is an aromatic hydrocarbon comprising ethylenic unsaturation, such as, for example, styrene. The solubility of the poly(arylene ether) in the composition is at least 10 grams per kilogram of composition at 25⁰C. In some embodiments, the solubility is at least 20 grams per kilogram, or at least 50 grams per kilogram, or at least 100 grams per kilogram, or at least 200 grams per kilogram, all at 25⁰C. In some embodiments, the solubility is less than or equal to 700 grams per kilogram, or less than or equal to 500 grams per kilogram, or less than or equal to 300 grams per kilogram, all at 25⁰C. The solubility of the poly(arylene ether) is determined according to a modified version of ASTM D3132-84, Standard Test Method of Solubility Range of Resins and Polymers (Reapproved 1996; Withdrawn 2005). Rather than testing solubility of a polymer resin in a variety of solvent compositions, as in ASTM D3132-84, solubility in a single solvent composition may be determined. For example, to determine whether the solubility of the poly(arylene ether) in the composition is at least 10 grams per kilogram of composition at 25⁰C, the following procedure may be used. Poly(arylene ether) (0.05 gram) is combined with solvent (4.95 grams) in a 15 milliliter cylindrical clear glass vial at 25⁰C. The vial is then closed with a screw cap and tumbled or rotated end-over-end at about one to five revolutions per minute for 24 hours at 25⁰C. At the end of 24 hours, the contents of the vial are visually inspected and classified as a complete solution (a single, clear liquid phase with no distinct solid or gel particles), a borderline solution (cloudy or turbid but without distinct phase separation), or insoluble (two phases; either a liquid with separate gel or solid phase or two separate liquids). If the contents of the vial are classified as a complete solution, then the poly(arylene ether) has a solubility of at least 10 grams per kilogram at 25⁰C.

In some embodiments, most or all of the poly(arylene ether) is dissolved in the composition at room temperature. Thus, in some embodiments, at least 90 weight percent, or at least 95 weight percent, or at least 98 weight percent, or at least 99 weight percent, of the poly(arylene ether) is soluble in the composition at 25⁰C. The weight percent of poly(arylene ether) dissolved in the composition at room temperature may be determined using a modified version of ASTM D 1766-05, Standard Test Method for Rubber Chemicals — Solubility. For example, rather than intentionally adding excess solid polymer, as in ASTM D 1766-05, poly(arylene ether) may be used at a specified concentration, such as 10 grams per kilogram at 25⁰C. Thus, 0.5 grams of poly(arylene ether) may be combined with 49.5 grams of solvent at 25⁰C in a 100 milliliter glass screw-cap vial. The vial is then placed in a mechanical shaker for a minimum of four hours. The vial is then held at 25⁰C with occasional shaking for an additional four hours. Then, any visible solids are allowed to settle. (An optional centrifuging step may be added to separate suspended solid.) A 25 -milliliter portion of the solution is removed by pipetting and transferred to a tared, ground glass, low- form, 50 milliliter covered weighing bottle. The mass of the bottle plus solution is determined. The solvent is then evaporated at a temperature less than or equal to HO⁰C until a constant mass is obtained. The mass of the weighing bottle plus residue is determined. If the initial bottle tare mass is A, and the mass of bottle plus solution is B, and the mass of the bottle plus residue is C, then the solubility of the poly(arylene ether) in grams per kilogram of composition is

= [(C - A)/(B - C)] x 1000

and the percent solubility is 100 times the actual solubility in grams per kilogram of composition divided by the theoretical solubility of 10 grams per kilogram.

The poly(arylene ether) is the product of oxidative polymerization of monomers comprising a first monohydric phenol and a second monohydric phenol. The first monohydric phenol has identical substituents in the 2- and 6-positions of the phenol ring, where ring substituents are as numbered as shown below with the phenolic hydroxy group in the 1 -position.

In some embodiments, the first monohydric phenol has the formula

wherein Z¹ and Z² are the same and may be halogen, unsubstituted or substituted C₁-C₁₂ hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C₁-C₁₂ hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Z³ and Z⁴ are the same or different and each independently may be hydrogen, halogen, unsubstituted or substituted C₁-C₁₂ hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C₁-C₁₂ hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C₂-C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms. As used herein, the term "hydrocarbyl", whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as "substituted", may contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue may also contain halogen atoms, nitro groups, cyano groups, carbonyl groups, carboxylic acid groups, amino groups, amide groups, sulfonyl groups, sulfoxyl groups, sulfonamide groups, hydroxyl groups, alkoxyl groups, or the like, or it may contain heteroatoms within the backbone of the hydrocarbyl residue.

In some embodiments, the first monohydric phenol is selected from the group consisting of 2,6-dimethylphenol, 2,6-diphenylphenol, and mixtures thereof. In some embodiments, the first monohydric phenol is 2,6-dimethylphenol. The second monohydric phenol has different substituents in the 2- and 6- positions. In some embodiments, the second monohydric phenol is free of ethylenic unsaturation and has the formula

wherein each Z⁵, Z⁶, Z⁷, and Z⁸ is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, Ci-Ci₂ hydrocarbyloxy, or Ci-Ci₂ halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, with the proviso that Z⁵ and Z⁶ are different, and with the proviso that Z⁵, Z⁶, Z⁷, and Z⁸ are free of ethylenic unsaturation.

In the embodiments in which the second monohydric phenol is free of ethylenic unsaturation, it may be, for example, 2-methylphenol, 2-ethylphenol, 2-(l- methylethyl)phenol, 2(l-methylpropyl)phenol, 2(l-methylbutyl)phenol, 2(1- methylpentyl)phenol, 2-(l-methylheptyl)phenol 2-(l-methylundecyl)phenol, 2- propylphenol, 2-cyclohexylphenol, 2-cyclopentylphenol, 2-cyclopropylphenol, 2-methyl-6-phenylphenol, 2-methyl-6-benzylphenol, 2-( 1 -phenylethyl)phenol, 2-methyl-6-( 1 -phenylethyl)phenol, 2-ethy 1-6-methylphenol, 2-methyl-6-( 1 - methylethyl)phenol, 2-methyl-6-( 1 -methylpropyl)phenol, 2-methyl-6-( 1 - methylbutyl)phenol, 2-methyl-6-( 1 -methylpentyl)phenol, 2-methyl-6-( 1 - methylheptyl)phenol, 2-methyl-6-(l -methylundecyl)phenol, 2-methyl-6- propylphenol, 2-cyclohexyl-6-methylphenol, 2-cyclopentyl-6-methylphenol, 2- cyclopropyl-6-methylphenol, 2-methyl-6-methoxyphenol, 2-methyl-5- isopropylphenol, 2-isopropyl-5-methylphenol, 2,5-dimethylphenol, 3- pentadecylphenol, and mixtures thereof. In some embodiments, the second monohydric phenol comprises ethylenic unsaturation. As used herein, the term "ethylenic unsaturation" refers collectively to aliphatic carbon-carbon double bonds and aliphatic carbon-carbon triple bonds. In some embodiments, the second monohydric phenol comprises at least one ethylenically unsaturated substituent bound directly to the phenol aromatic ring, wherein the ethylenically unsaturated substituent is

wherein n is 0 or 1, R⁷ and R⁸ and R⁹ are each independently is hydrogen or Ci-C₆ alkyl, R¹⁰ is Ci-Ci₂ hydrocarbylene, and X is -C(=O)-, -O- , -N(R¹¹)-, -C(=O)O-, or -C(=O)N(R^π)-, wherein R¹¹ is hydrogen, methyl, vinyl, or allyl. When the second monohydric phenol comprises ethylenic unsaturation, it may comprise more than one ethylenically unsaturated substituent.

In some embodiments, the second monohydric phenol comprises, in addition to the at least one ethylenically unsaturated substituent, at least one directly bound substituent such as halogen, unsubstituted or substituted C1-C12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, Ci-Ci₂ hydrocarbylthio, Ci-Ci₂ hydrocarbyloxy, or C₂-C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.

Suitable second monohydric phenols comprising an ethylenically unsaturated substituent include, for example, 2-vinylphenol, 2-allylphenol, 2-methyl-6- vinylphenol, 2-methyl-6-allylphenol, 2-(Λ/,Λ/-diallylaminomethyl)phenol, 2-(N,N- diallylpropionamido)phenol, 2-methyl-6-allyloxyphenol, and mixtures thereof. In some embodiments, the second monohydric phenol is 2-allylphenol, 2-methyl-6- allylphenol, or a mixture thereof.

When the second monohydric phenol comprises ethylenic unsaturation, the monomers may comprise, in addition to the first monohydric phenol and the second monohydric phenol, a third monohydric phenol different from the first monohydric phenol and the second monohydric phenol. The third monohydric differs from the first monohydric phenol in that it has different substituents in the 2- and 6- positions. The third monohydric differs from the second monohydric phenol in that it lacks ethylenic unsaturation. In some embodiments, the third monohydric phenol has the formula

wherein Z⁹, Z¹⁰, Z¹¹, and Z¹² each independently may be hydrogen, halogen, unsubstituted or substituted Ci -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C₁-C₁₂ hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C₁-C₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, with the proviso that Z⁹ and Z¹⁰ are different. When employed, the third monohydric phenol may be used in an amount of about 1 to about 89 weight percent, based on the total weight of the phenolic monomers. Within this range, the third monohydric phenol amount may be at least about 10 weight percent, or at least about 20 weight percent. Also within this range, the third monohydric phenol amount may be up to about 70 weight percent, or up to about 50 weight percent.

In addition to the monomers discussed above, the monomers may further comprise a dihydric phenol having the formula

wherein each occurrence of R¹ and R² is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted Ci -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, Ci -C 12 hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C₁-C₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; z is 0 or 1 ; and Y has a structure selected from the group consisting of

R³ O S O O R⁴

-o- -N- -c- -c- -s- -s- , and -c-

O R⁵

wherein each occurrence of R³ is independently selected from the group consisting of hydrogen and Ci-Ci₂ hydrocarbyl, and each occurrence of R⁴ and R⁵ is independently selected from the group consisting of hydrogen, C₁-C₁₂ hydrocarbyl, and Ci-C₆ hydrocarbylene wherein R⁴ and R⁵ collectively form a C₄-C₁₂ alkylene group.

In some embodiments, the dihydric phenol may be 3,3',5,5'-tetramethyl-4,4'- biphenol, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)methane, 1 , 1 -bis(4- hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1 , 1 -bis(4- hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)-n-butane, bis(4- hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1- bis(4-hydroxy-3-methylphenyl)cyclohexane, l,l-bis(4-hydroxy-3,5- dimethylphenyl)cyclopentane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cycloheptane, 1 , 1 -bis(4-hydroxy-3,5- dimethylphenyl)cycloheptane, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cy clooctane, 1,1- bis(4-hydroxy-3 ,5-dimethylphenyl)cyclooctane, 1 , 1 -bis(4-hydroxy-3- methylphenyl)cyclononane, l l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclononane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclodecane, 1 , 1 -bis(4-hydroxy-3,5- dimethylphenyl)cyclodecane, 1 , 1 -bis(4-hydroxy-3 -methylpheny^cycloundecane, 1,1- bis(4-hydroxy-3 ,5-dimethylphenyl)cycloundecane, 1 , 1 -bis(4-hydroxy-3- methylphenyl)cyclododecane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 1 , 1 -bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-2,6- dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1 , 1 -bis(4- hydroxyphenyl)cyclopentane, l,l-bis(4-hydroxyphenyl)cyclohexane, or a combination thereof.

When employed, the dihydric phenol may be used in an amount such that the weight ratio of total monohydric phenol to dihydric phenol is about 3 to about 110. Within this range, the weight ratio may be at least about 5, or at least about 7. Also within this range, the ratio may be up to about 50, or up to about 25.

In the embodiments in which the phenolic monomers are free of ethylenic unsaturation, they may comprise about 1 to about 90 weight percent of the first monohydric phenol and about 10 to about 99 weight percent of the second monohydric phenol. The weight percent of the first monohydric phenol may be at least about 5, or at least about 10, or at least about 20, or at least about 30. The weight percent of the first monohydric phenol may be up to about 80, or up to about 70. The weight percent of the second monohydric phenol may be at least about 20, or at least about 30, or at least about 40. The weight percent of the second monohydric phenol may be up to about 95, or up to about 90, or up to about 80, or up to about 70. In this context, all weight percents are based on the total weight of the monomers. In the embodiments in which the second phenolic monomer comprises ethylenic unsaturation, the phenolic monomers may comprise about 5 to about 95 weight percent of the first monohydric phenol and about 5 to about 95 weight percent of the second monohydric phenol, based on the total weight of phenolic monomers. Within the above range, the first phenolic monomer amount may be at least about 10 weight percent, or at least about 20 weight percent. Also within the above range, the first phenolic monomer amount may be up to about 90 weight percent, or up to about 80 weight percent. Within the above range, the second phenolic monomer amount may be at least about 10 weight percent, or at least about 20 weight percent. Also within the above range, the second phenolic monomer amount may be up to about 90 weight percent, or up to about 80 weight percent.

In the embodiments in which the second phenolic monomer comprises ethylenic unsaturation, the poly(arylene ether) necessarily comprises ethylenic unsaturation. In these embodiments, the composition may, optionally, further comprise a poly(arylene ether) free of ethylenic unsaturation.

The poly(arylene ether) prepared by oxidative copolymerization of the monomers may have an intrinsic viscosity of about 0.05 to about 1.5 deciliters per gram measured in chloroform at 25⁰C. Within this range, the intrinsic viscosity may be at least about 0.1 deciliter per gram, or at least about 0.15 deciliter per gram, or at least about 0.2 deciliter per gram, or at least about 0.3 deciliter per gram. Also within this range, the intrinsic viscosity may be up to about 1 deciliter per gram, or up to about 0.6 deciliter per gram.

