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

Abstract

Thermally stable polymers comprising resorcinol arylate chain members are prepared using an interfacial method comprising the steps of: (a) combining at least one resorcinol moiety and at least one catalyst in a mixture of water and at least one organic solvent substantially immiscible with water; and (b) adding to the mixture from (a) at least one dicarboxylic acid dichloride while maintaining the pH between 3 and 8.5 through the presence of an acid acceptor, wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups.

1. A block copolymer consisting essentially of resorcinol arylate polyester segments in combination with organic carbonate segments, substantially free of anhydride linkages linking at least two mers of the polymer chain, prepared by an interfacial method, comprising the steps of:
 (a) combining at least one resorcinol moiety and at least one catalyst in a mixture of water and at least one organic solvent substantially immiscible with water; and  
 (b) adding to the mixture from (a) at least one dicarboxylic acid dichloride while maintaining the pH between 3 and 8.5 through the presence of an acid acceptor, wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups.  
 
     
     
       2. The copolymer of  claim 1 , prepared by an interfacial method further comprising the step of: adjusting the pH of the reaction mixture to between 7 and 12 following addition of the at least one dicarboxylic acid dichloride. 
     
     
       3. The copolymer of  claim 2 , prepared by an interfacial method further comprising the step of: stirring the reaction mixture for at least 3 minutes at pH between 7 and 12. 
     
     
       4. The copolymer of  claim 1  wherein the at least one resorcinol moiety is selected from the group consisting of unsubstituted resorcinol, 2-methyl resorcinol, and mixtures thereof. 
     
     
       5. The copolymer of  claim 4  wherein the at least one resorcinol moiety is unsubstituted resorcinol. 
     
     
       6. The copolymer of  claim 1  wherein the at least one dicarboxylic acid dichloride is at least one member selected from the group consisting of isophthaloyl dichloride, terephthaloyl dichloride, naphthalene-2,6-dicarboxylic acid dichloride, sebacoyl chloride, cyclohexane-1,4-dicarboxylic acid dichloride and mixtures thereof. 
     
     
       7. The copolymer of  claim 6  wherein the at least one dicarboxylic acid dichloride is a mixture of isophthaloyl dichloride and terephthaloyl dichloride. 
     
     
       8. The copolymer of  claim 7  wherein the ratio of isophthaloyl dichloride to terephthaloyl dichloride is about 0.2-5:1. 
     
     
       9. The copolymer of  claim 8  wherein the ratio of isophthaloyl dichloride to terephthaloyl dichloride is about 0.8-2.5:1. 
     
     
       10. The copolymer of  claim 8  wherein the stoichiometric ratio of total phenolic groups to total acid chloride groups is about 1.5-1.01:1. 
     
     
       11. The copolymer of  claim 10  wherein the stoichiometric ratio of total phenolic groups to total acid chloride groups is about 1.2-1.02:1. 
     
     
       12. The copolymer of  claim 1  prepared by an interfacial method wherein the pH is maintained using an alkali metal hydroxide, an alkaline earth hydroxide, or an alkaline earth oxide. 
     
     
       13. The copolymer of  claim 12  prepared by an interfacial method wherein the pH is maintained using aqueous sodium hydroxide. 
     
     
       14. The copolymer of  claim 1  wherein the organic carbonate segments comprise at least one dihydroxy-substituted aromatic hydrocarbon. 
     
     
       15. The copolymer of  claim 14  wherein the dihydroxy-substituted aromatic hydrocarbon is bisphenol A. 
     
     
       16. The copolymer of  claim 14  further comprising at least one chain-stopper selected from the group consisting of mono-phenolic compounds, mono-carboxylic acid chlorides, mono-chloroformates, and mixtures thereof. 
     
     
       17. The copolymer of  claim 1  wherein the molecular weight of said copolymer decreases by less than 12% upon heating said polymer at a temperature of about 280-290° C. for five minutes. 
     
     
       18. The copolymer of  claim 17  wherein the molecular weight of said copolymer decreases by less than 5% upon heating at a temperature of about 280-290° C. for five minutes. 
     
     
       19. A block copolymer consisting essentially of resorcinol arylate polyester segments in combination with organic carbonate segments, substantially free of anhydride linkages linking at least two mers of the polymer chain, prepared by an interfacial method, comprising the steps of:
 (a) combining at least one of unsubstituted resorcinol and 2-methylresorcinol; and at least one catalyst selected from the group consisting of quaternary ammonium salts and tertiary amines, in a mixture of water and dichloromethane;  
 (b) adding to the mixture from (a) a mixture of isophthaloyl dichloride and terephthaloyl dichloride in a molar ratio of isophthalate to terephthalate of 0.4-2.5-1, while maintaining the pH between 3 and 8.5 through addition of aqueous sodium hydroxide, wherein the ratio of moles total acid chloride groups to moles total phenolic  phenolic groups to moles total acid chloride groups is 1.5-1.01:1;  
 (c) adjusting the pH of the reaction mixture to between 8.5 and 12 following addition of the dicarboxylic acid dichloride mixture, and stirring the reaction mixture for at least 3 minutes at said pH;  
 (d) combining the product from (c) with at least one diphenol, at least one mono-phenolic chain-stopper, and phosgene under basic conditions; and  
 (d e) isolating the copolymer, said copolymer decreasing in molecular weight by less than 12% upon heating at a temperature of about 280-290° C. for five minutes.  
 
     
     
       20. A block copolymer consisting essentially of resorcinol arylate polyester segments in combination with organic carbonate segments, substantially free of anhydride linkages linking at least two mers of the polymer chain, prepared by an interfacial method, comprising the steps of:
 ( a )  combining at least one of unsubstituted resorcinol and  2   - methylresorcinol; and at least one catalyst selected from the group consisting of quaternary ammonium salts and tertiary amines, in a mixture of water and dichloromethane;      ( b )  adding to the mixture from  ( a )  a mixture of isophthaloyl dichloride and terephthaloyl dichloride in a molar ratio of isophthalate to terephthalate of  0 . 4 - 2 . 5 - 1 , while maintaining the pH between  3  and  8 . 5  through addition of aqueous sodium hydroxide, wherein the ratio of moles total phenolic groups to moles total acid chloride groups is  1 . 5 - 1 . 01 : 1 ;      ( c )  adjusting the pH of the reaction mixture to between  8 . 5  and  12  following addition of the dicarboxylic acid dichloride mixture, and stirring the reaction mixture for at least  3  minutes at said pH;      ( d )  combining the product from  ( c )  with at least one dihydroxy - substituted aromatic hydrocarbon, at least one mono - phenolic chain - stopper, and phosgene under basic conditions; and      ( e )  isolating the copolymer, said copolymer decreasing in molecular weight by less than  12   %  upon heating at a temperature of about  280 - 290 ° C. for five minutes.