Process for Preparing Amine-Modified Polyester Resins with Improved Melt Flow

Abstract

The invention is directed to a process for preparing a linear or branched amine-modified thermoplastic resin with high flowability using as starting materials a linear or branched polyester and a primary or secondary aliphatic amine. The process does not require that the amine and polyester be combined in a liquid organic solvent during the process, and can be performed readily at ambient pressure. The amine-modified resins can be extruded and pelletized using normal operating conditions, making this process a versatile option for achieving a wide variety of viscosities in a simple, low cost, continuous operation.

1 . A solvent-free process for preparing an amine-modified thermoplastic polyester resin comprising:
 mixing a melted polyester of Formula 1:   
       
         
           
           
               
               
           
         
         
           wherein: 
           each T is independently a divalent C 6-10  aromatic group derived from a dicarboxylic acid or a chemical equivalent thereof; 
           each D is independently a divalent C 2-8  alkylene group derived from a dihydroxy compound or a chemical equivalent thereof; and 
           m is from 25 to 1000; 
         
         and a melted amine, having the formula NHR 1 R 2 ,
 wherein: 
 R 1  is C 6-36  alkyl, R 2  is selected from the group consisting of hydrogen, C 1 -C 36  alkyl, C 1 -C 36  alkylene-aryl, C 1 -C 36  alkylene-heteroaryl, C 1 -C 36  alkylene-cycloalkyl, C 1 -C 36  alkylene-heterocycloalkyl, and NHR 1 R 2  contains at least 10 carbons; 
 
         thereby forming an amine-modified thermoplastic polyester resin characterized by one or both of the following properties:
 (i) the resin comprises 0.01 to 5 weight percent of the amine; and 
 (ii) the ratio of the melt flow of the resin compared to the unmodified polyester of Formula 1, as measured according to ASTM D1238, is at least 1.05:1. 
 
       
     
     
         2 . The process of  claim 1 , wherein the polyester is a linear polyester having repeating structural units of Formula 1 
       
         
           
           
               
               
           
         
         and the resulting resin is a linear resin of Formula 2 
       
       
         
           
           
               
               
           
         
         
           wherein: 
           each T is independently a divalent C 6-10  aromatic group derived from a dicarboxylic acid or a chemical equivalent thereof; 
           each D is independently a divalent C 2-8  alkylene group derived from a dihydroxy compound or a chemical equivalent thereof; and 
           m and n are each selected from 25 to 1000 and n is less than m. 
         
       
     
     
         3 . The process of  claim 2 , wherein:
 each T in the resin of Formula 2 is independently phenyl or naphthyl; and   each D in the resin of Formula 2 is independently selected from the group consisting of ethylene, propylene, butylene, and dimethylenecyclohexene.   
     
     
         4 . The process of  claim 2 , wherein the polyester of Formula 1 is selected from the group consisting of poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(ethylene naphthalate), poly(butylene naphthalate), poly(1,3-propylene terephthalate), poly(cyclohexylenedimethylene terephthalate) and combinations thereof. 
     
     
         5 . The process of  claim 2 , wherein the polyester of Formula 1 is a post-consumer recycled polyester. 
     
     
         6 . The process of  claim 2 , wherein the polyester of Formula 1 further comprises 10 to 500 ppm of one or more metal cations selected from the group consisting of at least one of Ti, Sb, Sn, Zn, Ge, Zr, and Co. 
     
     
         7 . The process of  claim 2 , wherein the polyester resin of Formula 2 is characterized by a —COOH end group content of 10 meq/kg or less. 
     
     
         8 . The process of  claim 2 , wherein the amine has a boiling point that is 200° C. or higher at ambient pressure and a carbon to nitrogen ratio of 10:1 to 36:1. 
     
     
         9 . The process of  claim 2 , wherein the resin of Formula 2 comprises 0.05 to 2.5 weight percent of the reacted amine. 
     
