Poly(phenylene ether) copolymer and method of making
View Patent ↗A poly(phenylene ether) copolymer comprises about 5 to 40 mole percent repeat units derived from 2-phenylphenol and 60 to about 95 mole percent repeat units derived from 2,6-dimethylphenol, wherein the poly(phenylene ether) copolymer has a weight average molecular weight of at least 8,000 atomic mass units, as measured by gel permeation chromatography. A method of preparing the poly(phenylene ether) copolymer, comprises oxidatively copolymerizing a monomer mixture comprising about 5 to 40 mole percent 2-phenylphenol and about 60 to about 95 mole percent 2,6-dimethylphenol in the presence of a solvent, molecular oxygen, and a polymerization catalyst comprising a metal ion and at least one amine ligand to form a solution of the poly(phenylene ether) copolymer in the solvent, wherein a ratio of total moles of 2-phenylphenol and 2,6-dimethylphenol to moles of metal ion is about 10:1 to about 1200:1.
1. A poly(phenylene ether) copolymer comprising about 5 to 40 mole percent repeat units derived from 2-phenylphenol and 60 to about 95 mole percent repeat units derived from 2,6-dimethylphenol,
wherein the poly(phenylene ether) copolymer has a weight average molecular weight of 8,000 to about 200,000 atomic mass units, as measured by gel permeation chromatography; and
wherein the poly(phenylene ether) copolymer comprises:
a mole percent of 2-phenylphenol head units based on 100 mole percent total 2-phenylphenol head units and 2,6-dimethylphenol head units, and
a total mole percent of 2-phenylphenol repeat units, based on 100 mole percent total 2-phenylphenol repeat units and 2,6-dimethylphenol repeat units,
wherein the mole percent of 2-phenylphenol head units is greater than the total mole percent of 2-phenylphenol repeat units; and
wherein the poly(phenylene ether) copolymer is prepared by a process comprising:
oxidatively copolymerizing a monomer mixture comprising about 5 to 40 mole percent 2-phenylphenol and about 60 to about 95 mole percent 2,6-dimethylphenol in the presence of a solvent, molecular oxygen, and a polymerization catalyst comprising a metal ion and at least one amine ligand to form a solution of the poly(phenylene ether) copolymer in the solvent,
wherein a ratio of total moles of 2-phenylphenol and 2,6-dimethylphenol to moles of metal ion is about 20:1 to about 200:1; and
wherein a ratio of moles of amine groups in the amine ligands to moles metal ion is about 1:1 to about 5:1.
2. The poly(phenylene ether) copolymer of claim 1 , wherein the repeat units derived from 2-phenylphenol have the structure
or
a combination thereof; and
the repeat units derived from 2,6-dimethylphenol comprise repeat units having the structure
3. The poly(phenylene ether) copolymer of claim 1 , wherein a ratio of mole percent of 2-phenylphenol head units to total mole percent of 2-phenylphenol repeat units is about 1.1:1 to about 2:1.
4. The poly(phenylene ether) copolymer of claim 1 ,
wherein the repeat units derived from 2-phenylphenol have the structure
or
a combination thereof;
wherein the repeat units derived from 2,6-dimethylphenol comprise repeat units have the structure
wherein the poly(phenylene ether) copolymer comprises
a mole percent of 2-phenylphenol head units based on 100 mole percent total 2-phenylphenol head units and 2,6-dimethylphenol head units,
a total mole percent of 2-phenylphenol repeat units, based on 100 mole percent total 2-phenylphenol and 2,6-dimethylphenol repeat units, and
a ratio of the mole percent of 2-phenylphenol head units to the total mole percent of 2-phenylphenol repeat units of about 1.1:1 to about 2:1; and
wherein the copolymer has a weight average molecular weight of about 20,000 to about 200,000 atomic mass units, as measured by gel permeation chromatography.
5. A method of preparing a poly(phenylene ether) copolymer comprising about 5 to 40 mole percent repeat units derived from 2-phenylphenol and 60 to about 95 mole percent repeat units derived from 2,6-dimethylphenol,
wherein the poly(phenylene ether) copolymer has a weight average molecular weight of 8,000 to about 200,000 atomic mass units, as measured by gel permeation chromatography; and
wherein the poly(phenylene ether) copolymer comprises:
a mole percent of 2-phenylphenol head units based on 100 mole percent total 2-phenylphenol head units and 2,6-dimethylphenol head units, and
a total mole percent of 2-phenylphenol repeat units, based on 100 mole percent total 2-phenylphenol repeat units and 2,6-dimethylphenol repeat units,
wherein the mole percent of 2-phenylphenol head units is greater than the total mole percent of 2-phenylphenol repeat units,
the method comprising oxidatively copolymerizing a monomer mixture comprising about 5 to 40 mole percent 2-phenylphenol and about 60 to about 95 mole percent 2,6-dimethylphenol in the presence of a solvent, molecular oxygen, and a polymerization catalyst comprising a metal ion and at least one amine ligand to form a solution of the poly(phenylene ether) copolymer in the solvent,
wherein a ratio of total moles of 2-phenylphenol and 2,6-dimethylphenol to moles of metal ion is about 20:1 to about 200:1; and
wherein a ratio of moles of amine groups in the amine ligands to moles metal ion is about 1:1 to about 5:1.
6. The method of claim 5 , further comprising
mixing the solution of the poly(phenylene ether) copolymer in the solvent with an aqueous solution of a chelating agent, and
separating the solution of the poly(phenylene ether) copolymer from the aqueous solution of the chelating agent.
7. The method of claim 6 , further comprising precipitating the poly(phenylene ether) copolymer by combining an antisolvent with the separated solution of the poly(phenylene ether) copolymer in the solvent.
8. The method of claim 6 , further comprising removing the solvent from the separated solution of the poly(phenylene ether) copolymer by devolatizing extrusion.