In some embodiments, the poly(arylene ether) has a number average molecular weight of about 10,000 to about 50,000 atomic mass units. In one embodiment, the poly(arylene ether) has a number average molecular weight of about 15,000 to about 40,000 atomic mass units. In one embodiment, the poly(arylene ether) has a number average molecular weight of about 20,000 to about 30,000 atomic mass units. One advantage of the present composition is that it may exhibit lower viscosity than a composition containing a poly(2,6-dimethyl-l,4-phenylene ether) of the same molecular weight and in the same amount. Some embodiments are directed to particular poly(arylene ether) copolymers. Thus, one embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising: 2,6-dimethylphenol; and a phenyl- substituted monohydric phenol having the structure

wherein q is 0 or 1, and R¹² and R¹³ are independently hydrogen or Ci-C₆ alkyl; wherein when q is 0, the monomers further comprise 2-methylphenol, 2,2-bis(3,5- dimethyl-4-hydroxy)propane, or a mixture thereof. In some embodiments, q is 0. In some embodiments, q is 1. In some embodiments, q is 1, and R¹² and R¹³ are independently hydrogen or methyl. In some embodiments, q is 1, R¹² is hydrogen, and R¹³ is methyl. The copolymer may have a number average molecular weight of about 2,000 to about 50,000 atomic mass units, specifically about 4,000 to about 50,000 atomic mass units, more specifically about 7,000 to about 50,000 atomic mass units, even more specifically about 10,000 to about 50,000 atomic mass units. In some embodiments, the monomers comprise about 1 to about 90 weight percent of 2,6-dimethylphenol and about 10 to about 99 weight percent of the phenyl-substituted monohydric phenol, wherein all weight percents are based on the total weight of the monomers. The amount of 2,6-dimethylphenol may be at least about 20 weight percent, or at least about 40 weight percent, or at least about 60 weight percent, with correspondingly lower amounts of the phenyl-substituted monohydric phenol. In some embodiments, q is 0 and the monomers comprise about 1 to about 89 weight percent of 2,6-dimethylphenol, about 10 to about 98 weight percent of the phenyl- substituted monohydric phenol, and about 1 to about 89 weight percent of 2- methylphenol, 2,2-bis(3,5-dimethyl-4-hydroxy)propane, or a mixture thereof, wherein all weight percents are based on the total weight of the monomers. In these embodiments, the amount of the 2-methylphenol may be at least about 10 weight percent, or at least about 20 weight percent, or at least about 30 weight percent, or at least about 40 weight percent, or at least about 50 weight percent, with corresponding reductions in the amount of 2,6-dimethylphenol. Also in these embodiments, the amount of the 2,2-bis(3,5-dimethyl-4-hydroxy)propane may be at least about 5 weight percent, or at least about 10 weight percent, or at least about 15 weight percent, with corresponding reductions in the amount of 2,6-dimethylphenol. The poly(arylene ether) copolymer may be, for example, a random copolymer, a block copolymer (including a tapered block copolymer), or a graft copolymer. Illustrative preparations of poly(arylene ether) copolymers are presented in the working examples below. It will be understood that the poly(arylene ether) copolymers include not only the direct products of oxidative copolymerization, but also derivatives thereof in which the terminal hydroxy groups of the direct products of oxidative copolymerization are "capped" by reaction with a capping agent as described, for example, in U.S. Patent Nos. 6,352,782 Bl and 6,627,704 B2 to Yeager et al, 6,384,176 Bl to Braat et al, 6897282 B2 to Freshour et al., 6,962,965 B2 to Yeager, and U.S. Patent Application Publication Nos. US 2005/0075462 Al of Zarnoch et al., and US 2006/0041086 Al of Birsak et al.

One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 90 weight percent of 2,6- dimethylphenol and about 10 to about 99 weight percent of 2-methyl-6-(l-phenylethyl)phenol. One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 90 weight percent of 2,6-dimethylphenol and about 10 to about 99 weight percent of 2-methyl-6-(l-phenylethyl)phenol. One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 89 weight percent of 2-methylphenol. One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 89 weight percent of 2-methylphenol. One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 89 weight percent of 2,6- dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 20 weight percent of 2,2-bis(3,5- dimethyl-4-hydroxypheny)propane. One embodiment is a poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 20 weight percent of 2,2- bis(3,5-dimethyl-4-hydroxypheny)propane.

In some embodiments, the poly(arylene ether) copolymer has a solubility in a solvent of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and solvent. The solvent may be, for example, acetone, Λ/,Λ/-dimethylformamide, ethylene glycol monomethyl ether, toluene, trichloroethylene, ethyl acetate, or acetonitrile. The solubility may be about 10 to about 700 grams per kilogram, specifically about 100 to about 700 grams per kilogram, more specifically about 200 to about 700 grams per kilogram, even more specifically about 400 to about 700 grams per kilogram. Solubilities greater than 700 grams per kilogram are possible, but solutions containing more than 700 grams of poly(arylene ether) per kilogram of solution often have high viscosities that make the solutions difficult to work with. In some embodiments, the solvent is acetone. In some embodiments, the solvent is Λ/,Λ/-dimethylformamide. In some embodiments, the solvent is ethylene glycol monomethyl ether. In some embodiments, the solvent is toluene. In some embodiments, the solvent is trichloroethylene. In some embodiments, the solvent is ethyl acetate. In some embodiments, the solvent is acetonitrile.

In some embodiments, the composition comprises a solvent in addition to the poly(arylene ether). In these embodiments, the solvent may be selected from C₃-Cg ketones, C₄-Cg Λ/,JV-dialkylamides (including lactams), C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C₁-C₃ chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂- C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof. The carbon number ranges refer to the total number of carbon atoms in the solvent molecule. For example, a C₄-Ci₆ dialkyl ether has 4 to 16 total carbon atoms, and the two alkyl groups may be the same or different. As another example, the 2 to 6 carbons in the "C₂-C₆ alkyl cyanides" include the carbon atom in the cyanide group. Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. Specific JV,iV-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, JV-methyl-2-pyrrolidone (Chemical Abstracts Service Registry No. 872-50-4), and the like, and mixtures thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, and the like, and mixtures thereof. The dialkyl ether may, optionally, further include one or more ether oxygen atoms within the alkyl groups and one or more hydroxy group substituents on the alkyl groups. The aromatic hydrocarbon solvent may or may not comprise an ethylenically unsaturated solvent. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, styrene, divinylbenzenes, and the like, and mixtures thereof. The aromatic hydrocarbon solvent is preferably unhalogenated. That is, it does not include any fluorine, chlorine, bromine, or iodine atoms. Specific C₃-C₆ alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and the like, and mixtures thereof. Specific C₂-C₆ alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, and mixtures thereof. Specific C₂-C₆ dialkyl sulfoxides include, for example, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide, and the like, and mixtures thereof. In some embodiments, the solvent is acetone. In some embodiments, the solvent is methyl ethyl ketone. In some embodiments, the solvent is JV-methyl-2-pyrrolidone. In some embodiments, the solvent is ethylene glycol monomethyl ether. In some embodiments, the solvent is toluene.

When the solvent is an aromatic hydrocarbon solvent containing ethylenic unsaturation, such as styrene or divinyl benzene, the compositions may, optionally, include a polymerization inhibitor. Suitable polymerization inhibitors are known in the art and include, for example, diazoaminobenzene, phenylacetylene, sym- trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensates, iV,jV-dibutyl-o- phenylenediamine, JV-butyl-/?-aminophenol, 2,4,6-triphenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinones, p-methoxyphenol, t- butylhydroquinone, Ci-C₆-alkyl-substituted catechols, dialkylhydroquinone, 2,4,6- dichloronitrophenol, halogen-ortho-nitrophenols, alkoxyhydroquinones, mono- and di- and polysulfides of phenols and catechols, thiols, oximes and hydrazones of quinone, phenothiazine, dialkylhydroxylamines, and the like, and mixtures thereof. In some embodiments, the curing inhibitor comprises benzoquinone, hydroquinone, 4-t- butylcatechol, or a mixture thereof.

The composition components may be used in widely ranging amounts. In some embodiments, the composition comprises about 1 to about 70 weight percent of the poly(arylene ether) and about 30 to about 99 weight percent of the solvent. Within the above range, the composition may comprise the poly(arylene ether) in an amount of at least about 10 weight percent, or at least about 20 weight percent, or at least about 30 weight percent. Also within the above range, the composition may comprise the poly(arylene ether) in an amount of up to about 60 weight percent, or up to about 50 weight percent, or up to about 40 weight percent. Within the above range, the composition may comprise the solvent in an amount of at least about 40 weight percent, or at least about 50 weight percent, or at least about 60 weight percent. Also within the above range, the composition may comprise the solvent in an amount of up to about 90 weight percent, or up to about 80 weight percent, or up to about 70 weight percent.

The composition comprising the poly(arylene ether) and the solvent is useful for incorporating the poly(arylene ether) into a thermoset composition. Thus, in addition to the poly(arylene ether) and the solvent, the composition may, optionally, include a thermoset resin. Thermosets that may benefit from addition of the poly(arylene ether) include, for example, epoxy resins, cyanate ester resins, maleimide resins, benzoxazine resins, vinylbenzyl ether resins, alkene- or alkyne-containing monomers, arylcyclobutene resins, perfluorovinyl ether resins, oligomers and polymers with curable vinyl functionality, and combinations thereof.

The thermoset resin may be an epoxy resin. Particularly suitable epoxy resins include those described by the structure

wherein A is a an organic or inorganic radical of valence n, X is oxygen or nitrogen, m is 1 or 2 and consistent with the valence of X, R is hydrogen or methyl, n is 1 to about 1000, specifically 1 to 8, more specifically 2 or 3 or 4.

Suitable epoxies also include epoxies having the following structures

wherein each occurrence of R is independently hydrogen or methyl; each occurrence of M is independently C₁-C₁₈ hydrocarbylene optionally further comprising a member or members selected from oxirane, carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, nitrile; each occurrence of X is independently hydrogen, chloro, fluoro, bromo, C₁-C₁₈ hydrocarbyl optionally further comprising a member or members selected from carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, and nitrile; and each occurrence of B is independently a carbon-carbon single bond, Ci_Cig hydrocarbyl, C₁-C₁₂ hydrocarbyloxy, C₁-C₁₂ hydrocarbylthio, carbonyl, sulfide, sulfonyl, sulfinyl, phosphoryl, silane, or such groups further comprising a member or members selected from carboxyalkyl, carboxamide, ketone, aldehyde, alcohol, halogen, and nitrile.

Suitable epoxy resins of the present invention included those produced by the reaction of epichlorohydrin or epibromohydrin with a phenolic compound. Suitable phenolic compounds include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynapthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6- dimethylphenol) 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2 ' ,3 ,3 ' ,6,6 ' -hexamethylbiphenol, 3 ,3 ' ,5 ,5 ' -tetrabromo-2,2 '6,6 ' -tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5- dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'- isopropylidenebis(2,6-dibromophenol) (tetrabromobisphenol A), 4,4'- isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol A), 4,4'- isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(l,3- phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3- phenylphenol), 4,4'-(l,4-phenylenediisoproylidene)bisphenol (bisphenol P), 4,4'- ethylidenediphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'- thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6- dimethylphenol) 4,4'-sulfϊnyldiphenol, 4,4'-hexafluoroisoproylidene)bisphenol (Bisphenol AF), 4,4'-(l-phenylethylidene)bisphenol (Bisphenol AP), bis(4- hydroxyphenyl)-2,2-dichloroethylene (Bisphenol C), bis(4-hydroxyphenyl)methane (Bisphenol-F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-

(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (Bisphenol Z), 4,4'- (cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H- fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-l(3H)-one, l-(4- hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-lH-inden-5-ol, l-(4-hydroxy-3,5- dimethylphenyl)-l,3,3,4,6-pentamethyl-2,3-dihydro-lH-inden-5-ol, 3,3,3',3'- tetramethyl-2,2',3,3'-tetrahydro-l,l'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone (bisphenol K), tris(4-hydroxyphenyl)methane, tris(4- hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4- hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4- hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienyl bis(2-methylphenol), dicyclopentadienyl bisphenol, and the like.

Other suitable epoxy resins include Λ/-glycidyl phthalimide, Λ/-glycidyl tetrahydrophthalimide, phenyl glycidyl ether, p-butylphenyl glycidyl ether, styrene oxide, neohexene oxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethyleneglycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, bisphenol A-type epoxy compounds, bisphenol S-type epoxy compounds, resorcinol-type epoxy compounds, phenolnovolac-type epoxy compounds, ortho- cresolnovolac-type epoxy compounds, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, and phthalic acid diglycidyl ester. Also included are the glycidyl ethers of phenolic resins such as the glycidyl ethers of phenol-formaldehyde novolac, alkyl substituted phenol-formaldehyde resins including cresol-formaldehyde novolac, t-butylphenol-formaldehyde novolac, sec-butylphenol-formaldehdye novolac, tert- octylphenol-formaldehyde novolac, cumylphenol-formaldehyde novolac, decylphenol-formaldehdye novolac. Other useful epoxies are the glycidyl ethers of bromophenol-formaldehdye novolac, chlorophenol-formaldehyde novolac, phenol- bis(hydroxymethyl)benzene novolac, phenol-bis(hydroxymethylbiphenyl) novolac, phenol-hydroxybenzaldehdye novolac, phenol-dicylcopentadiene novolac, naphthol- formaldehyde novolac, naphthol-bis(hydroxymethyl)benzene novolac, naphthol- bis(hydroxymethylbiphenyl) novolac, naphthol-hydroxybenzaldehdye novolac, and naphthol-dicylcopentadiene novolac.

Also suitable as epoxy resins are the polyglycidyl ethers of polyhydric aliphatic alcohols. Examples of such polyhydric alcohols that may be mentioned are 1,4- butanediol, 1,6-hexanediol, polyalkylene glycols, glycerol, trimethylolpropane, 2,2- bis(4-hydroxy-cyclohexyl)propane, and pentaerythritol.

Further suitable epoxy resins are polyglycidyl esters which are obtained by reacting epichlorohydrin or similar epoxy compounds with an aliphatic, cycloaliphatic, or aromatic polycarboxylic acid, such as oxalic acid, adipic acid, glutaric acid, phthalic, isophthalic, terephthalic, tetrahydrophthalic or hexahydrophthalic acid, 2,6- naphthalenedicarboxylic acid, and dimerized fatty acids. Examples are diglycidyl terephthalate and diglycidyl hexahydrophthalate. Moreover, polyepoxide compounds which contain the epoxide groups in random distribution over the molecule chain and which can be prepared by emulsion copolymerization using olefmically unsaturated compounds that contain these epoxide groups, such as, for example, glycidyl esters of acrylic or methacrylic acid, can be employed with advantage in some cases.

