Poly(arylene ether) copolymer

Abstract

A poly(arylene ether) copolymer is the product of oxidative copolymerization of monomers including a monohydric phenol and a dihydric phenol of the formulawherein R3, R4, R5, and R6 are as defined herein. The poly(arylene ether) copolymer includes less than 0.1 weight percent of incorporated amine groups. A method of the manufacture of a poly(arylene ether) copolymer is also disclosed. A curable composition including the poly(arylene ether) copolymer and cured products derived therefrom are also described.

What is claimed is: 
     
         1 . A poly(arylene ether) copolymer,
 wherein the poly(arylene ether) copolymer is the product of oxidative copolymerization of monomers comprising a monohydric phenol and a dihydric phenol, wherein the dihydric phenol is of the formula   
       
         
           
           
               
               
           
         
         wherein R 3  and R 4  and R 5  and R 6  are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C 1-12  primary or secondary hydrocarbyl, C 1-12  hydrocarbylthio, C 1-12  hydrocarbyloxy, or C 2-12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Y has a structure 
       
       
         
           
           
               
               
           
         
         wherein each occurrence of R 7  is independently hydrogen or C 1-12  hydrocarbyl, and each occurrence of R 8  and R 9  is hydrogen, C 1-12  hydrocarbyl, or C 1-6  hydrocarbylene wherein R 8  and R 9  collectively form a C 4-12  cycloalkylene group; 
         wherein the poly(arylene ether) copolymer comprises less than or equal to 0.1 weight percent of incorporated amine groups. 
       
     
     
         2 . The poly(arylene ether) copolymer of  claim 1 , wherein the monohydric phenol comprises 2,6-dimethyl phenol, 2,3,6-trimethyl phenol, or a combination thereof, and the dihydric phenol comprises 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane. 
     
     
         3 . The poly(arylene ether) copolymer of  claim 1 , wherein the poly(arylene ether) copolymer has a number average molecular weight of 500 to 2,500 grams per mole and a weight average molecular weight of 1,000 to 6,000 grams per mole, wherein number average molecular weight and weight average molecular weight are as determined by gel permeation chromatography. 
     
     
         4 . The poly(arylene ether) copolymer of  claim 1 , wherein the poly(arylene ether) copolymer comprises 0.001 to 0.1 weight percent of incorporated amine groups. 
     
     
         5 . The poly(arylene ether) copolymer of  claim 1 , wherein the poly(arylene ether) copolymer comprises 0.01 to 0.1 weight percent of incorporated groups. 
     
     
         6 . The polyarene ether) copolymer of  claim 1 , wherein the oxidative copolymerization is in the presence of a catalyst composition excluding a secondary monoamine; and wherein the poly(arylene ether) copolymer is devoid of incorporated amine groups and the poly(arylene ether) copolymer has an average of 1.8 to 2 hydroxyl groups per molecule. 
     
     
         7 . The poly(arylene ether) copolymer of  claim 1 , wherein the oxidative copolymerization is in the presence of a catalyst composition excluding a secondary monoamine; and wherein the poly(arylene ether) copolymer is devoid of incorporated amine groups and has a ratio of weight average molecular weight to number average molecular weight of 1.9 to 3. 
     
     
         8 . The poly(arylene ether) copolymer of  claim 1 , wherein the oxidative copolymerization is in the presence of a catalyst composition excluding a secondary monoamine; and wherein the poly(arylene ether) copolymer is devoid of incorporated amine groups and has an intrinsic viscosity if 0.04 to 0.15 deciliter per gram measured at 25° C. in chloroform. 
     
     
         9 . The poly(arylene ether) copolymer of  claim 1 , wherein the poly(arylene ether) copolymer has an intrinsic viscosity if 0.04 to 0.15 deciliter per gram measured at 25° C. in chloroform. 
     
     
         10 . The poly(arylene ether) copolymer of  claim 5 , wherein the poly(arylene ether) copolymer has an average of 1.8 to 2 hydroxyl groups per molecule. 
     
     
         11 . A method of making a poly(arylene ether) copolymer, the method comprising:
 oxidatively copolymerizing a monohydric phenol and a dihydric phenol in a solvent in the presence of a catalyst composition comprising
 a metal source; 
 0.18 to 0.40 weight percent of a secondary alkylene diamine ligand; 
 0 to 0.2 weight percent of a secondary monoamine; and 
 a tertiary monoamine; 
 wherein weight percent of each component of the catalyst composition is based on the total weight of the monohydric phenol and the dihydric phenol; 
   to form the poly(arylene ether) copolymer.   
     
     
         12 . The method of  claim 11 , wherein the catalyst composition comprises 0.05 to 0.15 weight percent secondary monoamine; and wherein the poly(arylene ether) copolymer comprises 0.01 to 0.1 weight percent of incorporated amine groups. 
     
     
         13 . The method of  claim 11 , wherein the catalyst composition excludes a secondary monoamine and the poly(arylene ether) copolymer is devoid of incorporated amine groups. 
     
     
         14 . A poly(arylene ether) copolymer made by the method of  claim 11 , wherein the poly(arylene ether) copolymer has
 a number average molecular weight of 500 to 2,500 grams per mole and a weight average molecular weight of 1,000 to 6,000 grams per mole, wherein number average molecular weight and weight average molecular weight are as determined by gel permeation chromatography;   an intrinsic viscosity if 0.04 to 0.15 deciliter per gram measured at 25° C. in chloroform;   less than or equal to 0.1 weight percent of incorporated dibutylamine groups; and   0.5 to 1.5 weight percent of units derived from 3,3′,5,5′-tetramethyl-4,4′-biphenol.   
     
     
         15 . A curable composition comprising
 the poly(arylene ether) copolymer of  claim 1 ;   an auxiliary curable resin, a curable unsaturated monomer composition, or both; and   optionally, a curing promoter.   
     
     
         16 . The curable composition of  claim 15 , wherein the auxiliary curable resin comprises an epoxy resin, a cyanate ester resin, a maleimide resin, a benzoxazine resin, a vinylbenzyl ether resin, an arylcyclobutene resin, a perfluorovinyl ether resin, oligomers or polymers with curable vinyl functionality, or a combination thereof, and the curable unsaturated monomer composition comprises a monofunctional styrenic compound, a monofunctional (meth)acrylic compound, a polyfunctional allylic compound, a polyfunctional (meth)acrylate, a polyfunctional (meth)acrylamide, a polyfunctional styrenic compound, or a combination thereof 
     
     
         17 . The curable composition of  claim 15 , comprising
 the poly(arylene ether) copolymer of  claim 1 ,   an epoxy resin, a cyanate ester resin, or a combination thereof; and   optionally a curing promoter.   
     
     
         18 . A thermoset composition comprising a cured product of the composition of  claim 15 . 
     
     
         19 . An article comprising the thermoset composition of  claim 18 . 
     
     
         20 . The article of  claim 19 , wherein the article is in the form of a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, or a combination comprising at least one of the foregoing.