Thermally stable polymers, method of preparation, and articles made therefrom

An interfacial method for preparing a polymer consisting essentially of chain members derived from a mixture of terephthaloyl dichloride and isophthaloyl dichloride in a molar ratio in a range of about 0.4-2.5:1 and unsubstituted resorcinol, said polymer being substantially free of anhydride linkages linking at least two mers of the polymer chain, comprising the steps of:

• (a) combining unsubstituted resorcinol, at least one mono-phenolic chain-stopper, and at least one tertiary amine catalyst in a mixture of water and dichloromethane;
• (b) adding to the mixture from (a) a controlled stoichiometric ratio of acid chlorides and aqueous sodium hydroxide while maintaining the pH between about 4 and about 8.5, wherein the stoichiometric ratio of sodium hydroxide to acid chlorides is held at a constant value in a range between about 90% and about 99% during addition or is varied in a range of between 0% and 125% during addition, and wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups;
• and
• (c) adjusting the pH of the reaction mixture to a value in the range of about 7 and about 9 following complete addition of acid chlorides, and stirring the reaction mixture for a time sufficient to destroy any anhydride linkages in the polymer chain;
• wherein the polymer has a weight average molecular weight of at least about 900 compared to polystyrene standards and a phenolic end-group concentration in a range of between about 2 ppm and about 37,000 ppm.

A hydroxy-terminated polyester comprising chain members derived from a mixture of terephthaloyl dichloride and isophthaloyl dichloride in a molar ratio in a range of about 0.4-2.5:1 and unsubstituted resorcinol, said polymer being substantially free of anhydride linkages linking at least two mers of the polymer chain, the polymer being made by the steps of:

• (a) combining unsubstituted resorcinol, at least one mono-phenolic chain-stopper, and at least one tertiary amine catalyst in a mixture of water and dichloromethane;
• (b) adding to the mixture from (a) a controlled stoichiometric ratio of acid chlorides and aqueous sodium hydroxide while maintaining the pH between about 4 and about 8.5, wherein the stoichiometric ratio of sodium hydroxide to acid chlorides is held at a constant value in a range between about 90% and about 99% during addition or is varied in a range of between 0% and 125% during addition, and wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups;
• and
• (c) adjusting the pH of the reaction mixture to a value in the range of about 7 and about 9 following complete addition of acid chlorides, and stirring the reaction mixture for a time sufficient to destroy any anhydride linkages in the polymer chain;
• wherein the polyester has a weight average molecular weight of at least about 900 compared to polystyrene standards and a phenolic end-group concentration in a range of between about 2 ppm and about 37,000 ppm.

An interfacial method for preparing a copolymer comprising C3-20 straight chain alkylene, C3-10 branched alkylene, or C4-10 cyclo- or bicyclo-alkylene chain members derived from at least one dicarboxylic acid dichloride, in combination with chain members derived from at least one aromatic dicarboxylic acid dichloride and unsubstituted resorcinol, said polymer being substantially free of anhydride linkages linking at least two mers of the polymer chain, comprising the steps of:

• (a) combining unsubstituted resorcinol, at least one mono-phenolic chain-stopper, and at least one tertiary amine catalyst in a mixture of water and dichloromethane;
• (b) adding to the mixture from (a) a controlled stoichiometric ratio of acid chlorides and aqueous sodium hydroxide while maintaining the pH between about 4 and about 8.5, wherein the stoichiometric ratio of sodium hydroxide to acid chlorides is held at a constant value in a range between about 90% and about 99% during addition or is varied in a range of between 0% and 125% during addition, and wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups;
• and
• (c) adjusting the pH of the reaction mixture to a value in the range of about 7 and about 9 following complete addition of acid chlorides, and stirring the reaction mixture for a time sufficient to destroy any anhydride linkages in the polymer chain;
• wherein the molecular weight of said copolymer decreases by less than 30% upon heating said polymer at a temperature of about 280-290° C. for five minutes.