Examples of further epoxy resins that can be used are those based on heterocyclic ring systems, for example hydantoin epoxy resins, triglycidyl isocyanurate and its oligomers, triglycidyl-p-aminophenol, triglycidyl-p-aminodiphenyl ether, tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenyl ether, tetrakis(4- glycidyloxyphenyl) ethane, urazole epoxides, uracil epoxides, and oxazolidinone- modified epoxy resins. Other examples are polyepoxides based on aromatic amines, such as aniline, for example iV,jV-diglycidylaniline, diaminodiphenylmethane and Λ/,Λ/-dimethylaminodiphenylmethane or Λ/,N-dimethylaminodiphenyl sulfone and cycloalipahtic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate, 4,4'-(l,2-epoxyethyl)biphenyl, 4,4'-di(l,2- epoxyethyl)diphenyl ether, and bis(2,3-epoxycyclopentyl)ether.

Oxazolidinone-modifϊed epoxy resins are also suitable. Compounds of this kind are known. See, for example, Angew. Makromol. Chem., vol. 44, (1975), pages 151 to 163, and U.S. Patent No. 3,334,110 to Schramm. An example is the reaction product of bisphenol A diglycidyl ether with diphenylmethane diisocyanate in the presence of an appropriate accelerator.

Epoxy resin oligomers may be prepared by condensation of an epoxy resin with a phenol such as a bisphenol. A typical example is the condensation of bisphenol-A with a bisphenol-A diglycdyl ether to produce an oligomeric diglycidyl ether. In another example a phenol dissimilar to the one used to derive the epoxy resin may be used. For example tetrabromobisphenol-A may be condensed with bisphenol-A diglycidyl ether to produce an oligomeric diglycidyl ether containing halogens.

Further suitable polyepoxide compounds as well as curing agents for epoxy resins (including amine compounds, anhydrides, benzenediol compounds, bisphenol resin, polyhydric phenol resin, phenolic resins and others) are described in Henry Lee and Kris Neville, "Handbook of Epoxy Resins" McGraw-Hill Book Company, 1967, and Henry Lee "Epoxy Resins", American Chemical Society, 1970.

Examples of the amine compounds include aliphatic amine compounds, such as diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), diethylaminopropylamine (DEAPA), methylene diamine, N- aminoethylpyrazine (AEP), m-xylylene diamine (MXDA) and the like; aromatic amine compounds such as m-phenylene diamine (MPDA), 4,4'- diaminodiphenylmethane (MDA), diaminodiphenylsulfone (DADPS), diaminodiphenyl ether and the like; and secondary or tertiary amine compounds such as phenylmethyldimethylamine (BDMA), dimethylaminomethylphenol (DMP-IO), tris(dimethylaminomethyl)phenol (DMP-30), piperidine, 4,4'- diaminodicyclohexylmethane, 1 ,4-diaminocyclohexane, 2,6-diaminopyridine, m- phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-bis(4- aminophenyl)propane, benzidine, 4,4'-diaminophenyl oxide, 4,4'- diaminodiphenylsulfone, bis(4-aminophenyl)phenylphosphone oxide, bis(4- aminophenyl)methylamine, 1 ,5-diaminonaphthalene, /?-xylenediamine, hexamethylenediamine, 6,6'-diamine-2,2'-pyridyl, 4,4'-diaminobenzophenone, 4,4'- diaminoazobenzene, bis(4-aminophenyl)phenylmethane, l,l-bis(4- aminophenyl)cyclohexane, 1 , 1 -bis(4-amino-3-methylphenyl)cyclohexane, 2,5-bis(m- aminophenyl)-l,3,4-oxadiazole, 2,5-bis(p-aminophenyl)-l,3,4-oxadiazole, 2,5-bis(m- aminophenyl)thiazo(4,5-d)thiazole, 5,5'-di(m-aminophenyl)-(2,2')-bis-(l,3,4- oxadiazolyl), 4,4'-diaminodiphenylether, 4,4'-bis(p-aminophenyl)-2,2'-dithiazole, m- bis(4-/?-aminophenyl-2-thiazolyl)benzene, 4,4'-diaminobenzanilide, 4,4'- diaminophenyl benzoate, Λ/,Λf'-bis(4-aminobenzyl)-p-phenylenediamine, and 4,4'- methylenebis(2-chloroaniline); melamine, 2-amino-s-triazine, 2-amino-4-phenyl-s- triazine, 2-amino-4-phenyl-s-triazine, 2-amino-4,6-diethyl-s-triazine, 2-amino-4,6- diphenyl-s-triazine, 2-amino-4,6-bis(/?-methoxyphenyl)-s-triazine, 2-amino-4-anilino- s-triazine, 2-amino-4-phenoxy-s-triazine, 2-amino-4-chloro-s-triazine, 2-amino-4- aminomethyl-6-chloro-s-triazine, 2-(/?-aminophenyl)-4,6-dichloro-s-triazine, 2,4- diamino-s-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-6-phenyl-s-triazine, 2,4-diamino-6-benzyl-s-triazine, 2,4-diamino-6-(/?-aminophenyl)-s-triazine, 2,4- diamino-6-(m-aminophenyl)-s-triazine, 4-amino-6-phenyl-s-triazine-2-ol, and 6- amino-s-triazine-2,4-diol.

Examples of the anhydride compounds include maleic anhydride (MA), phthalic anhydride (PA), hexahydro-o-phthalic anhydride (HEPA), tetrahydrophthalic anhydride (THPA), pyromellitic dianhydride (PMDA) and trimellitic anhydride (TMA).

Examples of phenolic compounds useful as curatives include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynapthalene, 2- (diphenylphosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 2,2', 6,6'- tetramethylbiphenol, 2,2 ' ,3 ,3 ' ,6,6 ' -hexamethylbiphenol, 3 ,3 ' ,5 ,5 ' -tetrabromo- 2,2'6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2', 6,6'- tetramethyl-3,3'5-dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'- isopropylidenebis(2,6-dibromophenol) (tetrabromobisphenol A), 4,4'- isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol A), 4,4'- isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(l,3- phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3- phenylphenol), 4,4'-(l,4-phenylenediisoproylidene)bisphenol (bisphenol P), 4,4'- ethylidenediphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'- thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6- dimethylphenol) 4,4'sulfinyldiphenol, 4,4'-hexafluoroisoproylidene)bisphenol (Bisphenol AF), 4,4'-(l-phenylethylidene)bisphenol (Bisphenol AP), bis(4- hydroxyphenyl)-2,2-dichloroethylene (Bisphenol C), bis(4-hydroxyphenyl)methane (Bisphenol-F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-

(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (Bisphenol Z), 4,4'- (cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H- fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-l(3H)-one, l-(4- hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-lH-inden-5-ol, l-(4-hydroxy-3,5- dimethylphenyl)-l,3,3,4,6-pentamethyl-2,3-dihydro-lH-inden-5-ol, 3,3,3',3'- tetramethyl-2,2',3,3'-tetrahydro-l,l'-spirobi[indene]-5,6'-diol (Spirobiindane), dihydroxybenzophenone (bisphenol K), tris(4-hydroxyphenyl)methane, tris(4- hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4- hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4- hydroxyphenyl)ethane, and the like.

Also included are phenolic resins such as phenol-formaldehyde novolac, alkyl substituted phenol-formaldehyde resins including cresol-formaldehyde novolac, t-butylphenol-formaldehyde novolac, sec-butylphenol- formaldehdye novolac, tert-octylphenol-formaldehyde novolac, cumylphenol- formaldehyde novolac, and decylphenol-formaldehyde novolac. Other useful epoxies are the glycidyl ethers of bromophenol-formaldehdye novolac, chlorophenol- formaldehyde novolac, phenol-bis(hydroxymethyl)benzene novolac, phenol- bis(hydroxymethylbiphenyl) novolac, phenol-hydroxybenzaldehdye novolac, phenol- dicylcopentadiene novolac, naphthol-formaldehyde novolac, naphthol- bis(hydroxymethyl)benzene novolac, naphthol-bis(hydroxymethylbiphenyl) novolac, naphthol-hydroxybenzaldehdye novolac, naphthol-dicylcopentadiene novolac and the like. Examples of the other hardeners used in the epoxy resin composition include urea resin, melamine resin, polyamide resin, dicyanodiamide, boron fluoride-amine complex, and the like.

These hardeners can be used alone or in combination as a mixture of two or more different kinds of hardeners.

Hardening accelerators may be used in the present invention to enhance the rate of epoxy cure. Examples of hardening accelerators include: tertiary amines, tertiary phosphines, quaternary ammonium salts, quaternary phosphonium salts, boron fluoride complex salts, lithium-containing compounds, imidazole compounds or mixtures thereof.

Examples of the tertiary amines include: triethylamine, tributylamine, dimethylaniline, diethylaniline, α-methylbenzyldimethylamine, N,N- dimethylaminoethanol, Λ/,Λ/-dimethylaminocresol, tή(N,N- dimethylaminomethyl)phenol, and the like.

Examples of tertiary phosphines include triphenylphosphine and the like.

Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium iodide, triethylphenylethylammonium chloride, triethylphenylethylammonium bromide, triethylphenylethylammonium iodide, and the like.

Examples of quaternary phosphonium salts include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium acetate, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium phosphate, propyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, and the like.

Examples of imidazole compounds include 2-methylimidazole, 2-ethylimidazole, 2- laurylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 4-methylimidazole, A- ethylimidazole, 4-laurylimidazole, 4-heptadecylimidazole, 2-phenyl-4- methylimidazole, 2-phenyl-4-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 2- ethyl-4-hydroxymethylimidazole, 1 -cyanoethyl-4-methylimidazole, 2-phenyl-4,5- dihydroxymethylimidazole, and the like.

These hardening accelerators can be used alone or in combination as a mixture of two or more different kinds of hardening accelerators. In some embodiments, the hardening accelerator is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, ethyltriphenylphosphonium acetate, butyltriphenylphosphonium bromide, and mixtures thereof.

The amounts of the curing agents depend on kinds and amounts of epoxy resin, and can be suitably determined by a skilled person skilled without undue experimentation. Typically, the curing agents are based on the number of glycidyl group equivalents in the epoxy resin.

The thermoset resin may be a cyanate ester resin. Suitable cyanate ester resins include compounds having the structure

wherein A is a an organic or inorganic radical of valence n; and n is 1 to about 1000, specifically 2 to 8, more specifically 2 or 3 or 4.

Suitable cyanate ester resins further include those having the structures

wherein each occurrence of X is independently hydrogen, halogen, Ci_Ci8 hydrocarbyl, Ci_Ci2 alkoxy, Ci_Ci2 thioalkoxy (RS-), each optionally further comprising a member or members selected from carboxyalkyl, carboxamide, ketone, aldehyde, alcohol, halogen, and nitrile; each occurrence of A is independently a carbon-carbon single bond, sulfonyl, sulfide, carbonyl, oxy, or Ci_Ci8 hydrocarbylene optionally further comprising a member or members selected from carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, and nitrile; and each occurrence of M is independently chosen from Ci_Ci8 hydrocarbyl optionally further comprising a member or members selected from oxirane, carboxy, carboxamide, ketone, aldehyde, alcohol, halogen, and nitrile; n isl to about 10, specifically 1 to 5, and more specifically 1 or 2 or 3. Useful cyanate ester resins include cyanatobenzene, 4-cumylcyanatobenzene, dicyanatobenzenes, 2-t-butylcyanatobenzene, 2,5-di-t-butyl-l ,4-dicyanatobenzene, 2,5-di-t-butyl-l ,3-dicyanatobenzene, 4-chloro-l ,3-dicyanatobenzene, 1 ,3,5- tricyanatobenzene, 4,4'-cyanatobiphenyl 2,2'-dicyanatobiphenyl, 2,4-dimethyl-l,3- dicyanatobenzene, tetramethyldicyanatobenzene, 1,3-dicyanatonaphthalene, 1,4- dicyanatonaphthalene, 1,5-dicyanatonaphthalene, 1 ,6-dicyanatonaphthalene, 1,8- dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 2,2- bis(3,5-dibromo-4-cyanatophenyl)propane, 1 ,3,6-tricyanatonapthalene, 2,2-bis(4- cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3-chloro-4- cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 1 ,3-bis[4- cyanatophenyl- 1 -(I -methylethylidene)]benzene, 1,1,1 -tris(4-cyanatophenyl)ethane, l,4-bis[4-cyanatophenyl-l-(l-methylethylidene)]-benzene, and mixtures thereof. Additional suitable cyanate ester resins include prepolymers of 2,2-bis(4- cyanatophenyl)-propane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 1 ,3-bis[4- cyanatophenyl- 1 -(I -methylethylidene)]benzene, 1 ,4-bis[4-cyanatophenyl- 1 -(I - methylethylidene)]benzene, bis(4-cyanatophenyl)ether, bis(p- cyanophenoxyphenoxy)benzene, di(4-cyanatophenyl)ketone, bis(4- cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4- cyanatophenyl)phosphite, and tris(4-cyanatophenyl)phosphate. Also useful are other cyanates as disclosed in U.S. Pat. No. 5,215,860 to McCormick et al., col. 10, lines 19 to 38, as well as the cyanate ester resins sold as B-IO, T-30, M-IO, L-10, RTX-366, Quatrex-7187, and Primaset PT-30, PT-60, and PT-90.

Cyanate ester prepolymers that can be used in the present invention contain free cyanate ester groups and may be produced by partial curing of the cyanate ester resin in the presence or absence of a catalyst. A typical example of such a cyanate ester prepolymer is the partial reaction product of bis(3,5-dimethyl-4- cyanatophenyl)methane, sold under the trade names AroCy B-30, B-50, M-20, PT-60, PT-60S, and CT-90 by Lonza. Ltd., Switzerland. A detailed description of cyanate esters and cyanate ester prepolymers can be found in "The Chemistry and Technology of Cyanate Esters" by I. A. Hamerton, 1994, Blackie Academic and Professional, an imprint of Chapman and Hall. It is within the scope of the invention to employ mixtures of two or more different cyanate ester prepolymers and mixtures of one or more cyanate ester prepolymers with one or more cyanate ester-containing compounds that are not prepolymers.

