Polyesters including isosorbide as a comonomer and methods for making same

• US 5,959,066 A
• Filed: 04/23/1998
• Issued: 09/28/1999
• Est. Priority Date: 04/23/1998
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: HNA Holdings, Inc. (Celanese Corporation)
• Inventors: Johnson, Robert E., Khanarian, Garo, Charbonneau, Larry F., Witteler, Helmut B.
• Primary Examiner(s): Mosley, Terressa
• Application Number:
  US09/064,844
• Time in Patent Office: 523 Days
• Field of Search: 528/271, 528/272
• US Class Current: 528/271
• CPC Class Codes: C08G 63/672 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: C08G 63/80 Solid-state polycondensation

Abstract

An isotropic polyester polymer and method for making the polyester is prepared by (1) combining in a reactor a monomer containing a terephthaloyl moiety; optionally, one or more other monomers containing an aromatic diacid moiety; a monomer comprising an ethylene glycol moiety; a monomer containing an isosorbide moiety; optionally, one or more other monomers containing a diol moiety; and optionally, a monomer containing a diethylene glycol moiety; with a condensation catalyst suitable for condensing aromatic diacids and glycols; and (2) heating the monomers and catalyst to polymerize the monomers to yield a polyester having an inherent viscosity of at least about 0.35 dL/g.

Claims

1. A method for making a polyester polymer comprising:

(1) combining in a reactor a monomer comprising a terephthaloyl moiety;

optionally, one or more other monomers containing an aromatic diacid moiety;

a monomer comprising an ethylene glycol moiety;

a monomer comprising an isosorbide moiety;

optionally, one or more other monomers comprising a diol moiety; and

optionally, a monomer comprising a diethylene glycol moiety, with a condensation catalyst suitable for condensing aromatic diacids and glycols; and

(2) heating said monomers and said catalyst to a temperature sufficient to polymerize said monomers into a polyester polymer having at least terephthaloyl moieties, ethylene glycol moieties nd isosorbide moieties;

wherein said heating is continued for a sufficient time to yield an isotropic polyester having an inherent viscosity of at least about 0.35 dL/g when measured as a 1% (weight/volume) solution of said polyester in o-chlorophenol at a temperature of 25°

C.

2. The method according to claim 1, wherein said process further includes stirring of said monomers during said heating and the concurrent removal of by-products by distillation and/or evaporation.

3. The method according to claim 1, wherein said monomer comprising a terephthaloyl moiety is terephthalic acid.

4. The method according to claim 3, wherein water and unreacted monomer are removed while said monomers polymerize.

5. The method according to claim 1, wherein said monomer comprising a terephthaloyl moiety is dimethyl terephthalate.

6. The method according to claim 5, wherein methanol and unreacted monomer are removed while said monomers polymerize.

7. The method according to claim 1, wherein said process further comprises adding an additive to said process to help retain volatile components.

8. The method according to claim 7, wherein said additive is tetrahydronapthalene.

9. The method according to claim 1, wherein said one or more optional other diols are selected from the group consisting of aliphatic alkylene glycols and branched aliphatic glycols having from 3-12 carbon atoms and having the empirical formula HO--C_n H_2n --OH, where n is an integer from 3-12;

cis and trans-1,4-cyclohexanedimethanol and mixtures thereof;

triethylene glycol;

2,2-bis 4-(2-hydroxyethoxy)phenyl!propane;

1,1-bis 4-(2-hydroxyethoxy)phenyl!cyclohexane;

9,9-bis 4-(2-hydroxyethoxy)phenyl!fluorene;

1,4;

3,6-dianhydromannitol;

1,4;

3,6-dianhydroiditol; and

1,4-anhydroerythritol.

10. The method according to claim 1, wherein said one or more optional other aromatic diacids are selected from the group consisting of isophthalic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 4,4'"'"'-bibenzoic acid.

11. The method according to claim 1, wherein said monomers are included in amounts such that said terephthaloyl moieties are present in an amount of about 40 mole % to about 50 mole % of said polyester, one or more optional other aromatic diacid moieties are present in an amount up to about 10 mole % of said polyester, said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of said polyester, diethylene glycol moieties are present in an amount of about 0.25 mole % to about 10 mole % of said polyester, said isosorbide moieties are present in an amount of about 0.25 mole % to about 40 mole % of said polyester, and said one or more other diol moieties are present in an amount up to about 15 mole % of said polyester.

12. The method according to claim 11, wherein said monomers are included in amounts such that said terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester, one or more optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester, said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of said polyester, diethylene glycol moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester, said isosorbide moieties are present in an amount of about 0.25 mole % to about 30 mole % of said polyester, and other diol moieties are present in an amount up to about 10 mole % of said polyester.