A hydroxy-terminated polyester comprising C3-20 straight chain alkylene, C3-10 branched alkylene, or C4-10 cyclo- or bicyclo-alkylene chain members derived from at least one dicarboxylic acid dichloride, in combination with chain members derived from at least one aromatic dicarboxylic acid dichloride and unsubstituted resorcinol, said polymer being substantially free of anhydride linkages linking at least two mers of the polymer chain the polymer being made by the steps of:

• (a) combining unsubstituted resorcinol, at least one mono-phenolic chain-stopper, and at least one tertiary amine catalyst in a mixture of water and dichloromethane;
• (b) adding to the mixture from (a) a controlled stoichiometric ratio of acid chlorides and aqueous sodium hydroxide while maintaining the pH between about 4 and about 8.5, wherein the stoichiometric ratio of sodium hydroxide to acid chlorides is held at a constant value in a range between about 90% and about 99% during addition or is varied in a range of between 0% and 125% during addition, and wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups;
• and
• (c) adjusting the pH of the reaction mixture to a value in the range of about 7 and about 9 following complete addition of acid chlorides, and stirring the reaction mixture for a time sufficient to destroy any anhydride linkages in the polymer chain.

An interfacial method for preparing a block copolyestercarbonate comprising polyester block segments with chain members derived from at least one 1,3-dihydroxybenzene moiety and at least one aromatic dicarboxylic acid moiety;

• and polycarbonate block segments;
• wherein said copolyestercarbonate is substantially free of anhydride linkages linking at least two mers of the polyester blocks, comprising the steps of:
• (a) combining at least one 1,3-dihydroxybenzene moiety and at least one catalyst in a mixture of water and at least one organic solvent substantially immiscible with water;
• (b) adding to the mixture from (a) a controlled stoichiometric ratio of at least one acid chloride and at least one base while maintaining the pH between about 4 and about 8.5;
• (c) adjusting the pH of the reaction mixture to a value in the range of about 7 and about 9 following complete addition of acid chloride, and stirring the reaction mixture for a time sufficient to destroy any anhydride linkages in the polyester intermediate chain;
• wherein the polyester intermediate has a weight average molecular weight of at least about 900 compared to polystyrene standards and a phenolic end-group concentration in a range of between about 2 ppm and about 37,000 ppm;
• and
• (d) conducting a reaction of said polyester intermediate with a carbonate precursor in the presence of at least one organic dihydroxy compound different from the hydroxy-terminated polyester intermediate to form copolyestercarbonate.

An interfacial method for preparing a block copolyestercarbonate comprising polyester block segments with chain members derived from a mixture of terephthaloyl dichloride and isophthaloyl dichloride in a molar ratio in a range of about 0.4-2.5:1 and unsubstituted resorcinol, and polycarbonate segments with chain members derived from at least one of unsubstituted resorcinol and bisphenol A;

• wherein said copolyestercarbonate is substantially free of anhydride linkages linking at least two mers of the polyester blocks, comprising the steps of:
• (a) combining unsubstituted resorcinol, at least one mono-phenolic chain-stopper, and at least one tertiary amine catalyst in a mixture of water and dichloromethane;
• (b) adding to the mixture from (a) a controlled stoichiometric ratio of acid chlorides and aqueous sodium hydroxide while maintaining the pH between about 4 and about 8.5, wherein the stoichiometric ratio of sodium hydroxide to acid chlorides is held at a constant value in a range between about 90% and about 99% during addition or is varied in a range of between 0% and 125% during addition, and wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups;
• (c) adjusting the pH of the reaction mixture to a value in the range of about 7 and about 9 following complete addition of acid chlorides, and stirring the reaction mixture for a time sufficient to destroy any anhydride linkages in the polyester intermediate chain;
• wherein the polyester intermediate has a weight average molecular weight of at least about 900 compared to polystyrene standards and a phenolic end-group concentration in a range of between about 2 ppm and about 37,000 ppm;
• and
• (d) conducting a reaction of said polyester intermediate with phosgene in a mixture comprising water and dichloromethane in the presence of bisphenol A to form copolyestercarbonate.