Metal salt catalysts, such as metal carboxylates, can be used to accelerate the cure rate of cyanate ester resins. Catalysts include by manganese naphthenate, zinc naphthenate, cobalt naphthenate, nickel naphthenate, cerium naphthenate, manganese octanoate, zinc octanoate, cobalt octanoate, nickel octanoate and cerium octanoate. The amounts of metal catalysts are dependent on the amount of cyanate ester based resin, and may be appropriately used, considering the reaction of cyanate ester based resin, by a person skilled in the art.

The thermoset resin may be a maleimide resin. Suitable maleimides include those having the structure

wherein M is a radical and having a valence n and containing 2 to 40 carbon atoms and optionally one or more heteroatoms; each occurrence of Z is independently hydrogen, halogen, or Ci-Ci₈ hydrocarbyl; and n is 1 to about 10, specifically 2 or 3 or 4. M can be, for example, aliphatic, cycloaliphatic, aromatic, or heterocyclic. Suitable maleimides include those represented by the structures

wherein each occurrence of Z is independently hydrogen, C₁-C₁₈ hydrocarbyl, or halogen; A is C₁-C₁₈ hydrocarbylene, oxy, sulfone, sulfmyl, carboxylate, carbonyl, carbonamide, or sulfide; and n is 0 to about 10.

Specific examples of maleimide resins include

1 ,2-bismaleimidoethane, 1 ,6-bismaleimidohexane, 1 ,3-bismaleimidobenzene, 1 ,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4'- bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenylether, 3,3'- bismaleimidodiphenylsulfone, 4,4'-bismaleimidodiphenylsulfone, 4,4'- bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6- bismaleimidopyridine, l,3-bis(maleimidomethyl)cyclohexane, 1,3- bis(maleimidomethyl)benzene, 1 , 1 -bis(4-maleimidophenyl)cyclohexane, 1 ,3- bis(dichloromaleimido)benzene, 4,4'-bis(citraconimido)diphenylmethane, 2,2-bis(4- maleimidophenyl)propane, 1 -phenyl- 1 , 1 -bis(4-maleimidophenyl)ethane, α,α-bis(4- maleimidophenyl)toluene, 3,5-bismaleimido-l,2,4-triazole, N,N'- ethylenebismaleimide, Λ/,N'-hexamethylenebismaleimide, N,N'-m- phenylenebismaleimide, Λ/,N'-p-phenylenebismaleimide, N,N'-4,4'- diphenylmethanebismaleimide, Λ/,N'-4,4'-diphenyletherbismaleimide, N,N'-4,4'- diphenylsufonebismaleimide, Λ/,N'-4,4'-dicyclohexylmethanebismaleimide, N,N'-a,a'- 4,4'-dimethylenecyclohexanebismaleimide, Λ/,N'-m-methaxylenebismaleimide,

Λ/,N'-4,4'-diphenylcyclohexanebismaleimide, and

Λ/,N'-methylenebis(3-chloro-/?-phenylene)bismaleimide, as well as the maleimide resins disclosed in U.S. Pat. Nos. 3,562,223 to Bargain et al, and 4,211,860 and 4,211,861 to Stenzenberger. Maleimide resins can be prepared by methods known in the art, as described, for example, in U.S. Pat. No. 3,018,290 to Sauters et al. In some embodiments, the maleimide resin is JV,jV'-4,4'-diphenylmethane bismaleimide.

The maleimide resin can be a reaction product or prepolymer of a polyfunctional unsaturated imide, such as a bisiimide, and an effective chain-extending agent such as an amine-group-containing compound. Suitable amine-group-containing compounds include diamines, hydroxylamines, and polyamines. Examples include bis(4-(7V- methylamino)phenyl)methane, N, N '-dimethyl- 1 ,3-diaminobenzene 4,4'- diaminodicyclohexylmethane, 1 ,4-diaminocyclohexane, 2,6-diaminopyridine, m- phenylenediamine, /?-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2'-bis(4- aminophenyl)propane, benzidine, 4,4'-diaminophenyl oxide, 4,4'- diaminodiphenylsulfone, bis(4-aminophenyl)phenylphosphine oxide, bis(4- aminophenyl)methylamine, 1,5-diaminonaphthalene, m-xylenediamine, p- xylenediamine, hexamethylenediamime, 6,6'-diamine-2,2'-pyridyl, 4,4'- diaminobenzophenone, 4,4'-diaminoazobenzene, bis(4-aminophenyl)phenylmethane, 1 , 1 -bis(4-aminophenyl)cyclohexane, 1 , 1 -bis(4-amino-3-methylphenyl)cyclohexane, 2,5-bis(m-aminophenyl)-l,3,4-oxadiazole, 2,5-bis(/?-aminophenyl)-l,3,4-oxadiazole, 2,5-bis(m-aminophenyl)thiazo(4,5-d)thiazole, 5,5'-di(m-aminophenyl)-(2,2')-bis-

(1 ,3,4-oxadiazolyl), 4,4'-diaminodiphenylether, 4,4'-bis(p-aminophenyl)-2,2'- dithiazole, m-bis(4-/?-aminophenyl-2-thiazolyl)benzene, 4,4'-diaminobenzanilide, 4,4'- diaminophenyl benzoate, Λ/,N'-bis(4-aminobenzyl)-/?-phenylenediamine, 4,4'- methylenebis(2-chloroaniline), and the like.

Such reaction products can be prepared by methods known in the art, such as contacting about 0.1 to about 0.8 mole of the chain-extending agent with each mole of the bisimide in an organic solvent at a temperature of about 40 to about 200⁰C for a time of about 5 minutes to about 5 hours. The maleimide resin can be, for example, a hydrazide -modified bismaleimide as described in U.S. Pat. Nos. 4,211,860 and 4,211,861 to Stenzenberger. Suitable JV,JV '-unsaturated bismaleimide resins are commercially available from Technochemie GmbH as Compimide resins. The maleimide resin can be a mixture of maleimide resins tailored to meet specific processing requirements.

The thermoset resin may be a benzoxazine resin. Suitable benzoxazine resins include those having the structure

wherein B is a linear or branched hydrocarbon group having 1 to about 80 carbon atoms, specifically about 1 to 10 carbon atoms (in some embodiments, B is an alkyl group, a cycloalkyl group, carbonyl, sulfonyl, sulfmyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidene dialkylsilanyl, arylalkylsilanyl, or diarylsilanyl); n is 1 to 20, specifically 1 to 4, more specifically 2; and X is hydrogen, C₁-C₁₈ hydrocarbyl optionally substituted with one or more fluorine atoms, or Ci-C_4O hydrocarbyl amine (including polyamines). Depending on whether phenolic or phenoxy repeat units are desired in the polybenzoxazine, it may be desirable that at least one non-hydrogen X substituent be ortho, meta, or para to the oxygen atom of the benzoxazine.

As is well known, benzoxazine monomers are made from the reaction of aldehydes, phenols, and primary amines with or without solvent. U.S. Pat. No. 5,543,516 to Ishida describes a solventless method of forming benzoxazine monomers. An article by Ning and Ishida in Journal of Polymer Science, Chemistry Edition, vol. 32, page 1121 (1994) describes a procedure using a solvent. The procedure using solvent is generally common to the literature of benzoxazine monomers.

The preferred phenolic compounds include phenols and polyphenols. The use of polyphenols with two or more hydroxyl groups reactive in forming benzoxazines may result in branched and/or crosslinked products. The groups connecting the phenolic groups into a phenol can be branch points or connecting groups in the polybenzoxazine.

Suitable phenols of this invention for use in the preparation of benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3- allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydrooxynapthalene, 2- (diphenylphosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 4,4'- isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2-methylphenol), 4,4'- isopropylidenebis(2-allylphenol), 4,4'(l,3-phenylenediisopropylidene)bisphenol

(bisphenol M), 4,4'-isopropylidenebis(3-phenylphenol) 4,4'-(l,4- phenylenediisoproylidene)bisphenol (bisphenol P), 4,4'-ethylidenediphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'- sulfinyldiphenol, 4,4'-hexafluoroisoproylidenebisphenol (Bisphenol AF), 4,4 '-(1- phenylethylidene)bisphenol (Bisphenol AP), bis(4-hydroxyphenyl)-2,2- dichloroethylene (Bisphenol C), bis(4-hydroxyphenyl)methane (Bisphenol-F), 4,4'- (cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (Bisphenol Z), 4,4'- (cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H- fluorene-9,9-diyl)diphenol, isopropylidenebis(2-allylphenol), 3,3-bis(4- hydroxyphenyl)isobenzoflιran-l(3H)-one, l-(4-hydroxyphenyl)-3,3-dimethyl-2,3- dihydro-lH-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-l,l'-spirobi[indene]- 5,6'-diol (spirobiindane), dihydroxybenzophenone (bisphenol K), tris(4- hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3 -methyl-4-hydroxyphenyl)methane, tetrakis(4- hydroxyphenyl)ethane dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienyl bis(ortho-cresol), dicyclopentadienyl bisphenol, and the like.

The aldehyde used to form the benzoxazine can be any aldehyde. In some embodiments, the aldehyde has 1 to about 10 carbon atoms. In some embodiments, the aldehyde is formaldehyde. The amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl substituted aromatic, or an aromatic substituted alkyl amine. The amine can also be a polyamine, although the use of polyamines will, under some circumstances, yield polyfunctional benzoxazine monomers. Polyfunctional benzoxazine monomers are more likely to result in branched and/or crosslinked polybenzoxazines than monofunctional benzoxazines, which would be anticipated to yield thermoplastic polybenzoxazines.

The amines generally have 1 to about 40 carbon atoms unless they include aromatic rings, and then they may have 6 to about 40 carbon atoms. The amine of a di- or polyfunctional amine may also serve as a branch point to connect one polybenzoxazine to another. Thermal polymerization has been the preferred method for polymerizing benzoxazine monomers. The temperature to induce thermal polymerization is typically varied from about 150 to about 300° C. The polymerization is typically done in bulk, but could be done from solution or otherwise. Catalysts, such as carboxylic acids, have been known to slightly lower the polymerization temperature or accelerate the polymerization rate at the same temperature.

Cationic polymerization initiators have been found to result in polymerization of benzoxazine monomers at temperatures as low as cryogenic temperatures. Preferred temperatures are -100 to about 250° C, specifically about -60 to about 150° C for ease of handling the reactants and products. Some of the cationic initiators, for example PCI5, form repeating units from the benzoxazine monomers that include a salt of the amine. These repeating units have better solubility in polar solvents, such as water, than similar repeating units without the amine salt. The initiators of the current invention can be used either in the benzoxazine melt or in the presence of solvent, allowing the solvent content to be from 0 to nearly 100%. Many solvents can be used in cationic polymerizations, and their selection is known by those skilled in the art of cationic polymerization.

The polymers from the cationically initiated polymerization of benzoxazine are useful as molded articles with good thermal stability and/or flame resistance, such as molded circuit boards, flame resistant laminates, or other molded articles, and is a source of precursor to high temperature resistant chars. The common uses for high temperature resistant chars include aircraft brake discs, equipment for sintering reactions, and heat shields or heat shielding material. The polymers that include repeating units having amine salts can be used in applications for partially or fully water soluble polymers such as viscosity control agents.

Generally, cationic initiators can polymerize benzoxazine monomers or oligomers. Suitable cationic initiators include H₂SO₄, HClO₄, BF₃, AlCl₃, t-BuCl/Et₂AlCl, C1₂/BC1₃, AlBr₃, AlBr3. TiCl₄, I₂, SnCl₄, WCl₆, AlEt₂Cl, PF₅, VCl₄, AlEtCl₂, and BF₃Et₂O. In some embodiments, the polymerization initiator is PCI5, PCl₃, POCl₃, TiCIs, SbCl₅, (C6H₅)3C⁺(SbCl6)^~, or metallophorphyrin compounds such as aluminum phthalocyanine chloride, which are all known to result in similar polymers from cationically initiated polymerization of unsaturated monomers.

Suitable cationic initiators further include ethyl tosylate, methyl triflate, and triflic acid. Typically, each initiator initiates a polymer with from about 3 to about 3,000 repeat units, so the amount of initiator needed on a mole percent basis relative to the monomer is small. However, additional initiator may be needed to compensate for loss due to adventitious moisture and other reactants that deactivate cations. Desirably about 0.001 to about 50 mole percent initiator based upon the monomer and more desirably from about 0.01 to about 10 mole percent initiator is used for these cationically initiated polymerizations.

The thermoset resin may be a vinylbenzyl ether resin. Vinylbenzyl ether resins include those having the structure

wherein A is an organic or inorganic radical of valence n, X is oxygen or nitrogen, and n is from 1 to about 1000, specifically 2 to 8, more specifically 2, 3, or 4. They may be most readily prepared from condensation of a phenol with a vinyl benzyl halide, such as vinylbenzyl chloride to produce a vinylbenzyl ether. Bisphenol-A and trisphenols and polyphenols are generally used to produce poly(vinylbenzyl ethers) that may be used to produce crosslinked thermosetting resins. Vinyl benzyl ethers useful in the present invention include those produced from reaction of vinylbenzyl chloride or vinylbenzyl bromide with resorcinol, catechol, hydroquinone, 2,6- dihydroxy naphthalene, 2,7-dihydroxynapthalene, 2-

(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol) 2,2'-biphenol, 4,4- biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'- tetrabromo-2,2 '6,6 ' -tetramethylbiphenol, 3 ,3 ' -dibromo-2,2 ' ,6,6 ' -tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3 '5-dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol) (tetrabromobisphenol A), 4,4'- isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol A), 4,4'- isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'(1 ,3- phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3- phenylphenol), 4,4'-(l,4-phenylenediisoproylidene)bisphenol (bisphenol P), 4,4'- ethylidenediphenol (bisphenol E), 4,4'oxydiphenol, 4,4'thiodiphenol, 4,4'thiobis(2,6- dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol) 4,4'- sulfinyldiphenol, 4,4'-hexafluoroisoproylidene)bisphenol (Bisphenol AF), 4,4'-(l- phenylethylidene)bisphenol (Bisphenol AP), bis(4-hydroxyphenyl)-2,2- dichloroethylene (Bisphenol C), bis(4-hydroxyphenyl)methane (Bisphenol-F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'- (cyclohexylidene)diphenol (Bisphenol Z), 4,4'-(cyclododecylidene)diphenol 4,4'- (bicyclo[2.2. l]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4- hydroxyphenyl)isobenzoflιran-l(3H)-one, l-(4-hydroxyphenyl)-3,3-dimethyl-2,3- dihydro-lH-inden-5-ol, l-(4-hydroxy-3,5-dimethylphenyl)-l,3,3,4,6-pentamethyl-2,3- dihydro-lH-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-l,l'-spirobi[indene]- 5,6'-diol (Spirobiindane), dihydroxybenzophenone (bisphenol K), tris(4- hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3 -methy l-4-hydroxyphenyl)methane, tris(3 ,5 - dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3 ,5 - dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienyl bis(ortho-cresol), dicyclopentadienyl bisphenol, and the like.

