Glycolide-based polyesters

• US 9,624,341 B2
• Filed: 12/18/2013
• Issued: 04/18/2017
• Est. Priority Date: 12/20/2012
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Inventors: Bhattacharjee, Debkumar, Sehanobish, Kalyan
• Primary Examiner(s): JONES JR., ROBERT STOCKTON
• Application Number:
  US14/653,728
• Publication Number:
  US 20160002394A1
• Time in Patent Office: 1,217 Days
• CPC Class Codes: B29C 43/24 Calendering
• CPC Class Codes: B29K 2067/00 Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29L 2007/008 Wide strips, e.g. films, webs
• CPC Class Codes: C08G 63/00 Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule polyester-amides C08G69/44; polyester-imides C08G73/16
• CPC Class Codes: C08G 63/16 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/60 derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/66 Polyesters containing oxygen in the form of ether groups C08G63/42, C08G63/58 take precedence
• CPC Class Codes: C08J 2367/00 Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08J2377/12; of polyester-imides C08J2379/08; Derivatives of such polymers
• CPC Class Codes: C08J 2367/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers

Abstract

A polymer comprises reaction product of (a) one or more diacid, diester thereof, glycolide, and (b) one or more polyol, wherein component (a) comprises glycolide or combinations thereof, and component (b) comprises one or more polyol comprising a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, or combinations thereof.

Claims

1. A polymer comprising reaction product of component (a) comprises 70 mol. % or more of glycolide, and component (b) one or more polyol comprising a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, or combinations thereof.

2. The polymer of claim 1 wherein component (a) further comprises less than 30 mol. %, based on the total amount of component (a), of furan dicarboxylic acid (FDCA) or 1,5-naphthalene dicarboxylic acid (NDCA), one or more C1 to C10 alkyl diester thereof, or combinations thereof.

3. The polymer of claim 2 wherein component (a) comprises dimethyl furanoate (DMF).

4. The polymer of claim 2 wherein component (a) comprises dimethyl naphthanoate (DMN).

5. The polymer of claim 2 wherein component (a) comprises glycolide and one or more C₁ to C₁₀ alkyl diester of FDCA or NDCA or combinations thereof, based on the total amount of component (a).

6. The polymer of claim 1 wherein component (b) further comprises 10-90 mol. %, based on the total amount of component (b) polyol, of ethylene glycol.

7. The polymer of claim 1 wherein component (b) comprises 25 to 75 mol. %, based on the total amount of component (b), of 1,3-cyclohexanedimethanol and 25 to 75 mol. %, based on the total amount of component (b), of 1,4-cyclohexanedimethanol.

8. The polymer of claim 7 wherein component (b) comprises 45 to 65 mol. %, based on the total amount of component (b), of 1,3-cyclohexanedimethanol and 35 to 55 mol. %, based on the total amount of component (b), of 1,4-cyclohexanedimethanol.

9. The polymer of claim 8 wherein component (b) comprises 55 mol. %, based on the total amount of component (b), of 1,3-cyclohexanedimethanol and 45 mol. %, based on the total amount of component (b), of 1,4-cyclohexanedimethanol.

10. The polymer of claim 1 wherein component (b) comprises 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

11. A composition comprising a first polymer of claim 1 and one or more second polymer selected from the group consisting of (A) polymers of claim 1 different from the first polymer and (B) other polyesters which are reaction product of component (i) diacids, diesters or glycolides, and component (ii) polyols, wherein (x) component (i) does not include glycolide when component (ii) is a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and (y) wherein component (ii) does not include mixtures of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol when component (i) comprises glycolide.

12. The composition of claim 11 wherein at least one first polymer is the reaction product of glycolide with or without one or more C₁ to C₁₀ alkyl diesters of FDCA or NDCA, and at least one other polymer is the reaction product of glycolide and one more C₁ to C₁₀ alkyl diesters of FDCA or NDCA different from the diesters (if any) or combination of diesters (if any) present in the first polymer.

13. The composition of claim 11 wherein the other polyester (B) comprises a reaction product of component (i) and component (ii), where component (i) is selected from the group consisting of FDCA, one or more C₁ to C₁₀ alkyl diester thereof, NDCA, C₁ to C₁₀ alkyl diester thereof, or glycolide, or combinations thereof, and component (ii) is one or more polyol comprising isosorbide, ethylene glycol, a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, or combinations thereof;

provided that when component (i) comprises glycolide, component (ii) does not include mixtures of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

14. The composition of claim 11 wherein the other polyester (B) comprises aliphatic homopolymer polyglycolide or polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), copolymer polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), polyethylene terephthalate (PET), semi-aromatic copolymer PET, polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and aromatic copolymers from polycondensation of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid.

15. An article comprising one or more polymers of claim 1.

16. A film or sheet of one or more layers, wherein at least one layer comprises polymer comprising the reaction product of (a) one or more diacid, diester thereof, or glycolide, and (b) a polyol, wherein:

component (a) comprises 70 mol. % or more of glycolide, and

component (b) comprises one or more polyol comprising a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, or combinations thereof.

17. A method of forming a film comprising:

(i) extruding a polymer to form an extrudate;

(ii) shaping the extrudate by passing it through a flat or annular die such that the extrudate has a machine direction and a cross direction; and

(iii) cooling the extrudate;

wherein the polymer comprises reaction product of component (a) 70 mol. % or more of glycolide, and component (b) one or more polyol comprising a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol, or combinations thereof, wherein component (b) is not solely ethylene glycol.

18. The method of claim 17 comprising the further step of orienting the film in the machine or cross direction, or both.