Polyester and method for preparing such a polyester

Patent metadata

Field	Value
Publication number	US-9908968-B2
Application number	US-201515123724-A
Country	US
Kind code	B2
Filing date	Mar 11, 2015
Priority date	Mar 11, 2014
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

A polyester, including ethylene 2,5-furandicarboxylateunits, also includes diethylene glycol residues, the content of which is less than 0.045, in moles per mole of 2,5-furandicarboxylate moieties. The polyester composition can be prepared with a method where a starting mixture is subjected to esterification of 2,5-furandicarboxylic acid or transesterification of an ester thereof with ethylene glycol in the presence of a basic compound and/or an ammonium compound capable of suppressing the formation of diethylene glycol.

First claim

The invention claimed is:

1. A polyester comprising ethylene 2,5-furandicarboxylate moieties, which polyester also comprises diethylene glycol residues, wherein the content of diethylene glycol residues is less than 0.045, in moles per mole of 2,5-furandicarboxylate moieties.

2. The polyester according to claim 1 , which has a relative content of carboxylic acid end groups, expressed as the fraction of the molar amount of carboxylic acid end groups divided by the sum of the molar amounts of hydroxyl end groups and carboxylic acid end groups in the range of 0.10 to 0.70.

3. The polyester according to claim 2 , wherein the relative content of carboxylic acid end groups is in the range of 0.14 to 0.65.

4. The polyester according to claim 1 , wherein the amount of carboxylic acid end groups is in the range of 15 to 122 meq/kg.

5. The polyester according to claim 1 , which has an intrinsic viscosity of at least 0.45 dL/g.

6. The polyester according to claim 1 , which has a light absorbance of at most 0.08, measured as a 30 mg/mL solution in a dichloromethane:hexafluoroisopropanol 8:2 (vol/vol) mixture at 400 nm.

7. The polyester according to claim 1 , which has a polydispersity index in the range of 1.9 to 2.6.

8. The polyester according to claim 1 , which has a crystallinity of at least 25 J/g, measured by Differential Scanning calorimetry (DSC).

9. The polyester according to claim 1 , which has a melting point of at least 215° C.

10. A composition comprising the polyester according claim 1 , which has a moisture content of at most 100 ppmw, determined in accordance with ISO 15512.

11. A method for the preparation of a polyester comprising ethylene 2,5-furandicarboxylate moieties, which polyester also comprises diethylene glycol residues, wherein a starting mixture comprising 2,5-furandicarboxylic acid and ethylene glycol or comprising a dialkyl ester of 2,5-furandicarboxylic acid and ethylene glycol is subjected to esterification or transesterifiaction to form an ester composition, which ester composition thus obtained is subjected to polycondensation at reduced pressure in the presence of a polycondensation catalyst to obtain a polycondensate, wherein the esterification or transesterification takes place in the presence of a basic compound and/or an ammonium compound capable of suppressing the formation of diethylene glycol, whereby the content in said polyester of diethylene glycol residues is less than 0.045, in moles per mole of 2,5-furandicarboxylate moieties.

12. The method according to claim 11 , wherein the basic or ammonium compound is selected from the group consisting of tetraalkyl ammonium compounds, choline, alkali metal salts of carboxylic acids, alkaline earth metal salts of carboxylic acids, basic alkali metal salts of mineral acids, basic alkaline earth metal salts of mineral acids, alkali metal hydroxides, ammonium hydroxides and combinations thereof.

13. The method according to claim 12 , wherein the tetraalkylammonium compound is selected from tetraalkylammonium hydroxide compounds, and the basic alkali metal salt of mineral acid is Na 2 HPO 4 .

14. The method according to claim 11 , wherein the starting mixture comprises 2,5-furandicarboxylic acid and ethylene glycol.

15. The method according to claim 14 , wherein the esterification reaction between 2,5-furandicarboxylic acid and ethylene glycol is carried out at a temperature of 160 to 240° C. and a pressure of 0.9 to 5 bar for a period of 0.5 to 4 hr.

16. The method according to claim 11 , wherein the polycondensation comprises a pre-polycondensation reaction conducted at a pressure of 20 to 700 mbar and a polycondensation reaction conducted at 0.05 to 20 mbar.

17. The method according to claim 16 , wherein the combined period for the pre-polycondensation and the polycondensation reactions is in the range of 1.5 to 5 hours.

18. The method according to claim 11 , wherein during the polycondensation step ethylene glycol that is formed is removed from the ester composition that is subjected to polycondensation.

19. The method according to claim 11 , wherein the polycondensation catalyst is selected from the catalysts comprising one or more elements selected from tin, zinc, titanium and antimony.

20. The method according to claim 10 , wherein the polycondensation is carried out at a temperature of 245 to 270° C. and a pressure of 0.05 to 5 mbar.

21. The method according to claim 10 , wherein the polycondensate is crystallized at a temperature in the range of 90 to 200° C.

22. The method according to claim 11 , which further comprises a step of solid state polymerization.

23. The method according to claim 22 , wherein the solid state polymerization is carried out at a temperature in the range of 180° C. to 210° C.

24. The method according to claim 22 , which is carried out for a period up to 120 hr.

25. Polyester according to claim 1 , wherein the content of diethylene glycol residues is less than 0.040, in moles per mole of 2,5-furandicarboxylate moieties.

26. Polyester according to claim 1 , wherein the content of diethylene glycol residues is less than 0.030, in moles per mole of 2,5-furandicarboxylate moieties.

Assignees

• Furanix Technologies Bv
• Synvina C V

Inventors

• Kolstad Jeffrey John
• Wang Bing
• Schiavone Robert Joseph
• Andrews Marion L
• Van Berkel Jesper Gabriël
• Paschke Edward E

Classifications

• C08G63/181 Primary

  Acids containing aromatic rings · CPC title

• C08G63/16 Primary

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08G63/80

  Solid-state polycondensation · CPC title

• C08G63/866

  Antimony or compounds thereof · CPC title

• C08G63/82

  characterised by the catalyst used · CPC title