13. The method according to claim 1, further comprising increasing the molecular weight of said polyester by solid state polymerization.

14. The method according to claim 13, wherein said solid state polymerization comprises:

a) crystallizing said polyester by heating said polyester to a temperature in the range of about 115°

C. to about 140°

C. or treating said polyester with a solvent which reduces the glass transition temperature of the polyester allowing for crystallization; and

b) heating said polyester under vacuum or in a stream of inert gas at an elevated temperature above about 140°

C. but below the melting temperature of said copolyester to yield a copolyester having an increased inherent viscosity.

15. The method according to claim 14, wherein said heating step (b) is carried out at a temperature of about 195°

to about 198°

C. for about 10 hours.

16. The method according to claim 13, wherein said inherent viscosity is increased to at least about 0.8 dL/g.

17. The method according to claim 13, wherein said polyester comprises from about 0.25 mole % to about 10 mole % isosorbide moieties.

18. An isotropic polyester comprising terephthaloyl moieties;

optionally, other aromatic diacid moieties;

ethylene glycol moieties;

diethylene glycol moieties;

isosorbide moieties; and

, optionally, one or more other diol moieties, wherein said polyester has an inherent viscosity of at least about 0.35 dL/g when measured as a 1% (weight/volume) solution of said polyester in o-chlorophenol at a temperature of 25°

C.

19. The isotropic polyester according to claim 18, wherein said polyester comprises about 40% to about 50% of said terephthaloyl moieties and a total of up to about 10 mole % of said one or more optional other aromatic diacid moieties.

20. The isotropic polyester according to claim 19, wherein said terephthaloyl moieties are derived from terephthalic acid or dimethyl terephthalate.

21. The isotropic polyester according to claim 19, wherein said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of the polyester, said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 10 mole % of the polyester, said isosorbide moieties are present in an amount of about 0.25 mole % to about 40 mole % of the polyester, and said one or more other diol moieties are present in an amount up to about 15 mole % of the polyester.

22. The isotropic polyester according to claim 18, wherein said one or more other diol moieties are derived from aliphatic alkylene glycols or branched aliphatic glycols having from 3-12 carbon atoms and having the empirical formula HO--C_n H_2n --OH, where n is an integer from 3-12;

cis or trans-1,4-cyclohexanedimethanol or mixtures thereof;

triethylene glycol;

2,2-bis 4-(2-hydroxyethoxy)phenyl!propane;

1,1-bis 4-(2-hydroxyethoxy)phenyl!cyclohexane;

9,9-bis 4-(2-hydroxyethoxy)phenyl!fluorene;

1,4;

3,6-dianhydromannitol;

1,4;

3,6-dianhydroiditol;

or 1,4-anhydroerythritol.

23. The isotropic polyester according to claim 18, wherein said one or more optional other aromatic diacid moieties are derived from isophthalic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or 4,4'"'"'-bibenzoic acid.

24. The isotropic polyester according to claim 18, wherein terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester, said optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester, said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of said polyester, said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester, said isosorbide moieties are present in an amount of about 0.25 mole % to about 30 mole % of said polyester, and said other diol moieties are present in an amount up to about 10 mole % of said polyester.

25. The isotropic polyester according to claim 24, wherein said other diol moieties are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, or mixtures thereof.

26. The isotropic polyester according to claim 25, wherein said optional other aromatic diacid moieties are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'"'"'-bibenzoic acid, or mixtures thereof.

27. The isotropic polyester according to claim 18, wherein said polyester has an inherent viscosity of at least about 0.40 dL/g.

28. The isotropic polyester according to claim 18, wherein said terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester;

said one or more optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'"'"'-bibenzoic acid, or mixtures thereof;

said ethylene glycol moieties are present in an amount of about 38 mole % to about 49.5 mole % of said polyester;

said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester;

said isosorbide moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester; and

said optional other diol moieties are present in an amount up to about 2 mole % of said polyester and are cis-1,4-cyclohexanedimethanol moieties, trans-1,4-cyclohexanedimethanol moieties, or mixtures thereof;

wherein said polyester has an inherent viscosity of at least about 0.45 dL/g.

29. The isotropic polyester according to claim 18, wherein said terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester;

said one or more optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'"'"'-bibenzoic acid or mixtures thereof;

said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of said polyester;

said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester;

said isosorbide moieties are present in an amount of about 6 mole % to about 30 mole % of said polyester; and

said other diol moieties are present in an amount up to about 10 mole % of said polyester and are cis-1,4-cyclohexanedi-methanol moieties, trans-1,4-cyclohexanedimethanol moieties or mixtures thereof.

