# US 11,111,336 B2 · Poly(phenylene ether) copolymer process and compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,336 B2 - Document ID: US11111336B2 - Status: Granted - Kind: B2 - Application number: 16/497,553 - Filed: 2018-03-27 - Published: 2020-06-25 - Granted: 2021-09-07 - Earliest claimed: 2017-04-21 - Assignees: Shpp Global Technologies B.V. - Applicants: Shpp Global Technologies B.V. - Inventors: Eylem Tarkin-Tas; Huseyin Tas; Mark R. Denniston - Web page: https://patentgrep.com/patent/US11111336B2 ## CPC - C08G 65/44: by oxidation of phenols - C08G 65/4087: {characterised by the catalyst used} - C08G 65/4093: {characterised by the process or apparatus used} - C08L 71/123: {not modified by chemical after-treatment} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A poly(phenylene ether) copolymer of 2-methyl-6-phenylphenol and a dihydric phenol having an absolute number average molecular weight of 1,000 to 10,000 grams/mole is made by polymerization of 2-methyl-6-phenylphenol and a dihydric phenol in the presence of molecular oxygen, a polymerization catalyst comprising a metal ion and at least one amine ligand, and a solvent composed of at least 95 weight percent of a C1-C3 alcohol selected from methanol, ethanol, 1-propanol, and 2-propanol. The poly(phenylene ether) copolymer can be, for example, a copolymer of 2-methyl-6-phenylphenol, 2,2-bis(3,5-dimethyl-4-hydroxyphenol)propane, and optionally 2,6-dimethylphenol. The poly(phenylene ether) copolymer finds utility in curable compositions, cured compositions, and articles. ## Claims ### Claim 1 A process for forming a poly(phenylene ether) copolymer, the process comprising: reacting a monohydric phenol comprising 2-methyl-6-phenylphenol and a dihydric phenol in the presence of molecular oxygen, a polymerization catalyst comprising a metal ion and at least one amine ligand, and a solvent to form a copolymer of 2-methyl-6-phenylphenol and the dihydric phenol; wherein: the monohydric phenol comprises, based on the total weight of monohydric phenol and dihydric phenol, less than 0.5 weight percent of monohydric phenols having identical substituents in the 2- and 6-positions of the phenolic ring; the copolymer comprises less than 0.005 weight percent of di(C1-C6-alkyl)amino groups, based on the weight of the copolymer; the copolymer has an absolute number average molecular weight of 1,000 to 10,000 grams/mole, calculated from integrated areas under resonance peaks in the 1H-NMR spectrum of the copolymer; and the solvent comprises, based on the total weight of the solvent, at least 95 weight percent of a C1-C3 alcohol selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol. ### Claim 2 (depends on 1) The process of claim 1, wherein the polymerization catalyst comprises copper ion, bromide ion, and N,N′-di-tert-butylethylenediamine. ### Claim 3 (depends on 1) The process of claim 1, wherein the copolymer has an absolute number average molecular weight of 1,000 to 5,000 grams/mole. ### Claim 4 (depends on 1) The process of claim 1, wherein the copolymer comprises 80 to 99 weight percent of repeat units derived from the monohydric phenol and 1 to 20 weight percent of repeat units derived from the dihydric phenol. ### Claim 5 (depends on 1) The process of claim 1, wherein the dihydric phenol has the structure: wherein each occurrence of R1 and R2 and R3 and R4 is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, and C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; z is 0 or 1; and Y is selected from the group consisting of wherein each occurrence of R5-R8 is independently hydrogen, C1-C12 hydrocarbyl, or C1-C6 hydrocarbylene wherein the two occurrences of R5 collectively form a C4-C12 alkylene group. ### Claim 6 (depends on 5) The process of claim 5, wherein z is 1. ### Claim 7 (depends on 1) The process of claim 1, wherein the dihydric phenol comprises 2,2-bis(3,5-dimethyl-4-hydroxyphenol)propane. ### Claim 8 (depends on 1) The process of claim 1, wherein the amine ligand comprises a di(C1-C6-alkyl)amine; and wherein the copolymer of 2-methyl-6-phenylphenol and the dihydric phenol comprises less than 0.005 weight percent of di(C1-C6-alkyl)amino groups, based on the weight of the copolymer. ### Claim 9 (depends on 1) The process of claim 1, wherein the solvent comprises at least 99 weight percent methanol. ### Claim 10 (depends on 1) The process of claim 1, wherein: the dihydric phenol comprises 2,2-bis(3,5-dimethyl-4-hydroxyphenol)propane; the at least one amine ligand comprises di(n-butyl)amine; the solvent comprises at least 99 weight percent methanol; and the copolymer of 2-methyl-6-phenylphenol and the dihydric phenol comprises less than 0.005 weight percent of di(n-butyl)amino groups, based on the weight of the copolymer. ### Claim 11 A poly(phenylene ether) copolymer derived from a monohydric phenol comprising 2-methyl-6-phenylphenol and a dihydric phenol, wherein: the monohydric phenol comprises, based on the total weight of monohydric phenol and dihydric phenol, less than 0.5 weight percent of monohydric phenols having identical substituents in the 2- and 6-positions of the phenolic ring; the copolymer comprises less than 0.005 weight percent of di(C1-C6-alkyl)amino groups, based on the weight of the copolymer; and the copolymer has an absolute number average molecular weight of 1,000 to 10,000 grams/mole, calculated from integrated areas under resonance peaks in the 1H-NMR spectrum of the copolymer. ### Claim 12 (depends on 11) The poly(phenylene ether) copolymer of claim 11, wherein the copolymer has an absolute number average molecular weight of 1,000 to 5,000 grams/mole. ### Claim 13 (depends on 11) The poly(phenylene ether) copolymer of claim 11, wherein the copolymer comprises 80 to 99 weight percent of repeat units derived from the monohydric phenol and 1 to 20 weight percent of repeat units derived from the dihydric phenol. ### Claim 14 A poly(phenylene ether) copolymer having the structure: wherein: R is independently at each occurrence methyl or di(n-butyl)aminomethyl; provided that the copolymer comprises, on average, less than or equal to 0.005 weight percent of di(n-butyl)aminomethyl groups, based on the weight of the copolymer; and x and y are independently at each occurrence zero to 50, provided that the sum of x and y is 4 to 53. ### Claim 15 (depends on 14) The poly(phenylene ether) copolymer of claim 14, wherein the sum of x and y is 8 to 20. ### Claim 16 (depends on 11) A curable composition, comprising a thermosetting resin and the poly(phenylene ether) copolymer of claim 11. ### Claim 17 (depends on 16) A cured composition obtained by heating the curable composition of claim 16 for a time and temperature sufficient to effect curing. ### Claim 18 (depends on 17) An article comprising the cured composition of claim 17.