The thermoset resin may be an alkene-containing monomer or an alkyne-containing monomer. Suitable alkene- and alkyne-containing monomers include those described in U.S. Patent No. 6,627,704 to Yeager et al. One class of alkene-containing monomers is the acrylate-containing compounds having the structure

wherein A is an organic or inorganic radical of valence n; X is nitrogen or oxygen; Y is oxygen or sulfur; and each occurrence of Z is independently chosen from hydrogen, halogen, and C1-C24 hydrocarbyl. Suitable alkene-containing monomers include acrylate- and methacrylate-functionalized materials capable of undergoing free radical polymerization. They can be monomers and/or oligomers such as (meth)acrylates, (meth)acrylamides, JV-vinylpyrrolidone and vinylazlactones as disclosed in U.S. Pat. No. 4,304,705 of Heilman et al. (As used herein, the prefix "(meth)acryl-" means acryl- or methacryl-.) Such monomers include mono-, di-, and polyacrylates and methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid, n-hexyl acrylate, tetrahydrofurfuryl acrylate, JV-vinylcaprolactam, N- vinylpyrrolidone, acrylonitrile, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4- butanetriol trimethacrylate, 2- phenoxyethyl acrylate, 1 ,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexaacrylate, bis[l-(2-acryloxy)]-p- ethoxyphenyldimethylmethane, 2,2-bis[l-(3-acryloxy-2- hydroxy)]propoxyphenylpropane, tris(hydroxyethyl)isocyanurate trimethacrylate; the bis-acrylates and bis-methacrylates of polyethylene glycols of number average molecular weight 200-500 atomic mass units, and bis-acrylates and bis-methacrylates of polybutadienes of number average molecular weight 1000-10,000 atomic mass units, copolymerizable mixtures of acrylated monomers such as those disclosed in U.S. Pat. No. 4,652,274 to Boettcher et al.; and acrylated oligomers such as those disclosed in U.S. Pat. No. 4,642,126 to Zador et al.

It may be desirable to crosslink the alkene- or alkyne-containing monomer. Particularly useful as crosslinker compounds are acrylates such as allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,3- propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1 ,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexaacrylate, bis[l-(2- acryloxy)]-p-ethoxyphenyldi- methylmethane, 2,2-bis[ 1 -(3-acryloxy-2- hydroxy)]propoxyphenylpropane, tris(hydroxyethyl)isocyanurate trimethacrylate; and the bis-acrylates and bis- methacrylates of polyethylene glycols of average molecular weight 200-500 atomic mass units..

Also included are allylic resins and styrenic resins for example triallylisocyanuate, trimethallylisocyanurate, trimethallylcyanurate, triallylcyanurate, divinyl benzene, and dibromostyrene, as well as others described in U.S. Patent No. 6,627,704 to Yeager et al.

The thermoset resin may be an arylcyclobutene resin. Arylcyclobutenes include those derived from compounds of the general structure

wherein B is an organic or inorganic radical of valence n (including carbonyl, sulfonyl, sulfϊnyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidene dialkylsilanyl, arylalkylsilanyl, diarylsilanyl, and C₆-C₂O phenolic compounds); each occurrence of X is independently hydroxy or Ci-C₂₄ hydrocarbyl (including linear and branched alkyl and cycloalkyl); each occurrence of Z is independently hydrogen, halogen, or Ci-Ci₂ hydrocarbyl; and n is 1 to 1000, specifically 1 to 8, more specifically 2 or 3 or 4. Other useful arylcyclobutenes and methods of arylcyclobutene synthesis may be found in U.S. Patent Nos. 4,743,399, 4,540,763, 4,642,329, 4,661,193, and 4,724,260 to Kirchhoff et al., and 5,391,650 to Brennan et al. The thermoset resin may be a perfluorovinyl ether resin. Useful perfluorovinyl ethers include those having the structure

wherein A is a divalent organic or inorganic radical of valence n; and n is 1 to about 1000, specifically 1 to 8, more specifically 2 or 3 or 4.

Perfluorovinyl ethers are typically synthesized from phenols and bromotetrafluoroethane followed by zinc catalyzed reductive elimination producing ZnFBr and the desired perfluorovinylether. By this route bis, tris, and other polyphenols can produce bis-, tris- and poly(perfluorovinylether)s. Phenols useful in their synthesis include resorcinol, catechol, hydroquinone, 2,6-dihydroxy naphthalene, 2,7-dihydroxynapthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6- dimethylphenol) 2,2'-biphenol, 4,4-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2 ' ,3 ,3 ' ,6,6 ' -hexamethylbiphenol, 3 ,3 ' ,5 ,5 ' -tetrabromo-2,2 '6,6 ' -tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3'5- dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'- isopropylidenebis(2,6-dibromophenol) (tetrabromobisphenol A), 4,4'- isopropylidenebis(2,6-dimethylphenol) (teramethylbisphenol A), 4,4'- isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4 '-(1,3- phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3- phenylphenol) 4,4'-(l,4-phenylenediisoproylidene)bisphenol (bisphenol P), 4,4'- ethylidenediphenol (bisphenol E), 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'- thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol, 4,4'-sulfonylbis(2,6- dimethylphenol) 4,4 '-sulfinyldiphenol, 4,4 ' -hexafluoroisoproylidenebisphenol (Bisphenol AF), 4,4'(l-phenylethylidene)bisphenol (Bisphenol AP), bis(4- hydroxyphenyl)-2,2-dichloroethylene (Bisphenol C), bis(4-hydroxyphenyl)methane (Bisphenol-F), bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-

(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol (Bisphenol Z), 4,4'- (cyclododecylidene)diphenol 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H- fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-l(3H)-one, l-(4- hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-lH-inden-5-ol, l-(4-hydroxy-3,5- dimethylphenyl)-l,3,3,4,6-pentamethyl-2,3-dihydro-lH-inden-5-ol, 3,3,3',3'- tetramethyl-2,2',3,3'-tetrahydro-l,r-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone (bisphenol K), tris(4-hydroxyphenyl)methane, tris(4- hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4- hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4- hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienyl bis(2-methylphenol), dicyclopentadienyl bisphenol, and the like.

The thermoset resin may be an oligomer or polymer with curable vinyl functionality. Such materials include oligomers and polymers having crosslinkable unsaturated bonding. Examples include styrene butadiene rubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR) having unsaturated bonding based on butadiene; natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber having unsaturated bonding based on isoprene; ethylene-α-olefm copolymer elastomers having unsaturated bonding based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1 ,4-dihexadiene (1,4- HD) (namely, ethylene-α-olefm copolymers obtained by copolymerizing ethylene, an α-olefm, and a diene, such as ethylene-propylene-diene terpolymer (EPDM) and ethylene -butene-diene terpolymer (EBDM)). In some embodiments, an EBDM is used. Examples also include hydrogenated nitrile rubber, fluorocarbon rubbers such as vinylidenefluoride-hexafluoropropene copolymer and vinylidenefluoride- pentafluoropropene copolymer, epichlorohydrin homopolymer (CO), copolymer rubber (ECO) prepared from epichlorohydrin and ethylene oxide, epichlorohydrin allyl glycidyl copolymer, propylene oxide allyl glycidyl ether copolymer, propylene oxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfϊde rubber (T) and ethylene acrylic rubber. Further examples include various liquid rubbers, for example various types of liquid butadiene rubbers, and the liquid atactic butadiene rubber that is butadiene polymer with 1 ,2-vinyl connection prepared by anionic living polymerization. It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene type hydrocarbon polymer, and polynorbornene (for example, as sold by Elf Atochem).

Polybutadiene resins, generally polybutadienes containing high levels of 1,2 addition, are desirable for thermosetting matrices. Also included are the functionalized polybutadienes and poly(butadiene-styrene) random copolymers sold by Ricon Resins, Inc. under the trade names RICON, RICACRYL, and RICOBOND resins. These include polybutadienes containing both low vinyl content such as RICON 130, 131, 134, 142, and polybutadienes containing high vinyl content such as RICON 150, 152, 153, 154, 156, 157, and P30D; also random copolymers of styrene and butadiene including RICON 100, 181, 184, and maleic anhydride grafted polybutadienes and the alcohol condensates derived therefrom such as RICON 130MA8, RICON MAl 3, RICON 130MA20, RICON 13 IMAS, RICON 13 IMAlO, RICON MA17, RICON MA20, RICON 184MA6 and RICON 156MA17; also included are polybutadienes which may be used to improve adhesion including RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, and RICACRYL 3500; also are included the polybutadienes RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene); also are included are (meth)acrylic functionalized polybutadienes such as polybutadiene diacrylates and polybutadiene dimethacrylates. These materials are sold under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Also are included are powder dispersions of functional polybutadiene derivatives including, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 1731 HS, and RICOBOND 1756 HS. Further butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those with number average molecular weights of about 3,000 to about 50,000 atomic mass units and polybutadiene homopolymers having number average molecular weights of about 3,000 to about 50,000 atomic mass units. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethylmaleic acid, or hydroxylated functionality. Further examples of oligomers and polymers with curable vinyl functionality include the unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid and citraconic acid, unsaturated epoxy acrylate resin based on acryloyl group, methacryloyl group and allyl group, urethane acrylate resin, polyether acrylate resin, polyalcohol acrylate resin, alkyd acrylate resin, polyester acrylate resin, spiroacetal acrylate resin, diallyl phthalate resin, diallyl tetrabromophthalate resin, diethleneglycol bisallylcarbonate resin, and polyethlene polythiol resin.

Crosslinking agents may be added, such as compounds containing alkene or alkyne functionality. They include, for example, such maleimides as N,N'-m- phenylenebisamide, triallylisocyanuate, trimethallylisocyanurate, trimethallylcyanurate, and triallylcyanurate.

When the composition comprises poly(arylene ether), solvent, and a thermoset resin, it may comprise about 1 to about 70 weight percent of the poly(arylene ether), about 10 to about 79 weight percent of the solvent, and about 20 to about 89 weight percent of the thermoset resin, all based on the total weight of the composition. Specifically, the poly(arylene ether) amount may be about 10 to about 50 weight percent, more specifically about 20 to about 40 weight percent. Specifically, the solvent amount may be about 20 to about 60 weight percent, more specifically about 30 to about 50 weight percent. Specifically, the thermoset resin amount may be about 30 to about 80 weight percent, more specifically about 40 to about 70 weight percent.

When the composition comprises a thermoset resin, it may, optionally, further comprise a filler and/or one or more additives for thermoset compositions, including curing promoters, curing inhibitors, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof. When used, the additional components are generally selected to have a substantially lower volatility than the solvent. In some embodiments, the composition has a gel temperature less than or equal to 25⁰C. Gel temperature may be determined by a tilt test in which a gelled composition is gradually warmed in a test tube and the melting point is observed when the gel begins to flow under its own weight when the upright test tube is tilted. See, A. Hiltner in J. Brandup and E. H. Immergut, Eds., "Polymer Handbook", Wiley- Interscience, New York: 1989, page VII/591.

One embodiment is a composition consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and a solvent selected from C₃-Cg ketones, C₄-Cs N,N-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C₁-C₃ chlorinated hydrocarbons, C₂-C₆ alkyl cyanides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 10 to about 700 grams per kilogram of composition at 25⁰C.

One embodiment is a composition comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and about 10 to about 70 weight percent of a second monohydric phenol selected from 2- methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; wherein the monomers are free of ethylenic unsaturation; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C. In some embodiments, the monomers further comprise a dihydric phenol selected from 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 10 to about 70 weight percent of a second monohydric phenol selected from 2- methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof, and optionally, a dihydric phenol selected from 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy- 2,6-dimethylphenyl)propane, 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2 ' 6,6 ' -tetramethyl-3 ,3 '5,5' -tetrabromo- 4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'-biphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; wherein the monomers are free of ethylenic unsaturation; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, comprising: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and about 10 to about 70 weight percent of a second monohydric phenol selected from 2-methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof; wherein the monomers are free of ethylenic unsaturation; wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; about 20 to about 80 weight percent of a solvent selected from acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C. In some embodiments, the monomers further comprise about 2 to about 20 weight percent of a dihydric phenol selected from 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy- 2,6-dimethylphenyl)propane, 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid 2,2 ' 6,6 ' -tetramethyl-3 ,3 '5,5' -tetrabromo- 4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'-biphenol, and mixtures thereof.

