Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom

Abstract

Disclosed herein is a method for producing a 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine. The method comprises forming a reaction mixture comprising at least one substituted or unsubstituted phenolphthalein, at least one substituted or unsubstituted primary hydrocarbyl amine, and an acid catalyst; and heating the reaction mixture to a temperature of less than 180° C. to remove a distillate comprising water and form a crude 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine product; where the 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine has a formula: where R 1 is selected from the group consisting of a hydrogen and a hydrocarbyl group, and R 2 is selected from the group consisting of a hydrogen, a hydrocarbyl group, and a halogen.

1 . A method for producing a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine, comprising: 
 forming a reaction mixture comprising at least one substituted or unsubstituted phenolphthalein, at least one substituted or unsubstituted primary aryl amine, and an acid catalyst; and    heating the reaction mixture to a temperature of less than 180° C., removing a distillate comprising water and isolating a product comprising 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine having the formula:                          wherein R 1  is an aryl group and R 2  is selected from the group consisting of a hydrogen, a hydrocarbyl group, and a halogen.    
     
     
         2 . The method of  claim 1 , wherein the product purity is at least 99.9 area percent 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine by HPLC analysis.  
     
     
         3 . The method of  claim 1 , wherein the acid catalyst is selected from a group consisting of a substituted or an unsubstituted aliphatic amine hydrochloride, an aromatic amine hydrochloride, or mixtures of the foregoing amine hydrochlorides.  
     
     
         4 . The method of  claim 1 , wherein the reaction mixture comprises phenolphthalein and aniline.  
     
     
         5 . The method of  claim 1 , wherein the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine is 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine.  
     
     
         6 . The method of  claim 1 , further comprising: 
 combining the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine product with an aqueous base to provide a first solution;    treating the first solution with a solid adsorbent and then filtering the first solution to provide a second solution,    treating the second solution with an aqueous acid to form a precipitate and;    isolating the precipitate comprising 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine.    
     
     
         7 . The method of  claim 6 , wherein the aqueous base comprises an alkali metal or alkaline earth metal hydroxide, carbonate, or bicarbonate.  
     
     
         8 . The method of  claim 6 , wherein the solid adsorbent comprises an activated carbon.  
     
     
         9 . The method of  claim 6 , wherein the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine is 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine  
     
     
         10 . The method of  claim 1 , further comprising contacting the product comprising 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine with an aliphatic alcohol and isolating a purified 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine.  
     
     
         11 . The method of  claim 10 , wherein the purified 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine comprises less than or equal to 1,000 parts per million of a substituted or an unsubstituted phenolphthalein relative to an overall weight of 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine.  
     
     
         12 . The method of  claim 10 , wherein the aliphatic alcohol is methanol, ethanol, iso-propanol, iso-butanol, n-butanol, tertiary butanol, n-pentanol, iso-pentanol, cyclohexanol, ethylene glycol, propylene glycol, neopentyl glycol or mixtures of the foregoing aliphatic alcohols.  
     
     
         13 . The method of  claim 10 , wherein the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine is 2-phenyl-3,3-(bis-4-hydroxyphenyl)phthalimidine  
     
     
         14 . A method for purifying 2-phenyl-3,3-bis(4-hydroxphenyl)phthalimidine, comprising: 
 combining a mixture comprising 2-phenyl-3,3-bis(4-hydroxphenyl)phthalimidine mixture with an aqueous base to provide a first solution;    treating the first solution with an activated carbon and filtering to provide a second solution;    treating the second solution with an aqueous acid to form a precipitate; and    isolating the precipitate comprising the 2-phenyl-3,3-bis(4-hydroxphenyl)phthalimidine mixture.    
     
     
         15 . The method of  claim 14 , wherein the 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine mixture comprises less than or equal to about 1000 parts per million of phenolphthalein relative to an overall weight of 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine.  
     
     
         16 . A polycarbonate composition comprising structural units derived from the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine produced by the method of  claim 1 .  
     
     
         17 . A polycarbonate composition comprising structural units derived from the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine produced by the method of  claim 6 .  
     
     
         18 . A polycarbonate composition comprising structural units derived from the 2-aryl-3,3-bis(4-hydroxyphenyl)phthalimidine produced by the method of  claim 10 .  
     
     
         19 . An article comprising the polymer composition of  claim 16 .  
     
     
         20 . An article comprising the composition of  claim 17 .  
     
     
         21 . An article comprising the composition of  claim 18 .  
     
     
         22 . A method for producing 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine, comprising: 
 a) forming a reaction mixture comprising at least one substituted or unsubstituted phenolphthalein, at least one substituted or unsubstituted primary aryl amine, and an acid catalyst;    heating the reaction mixture to a temperature of less than 180° C., removing a distillate comprising water and isolating a product mixture comprising 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine having the formula:                          wherein R 1  is an aryl group and R 2  is selected from the group consisting of a hydrogen, a hydrocarbyl group, and a halogen;    b) combining the product mixture from step a) with an aqueous base to provide a first solution, treating the first solution with a carbon adsorbent and filtering to provide a second solution, treating the second solution with an aqueous acid to form a precipitate, and isolating the precipitate;    c) contacting the precipitate from step b) with an aliphatic alcohol to produce a purified 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine and isolating the purified 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine,    wherein the purified 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine comprises less than or equal to 1,000 parts per million of a substituted or an unsubstituted phenolphthalein relative to the overall weight of 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine.    
     
     
         23 . The method of  claim 22 , wherein the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine is 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine.  
     
     
         24 . A polycarbonate composition comprising structural units derived from the 2-aryl-3,3,-bis(hydroxyphenyl)phthalimidine produced by the method of  claim 22 .  
     
     
         25 . An article comprising the polycarbonate composition of  claim 24 .  
     
     
         26 . The polycarbonate of  claim 16 , wherein the polycarbonate is prepared by melt transesterification polymerization.  
     
     
         27 . The polycarbonate of  claim 16 , wherein the polycarbonate is prepared by interfacial polymerization.  
     
     
         28 . The polycarbonate of  claim 27 , wherein the interfacial polymerization is a bischloroformate polymerization method.  
     
     
         29 . The polycarbonate of  claim 27 , wherein the interfacial polymerization comprises a tubular reactor.