30. The isotropic polyester according to claim 18, further comprising an additive wherein said additive is a plasticizer, pigment, flame retardant, reinforcing agent, thermal stabilizer, ultraviolet light stabilizer, impact modifier or flow enhancer.

31. The isotropic polyester according to claim 30, wherein said additive is glass fibers.

32. An isotropic polyester comprising terephthaloyl moieties;

optionally, other aromatic diacid moieties;

ethylene glycol moieties;

optionally, diethylene glycol moieties;

isosorbide moieties; and

optionally, one or more other diol moieties wherein said polyester has an inherent viscosity of at least about 0.5 dL/g when measured as a 1% (weight/volume) solution of said polyester in o-chlorophenol at a temperature of 25°

C.

33. The isotropic polyester according to claim 32, wherein said polyester comprises about 40% to about 50% terephthaloyl moieties and a total of up to about 10 mole % of one or more optional other aromatic diacid moieties.

34. The isotropic polyester according to claim 33, wherein said terephthaloyl moieties are derived from terephthalic acid or dimethyl terephthalate.

35. The isotropic polyester according to claim 33, wherein said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of the polyester, said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 10 mole % of the polyester, said isosorbide moieties are present in an amount of about 0.25 mole % to about 40 mole % of the polyester, and said one or more other diol moieties are present in an amount up to about 15 mole % of the polyester.

36. The isotropic polyester according to claim 32, wherein said one or more other diol moieties are derived from aliphatic alkylene glycols or branched aliphatic glycols having from 3-12 carbon atoms and having the empirical formula HO--C_n H_2n --OH, where n is an integer from 3-12;

cis or trans-1,4-cyclohexanedimethanol or mixtures thereof;

triethylene glycol;

2,2-bis 4-(2-hydroxyethoxy)phenyl!propane;

1,1-bis 4-(2-hydroxyethoxy)phenyl!cyclohexane;

9,9-bis 4-(2-hydroxyethoxy)phenyl!fluorene;

1,4;

3,6-dianhydromannitol;

1,4;

3,6-dianhydroiditol;

or 1,4-anhydroerythritol.

37. The isotropic polyester according to claim 32, wherein said one or more optional other aromatic diacid moieties are derived from isophthalic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or 4,4'"'"'-bibenzoic acid.

38. The isotropic polyester according to claim 32, wherein said terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester, said optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester, said ethylene glycol moieties are present in an amount of about 10 mole % to about 49.5 mole % of said polyester, said isosorbide moieties are present in an amount of about 0.25 mole % to about 30 mole % of said polyester, and said optional other diol moieties are present in an amount up to about 10 mole % of said polyester.

39. The isotropic polyester according to claim 38, wherein said other diol moieties are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, or mixtures thereof.

40. The isotropic polyester according to claim 39, wherein said optional other aromatic diacid monomer units are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'"'"'-bibenzoic acid, or mixtures thereof.

41. The isotropic polyester according to claim 32, wherein said polyester has an inherent viscosity of at least about 0.65 dL/g.

42. The isotropic polyester according to claim 32, wherein said terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester;

said one or more optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'"'"'-bibenzoic acid, or mixtures thereof;

said ethylene glycol moieties are present in an amount of about 38 mole % to about 49.5 mole % of said polyester;

said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester;

said isosorbide moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester; and

said optional other diol moieties are present in an amount up to about 2 mole % of said polyester and are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol, or mixtures thereof;

wherein said polyester has an inherent viscosity of at least about 0.45 dL/g.

43. The isotropic polyester according to claim 32, wherein said terephthaloyl moieties are present in an amount of about 45 mole % to about 50 mole % of said polyester;

said one or more optional other aromatic diacid moieties are present in an amount up to about 5 mole % of said polyester and are derived from isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'"'"'-bibenzoic acid, or mixtures thereof;

said ethylene glycol moieties are present in an amount of about 10 mole % to about 44 mole % of said polyester;

said diethylene glycol moieties are present in an amount of about 0.25 mole % to about 5 mole % of said polyester;

said isosorbide moieties are present in an amount of about 6 mole % to about 30 mole % of said polyester; and

said other diol moieties are present in an amount up to about 10 mole % of said polyester and are derived from cis-1,4-cyclohexanedimethanol, trans-1,4-cyclohexanedimethanol or mixtures thereof;

wherein said polyester has an inherent viscosity of at least about 0.65 dL/g.

44. The isotropic polyester according to claim 32, further comprising an additive wherein said additive is a plasticizer, pigment, flame retardant, reinforcing agent, thermal stabilizer, ultraviolet light stabilizer, impact modifier or flow enhancer.

45. The isotropic polyester according to claim 44, wherein said additive is glass fibers.