BIO-BASED TERPOLYMERS AND PROCESS OF MAKING THE SAME
Polyamide terpolymer compositions, which contain biobased monomers and are suitable for making shaped articles, are disclosed. Comprised of three monomeric species polymerized randomly, including hexamethylene diamine, adipic acid and a bio-based monomer, the compositions are easier to process and have better dye uniformity than polyamides formed from melt-blended biobased components, and are comparable in dyeability, color fastnessand appearance retention performance to non-biobased polyamide copolymers.
1 . A random, high viscosity terpolymer comprising the condensation polymer of three component intermediates comprising:
a) a first constituent comprising hexamethylene diamine,
b) a second constituent unit comprising adipic acid, and
c) a third constituent unit comprising at least one diacid selected from the group consisting of: Azelaic acid, sebacic acid, and 11-carboxyl-undecanoic acid (C11 aliphatic dicarboxylic acid),
wherein the sum of the first and the second constituent units is present at a weight percentage from about 55% to about 99.5% of the terpolymer, and the third constituent is present at a weight percentage of about 0.5% to about 45% of the terpolymer; and further wherein the intrinsic viscosity of the terpolymer is greater than about 2.7 IV (in sulfuric acid) and the number average molecular weight is greater than about 10,000 grams per mole.
2 . The random terpolymer of claim 1 , wherein said third constituent unit is sebacic acid.
3 . The random terpolymer of claim 1 , wherein said first constituent unit further comprises methylpentamethylene diamine present at a weight percentage of from about 0.10% to about 10% of the terpolymer.
4 . The random terpolymer of claim 1 , wherein said second constituent unit further comprises an acid selected from the group consisting of isophthalic acid, 5-sulfoisophthalic acid, or terephthalic acid, wherein said acid is present at a weight percentage of from about 0.10% to about 10% of the terpolymer.
5 . The random terpolymer of claim 2 , wherein said third constituent unit is present at a weight percentage of about 4.5% of the terpolymer.
6 . The random terpolymer of claim 1 , further comprising a melt blended additive selected from the group consisting of: virgin thermoplastic, recycled thermoplastic, polyethylene terephthalate, colorants, titanium dioxide, anti-microbial agents, stabilizers, flame retardants, and anti-oxidants.
7 . A molded article made from the random terpolymer of claim 1 .
8 . The molded article of claim 7 further comprising a component selected from the group consisting of: virgin thermoplastic, recycled thermoplastic, polyethylene terephthalate, colorants, titanium dioxide, anti-microbial agents, stabilizers, flame retardants, and anti-oxidants.
9 . A fiber comprising a random, high viscosity terpolymer comprising the condensation polymer of three component intermediates comprising:
a) a first constituent unit comprising hexamethylene diamine
b) a second constituent unit comprising adipic acid, and
c) a third constituent unit comprising at least one diacid selected from the group consisting of: Azelaic acid, sebacic acid, and 11-carboxyl-undecanoic acid (C11 aliphatic dicarboxylic acid),
wherein the sum of the first and the second constituent units is present at a weight percentage from about 55% to about 99.5% of the terpolymer, and the third constituent is present at a weight percentage of about 0.5% to about 45% of the terpolymer; and further wherein the intrinsic viscosity of the terpolymer is greater than about 2.7 IV (in sulfuric acid) and the average number molecular weight is greater than about 10,000 grams per mole.
10 . The fiber of claim 9 , wherein said third constituent unit is sebacic acid.
11 . The fiber of claim 9 , wherein said first constituent unit further comprises methylpentamethylene diamine present at a weight percentage of from about 0.10% to about 10% of the terpolymer.
12 . The fiber of claim 9 , wherein said second constituent unit further comprises an acid selected from the group consisting of isophthalic acid, 5-sulfoisophthalic acid, or terephthalic acid, wherein said acid is present at a weight percentage of from about 0.10% to about 10% of the terpolymer.
13 . The fiber of claim 10 , wherein said third constituent unit is present at a weight percentage of about 4.5% of the terpolymer.
14 . The fiber of claim 9 , further comprising a component selected from the group consisting of: virgin thermoplastic, recycled thermoplastic, polyethylene terephthalate, colorants, titanium dioxide, anti-microbial agents, stabilizers, flame retardants, and anti-oxidants.
15 . A carpet comprising the fiber of claim 9 .
16 . A fabric comprising the fiber of claim 9 .
17 . A process for making a random, high viscosity terpolymer comprising:
(a) providing a blend of first and second co-monomer salts to a first reactor, wherein the first co-monomer salt comprises hexamethylene diamine and a diacid component selected from azelaic acid, sebacic acid, and 11-carboxyl-undecanoic acid (C11 aliphatic dicarboxylic acid), and the second co-monomer salt comprises adipic acid and hexamethylene diamine; (b) copolymerizing said blended salts, wherein said copolymerizing occurs in a second reactor; and (c) conditioning the resulting polymer to achieve an IV (in sulfuric acid) of greater than 2.7.
18 . The process of claim 17 , wherein said first reactor is an evaporator.
19 . The process of claim 18 , wherein said second reactor is an autoclave.
20 . The process of claim 17 , wherein said diacid is maintained at a weight percentage of from about 0.5% to about 45% of the polymer.
21 . The process of claim 17 , wherein said diacid is sebacic acid.
22 . The process of claim 21 , wherein said sebacic acid is maintained at a weight percentage of about 4.5% of the polymer.
23 . The process of one of claim 17 , wherein said conditioning occurs at a temperature of about 180° C. for about 10 hours.
24 . The process of claim 17 , wherein a portion of the hexamethylene diamine is replaced by Methylpentamethylene diamine present at a weight percentage of from about 0.1% to about 10% by weight of the polymer.
25 . The process of claim 17 , wherein a portion of the adipic acid is replaced by an acid selected from the group consisting of isophthalic acid, 5-sulfoisophthalic acid, or terephthalic acid, wherein said acid is present at a weight percentage of from about 0.10% to about 10% of the polymer.