Method for the preparation of a polyester block copolymer, a polyester block copolymer composition and method for the preparation thereof

• US 20040010092A1
• Filed: 04/30/2003
• Published: 01/15/2004
• Est. Priority Date: 08/05/1999
• Status: Active Grant

• Current Assignee: Jun Watanabe
• Original Assignee: Jun Watanabe
• Inventors: Watanabe, Jun
• Granted Patent: US 7,196,123 B2
• Time in Patent Office: Days
• US Class Current: 525/418
• CPC Class Codes: C08G 2261/126 block
• 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 63/91 Polymers modified by chemical after-treatment
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: C08K 5/09 Carboxylic acids; Metal salts thereof; Anhydrides thereof
• CPC Class Codes: C08K 5/15 Heterocyclic compounds having oxygen in the ring
• CPC Class Codes: C08K 5/29 Compounds containing one or more carbon-to-nitrogen double bonds
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• 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
• CPC Class Codes: H05B 3/56 Heating cables

Abstract

The present invention I relates to a method for the preparation of a polyester block copolymer (P1) characterized in that in the method for the preparation of 100% by weight of the polyester block copolymer (P1) by allowing to react A% by weight of a crystalline aromatic polyester with B% by weight of lactones (A+B=100), (B+0.5)% by weight of lactones are added into A% by weight of a crystalline aromatic polyester, and not less than 0.5% by weight of unreacted lactones are remained with respect to 100% by weight of the polyester block copolymer (P1) after reaction.

The present invention II relates to a method for the preparation of a polyester block copolymer (P′1) having a high molecular weight characterized in that the polyester block copolymer (P1) is allowed to further react in a solid phase.

The present invention III relates to a polyester block copolymer composition (R) obtained by thermally-processing a polyester block copolymer composition (Q) obtained by melt-mixing 100 parts by weight of a polyester block copolymer (P) with 0.1-5 parts by weight of an epoxy compound (C) having one or more epoxy groups under an inert gas atmosphere and not less than 120° C. in a solid phase, and further, at a temperature lower than a melting point of the polyester block copolymer composition (R).

The present invention IV relates to a polyester block copolymer composition which comprises thermally-kneading 0.5-5.0 parts by weight of a mono or more functional epoxy compound (C) and 0.01-3.0 parts by weight of a complex-formable agent for a metal (G) such as an oxalic acid derivative and a salicylic acid derivative or a hydrazide derivative with 100 parts by weight of a polyester block copolymer (P1) obtained by a reaction of a crystalline aromatic polyester (A1) with lactones (B).

The present invention V relates to a polyester block copolymer composition which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), adding and thermally-kneading 0.5-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups (including at least 0.2 part by weight of two or more functional epoxy compound) and, optionally, 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-100% by mol of at least one of a multifunctional compound (D) having at least three pieces of at least one kind of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).

The present invention VI relates to a polyester block copolymer composition which comprises, in obtaining said polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), adding and thermally-kneading 0.1-5.0 parts by weight of an epoxy compound (C) having one or more pieces of epoxy groups and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-200% by mol of at least one of an aliphatic or aromatic multifunctional compound (D) having at least three pieces of carboxylic group hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).

The present invention VII relates to a polyester block copolymer composition (R) which comprises, in obtaining the polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), heating a polyester block copolymer composition (Q) at a solid phase, and the composition (Q) is obtained by adding and thermally-kneading 0.1-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups to 100 parts by weight of a polyester block copolymer (P) obtained by allowing to react 0.1-200% by mol of at least one of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1).

Claims

1. A method for the preparation of a polyester block copolymer (P1) characterized in that in the method for the preparation of 100% by weight of the polyester block copolymer (P1) by allowing to react A% by weight of a crystalline aromatic polyester (A1) with B% by weight of lactones (B) (A+B=100), (B+0. 5)% by weight of lactones (B) are introduced into A% by weight of a crystalline aromatic polyester (A1), and not less than 0.5% by weight of unreacted lactones are remained with respect to 100% by weight of the polyester block copolymer (P1) after preparation of the copolymer.

2. A method for the preparation of a polyester block copolymer (P1) as claimed in claim 1, wherein (B+2.5)% by weight of said lactones (B) are introduced and not less than 2.5% by weight of unreacted lactones are remained with respect to 100% by weight of said polyester block copolymer (P1) after preparation of the copolymer.

3. A method for the preparation of a polyester block copolymer (P1) as claimed in claim 1 or 2, wherein reaction proportion (A)/(B) of saidcrystalline aromatic polyester (A1) with respect to said lactones (B) is 95/5-20/80.

