Process for the production of aliphatic-aromatic polyesters

Patent metadata

Field	Value
Publication number	US-10301425-B2
Application number	US-201515516503-A
Country	US
Kind code	B2
Filing date	Oct 2, 2015
Priority date	Oct 3, 2014
Publication date	May 28, 2019
Grant date	May 28, 2019

Abstract

This invention relates to a process for the production of polyesters comprising an esterification/transesterification stage and a polycondensation stage, characterized in that the said polycondensation stage is carried out in the presence of a catalyst comprising a mixture of at least one Titanium-based compound and at least one Zirconium-based compound in which the Ti/(Ti+Zr) ratio by weights is equal to or greater than 0.01 and equal to or less than 0.70.

First claim

The invention claimed is:

1. A process for the production of polyesters comprising:
a) a dicarboxylic component comprising:
a1) 40-60% mol of units deriving from at least one aromatic dicarboxylic acid,
a2) 60-40% mol of units deriving from at least one aliphatic dicarboxylic acid,
b) a diol component comprising units deriving from at least one aliphatic diol;

said process comprising an esterification step and a following polycondensation step, wherein: said esterification step is performed in the presence of an esterification catalyst selected from Titanium compounds, and
said polycondensation step is performed in the presence of a catalyst comprising a mixture of at least one Titanium-based compound and at least one Zirconium-based compound in which the weight ratio Ti/(Ti+Zr) is equal to or higher than 0.01 and equal to or lower than 0.70.

2. The process according to claim 1 , in which said aliphatic diol is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-hheptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-cyclohexanedimethanol, neopentylglycol, 2-methyl-1,3-propanediol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol, cyclohexanediol, cyclohexanemethanediol, pentaerythritol, glycerol, polyglycerol, trimethylolpropane, polyalkylene glycols with molecular weight of 100-4000 and mixtures thereof.

3. The process according to claim 1 , in which said aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid, their esters, their salts and mixtures thereof.

4. The process according to claim 1 , in which said aliphatic dicarboxylic acid is selected from the group consisting of saturated dicarboxylic acids C 2 -C 24 , their alkylic esters C 1 -C 24 , their salts and mixtures thereof.

5. The process according to claim 1 , in which said esterification step the molar ratio between the, aliphatic diols and the dicarboxylic acids, their ester and their salts is between 1 and 2.5.

6. The process according to claim 1 , in which the esterification step is performed at a temperature of 200-250° C. and at a pressure of 0.7-1.5 bar.

7. The process according to claim 1 , in which the esterification step is performed in the presence of an organometallic catalyst selected from the group consisting of the organometallic compounds of Tin, Titanium, Zirconium, Antimony, Cobalt, Lead, Aluminium, Zinc and mixtures thereof.

8. The process according to claim 7 , in which said organometallic catalyst is present, in the esterification step, in a concentration of 12-120 ppm of metal with respect to the amount of polyester theoretically obtained by conversion of all the dicarboxylic acid fed to the process.

9. The process according to claim 1 , in which said Titanium-based compound of the polycondensation step is a Titanate having general formula Ti(OR) 4 in which R is a ligand group comprising one or more atoms of Carbon, Oxygen Phosphorus, Silica, and/or Hydrogen.

10. The process according to claim 9 , in which said R is selected from the group consisting of H, triethanolamine, citric acid, glycolic acid, malic acid, succinic acid, ethanediamine, linear and branched alkyl residues C 1 -C 12 .

11. The process according to claim 10 , in which said R is selected from linear or branched alkyl residues C 1 -C 12 .

12. The process according to claim 11 , in which said R is n-butyl.

13. The process according to claim 1 , in which said Zirconium-based compound of the polycondensation phase is a Zirconate having general formula Zr(OR) 4 in which R is a ligand group comprising one or more atoms of Carbon, Oxygen Phosphorus, Silica, and/or Hydrogen.

14. The process according to claim 13 , in which said R is selected from the group consisting of H, triethanolamine, citric acid, glycolic acid, malic acid, succinic acid, ethanediamine, linear and branched alkyl residues C 1 -C 12 .

15. The process according to claim 14 , in which said R is selected from linear or branched alkyl residues C 1 -C 12 .

16. The process according to claim 15 , in which said R is n-butyl.

17. The process according to claim 1 , in which said polycondensation catalyst comprises a mixture of tetra n-butyl Titanate and tetra n-butyl Zirconate.

18. The process according to claim 1 , in which said polycondensation step is performed at a temperature of 220-250° C. and at a pressure<5 mbar.

19. The process according to claim 1 , in which said polycondensation step is performed in the presence of a total amount of Titanium and Zirconium-based catalyst of 80-500 ppm of metal, with respect to the amount of polyester theoretically obtainable by conversion of all the dicarboxylic acid fed to the process.

20. The process according to claim 1 , comprising, after the polycondensation step, one or more steps of chain extension, reactive processing and/or of reactive extrusion.

21. A process for producing a polyester which comprises using as a catalyst a mixture of at least one Titanium-based compound and at least one Zirconium-based compound in which the weight ratio Ti/(Ti+Zr) is equal to or higher than 0.01 and equal to or lower than 0.70 wherein the polyester comprises:
a) a dicarboxylic component comprising:
a1) 40-80% mol of units deriving from at least one aromatic dicarboxylic acid,
a2) 20-60% mol of units deriving from at least one aliphatic dicarboxylic acid,
b) a diol component comprising units deriving from at least one aliphatic diol.

Assignees

• Novamont Spa

Inventors

• Faiella Federico
• Milizia Tiziana
• Vallero Roberto

Classifications

• C08G63/46

  Polyesters chemically modified by esterification (C08G63/20 takes precedence; by after-treatment C08G63/91) · CPC title

• C08G63/181

  Acids containing aromatic rings · CPC title

• C08G63/183 Primary

  Terephthalic acids · CPC title

• C08G63/85

  Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof {(C08G63/823 takes precedence)} · CPC title

• C08G63/16 Primary

  Dicarboxylic acids and dihydroxy compounds · CPC title