     
         10 . The process of  claim 2 , wherein the resin further comprises 1 to 60 weight percent of a filler selected from the group consisting of fiber glass, carbon fibers, ceramic fibers, talc, clay, mica, wollastonite, silica, quartz, alumina, barium sulfate, carbon, graphite, metal oxides, glass beads, glass flakes, milled glass, and any combination thereof. 
     
     
         11 . The process of  claim 10 , comprising 10 to 40 weight percent fiber glass with a diameter of 9 to 20 microns. 
     
     
         12 . The process of  claim 2 , wherein 500 ppm or less of an organic solvent is present. 
     
     
         13 . The process of  claim 2 , wherein the process is a continuous process and wherein the blend comprising the polyester of Formula A and the amine NHR 1 R 2  are mixed in a single screw or twin screw extruder with no external vacuum applied. 
     
     
         14 . The process of  claim 2 , wherein mixing occurs at a temperature in the range of 200° C. to 350° C. 
     
     
         15 . The process of  claim 2 , wherein the resin of Formula 2 has a temperature of crystallization higher than the temperature of crystallization of polyester of Formula 1. 
     
     
         16 . The process of  claim 2 , the ratio of the melt flow of the resin of Formula 2 compared to the unmodified polyester of Formula 1, as measured according to ASTM D1238, is at least 1.1:1. 
     
     
         17 . The process of  claim 2 , wherein the resin of Formula 2 has a melt viscosity at 250° C. of 20 to 100 cc/10 minute. 
     
     
         18 . The process of  claim 2 , wherein 50 percent or more of the ester linkages in Formula 1 are terephthalate ester linkages. 
     
     
         19 . The process of  claim 2 , wherein the resin of Formula 2 is essentially free of metal cations or metal oxides selected from the group consisting of Pb, Hg, As, and Cd. 
     
     
         20 . An amine-modified polyester resin of Formula 2 
       
         
           
           
               
               
           
         
         prepared by the process of mixing a linear or branched polyester having repeating structural units of Formula 1 
       
       
         
           
           
               
               
           
         
         and an amine of formula NHR 1 R 2  in an extruder, with no applied vacuum and a temperature of 200 to 350° C.; wherein: 
         R 1  is C 6-36  alkyl R 2  is selected from the group consisting of hydrogen, C 1 -C 36  alkyl, C 1 -C 36  alkylene-aryl, C 1 -C 36  alkylene-heteroaryl, C 1 -C 36  alkylene-cycloalkyl, C 1 -C 36  alkylene-heterocycloalkyl, and NHR 1 R 2  contains at least 10 carbons; 
         each T is independently a divalent C 6-10  aromatic group derived from a dicarboxylic acid or a chemical equivalent thereof; 
         each D is independently a divalent C 2-8  alkylene group derived from a dihydroxy compound or a chemical equivalent thereof; 
         m and n vary from 25 to 1000 and n is less than m; and 
       
       wherein the resin is characterized by one or both of the following properties:
 (i) the resin comprises 0.01 to 5 weight percent of the amine; and 
 (ii) the ratio of the melt flow of the resin compared to the unmodified polyester of Formula 1, as measured according to ASTM D1238, is at least 1.05:1. 
 
     
     
         21 . The resin prepared by the process of  claim 20 , wherein the mixture further comprises 1 to 60 weight percent of a filler selected from the group consisting of fiber glass, carbon fibers, ceramic fibers, talc, clay, mica, wollastonite, silica, quartz, alumina, barium sulfate, carbon, graphite, metal oxides, glass beads, glass flakes, milled glass, and any combination thereof. 
     
     
         22 . The resin prepared by the process of  claim 20 , wherein the filler is 10 to 40 weight percent of a 9 to 20 micron diameter glass fiber. 
     
     
         23 . An article comprising the composition prepared by the process of  claim 1 . 
     
     
         24 . The article of  claim 23 , wherein the article is an extruded film or an injection molded article. 
     
     
         25 . The article of  claim 24  in the form of a component for an electronic device. 
     
     
         26 . A method for forming an article, comprising shaping, extruding, blow molding, or injection molding a composition prepared by the process of  claim 1 .