One embodiment is a method of preparing a poly(arylene ether) composition, comprising: adjusting the temperature of a solvent to a temperature in a range from about 3O⁰C to the atmospheric boiling point of the solvent; wherein the solvent is selected from C₃-Cs ketones, C₄-Cs N,N-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof; combining the temperature-adjusted solvent with a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and agitating the combined solvent and poly(arylene ether) to form the poly(arylene ether) composition; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C. In the step of combining the temperature-adjusted solvent with a poly(arylene ether), it is sometimes desirable to gradually add the poly(arylene ether) to the solvent.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and a solvent selected from C₃-Cs ketones, C₄- C₈ Λ/,JV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, Ci-C₃ chlorinated hydrocarbons, C₂-C₆ alkyl cyanides, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 10 to about 700 grams per kilogram of composition at 25⁰C. One embodiment is a composition, comprising: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and about 10 to about 70 weight percent of a second monohydric phenol selected from 2- allylphenol, 2-methyl-6-allylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C. The monomers may, optionally, further comprise a dihydric phenol selected from 2,2- bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4- bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4- hydroxyphenyl)pentanoic acid 2,2 ' 6,6 ' -tetramethyl-3 ,3 '5,5' -tetrabromo-4,4 ' - biphenol, 2,2'5,5'-tetramethyl-4,4'-biphenol, and mixtures thereof.

One embodiment is a composition, consisting of: a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 10 to about 70 weight percent of a second monohydric phenol selected from 2- allylphenol, 2-methyl-6-allylphenol, and mixtures thereof, and, optionally, about 2 to about 20 weight percent of a dihydric phenol selected from 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3 ,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and a solvent selected from methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a composition, comprising: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 96 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 2 to about 30 weight percent of a second monohydric phenol selected from 2-allylphenol, 2-methyl-6-allylphenol, and mixtures thereof, and about 2 to about 68 weight percent of a third monohydric phenol selected from 2-methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol, the second monohydric phenol, and third monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and about 20 to about 80 weight percent of a solvent selected from methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C. The monomers may, optionally, further comprise about 2 to about 20 weight percent of a dihydric phenol selected from 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof.

One embodiment is a composition, consisting of: about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 96 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 2 to about 30 weight percent of a second monohydric phenol selected from 2-allylphenol, 2-methyl-6-allylphenol, and mixtures thereof, about 2 to about 68 weight percent of a third monohydric phenol selected from 2-methylphenol, 2-methyl-6-phenylphenol, and mixtures thereof, and optionally, about 2 to about 20 weight percent of a dihydric phenol selected from 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3 ,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol, the second monohydric phenol, and third monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and about 20 to about 80 weight percent of a solvent selected from methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof; wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

One embodiment is a method of preparing a poly(arylene ether) composition, comprising: adjusting the temperature of a solvent to a temperature in a range from about 3O⁰C to the atmospheric boiling point of the solvent; wherein the solvent is selected from C₃-Cg ketones, C₄-Cg Λ/,JV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof; combining the temperature-adjusted solvent with a poly(arylene ether) that is the product of oxidative polymerization of monomers a first monohydric phenol having identical substituents in the 2- and 6- positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and agitating the combined solvent and poly(arylene ether) to form the poly(arylene ether) composition; wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C. In the step of combining the temperature-adjusted solvent with a poly(arylene ether), it is sometimes desirable to gradually add the poly(arylene ether) to the solvent.

The invention is further illustrated by the following non- limiting examples.

PREPARATIVE EXAMPLE 1 This example describes preparation of the monohydric phenol monomer 2-methyl-6- (l-phenylethyl)phenol (Chemical Abstracts Registry No. 17959-01-2). A 500- milliliter, three-neck, round bottom flask equipped with a mechanical stirrer, condenser, and nitrogen bypass connected to an oil bubbler was charged with 109.0 grams (0.0593 mole) of 2-methylphenol and heated to 60⁰C. The reaction mixture was treated with 1.60 grams (0.0593 mole) of aluminum flakes. After 0.5 hour, the aluminum flakes had dissolved, leaving a light brown, clear liquid. The mixture was heated to 180⁰C, at which point the evolution of gas was observed. The liquid was maintained at 18O⁰C for an additional 0.5 hour. The mixture was then cooled to 35°C, and styrene (105.0 grams, 1.008 moles) was added drop-wise through a pressure equalized addition funnel. The mixture was heated at 150⁰C for 1 hour, then cooled to room temperature. Water (100 milliliters), toluene (200 milliliters), chloroform (600 milliliters), and 0.1 M hydrochloric acid (100 milliliters) were added, and the aqueous and organic layer was separated. The organic layer was washed with 3 x 100 milliliters of water and dried over magnesium sulfate. The solvent was removed under vacuum. The product was distilled under vacuum, exhibiting a boiling point of 155°C at 0.1 kilopascal (1 torr). ¹H-NMR (D₆-DMSO) δ (ppm) 8.26 (s, IH); 7.26 (m, 4H); 7.14 (m, IH); 6.97 (d, IH); 6.93 (d, IH); 6.72 (t, IH); 4.59 (q, IH); 2.19 (s, 3H); 1.52 (d, 3H).

PREPARATIVE EXAMPLE 2

This example describes a typical preparation of a homopolymer of 2,6- dimethylphenol. A five-neck, 1 -liter round bottom flask equipped with an overhead stirrer, thermometer, and an oxygen diptube was charged with 0.125 grams (0.725 millimole) of JV,JV'-di-t-butylethylenediamine (DBEDA), 1.6 grams (15.8 millimole) of Λ/,Λ/-dimethylbutylamine (DMBA), 0.5 grams (3.87 millimole) of di-n-butylamine (DBA), 0.14 grams of methyltri-(C₈-Cio)-alkylammonium chloride obtained as Adogen 464, 100 grams of toluene, and 7.5 grams of a 50% toluene solution of 2,6- dimethylphenol (7.50 grams solution, 3.75 grams monomer, 31 millimoles monomer). A copper catalyst, 0.425 grams, (produced from a stock solution prepared by adding 14.3 grams of cuprous oxide to 187.07 grams of 48% hydrobromic acid), was added. With vigorous stirring oxygen was passed through the solution at 2 standard cubic feet per minute (SCFM) and a solution of 2,6-dimethylphenol (67.50 grams solution, 33.75 grams solution, 277 millimoles monomer). The reaction mixture was stirred for an additional 3 hours using a water bath to maintain a temperature of less than 35°C. The solution was then treated with 10 milliliters of glacial acetic acid to quench the catalyst. The polymer was isolated from the organic phase by methanol precipitation, and the resulting wet cake was dissolved in toluene and reprecipitated into methanol. The isolated solid dried overnight at 70⁰C under vacuum.

Properties are summarized in Table 1. Weight average molecular weight (M_w), number average molecular weight (M_n), polydispersity index (M_w/M_n), and Z average molecular weight (M_z) were determined by gel permeation chromatography in chloroform using polystyrene standards. Molecular weights are expressed in atomic mass units (AMU). Glass transition temperature was determined by differential scanning calorimetry (DSC), using a Perkin Elmer Differential Scanning Calorimeter, a scan rate of 2O⁰C per minute, and a nitrogen atmosphere.

PREPARATIVE EXAMPLE 3

Homopolymerization of 2-methyl-6-phenylphenol was conducted according to the procedure of Preparative Example 2, except that 2-methyl-6-phenylphenol was substituted (equimolar) for 2,6-dimethylphenol. Physical properties of the homopolymer so obtained are presented in Table 1.

PREPARATIVE EXAMPLE 4

This example describes a typical preparation of a poly(arylene ether) copolymer (poly(2,6-dimethyl- 1 ,4-phenylene-co-2-methyl-6-phenyl- 1 ,4-phenylene ether) using an equimolar mixture of 2,6-dimethylphenol and 2-methyl-6-phenylphenol as comonomers. A five-neck, 1 -liter round bottom flask equipped with an overhead stirrer, thermometer, and an oxygen diptube was charged with 0.125 grams (0.725 millimole) of DBEDA, 1.6 grams (15.8 millimoles) of DMBA, 0.5 grams (3.87 millimoles) of DBA, 0.14 grams of Adogen 464, 100 grams of toluene, and 5.6875 grams of a 50% toluene solution of 2-methyl-6-phenylphenol (2.84 grams, 15.6 millimoles; 10% of the total 2-methyl-6-phenylphenol) and 3.75 grams of a 50% toluene solution of 2,6-dimethylphenol (1.88 grams, 15.6 millimoles; 10% of the total 2,6-dimethylphenol). A copper catalyst, 0.425 grams, produced from a stock solution prepared by adding 14.3 grams of cuprous oxide to 187.07 grams of 48% hydrobromic acid, was added. An addition funnel was charged with 51.2 grams of a 50% toluene solution of 2-methyl-6-phenylphenol (25.59grams, 140.6 millimoles, 90% of total 2-methyl-6-phenylphenol) and 33.8 grams of a 50% toluene solution of 2,6-dimethylphenol (16.88 grams, 140.6 millimoles, 90% of the total 2,6- dimethylphenol). With vigorous stirring, oxygen was passed through the solution at 2 SCFM while the toluene solution of 2-methyl-6-phenylphenol/2,6-dimethylphenol was added drop-wise to the reaction mixture over a period of 30 minutes. After addition was complete, the reaction mixture was stirred for an additional 2 hours. The solution was then treated with 10 milliliters of glacial acetic acid to quench the catalyst, and the polymer was isolated from solution by methanol precipitation. The isolated filter cake was redissolved into toluene and methanol reprecipitated. Physical properties of the copolymer so obtained are presented in Table 1.

PREPARATIVE EXAMPLES 5-7

The procedure of Preparative Example 4 was used to prepare copolymers having the monomer compositions and properties specified for Preparative Examples 5-7 in Table 1. 2-Methyl-6-(l-phenylethyl)phenol (Chemical Abstracts Registry No. 17959-01-02) was synthesized as described in Preparative Example 1. 2- Methylphenol (ortho-cresol; Chemical Abstracts Registry No. 95-48-7), was obtained from Aldrich. Physical properties of the copolymers so obtained are presented in Table 1.

Table 1

EXAMPLES 1-4, COMPARATIVE EXAMPLES 1 AND 2

These examples describe testing of the solubility of the poly(arylene ether) homopolymers and copolymers whose preparation was described in Preparative Examples 2-7. Comparative Example 1 uses the homopolymer of 2,6-dimethylphenol prepared in Preparative Example 2. Comparative Examples 2 uses the homopolymer of 2-methyl-6-phenylphenol prepared in Preparative Example 3. Examples 1-4 use the copolymers prepared in Preparative Examples 4-7, respectively. Mixtures consisting of 20 weight percent poly(arylene ether) and 80 weight percent JV-methyl- 2-pyrrolidone (NMP), methyl ethyl ketone (MEK), or toluene were prepared at room temperature (23⁰C). The polymers were dissolved in the designated solvent with stirring at room temperature and allowed to stand at room temperature for four hours. Mixtures were visually inspected and categorized as either inhomogeneous/insoluble (I/I; phase separated solid, or liquid), homogeneous/insoluble (H/I; gel-like), or homogenous and soluble (H/S; formed a transparent solution). The results, presented in Table 2, show that inventive copolymer compositions corresponding to Examples 1-4 all produced homogeneous solutions at room temperature in MEK, NMP, and toluene. Gelation of the solution was determined using the tilt method described in A. Hiltner in J. Brandup and E. H. Immergut, Eds., "Polymer Handbook", Wiley-Interscience, New York: 1989, page VII/591. Specifically, In the Table 2 summary of gelation properties, "Y" means gelling occurred at 25⁰C, "N" means no gelling occurred at 25⁰C, and "NM" means not measured.

Table 2

Table 2 (cont.)

This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.

The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Further, it should further be noted that the terms "first," "second," and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity).

Claims

CLAIMS:

1. A composition, comprising:

a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and

a solvent selected from the group consisting of C₃-Cs ketones, C₄-Cs Λ/,jV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C1-C3 chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof;

wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C.

2. A composition, comprising:

a solvent comprising a C₃-Cs ketone;

wherein the poly(arylene ether) has a solubility in acetone of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and acetone.

3. A composition, comprising:

a solvent comprising a C₄-Cs N,N-dialkylamide; wherein the poly(arylene ether) has a solubility in Λ/,Λ/-dimethylformamide of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and Λ/,Λ/-dimethylformamide.

4. A composition, comprising:

a solvent comprising a C₄-Ci₆ dialkyl ether;

wherein the poly(arylene ether) has a solubility in ethylene glycol monomethyl ether of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethylene glycol monomethyl ether.

5. A composition, comprising:

a solvent comprising a C₆-Ci₂ aromatic hydrocarbon;

wherein the poly(arylene ether) has a solubility in toluene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and toluene.

6. A composition, comprising:

a solvent comprising a C₁-C₃ chlorinated hydrocarbon; wherein the poly(arylene ether) has a solubility in trichloro ethylene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and trichloroethylene.

7. A composition, comprising:

a solvent comprising a C₃-C₆ alkyl alkanoate;

wherein the poly(arylene ether) has a solubility in ethyl acetate of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethyl acetate.

8. A composition, comprising:

a solvent comprising a C₂-C₆ alkyl cyanide;

wherein the poly(arylene ether) has a solubility in acetonitrile of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and acetonitrile.

9. The composition of any of claims 1 - 8, wherein the poly(arylene ether) has a solubility in the composition of 10 to about 700 grams per kilogram of composition at

25⁰C

10. The composition of any of claims 1 - 9, wherein the first monohydric phenol has the formula

wherein Z¹ and Z² are the same and selected from the group consisting of halogen, unsubstituted or substituted Ci -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C₁-C₁₂ hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Z³ and Z⁴ are the same or different and each independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C₁-C₁₂ hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C₁-C₁₂ hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.

11. The composition of any of claims 1 - 10, wherein the first monohydric phenol is selected from the group consisting of 2,6-dimethylphenol, 2,6-diphenylphenol, and mixtures thereof.

12. The composition of any of claims 1 - 11, wherein the first monohydric phenol is 2,6-dimethylphenol.

13. The composition of any of claims 1 - 12, wherein the second monohydric phenol has the formula

wherein Z⁵, Z⁶, Z⁷, and Z⁸ are each independently hydrogen, halogen, unsubstituted or substituted C₁-C₁₂ hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C₁-C₁₂ hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C₁-C₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, with the proviso that Z⁵ and Z⁶ are different.

