Polymerization Process

Abstract

The present invention relates to a process comprising the step of melt-mixing a semi-aromatic polyamide (A) having a melting point on second heating of 295° C. or less comprising terephthalamide repeat units and a polyamide oligomer (B) comprising terephthalamide repeat units and having an amine end group concentration of less than 2000 me q/Kg and an inherent viscosity of at least 0.10, at a temperature which is greater than the melting point on first heating of both semi-aromatic polyamide (A) and polyamide oligomer (B) for a time period sufficient to produce semi-aromatic polyamide (C) having a melting point on second heating which is greater than or equal to 300° C.

1 . A process comprising the step of melt-mixing a semi-aromatic polyamide (A) having a melting point on second heating of 295° C. or less comprising terephthalamide repeat units and a polyamide oligomer (B) comprising terephthalamide repeat units and having an amine end group concentration of less than 2000 me q/Kg and an inherent viscosity of at least 0.10 measured according to ISO 307:2007, at a temperature which is greater than the melting point on first heating of both semi-aromatic polyamide (A) and polyamide oligomer (B) for a time period sufficient to produce semi-aromatic polyamide (C) having a melting point on second heating which is greater than or equal to 300° C., wherein said melting points on first and second heating are determined according to ASTM D3418:2015. 
     
     
         2 . The process of  claim 1  wherein semi-aromatic polyamide (A) comprises:
 (a) At least one dicarboxylic acid comprising:
 (i) greater than 20 to about 100 mole percent terephthalic acid; 
 (ii) from 0 to about 80 mole percent dicarboxylic acid selected from isophthalic acid and aliphatic diacids comprising 4 to 20 carbon atoms; and 
 
 (b) at least one aliphatic diamine having 4 to 20 carbon atoms; and optionally 
 (c) an aliphatic lactam or an aliphatic amino carboxylic acid with 6 to 20 carbon atoms. 
 
     
     
         3 . The process of  claim 1  wherein polyamide oligomer (B) comprises the same terephthalamide repeat units of semi-aromatic polyamide (A). 
     
     
         4 . The semi-aromatic polyamide (A) of  claim 1  selected from the group consisting of: PA6T/6I, PA6T/610, 6T/66, PA 6T/612, PA10T/1010, PA10T/101, PA 10T/11, PAST/510, 6T/DT, PA4T/410, PA6T/9T, PA9T/10T, PAST/5I, PA6T/6I/6, and PA6T/6I/66. 
     
     
         5 . The process of  claim 1  in which the melt-mixing takes place in an extruder. 
     
     
         6 . The process of  claim 5  wherein the extruder is a twin-screw extruder. 
     
     
         7 . The process of  claim 1  wherein polyamide oligomer (B) has an amine end group concentration of less than or equal to 1000 meq/Kg and an IV of at least 0.15. 
     
     
         8 . The process of  claim 1  wherein the time period is less than 3 minutes. 
     
     
         9 . The process of  claim 1  wherein the time period is less than 1 minute. 
     
     
         10 . An article comprising semi-aromatic polyamide (C) prepared by the process of  claim 1 . 
     
     
         11 . The article of  claim 10  selected from the group consisting of automotive engine parts, automotive under the hood parts, electronic parts, an electrical part in a vehicle, a connector, a plug, a sensor, a relay, a solenoid, a switch, and parts for water management systems. 
     
     
         12 . The process of  claim 1  wherein the weight percent of semi-aromatic polyamide (A) ranges from 60 to 90 and polyamide oligomer (B) ranges from 10 to 40 weight percent based on the weight percent of A and B. 
     
     
         13 . The process of  claim 1  wherein semi-aromatic polyamide (C) comprises at least 5 mole percent higher terephthalamide content than semi-aromatic polyamide (A). 
     
     
         14 . The process of  claim 1  wherein semi-aromatic polyamide (C) has an excess of amine end groups. 
     
     
         15 . The process of  claim 1  wherein semi-aromatic polyamide (C) has an excess of acid end groups. 
     
     
         16 . The process of  claim 1  wherein the melt-mixing temperature is between 425° C. and 250° C. 
     
     
         17 . A semi-aromatic polyamide prepared by the process of  claim 1  having a melting point of at least 300° C. and a freezing point which is at least 4° C. greater than a semi-aromatic polyamide comprising the same molar concentration of repeat units but prepared by an all-melt process. 
     
     
         18 . A semi-aromatic polyamide having a melting point of at least 300° C. and a freezing point which is at least 4° C. greater than a semi-aromatic polyamide comprising the same molar concentration of repeat units but prepared by an all-melt process. 
     
     
         19 . A process comprising the step of melt-mixing a semi-aromatic polyamide (A) having a melting point on second heating of 295° C. or less comprising terephthalamide repeat units and a polyamide oligomer (B) having a melting point on second heating at least 10° C. greater than the melting point on second heating of semi-aromatic polyamide (A), said polyamide oligomer (B) comprising terephthalamide repeat units and having an amine end group concentration of less than 2000 me q/Kg and an inherent viscosity of at least 0.10 measured according to ISO 307:2007, at a temperature which is greater than the melting point on first heating of both semi-aromatic polyamide (A) and polyamide oligomer (B) for a time period sufficient to produce semi-aromatic polyamide (C) having a melting point on second heating which is greater than or equal to 300° C., wherein said melting points on first and second heating are determined according to ASTM D3418:2015. 
     
     
         20 . The process of  claim 1  wherein the time period sufficient to produce semi-aromatic polyamide (C) ranges from about 15 seconds to 4 minutes. 
     
     
         21 . The process of  claim 1  wherein the melt-mixing temperature ranges from about 305° C. to 400° C. 
     
     
         22 . The process of  claim 1  wherein polyamide oligomer (B) comprises at least 10 mole percent higher terephthalamide content than semi-aromatic polyamide (A). 
     
     
         23 . The process of  claim 1  wherein polyamide oligomer (B) has at least a 10 mol % higher hexamethylene terephthalamide content than semi-aromatic polyamide (A) based on the total molar dicarboxylic acid content in semi-aromatic polyamide (A).