4. A method for the preparation of a polyester block copolymer (P1) as claimed in claims 1-3, wherein said unreacted lactones are removed from said polyester block copolymer (P1).

5. A method for the preparation of a polyester block copolymer (P1) as claimed in any one of claims 1-4, wherein said unreacted lactones are continuously removed.

6. A method for the preparation of a polyester block copolymer (P1) as claimed in any one of claims 1-5, wherein said crystalline aromatic polyester (A1) and said lactones (B) are continuously supplied into a reaction vessel and addition-polymerized, and said polyester block copolymer (P1) is continuously taken out.

7. A method for the preparation of a polyester block copolymer (P1) as claimed in any one of claims 1-6, wherein said crystalline aromatic polyester (A1) is a polybutylene terephthalate.

8. A method for the preparation of a polyester block copolymer (P1) as claimed in any one of claims 1-7, wherein said lactones (B) are a caprolactone.

9. A method for the preparation of a polyester block copolymer (P′

1) having a high molecular weight characterized in that a reaction is further conducted in a solid phase after having prepared said polyester block copolymer (P1) as claimed in any one of claims 1-8.

10. A method for the preparation of a polyester block copolymer (P′

1) having a high molecular weight as claimed in claim 9, wherein said reaction in a solid phase is continuously conducted.

11. A polyester block copolymer composition (R) obtained by thermally-processing a polyester block copolymer composition (Q) obtained by melt-mixing 100 parts by weight of a polyester block copolymer (P) with 0.1-5 parts by weight of an epoxy compound (C) having one or more epoxy groups under an inert gas atmosphere and not less than 120°

C. in a solid phase, and further, at a temperature lower than a melting point of the polyester block copolymer composition (R) obtained.

12. A polyester block copolymer composition (R) as claimed in claim 11, characterized in that said polyester block copolymer (P) is a polyester block copolymer (P1) obtained by allowing to react a crystalline aromatic polyester (A1) with lactones (B).

13. A polyester block copolymer composition (R) as claimed in claim 11, characterized in that the polyester block copolymer (P) is a polyester block copolymer (P2) obtained by a polycondensation and/or ring-opening polymerization of monomer components constructing a crystalline polyester (A1);

monomer components constructing a low crystalline polyester (A4);

an aliphatic polyether (A2); and

/or polylactone (A3).

14. A polyester block copolymer composition (R) as claimed in any one of claims 11-13, characterized in that said epoxy compound (C) is an epoxy compound (C2) having two or more epoxy groups.

15. A polyester block copolymer composition (R) as claimed in any one of claims 11-14 which is obtained by thermally-processing said polyester block copolymer composition (Q) at not less than 150°

C. and, moreover, at a temperature of 100- to 5°

C.-lower than a melting point of said polyester block copolymer composition (R).

16. A polyester block copolymer composition (R) as claimed in any one of claims 11-15 which is obtained by further thermally-processing after preheating at a temperature lower than a melting point of the polyester block copolymer composition (R) and, moreover, at a temperature of not more than 150°

C.

17. A polyester block copolymer composition (R) as claimed in any one of claims 11-16, wherein there are mixed at least one kind of compounds selected from the group consisting of a hindered phenol-based compound, a sulphur-based compound, a phosphorus-based compound, a phenyl amine-based compound, and a hindered amine-based compound.

18. A polyester block copolymer composition (R) as claimed in any one of claims 11-17, wherein an acid value is not more than 0.5 mgKOH/g in said polyester block copolymer composition (R) and, moreover, a melting point (Tm(R))) of said composition (R) is 10°

C.-lower than a melting point (Tm(P))) of said polyester block copolymer (P) which is a raw material.

Tm (P)−

10°

≦

Tm(R)

19. A polyester block copolymer composition (R) as claimed in any one of claims 11-18, wherein a melt viscosity stability (MI(T, P, t+10)/(MI(T, P, t)) is 0.5-2.0 in said polyester block copolymer composition (R), in the formula, a melt index (MI(T, P, t)) value is a value measured at a heating temperature (T), loading (P), and heating time of period (t) based on a method described in Table 1 of JIS K7210, and herein, T is a temperature of 5°

C.-higher than a melting point of said composition (R) and, it is a minimum temperature of experimental temperatures described in Table 1 of the JIS K7210, and P is a value selected as ranging in 1-30 g/10 minutes in an MI value, and the (MI(T, P, t)) is a value in which. the heating time of period is t+10 minutes in conditions of the T and P.