14. The composition of any of claims 1 - 13, wherein the second monohydric phenol is selected from the group consisting of 2-methylphenol, 2-ethylphenol, 2-(l- methylethyl)phenol, 2(l-methylpropyl)phenol, 2(l-methylbutyl)phenol, 2(1- methylpentyl)phenol, 2-(l-methylheptyl)phenol 2-(l-methylundecyl)phenol, 2- propylphenol, 2-cyclohexylphenol, 2-cyclopentylphenol, 2-cyclopropylphenol, 2-methy 1-6-phenylphenol, 2-methyl-6-benzylphenol, 2-( 1 -phenylethyl)phenol, 2-methyl-6-(l-phenylethyl)phenol, 2-ethyl-6-methylphenol, 2-methyl-6-(l- methylethyl)phenol, 2-methyl-6-( 1 -methylpropyl)phenol, 2-methyl-6-( 1 - methylbutyl)phenol, 2-methyl-6-( 1 -methylpentyl)phenol, 2-methyl-6-( 1 - methylheptyl)phenol, 2-methyl-6-(l -methylundecyl)phenol, 2-methyl-6- propylphenol, 2-cyclohexyl-6-methylphenol, 2-cyclopentyl-6-methylphenol, 2- cyclopropyl-6-methy lphenol, 2-methyl-6-methoxyphenol, 2-methyl-5 - isopropylphenol, 2-isopropyl-5-methylphenol, 2,5-dimethylphenol, 3- pentadecylphenol, and mixtures thereof.

15. The composition of any of claims 1 - 14, wherein the second monohydric phenol is selected from the group consisting of 2-methylphenol, 2-phenylphenol, 2- methyl-6-phenylphenol, and mixtures thereof.

16. The composition of any of claims 1 - 15, wherein the monomers further comprise a dihydric phenol having the formula

R³ O S O O R⁴ O , N , C > C _' S > S _' ^and C

O R⁵

wherein each occurrence of R³ is independently selected from the group consisting of hydrogen and C₁-C₁₂ hydrocarbyl, and each occurrence of R⁴ and R⁵ is independently selected from the group consisting of hydrogen, Ci-Ci₂ hydrocarbyl, and Ci-C₆ hydrocarbylene wherein R⁴ and R⁵ collectively form a C4-C12 alkylene group.

17. The composition of any of claims 1 - 16, wherein the dihydric phenol is selected from the group consisting of 3,3',5,5'-tetramethyl-4,4'-biphenol, 2,2-bis(3- methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)methane, 1 , 1 -bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)propane 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 1 , 1 -bis(4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)- n-butane, bis(4-hydroxyphenyl)phenylmethane, 2 ,2-bis(4-hydroxy-3 - methylphenyl)propane, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane, 1 , 1 -bis(4- hydroxy-3 ,5 -dimethy lphenyl)cyclopentane, 1 , 1 -bis(4-hydroxy-3 ,5 - dimethylphenyl)cyclohexane, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cycloheptane, 1,1- bis(4-hydroxy-3,5-dimethylphenyl)cycloheptane, l,l-bis(4-hydroxy-3- methylphenyl)cyclooctane, 1 , 1 -bis(4-hydroxy-3 ,5 -dimethylpheny^cyclooctane, 1,1- bis(4-hydroxy-3 -methylphenyl)cyclononane, 11,1 -bis(4-hydroxy-3 ,5 - dimethylphenyl)cyclononane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclodecane, 1,1- bis(4-hydroxy-3 ,5 -dimethy lphenyl)cyclodecane, 1 , 1 -bis(4-hydroxy-3- methylphenyl)cycloundecane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cycloundecane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclododecane, 1 , 1 -bis(4-hydroxy-3,5- dimethylphenyl)cyclododecane, 1 , 1 -bis(4-hydroxy-3-t-butylphenyl)propane, 2,2- bis(4-hydroxy-2,6-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)cyclopentane, 1 , 1 -bis(4- hydroxyphenyl)cyclohexane, and mixtures thereof.

18. The composition of any of claims 1 - 17, wherein the monomers comprise about 1 to about 90 weight percent of the first monohydric phenol and about 10 to about 99 weight percent of the second monohydric phenol, based on the total weight of the monomers.

19. The composition of any of claims 1 - 18, wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 1.5 deciliters per gram, measured at 25⁰C in chloroform.

20. The composition of any of claims 1 - 19, wherein the poly(arylene ether) has an intrinsic viscosity of about 0.2 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform.

21. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C3-C8 ketone.

22. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof.

23. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises acetone.

24. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C₄-C₈ JWdialkylamide.

25. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of dimethylformamide, dimethylacetamide, JV-methyl-2- pyrrolidone, and mixtures thereof.

26. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises JV-methyl-2-pyrrolidone.

27. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C4-C16 dialkyl ether.

28. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of ethylene glycol monomethyl ether, tetrahydrofuran, dioxane, and mixtures thereof.

29. The composition of any of claims 1 and 9 - 20, wherein the solvent is ethylene glycol monomethyl ether.

30. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C₆-Ci₂ aromatic hydrocarbon.

31. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of benzene, toluene, xylenes, styrene, divinylbenzenes, and mixtures thereof.

32. The composition of any of claims 1 and 9 - 20, wherein the solvent is toluene.

33. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C1-C3 chlorinated hydrocarbon.

34. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of trichloroethylene, trichloroethane, methylene chloride, and mixtures thereof.

35. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C3-C6 alkyl alkanoate.

36. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and mixtures thereof.

37. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C₂-C₆ alkyl cyanide.

38. The composition of any of claims 1 and 9 - 20, wherein the solvent is selected from the group consisting of acetonitrile, propionitrile, butyronitrile, and mixtures thereof.

39. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises a C₂-C₆ dialkyl sulfoxide.

40. The composition of any of claims 1 and 9 - 20, wherein the solvent comprises dimethyl sulfoxide.

41. The composition of any of claims 1 - 40, comprising about 1 to about 70 weight percent of the poly(arylene ether) and about 30 to about 99 weight percent of the solvent, based on the total weight of the composition.

42. The composition of any of claims 1 - 41, comprising about 10 to about 50 weight percent of the poly(arylene ether) and about 50 to about 90 weight percent of the solvent, based on the total weight of the composition.

43. The composition of any of claims 1 - 42, wherein the poly(arylene ether) has a solubility in the composition of at least 100 grams per kilogram of composition at

25⁰C.

44. The composition of any of claims 1 - 43, wherein the poly(arylene ether) has a solubility in the composition of at least 200 grams per kilogram of composition at

25⁰C.

45. The composition of any of claims 1 - 44, wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

46. The composition of any of claims 1 - 45, having a gel temperature less than or equal to 25⁰C.

47. The composition of any of claims 1 - 46, further comprising a thermoset resin.

48. The composition of any of claims 1 - 47, further comprising a filler.

49. The composition of any of claims 1 - 48, further comprising an additive selected from the group consisting of curing promoters, curing inhibitors, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof.

50. A composition, consisting of:

a solvent selected from the group consisting of C₃-Cg ketones, C₄-Cg Λ/,jV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof;

wherein the poly(arylene ether) has a solubility in the composition of about 10 to about 700 grams per kilogram of composition at 25⁰C.

51. A composition, comprising:

a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising

about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and

about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6- phenylphenol, and mixtures thereof; wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; wherein the monomers are free of ethylenic unsaturation; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and

a solvent selected from the group consisting of acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof;

wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C; and

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

52. The composition of claim 51, wherein the monomers further comprise a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3 ,5- dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2 '6,6 ' -tetramethyl-3 ,3 ' 5 ,5 ' -tetrabromo-4,4 ' -biphenol, 2,2 '5 ,5 ' -tetramethyl-4,4 '- biphenol, and mixtures thereof.

53. A composition, consisting of:

about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol,

about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6- phenylphenol, and mixtures thereof, and

optionally, a dihydric phenol selected from the group consisting of 2,2- bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6- dimethylphenyl)propane, 4,4-bis(3 ,5-dimethyl-4- hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'- tetramethyl-4,4'-biphenol, and mixtures thereof;

wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; wherein the monomers are free of ethylenic unsaturation; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

54. A composition, comprising:

about 20 to about 50 weight percent of a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising

about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6- phenylphenol, and mixtures thereof;

wherein the monomers are free of ethylenic unsaturation; wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; about 20 to about 80 weight percent of a solvent selected from the group consisting of acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof;

wherein the weight percents of the poly(arylene ether) and the solvent are based on the total weight of the composition;

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

55. The composition of claim 54, wherein the monomers further comprise about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid, 4,4-bis(4- hydroxyphenyl)pentanoic acid, 2,2 ' 6,6 ' -tetramethyl-3 ,3 '5,5' -tetrabromo-4,4 ' - biphenol, 2,2'5,5'-tetramethyl-4,4'-biphenol, and mixtures thereof.

56. A composition, consisting of:

optionally, about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6- dimethylphenyl)propane, 4,4-bis(3 ,5-dimethyl-4- hydroxyphenyl)pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo-4,4'-biphenol, 2,2'5,5'- tetramethyl-4,4'-biphenol, and mixtures thereof;

wherein the monomers are free of ethylenic unsaturation; wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers;

about 20 to about 80 weight percent of a solvent selected from the group consisting of acetone, methyl ethyl ketone, JV-methyl-2-pyrrolidone, toluene, and mixtures thereof;

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

57. A method of preparing a poly(arylene ether) composition, comprising:

adjusting the temperature of a solvent to a temperature in a range from about 3O⁰C to the atmospheric boiling point of the solvent; wherein the solvent is selected from the group consisting of C₃-Cg ketones, C₄-Cg Λ/,JV-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof;

combining the temperature-adjusted solvent with a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol having different substituents in the 2- and 6-positions; wherein the monomers are free of ethylenic unsaturation; and

agitating the combined solvent and poly(arylene ether) to form the poly(arylene ether) composition; wherein the poly(arylene ether) has a solubility in the composition of at least 10 grams per kilogram of composition at 25⁰C.

58. The method of claim 57, wherein said combining the temperature-adjusted solvent with a poly(arylene ether) comprises adding the poly(arylene ether) to the solvent.

59. A composition, comprising:

a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and

a solvent selected from the group consisting of C₃-C₈ ketones, C₄-C₈ N,N-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C1-C3 chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof;

60. The composition of claim 59, wherein the poly(arylene ether) has a solubility in the composition of 10 to about 700 grams per kilogram of composition at 25⁰C

61. The composition of any of claims 59 - 60, wherein the first monohydric phenol has the formula

62. The composition of any of claims 59 - 61, wherein the first monohydric phenol is selected from the group consisting of 2,6-dimethylphenol, 2,6- diphenylphenol, and mixtures thereof.

63. The composition of any of claims 59 - 62, wherein the first monohydric phenol is 2,6-dimethylphenol.

64. The composition of any of claims 59 - 63, wherein the second monohydric phenol comprises at least one ethylenically unsaturated substituent bound directly to the phenol aromatic ring, wherein the ethylenically unsaturated substituent is

wherein n is 0 or 1, R⁷, R⁸, and R⁹ are each independently hydrogen or Ci-C₆ alkyl, R¹⁰ is C₁-C₁₂ hydrocarbylene, and X is selected from the group consisting of -C(=O)-, -O- , -N(R¹¹)-, -C(=O)O-, or -C(=0)N(R^π)-, wherein R¹¹ is hydrogen, methyl, vinyl, or allyl.

65. The composition of claim 64, wherein the second monohydric phenol comprises, in addition to the at least one ethylenically unsaturated substituent, at least one directly bound substituent selected from the group consisting of halogen, unsubstituted or substituted C1-C12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, Ci-Ci₂ hydrocarbyloxy, or C₂-Ci₂ halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.

66. The composition of any of claims 59 - 65, wherein the second monohydric phenol is selected from the group consisting of 2-vinylphenol, 2-allylphenol, 2- methyl-6-vinylphenol, 2-methyl-6-allylphenol, 2-(N,N-diallylaminomethyl)phenol, 2- (N,N-diallylpropionamido)phenol, 2-methyl-6-allyloxyphenol, and mixtures thereof.

67. The composition of any of claims 59 - 66, wherein the second monohydric phenol is 2-allylphenol, 2-methyl-6-allylphenol, or a mixture thereof.

68. The composition of any of claims 59 - 67, wherein the monomers further comprise a third monohydric phenol different from the second monohydric phenol and having the formula

wherein Z⁹, Z¹⁰, Z¹¹, and Z¹² are each independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C₁-C₁₂ hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, Ci -C 12 hydrocarbylthio, C₁-C₁₂ hydrocarbyloxy, or C₁-C₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, with the proviso that Z⁹ and Z¹⁰ are different.

69. The composition of any of claims 59 - 68, wherein the monomers further comprise a dihydric phenol having the formula

-o- -

wherein each occurrence of R³ is independently selected from the group consisting of hydrogen and C₁-C₁₂ hydrocarbyl, and each occurrence of R⁴ and R⁵ is independently selected from the group consisting of hydrogen, C₁-C₁₂ hydrocarbyl, and Ci-C₆ hydrocarbylene wherein R⁴ and R⁵ collectively form a C4-C12 alkylene group.

70. The composition of claim 69, wherein the dihydric phenol is selected from the group consisting of 3,3',5,5'-tetramethyl-4,4'-biphenol, 2,2-bis(3-methyl-4- hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, l,l-bis(4- hydroxyphenyl)methane, 1 , 1 -bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)propane 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 1 , 1 -bis(4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)- n-butane, bis(4-hydroxyphenyl)phenylmethane, 2 ,2-bis(4-hydroxy-3 - methylphenyl)propane, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane, 1 , 1 -bis(4- hydroxy-3 ,5 -dimethy lphenyl)cyclopentane, 1 , 1 -bis(4-hydroxy-3 ,5 - dimethylphenyl)cyclohexane, 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cycloheptane, 1,1- bis(4-hydroxy-3,5-dimethylphenyl)cycloheptane, l,l-bis(4-hydroxy-3- methylphenyl)cyclooctane, 1 , 1 -bis(4-hydroxy-3 ,5 -dimethylpheny^cyclooctane, 1,1- bis(4-hydroxy-3 -methylphenyl)cyclononane, 11,1 -bis(4-hydroxy-3 ,5 - dimethylphenyl)cyclononane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclodecane, 1,1- bis(4-hydroxy-3 ,5 -dimethy lphenyl)cyclodecane, 1 , 1 -bis(4-hydroxy-3- methylphenyl)cycloundecane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cycloundecane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclododecane, 1 , 1 -bis(4-hydroxy-3,5- dimethylphenyl)cyclododecane, 1 , 1 -bis(4-hydroxy-3-t-butylphenyl)propane, 2,2- bis(4-hydroxy-2,6-dimethylphenyl)propane 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)cyclopentane, 1 , 1 -bis(4- hydroxyphenyl)cyclohexane, and combinations thereof.

