Copolyamide compositions with reduced crystallization rates

Abstract

A copolyamide composition comprising a statistical copolyamide containing 70-99 wt % of diamine and dicarboxylic acid repeat units and 1-30 wt % of lactam or AA-BB repeat units, whereby incorporation of the comonomer lactam or AA-BB unit reduces the crystallization rate (longer crystallization times) while maintaining (1) high melting point, (2) low potential plate out, (3) low oxygen permeation, (4) high tensile strength and (5) puncture/tear resistance.

1 .- 27 . (canceled) 
     
     
         28 . A process for preparing a statistical copolyamide, the process comprising:
 adding to a heated solution comprising first AA-BB repeating units comprising a first diacid and a first diamine one of either
 (i) second AA-BB repeating units comprising a second diacid and a second diamine or 
 (ii) lactam repeating units comprising a lactam; and dissolving to form a solution; 
   polymerizing the solution to form pellets; and   solid state polymerizing the pellets in an inert atmosphere at a temperature less than 220° C. to form the statistical copolyamide.   
     
     
         29 . The process of  claim 28 , wherein the first diacid is adipic acid and the first diamine is hexamethylene diamine. 
     
     
         30 . The process of  claim 28 , wherein adding includes the second AA-BB repeating units, and wherein the second diacid is different from the first diacid, and the second diamine is different from first diamine. 
     
     
         31 . The process of  claim 28 , wherein adding includes the second AA-BB repeating units, and wherein the second diacid is a dicarboxylic acid selected from adipic acid, azelaic acid, sebacic acid, undecanedioic acid, tetradecanedioic acid, isophthalic acid. 
     
     
         32 . The process of  claim 28 , wherein adding includes the second AA-BB repeating units, and wherein the second diamine is selected from 2-methyl-1,5-diaminopentane; 2,4,4-trimethyl-1,6-hexamethylenediamine; 1-8-diaminooctane; 2-methyl-1,8-diaminooctane; 1,9-nonanediamine; 5-methyl-1,9-nonanediamine; 1,10-diaminodecane; 1,11-diaminoundecane; 1,12-diaminododecane; 1,13-diaminotridecane; 1,14-diaminotetradecane; 1,16-diaminohexadecane; and 1,18-diaminooctadecane. 
     
     
         33 . The process of  claim 28 , wherein adding includes the lactam repeating units, and wherein the lactam is selected from the group consisting of butyrolactam, valerolactam, ϵ-caprolactam, enantiolactam, capryllactam, laurolactam, 12-aminodoecanolactam, 2-azacyclononone; and 1-aza-2-cyclooctanone. 
     
     
         34 . The process of  claim 28 , wherein the first AA-BB repeating units comprise where the first diacid is adipic acid and the first diamine is hexamethylene diamine, and wherein adding includes the lactam repeating units comprise the lactam, and the statistical copolyamide is PA66-s-6. 
     
     
         35 . The process of  claim 28 , wherein the statistical copolyamide is PA66-s-6,9 or PA66-s-6,I. 
     
     
         36 . The process of  claim 28 , wherein solid state polymerizing is conducted at one or more of: a temperature ranging from 160° C. and 220° C., a time of about 3 hours, or a nitrogen flow atmosphere of 30% of 3.62 SCFM. 
     
     
         37 . The process of  claim 28 , further comprising extruding the statistical copolyamide to form a cast film. 
     
     
         38 . The process of  claim 28 , further comprising extruding the statistical copolyamide through a circular die, blowing through an air ring, and winding into a blown film. 
     
     
         39 . The process of  claim 28 , the statistical copolyamide having Formula (3): 
       
         
           
           
               
               
           
         
         wherein in Formula (3):
 c=70-99 wt %; 
 d=2-16; 
 e=1-30 wt %, and 
 wherein the statistical copolyamide has a relative viscosity according to ASTM D789 (9.34) of 60-350 and a single melting point greater than 220° C. 
 
       
     
     
         40 . The process of  claim 28 , the statistical copolyamide having Formula (4): 
       
         
           
           
               
               
           
         
         wherein in Formula (4):
 c=75-99 wt %; 
 d=4-12; and 
 e=1-25 wt %, and 
 wherein the statistical copolyamide has a relative viscosity according to ASTM D789 (9.34) of 60-350 and a single melting point greater than 220° C. 
 
       
     
     
         41 . The process of  claim 28 , the statistical copolyamide having Formula (5): 
       
         
           
           
               
               
           
         
         wherein in Formula (5):
 c=75-99 wt %; 
 f=2-16; 
 g=2-16; and 
 h=1-25 wt %, and 
 wherein the statistical copolyamide has a relative viscosity according to ASTM D789 (9.34) of 60-350 and a single melting point greater than 220° C. 
 
       
     
     
         42 . The process of  claim 28 , wherein the statistical copolyamide has a single melting point greater than 220° C., a maximum crystallization temperature of 185° C., or both. 
     
     
         43 . The process of  claim 28 , wherein the statistical copolyamide has a relative viscosity according to ASTM D789 (9.34) of 60-350. 
     
     
         44 . The process of  claim 28 , wherein after solid state polymerizing, the statistical copolyamide is further blended with one or more additives to form a copolyamide composition. 
     
     
         45 . The process of  claim 44 , wherein the copolyamide composition comprises:
 the statistical copolyamide having 70 wt % to 99 wt % of the first AA-BB repeating units and 1 wt % to 30 wt % of one of either (i) the second AA-BB repeating units or (ii) the lactam repeating units; and the copolyamide composition having a concentration of one or more of:
 60 ppm to 500 ppm copper; 
 250 ppm to 5,000 ppm lubricant; 
 10 ppm to 5,000 ppm anti-block agent. 
   
     
     
         46 . The process of  claim 44 , wherein the copolyamide composition exhibits a delta end group value of 1 to 50 microequivalents/gram, an amine end group value of 5 to 79 microequivalents/gram, or both. 
     
     
         47 . A cast or blown film comprising a statistical copolyamide formed by solid state polymerizing and having Formula (4) 
       
         
           
           
               
               
           
         
         wherein in Formula (4):
 c=75-99 wt %; 
 d=4-12; and 
 e=1-25 wt %, and 
 
         wherein the statistical copolyamide has a relative viscosity 60 to 365; a single melting point greater than 220° C., and a maximum crystallization temperature of 185° C. 
       
     
     
         48 . The cast or blown film according to  claim 47  and having an ultimate tensile strength of greater than 100 MPa and less than 140 MPa, an elongation to break of greater than 350% and less than 600%, a tear strength according to ASTM D1922 of greater than 50 grams and less than 150 grams, a Dart drop puncture resistance according to ASTM D1709 of greater than 2,000 grams, and an oxygen transmission rate of no greater than 1.5 cm 3 /100 in 2 -day-atm. 
     
     
         49 . A film composition comprising a statistical copolyamide formed by solid state polymerizing, the film composition comprising:
 from 66 to 99 mol % of a comonomer prepared from hexamethylene diamine and adipic acid; and   from 1 to 34 mol % of a lactam comonomer.