Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels
View Patent ↗This disclosure relates to an aliphatic-aromatic copolyester of poly(butylene-co-adipate terephthalate) that is prepared from recycled polyethylene terephthalate in the presence of titanium catalyst and a phosphorous containing compound. The copolyester is contaminated with little or no ethylene glycol and/or isophthalic acid, which are artifacts of preparing the copolyester from recycled PET. Advantageously, because there is little or no contamination from ethylene glycol and/or isophthalic acid in the copolyester, there is essentially no depression in the material's melting temperature.
1. A poly(butylene terephthalate-co-adipate) copolymer comprising a polybutylene terephthalate residue, an adipic acid residue, and a tetraisopropyl titanate residue complexed to a phosphoric acid residue, wherein: the poly(butylene terephthalate-co-adipate) copolymer is prepared by the process of ester interchange and polymerization of 1,4-butane diol using:
from 20 to 95 mol percent adipic acid, and
from 5 to 80 mol percent of terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate and containing polyethylene terephthalate-derived ethylene glycol and polyethylene terephthalate-derived isophthalic acid; and
0.05 to 1 mol percent of phosphoric acid based on poly(butylene terephthalate-co-adipate) copolymer and from 10 to 1000 ppm of tetraisoproyl titanate based on the total weight of the reactants, wherein the molar ratio of phosphoric acid to tetraisopropyl titanate is 1:1; and wherein the process comprises:
the adipic acid and terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate are added to a solution of phosphoric acid and tetraisopropyl titanate in 1,4-butanediol that has been heated to 175° C.;
the solution of adipic acid, terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate, phosphoric acid, and tetraisopropyl titanate in 1,4-butanediol is heated to 220° C. for ester interchange;
the temperature of the solution of adipic acid, terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate, phosphoric acid, and tetraisopropyl titanate in 1,4-butanediol is then heated to 250° C. at a pressure of 1 Torr for polymerization until the clear point is reached; and wherein:
the poly(butylene terephthalate-co-adipate) copolymer comprising a polybutylene terephthalate residue, an adipic acid residue, and a tetraisopropyl titanate residue complexed to a phosphoric acid residue has a melt temperature of from 100 to 125° C. and an intrinsic viscosity of greater than 1.0 deciliter per minute as measured in a 60:40 by weight phenol/1,1,2,2-tetrachloroethane mixture at 23° C.; and
the backbone of the poly(butylene terephthalate-co-adipate) copolymer consists of 5 weight percent or less of polyethylene terephthalate-derived ethylene glycol and 3 weight percent or less of polyethylene terephthalate-derived isophthalic acid in the backbone of the poly(butylene terephthalate-co-adipate) copolymer.
2. The poly(butylene terephthalate-co-adipate) copolymer of claim 1 consisting of less than 4 mole % of polyethylene terephthalate-derived ethylene glycol groups in the backbone.
3. The poly(butylene terephthalate-co-adipate) copolymer of claim 1 consisting of less than or equal to 2 mole % of polyethylene terephthalate-derived ethylene glycol groups and 3 weight percent or less of polyethylene terephthalate-derived isophthalate groups in the backbone.
4. The poly(butylene terephthalate-co-adipate) copolymer of claim 1 consisting of less than 10 mole % of a combination of polyethylene terephthalate-derived ethylene glycol groups and polyethylene terephthalate-derived isophthalate groups in the backbone.
5. A composition comprising the poly(butylene terephthalate-co-adipate) copolymer of claim 1 and at least one additive selected from the group consisting of a nucleating agent, an antioxidant, a UV stabilizer, a starch plasticizer, an epoxy compound, a melt strength additive, an alcohol, an acetate, an alcohol-acetate copolymer, a crosslinker, an anti-aging agent, a retrogradation agent, an anti-blocking agent, water, and an odor-controlling agent, or combinations thereof; and an additional thermoplastic polymer.
6. A poly(butylene terephthalate-co-adipate) copolymer having ethylene glycol and isophthalic acid in the backbone, wherein the poly(butylene terephthalate-co-adipate) copolymer consists of a polyester component residue, an adipic acid component residue, and a tetraisopropyl titanate residue complexed to a phosphoric acid residue, wherein: the poly(butylene terephthalate-co-adipate) copolymer is prepared by the process of ester interchange and polymerization of 1,4-butane diol and:
from 20 to 95 mol percent adipic acid, and
from 5 to 80 mol percent of terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate and containing polyethylene terephthalate-derived ethylene glycol and polyethylene terephthalate-derived isophthalic acid; and
0.05 to 1 mol percent of phosphoric acid based on poly(butylene terephthalate-co-adipate) copolymer and from 10 to 1000 ppm of tetraisoproyl titanate based on the total weight of the reactants, wherein the molar ratio of phosphoric acid to tetraisopropyl titanate is 1:1; and wherein:
the adipic acid and terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate are added to a solution of phosphoric acid and tetraisopropyl titanate in 1,4-butanediol that has been heated to 175° C.;
the solution of adipic acid, terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate, phosphoric acid, and tetraisopropyl titanate in 1,4-butanediol is heated to 220° C. for ester interchange;
the temperature of the solution of adipic acid, terephthalic acid or dimethyl terephthalate derived from polyethylene terephthalate, phosphoric acid, and tetraisopropyl titanate in 1,4-butanediol is then heated to 250° C. at a pressure of 1 Torr for polymerization until the clear point is reached; and wherein:
the poly(butylene terephthalate-co-adipate) copolymer comprising a polybutylene terephthalate residue, an adipic acid residue, and a tetraisopropyl titanate residue complexed to a phosphoric acid residue has a melt temperature of from 100 to 125° C. and an intrinsic viscosity of greater than 1.0 deciliter per minute as measured in a 60:40 by weight phenol/1,1,2,2-tetrachloroethane mixture at 23° C.; and wherein:
the backbone of the poly(butylene terephthalate-co-adipate) copolymer consists of 5 weight percent or less of polyethylene terephthalate-derived ethylene glycol and 3 weight percent or less of polyethylene terephthalate-derived isophthalic acid in the backbone of the poly(butylene terephthalate-co-adipate) copolymer.