71. The composition of any of claims 59 - 70, wherein the monomers comprise about 5 to about 95 weight percent of the first monohydric phenol and about 5 to about 95 weight percent of the second monohydric phenol, based on the total weight of the monomers.

72. The composition of any of claims 59 - 71, wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 1.5 deciliters per gram, measured at 25⁰C in chloroform.

73. The composition of any of claims 59 - 72, wherein the poly(arylene ether) has an intrinsic viscosity of about 0.2 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform.

74. The composition of any of claims 59 - 73, wherein the solvent comprises a C3-C8 ketone.

75. The composition of any of claims 59 - 74, wherein the solvent is selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof.

76. The composition of any of claims 59 - 75, wherein the solvent comprises acetone.

77. The composition of any of claims 59 - 73, wherein the solvent comprises a C₄-C₈ N,N-dialkylamide.

78. The composition of any of claims 59 - 73, wherein the solvent is selected from the group consisting of dimethylformamide, dimethylacetamide, N-methyl-2- pyrrolidone, and mixtures thereof.

79. The composition of any of claims 59 - 73, wherein the solvent comprises N- methyl-2-pyrrolidone.

80. The composition of any of claims 59 - 73, wherein the solvent comprises a C₄- Ci6 dialkyl ether.

81. The composition of any of claims 59 - 73, wherein the solvent is selected from the group consisting of ethylene glycol monomethyl ether, tetrahydrofuran, dioxane, and mixtures thereof.

82. The composition of any of claims 59 - 73, wherein the solvent is ethylene glycol monomethyl ether.

83. The composition of any of claims 59 - 73, wherein the solvent comprises a C₆- C₁₂ aromatic hydrocarbon.

84. The composition of any of claims 59 - 73, wherein the solvent is selected from the group consisting of benzene, toluene, xylenes, styrene, divinylbenzenes, and mixtures thereof.

85. The composition of any of claims 59 - 73, wherein the solvent is toluene.

86. The composition of any of claims 59 - 73, wherein the solvent comprises a Ci- C3 chlorinated hydrocarbon.

87. The composition of any of claims 59 - 73, wherein the solvent is selected from the group consisting of trichloroethylene, trichloroethane, methylene chloride, and mixtures thereof.

88. The composition of any of claims 59 - 73, wherein the solvent comprises a C3- Ce alkyl alkanoate.

89. The composition of any of claims 59 - 73, wherein the solvent is selected from the group consisting of methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and mixtures thereof.

90. The composition of any of claims 59 - 73, wherein the solvent comprises a C₂- Ce alkyl cyanide.

91. The composition of any of claims 59 - 73, wherein the solvent is selected from the group consisting of acetonitrile, propionitrile, butyronitrile, and mixtures thereof.

92. The composition of any of claims 59 - 73, wherein the solvent comprises a C₂- Ce dialkyl sulfoxide.

93. The composition of any of claims 59 - 73, wherein the solvent comprises dimethyl sulfoxide.

94. The composition of any of claims 59 - 93, comprising about 1 to about 70 weight percent of the poly(arylene ether) and about 30 to about 99 weight percent of the solvent, based on the total weight of the composition.

95. The composition of any of claims 59 - 94, comprising about 10 to about 50 weight percent of the poly(arylene ether) and about 50 to about 90 weight percent of the solvent, based on the total weight of the composition.

96. The composition of any of claims 59 - 95, wherein the poly(arylene ether) has a solubility in the composition of at least 100 grams per kilogram of composition at

25⁰C.

97. The composition of any of claims 59 - 96, wherein the poly(arylene ether) has a solubility in the composition of at least 200 grams per kilogram of composition at

25⁰C.

98. The composition of any of claims 59 - 97, wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

99. The composition of any of claims 59 - 98, having a gel temperature less than or equal to 25⁰C.

100. The composition of any of claims 59 - 99, further comprising a poly(arylene ether) that is the product of oxidative polymerization of monomers that are free of ethylenic unsaturation.

101. The composition of any of claims 59 - 100, further comprising a thermoset resin.

102. The composition of claim 101, further comprising a filler.

103. The composition of claim 101, further comprising an additive selected from the group consisting of curing promoters, curing inhibitors, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow- promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof.

104. A composition, comprising:

a solvent comprising a C₃-Cs ketone;

wherein the poly(arylene ether) has a solubility in methyl ethyl ketone of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and methyl ethyl ketone.

105. A composition, comprising :

a solvent comprising a C₄-Cg N,N-dialkylamide;

wherein the poly(arylene ether) has a solubility in N-methyl-2-pyrrolidone of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and N-methyl-2-pyrrolidone.

106. A composition, comprising:

a solvent comprising a C₄-Ci₆ dialkyl ether; wherein the poly(arylene ether) has a solubility in ethylene glycol monomethyl ether of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethylene glycol monomethyl ether.

107. A composition, comprising:

a solvent comprising a C₆-Ci₂ aromatic hydrocarbon;

108. A composition, comprising:

a solvent comprising a C₁-C₃ chlorinated hydrocarbon;

wherein the poly(arylene ether) has a solubility in trichloroethylene of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and trichloroethylene .

109. A composition, comprising:

a solvent comprising a C₃-C₆ alkyl alkanoate; wherein the poly(arylene ether) has a solubility in ethyl acetate of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) and ethyl acetate.

110. A composition, comprising:

a solvent comprising a C₂-C₆ alkyl cyanide;

111. A composition, consisting of:

a solvent selected from the group consisting of C₃-Cs ketones, C₄-Cs N₅N- dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, C1-C3 chlorinated hydrocarbons, C₃-C₆ alkyl alkanoates, C₂-C₆ alkyl cyanides, C₂-C₆ dialkyl sulfoxides, and mixtures thereof;

112. A composition, comprising:

a poly(arylene ether) that is the product of oxidative polymerization of monomers comprising about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, and

about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6- allylphenol, and mixtures thereof;

wherein the weight percents of the first monohydric phenol and the second monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 0.6 deciliter per gram, measured at 25⁰C in chloroform; and

a solvent selected from the group consisting of methyl ethyl ketone, N-methyl- 2-pyrrolidone, toluene, and mixtures thereof;

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

113. The composition of claim 112, wherein the monomers further comprise a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3 ,5- dimethyl-4-hydroxyphenyl)-pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid 2,2'6,6'-tetramethyl-3,3'5,5'-tetrabromo4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'- biphenol, and mixtures thereof.

114. A composition, consisting of:

about 30 to about 90 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 10 to about 70 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6- allylphenol, and mixtures thereof, and

optionally, about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6- dimethylphenyl)propane, 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)- pentanoic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid 2,2'6,6'- tetramethyl-3,3 '5,5 '-tetrabromo4,4'-biphenol, 2,2'5,5 '-tetramethyl- 4,4'-biphenol, and mixtures thereof;

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

115. A composition, comprising :

about 30 to about 96 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol,

about 2 to about 30 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6- allylphenol, and mixtures thereof, and about 2 to about 68 weight percent of a third monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6- phenylphenol, and mixtures thereof;

wherein the weight percents of the first monohydric phenol, the second monohydric phenol, and third monohydric phenol are based on the total weight of monomers; and wherein the poly(arylene ether) has an intrinsic viscosity of about 0.1 to about 0.6 deciliters per gram, measured at 25⁰C in chloroform; and

about 20 to about 80 weight percent of a solvent selected from the group consisting of methyl ethyl ketone, N-methyl-2-pyrrolidone, toluene, and mixtures thereof;

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

116. The composition of claim 115, wherein the monomers further comprise about 2 to about 20 weight percent of a dihydric phenol selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)-pentanoic acid, 4,4-bis(4- hydroxyphenyl)pentanoic acid 2,2'6,6'-tetramethyl-3,3 '5,5 '-tetrabromo4,4'-biphenol, 2,2'5,5'-tetramethyl-4,4'-biphenol, and mixtures thereof.

117. A composition, consisting of:

about 30 to about 96 weight percent of a first monohydric phenol comprising 2,6-dimethylphenol, about 2 to about 30 weight percent of a second monohydric phenol selected from the group consisting of 2-allylphenol, 2-methyl-6- allylphenol, and mixtures thereof,

about 2 to about 68 weight percent of a third monohydric phenol selected from the group consisting of 2-methylphenol, 2-methyl-6- phenylphenol, and mixtures thereof, and

wherein the poly(arylene ether) is soluble in the composition at 25⁰C.

118. A method of preparing a poly(arylene ether) composition, comprising: adjusting the temperature of a solvent to a temperature in a range from about 3O⁰C to the atmospheric boiling point of the solvent; wherein the solvent is selected from the group consisting Of C₃-C₈ ketones, C₄-C₈ N,N-dialkylamides, C₄-Ci₆ dialkyl ethers, C₆-Ci₂ aromatic hydrocarbons, and mixtures thereof;

combining the temperature-adjusted solvent with a poly(arylene ether) that is the product of oxidative polymerization of monomers a first monohydric phenol having identical substituents in the 2- and 6-positions, and a second monohydric phenol comprising ethylenic unsaturation and having different substituents in the 2- and 6-positions; and

agitating the combined solvent and poly(arylene ether) to form the poly(arylene ether) composition;

wherein the poly(arylene ether) has a solubility in the composition of about 100 to about 700 grams per kilogram of composition at 25⁰C.

119. The method of claim 118, wherein said combining the temperature-adjusted solvent with a poly(arylene ether) comprises adding the poly(arylene ether) to the solvent.

120. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising:

2,6-dimethylphenol; and

a phenyl-substituted monohydric phenol having the structure

wherein q is 0 or 1, and R¹² and R¹³ are independently hydrogen or Ci-C₆ alkyl; wherein when q is 0, the monomers further comprise 2-methylphenol, 2,2-bis(3,5-dimethyl-4-hydroxy)propane, or a mixture thereof.

121. The poly(arylene ether) copolymer of claim 120, wherein the poly(arylene ether) copolymer has a solubility in a solvent of at least 10 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and solvent; wherein the solvent is selected from the group consisting of acetone, Λ/,Λ/-dimethylformamide, ethylene glycol monomethyl ether, toluene, trichloroethylene, ethyl acetate, and acetonitrile.

122. The poly(arylene ether) copolymer of any of claims 120 - 121, wherein the poly(arylene ether) copolymer has a solubility in acetone of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and acetone.

123. The poly(arylene ether) copolymer of any of claims 120 - 122, wherein the poly(arylene ether) copolymer has a solubility in Λ/,Λ/-dimethylformamide of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and Λ/,Λ/-dimethylformamide.

124. The poly(arylene ether) copolymer of any of claims 120 - 123, wherein the poly(arylene ether) copolymer has a solubility in ethylene glycol monomethyl ether of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and ethylene glycol monomethyl ether.

125. The poly(arylene ether) copolymer of any of claims 120 - 124, wherein the poly(arylene ether) copolymer has a solubility in toluene of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and toluene.

126. The poly(arylene ether) copolymer of any of claims 120 - 125, wherein the poly(arylene ether) copolymer has a solubility in trichloroethylene of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and trichloroethylene.

127. The poly(arylene ether) copolymer of any of claims 120 - 126, wherein the poly(arylene ether) copolymer has a solubility in ethyl acetate of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and ethyl acetate.

128. The poly(arylene ether) copolymer of any of claims 120 - 127, wherein the poly(arylene ether) copolymer has a solubility in acetonitrile of about 200 to about 700 grams per kilogram at 25⁰C, based on the total weight of poly(arylene ether) copolymer and acetonitrile.

129. The poly(arylene ether) copolymer of any of claims 120 - 128, wherein q is 0.

130. The poly(arylene ether) copolymer of any of claims 120 - 128, wherein q is 1.

131. The poly(arylene ether) copolymer of any of claims 120 - 128, wherein q is 1, and R¹² and R¹³ are independently hydrogen or methyl.

132. The poly(arylene ether) copolymer of any of claims 120 - 128, wherein q is 1, R¹² is hydrogen, and R¹³ is methyl.

133. The poly(arylene ether) copolymer of any of claims 120 - 132, having a number average molecular weight of about 2,000 to about 50,000 atomic mass units.

134. The poly(arylene ether) copolymer of any of claims 120 - 133, wherein the monomers comprise about 1 to about 90 weight percent of 2,6-dimethylphenol and about 10 to about 99 weight percent of the phenyl-substituted monohydric phenol, wherein all weight percents are based on the total weight of the monomers.

135. The poly(arylene ether) copolymer of any of claims 120 - 128, wherein q is 0, and wherein the monomers comprise

about 1 to about 89 weight percent of 2,6-dimethylphenol;

about 10 to about 98 weight percent of the phenyl-substituted monohydric phenol; and about 1 to about 89 weight percent of 2-methylphenol, 2,2-bis(3,5-dimethyl-4- hydroxy)propane, or a mixture thereof;

wherein all weight percents are based on the total weight of the monomers.

136. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 90 weight percent of 2,6-dimethylphenol and about 10 to about 99 weight percent of 2-methyl-6-(l-phenylethyl)phenol.

137. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 90 weight percent of 2,6-dimethylphenol and about 10 to about 99 weight percent of 2-methyl-6-(l-phenylethyl)phenol.

138. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 89 weight percent of 2-methylphenol.

139. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 89 weight percent of 2-methylphenol.

140. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers comprising about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 20 weight percent of 2,2-bis(3,5-dimethyl-4-hydroxypheny)propane.

141. A poly(arylene ether) copolymer formed by oxidative copolymerization of monomers consisting of about 1 to about 89 weight percent of 2,6-dimethylphenol, and about 10 to about 98 weight percent of 2-methyl-6-phenylphenol, and about 1 to about 20 weight percent of 2,2-bis(3,5-dimethyl-4-hydroxypheny)propane.