Biodegradable aliphatic-aromatic copolyesters, compositions thereof, methods of manufacture, and articles thereof

Patent metadata

Field	Value
Publication number	US-9828485-B2
Application number	US-201414321025-A
Country	US
Kind code	B2
Filing date	Jul 1, 2014
Priority date	Sep 23, 2009
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

Biodegradable compositions containing an aliphatic-aromatic copolyester derived from aromatic polyesters. Methods of making the compositions and articles made from the compositions.

First claim

What is claimed is:

1. A biodegradable composition comprising a combination of:
(i) from more than 93.4 wt. %, based on the total weight of the composition, of an aliphatic-aromatic copolyester having a number average molecular weight of at least 20,000 Daltons, a polydispersity index from 2 to 6, a Tg from −35° C. to 0° C., and a Tm from 90° C. to 160° C., wherein the aliphatic-aromatic copolyester comprises:
(a) a first dihydric alcohol group derived from a first dihydric alcohol selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, tetramethyl cyclobutanediol, isosorbide, cyclohexane dimethanol, hexylene glycols, bio-derived diols and a combination thereof,
(b) an aromatic dicarboxylic acid group derived from
an aromatic polyester selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), polytrimethylene terephthalate, and a combination thereof,

(c) an aliphatic dicarboxylic acid group derived from an aliphatic dicarboxylic acid having the general formula (CH 2 ) m (COOH) 2 , wherein m is an integer from 2 to 10,
(d) a second dihydric alcohol group derived from the aromatic polyester and incorporated into the aliphatic-aromatic copolyester when the aromatic polyester reacts with the first dihydric alcohol and the aliphatic dicarboxylic acid, wherein the second dihydric alcohol group is the residue of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, tetramethyl cyclobutanediol, isosorbide, a cyclohexanedimethanol, a hexylene glycol, a bio-derived diol, and a combination thereof,
(e) the residue of from more than 0 to 0.10 wt. %, based on the aliphatic-aromatic copolyester, of phosphoric acid, and
(f) the residue of from more than 0 to 1.50 wt. %, based on the aliphatic-aromatic copolyester, of an addition copolymer comprising the residue of a glycidyl monomer; and

(ii) from 0 to 5 wt. % of a nucleating agent, an antioxidant, or combination thereof, wherein the sum of the wt. % of (i) and (ii) is 100 wt. %,
wherein a film extruded from the composition is white.

2. The composition of claim 1 , wherein the addition copolymer comprises a residue selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and a combination thereof; and a residue selected from the group consisting of methyl methacrylate, methyl acrylate, styrene, alpha-methyl styrene, butyl methacrylate, butyl acrylate, and a combination thereof.

3. The composition of claim 1 , wherein the aromatic dicarboxylic acid group is a terephthalic acid group, isophthalic acid group, or a mixture thereof.

4. The composition of claim 3 , wherein the isophthalic acid group is present in an amount from 0.2 to 3.0 mole % of the total moles of acid groups in the composition.

5. The composition of claim 1 , wherein the first dihydric alcohol group is present in an amount from 80 mole % to 99.4 mole %, and the second dihydric alcohol group is present in an amount from 0.6 mole % to 20.0 mole %, each based on the total moles of dihydric alcohol groups in the composition.

6. The composition of claim 1 , wherein the aromatic dicarboxylic group and the aliphatic dicarboxylic group are present in a mole ratio of aromatic dicarboxylic group:aliphatic dicarboxylic group from 0.6:1 to 1.3:1.

7. The composition of claim 1 , wherein the first dihydric alcohol is selected from the group consisting of 1,4-butanediol, 1,3-propanediol, and combinations thereof and the second dihydric alcohol is ethylene glycol.

8. The composition of claim 1 , wherein the aliphatic dicarboxylic acid is adipic acid.

9. The composition of claim 1 , wherein the composition comprises from 0.01 to 5.00 wt. % of an additive selected from the group consisting of the nucleating agent, the antioxidant, a UV stabilizer, a plasticizer, an epoxy compound, and a combination thereof.

10. The composition of claim 1 , wherein the aromatic polyester is a poly(trimethylene terephthalate) derived from petroleum-derived 1,3-propanediol, poly(trimethylene terephthalate) derived from bio-derived 1,3-propanediol, poly(butylene terephthalate) derived from petroleum-derived 1,4-butanediol, poly(butylene terephthalate) derived from bio-derived 1,4-butanediol, poly(trimethylene terephthalate) derived from post-consumer poly(ethylene terephthalate), poly(butylene terephthalate) derived from post-consumer poly(ethylene terephthalate), virgin poly(ethylene terephthalate), recycled poly(ethylene terephthalate), post-consumer poly(ethylene terephthalate), recycled poly(trimethylene terephthalate), recycled copolyesters of terephthalic acid with ethylene glycol and cyclohexane dimethanol, and combinations thereof.

11. The composition of claim 1 , wherein the aromatic polyester is poly(butylene terephthalate) and the composition contains poly(butylene terephthalate) residues selected from the group consisting of butane diol, titanium, tin, epoxies, and combinations thereof.

12. The composition of claim 1 , wherein the aromatic polyester is poly(trimethylene terephthalate) and the composition contains poly(trimethylene terephthalate) residues selected from the group consisting of propane diol, titanium, tin, and combinations thereof.

13. The composition of claim 1 , wherein the aromatic polyester is a poly(ethylene terephthalate) homopolymer, a poly(ethylene terephthalate) copolymer, or a combination thereof, and the aliphatic-aromatic copolyester comprises an ethylene glycol group, diethylene glycol group, isophthalic acid group, antimony-containing compound, germanium-containing compound, titanium-containing compound, cobalt-containing compound, tin-containing compounds, aluminum, aluminum salt, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, alkaline salt, alkaline earth metal salt, phosphorous-containing compound or anion, sulfur-containing compound or anion, naphthalene dicarboxylic acid group, 1,3-propanediol group, or a combination thereof.

14. The composition of claim 1 , wherein the film extruded from the composition has a modulus of elasticity of at least 520 N/mm2 as determined in accordance with as ISO 527, a tensile strength of at least 27 N/mm2 as determined in accordance with as per ISO 527, a tear strength of at least 38 J/mm as determined in accordance with as DIN 53373.

15. A process for making the composition of claim 1 , the process comprising
a) reacting
(1) the aromatic polyester selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), polytrimethylene terephthalate, and a combination thereof, with
(2) the first dihydric alcohol selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol tetramethyl cyclobutanediol, isosorbide, cyclohexanedimethanol, bio-derived diols, and hexylene glycol, and
(3) an aliphatic dicarboxylic acid of the formula (CH 2 ) m (COOH) 2 , wherein m is 4 to 10,

at a temperature from 160° C. to less than 250° C. in the presence of a titanium alkoxide catalyst to form a first mixture;
b) subjecting the first mixture to vacuum distillation at a pressure of less than 2 Torr and a temperature of 220° C. to less than 260° C., to form a molten copolyester; and
c) reacting the molten copolyester with from more than 0 to 1.50 wt. % of phosphoric acid, from more than 0 to 1.50 wt. % of an addition copolymer comprising the residue of a glycidyl monomer, or a combination thereof, for at least 5 minutes, to form the aliphatic-aromatic c

Assignees

• Sabic Global Technologies Bv

Inventors

• Kannan Ganesh
• Alidedeoglu Husnu Alp
• Gallucci Robert Russell

Classifications

• C08J2367/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence) · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08J2367/04

  Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence) · CPC title

• C08G63/916

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08L67/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) · CPC title