Thermoplastic aromatic polyesters comprising tetrahydrofuran-dimethanol motifs

Patent metadata

Field	Value
Publication number	US-2017190832-A1
Application number	US-201515308661-A
Country	US
Kind code	A1
Filing date	May 5, 2015
Priority date	May 9, 2014
Publication date	Jul 6, 2017
Grant date	—

Abstract

A thermoplastic polyester includes: at least one tetrahydrofuran-dimethanol diol motif (A); and at least one aromatic acid motif (B) selected from terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid and 1,4-naphthalene dicarboxylic acid, the glass transition temperature thereof being higher than, or equal to, 50° C. A method for producing polyester including the motifs (A) and (B) is also described.

First claim

1 . A thermoplastic polyester comprising diol units and aromatic acid units and wherein the polyester further comprises:
at least one tetrahydrofuran-dimethanol diol unit (A); and at least one aromatic acid unit (B) chosen from terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid; the glass transition temperature of which is greater than or equal to 50° C.

2 . The polyester as claimed in claim 1 , wherein the aromatic acid units of the polyester consist of aromatic acid units (B) chosen from terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid units, and mixtures thereof.

3 . The polyester as claimed in claim 1 , wherein the glass transition temperature is greater than or equal to 55° C., preferably greater than 60° C.

4 . The polyester as claimed in claim 1 , wherein the polyester has a degree of crystallinity of less than 50%, advantageously less than 35%.

5 . The polyester as claimed in claim 1 , wherein the polyester is amorphous.

6 . The polyester as claimed in claim 1 , wherein the polyester has a weight-average molar mass of greater than 7500 g/mol, preferably greater than 10 000 g/mol, most preferentially greater than 20 000 g/mol.

7 . The polyester as claimed in claim 1 , wherein the unit (B) is a terephthalic acid unit.

8 . The polyester as claimed in claim 1 , further comprising at least one aliphatic diol unit (C) other than the diol (A).

9 . The polyester as claimed in claim 8 , wherein the aliphatic diol unit (C) is a unit chosen from linear aliphatic diols (C1), cycloaliphatic diols (C2), branched aliphatic diols (C3), or a mixture of these units.

10 . The polyester as claimed in claim 9 , wherein the aliphatic diol unit (C) is a linear aliphatic diol unit (C1) or a mixture of these units (C1).

11 . The polyester as claimed in claim 10 , wherein the polyester comprises, relative to the total amount of diol units (A) and (C1):
from 1 to 99 units (A), advantageously from 5 to 90, preferentially from 20 to 80; and from 1 to 99 units (C1), advantageously from 10 to 95, preferentially from 20 to 80.

12 . The polyester as claimed in claim 9 , wherein the aliphatic diol unit (C) is a cycloaliphatic diol unit (C2) or a mixture of these units (C2).

13 . The polyester as claimed in claim 12 , wherein the polyester comprises, relative to the total amount of diol units (A) and (C2):
from 1 to 99 units (A), advantageously from 5 to 98, preferentially from 80 to 95; and from 1 to 99 units (C2), advantageously from 2 to 95, preferentially from 5 to 20.

14 . The polyester as claimed in claim 9 , wherein the aliphatic diol unit (C) comprises at least one mixture of at least one linear aliphatic diol unit (C1) and of at least one cycloaliphatic diol unit (C2).

15 . The polyester as claimed in claim 14 , wherein the polyester comprises, relative to the total amount of diol units (A) and (C):
from 1 to 98 units (A), advantageously from 5 to 90, preferentially from 20 to 85; from 1 to 98 units (C1), advantageously from 5 to 60, preferentially from 5 to 40; and from 1 to 98 units (C2), advantageously from 5 to 60, preferentially from 5 to 40.

16 . The polyester as claimed in claim 9 , wherein the polyester comprises at least one linear aliphatic diol unit (C1) chosen from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, or a mixture of aliphatic diol units comprising at least one of these units, preferentially ethylene glycol and 1,4-butanediol, very preferentially ethylene glycol.

17 . The polyester as claimed in claim 9 , wherein the cycloaliphatic diol unit (C2) comprises at least one unit chosen from the following units:

18 . The polyester as claimed in claim 17 , wherein the cycloaliphatic diol unit (C2) comprises at least one unit chosen from the following units:

preferentially a unit:

19 . The polyester as claimed in claim 8 , wherein the polyester comprises, relative to the total amount of diol units (A) and (C):
from 1 to 99 units (A), advantageously from 5 to 95; and from 1 to 99 units (C), advantageously from 5 to 95.

20 . A process for producing thermoplastic polyester, which comprises:
a step of introducing, into a reactor, monomers comprising at least one tetrahydrofuran-dimethanol diol (A), at least one aromatic acid (B) chosen from terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid and/or a diester of this acid and optionally at least one aliphatic diol (C) other than the diol (A); and a step of polymerizing the monomers so as to form the polyester, comprising: a first stage during which the reaction medium is stirred, preferably under pressure or a stream of an inert gas, at a temperature ranging from 140 to 250° C. in order to form oligomers; a second stage during which the oligomers formed are stirred under vacuum, at a temperature ranging from 230 to 310° C. in order to form the polyester; a step of recovering the polyester at the end of the polymerizing step.

21 . The process as claimed in claim 20 , wherein, relative to the total moles of monomers (A), (B) and optional (C) introduced into the reactor, the molar percentage of acid and/or of acid diester (B) ranges from 25% to 45%.

22 . A polyester that can be obtained according to the process of claim 20 .

Assignees

• Roquette Freres

Inventors

• Jacquel Nicolas
• Degand Gabriel
• Saint-Loup Rene

Classifications

• C08G63/181

  Acids containing aromatic rings · CPC title

• C08G63/183

  Terephthalic acids · CPC title

• C08G63/189 Primary

  containing a naphthalene ring · CPC title

• C08G63/42

  Cyclic ethers (C08G59/00 takes precedence); Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters · CPC title