20. A method for the preparation of a polyester block copolymer composition (R) characterized in that there is thermally-treated a polyester block copolymer composition (Q) in which 100 parts by weight of a polyester block copolymer (P) is thermally mixed with 0.1-5 parts by weight of an epoxy compound (C) having at least one epoxy groups under an inert gas atmosphere and at not less than 120°

C. and a temperature less than a melting point of the obtained polyester block copolymer composition (R) in a solid phase.

21. A polyester block copolymer composition which comprises thermally-kneading 100 parts by weight of a polyester block copolymer (P1) obtained by a reaction of a crystalline aromatic polyester (A1) with lactones (B) with 0.5-5.0 parts by weight of a mono or more functional epoxy compound (C) and 0.01-3.0 parts by weight of a complex-formable agent for a metal (G).

22. A polyester block copolymer composition as claimed in claim 21, wherein said crystalline aromatic polyester (A1) is a polyester of an aromatic dicarboxylic acid which is an acid component (a) and an aliphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which are optionally added with an aliphatic diol, an aromatic diol, and/or a cycloaliphatic diol which are a diol component (b).

23. A polyester block copolymer composition as claimed in claim 21, wherein said crystalline aromatic polyester (A1) contains not less than 50% by weight of total of butylene terephthalate and ethylene terephthalate units.

24. A polyester block copolymer composition as claimed in any one of claims 21-23, wherein a copolymerization proportion (A1/B) of said crystalline aromatic polyester (A1) with said lactones (B) is 97/3-50/50 by weight.

25. A polyester block copolymer composition as claimed in any one of claims 21-24, wherein said epoxy compound (C) is a glycidyl type epoxy compound, a compound shown by any one of general formulae (I)-(V) described below, and a mixture thereof,

26. A polyester block copolymer composition as claimed in any one of claims 21-25, wherein said complex-formable agent for a metal (G) is at least one selected from the group consisting of an oxalic acid derivative, a salicylic acid derivative, and a hydrazide derivative.

27. A heat-sensitive body for a heater cable composed of a polyester block copolymer composition as claimed in any one of claims 21-26.

32. A polyester block copolymer composition as claimed in any one of claims 28-30, wherein a copolymerization proportion of said crystalline aromatic polyester (A1) with said lactones (B) is the same proportion as described in claim 24.

34. A polyester block copolymer composition as claimed in any one of claims 28-33, wherein said epoxy compound (C) is the same compound as described in claim 25.

28. A polyester block copolymer composition which in obtaining said polyester block copolymer composition by allowing to react said crystalline aromatic polyester (A1) with lactones (B), comprises adding 0.5-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups (including at least 0.2 part by weight of two or more functional epoxy compound) and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-100% by mol of at least one kind of a multifunctional compound (D) having at least three pieces of at least one of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1), followed by thermally-kneading.

30. A polyester block copolymer composition as claimed in claim 28 or 29, wherein said crystalline aromatic polyester (A1) is a polyester of an aromatic dicarboxylic acid which is an essential acid component (a), an aliphatic dicarboxylic acid and/or a cycloaliphatic dicarboxylic acid which are optionally added with an aliphatic diol, and an aromatic diol, and/or a cycloaliphatic diol which are a diol component (b).

31. A polyester block copolymer composition as claimed in any one of claims 28-30, wherein said crystalline aromatic polyester (A1) contains not less than 50% by weight of total of butylene terephthalate and/or ethylene terephthalate units.

35. A polyester block copolymer composition as claimed in any one of claims 28-34, which is employed for blow molding.

29. A polyester block copolymer composition which comprises, in obtaining said polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), adding 0.1-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups and 0-2.0 parts by weight of a carbodiimide compound (E) to 100 parts by weight of a polyester block copolymer (P3) obtained by allowing to react 0.1-200% by mol of at least one kind of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A1), followed by thermally-kneading.

[be common in the present inventions V and VI]

33. A polyester block copolymer composition as claimed in any one of claims 29-32, wherein at least one kind of said multifunctional compound (D) contains carboxylic group (i) or an ester-formable group therefrom.

36. A polyester block copolymer composition (R) which comprises, in obtaining said polyester block copolymer composition by allowing to react the crystalline aromatic polyester (A1) with lactones (B), heating a polyester block copolymer composition (Q) at a solid phase, and said composition (Q) is obtained by formulating 0.1-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups with 100 parts by weight of a polyester block copolymer (P) obtained by allowing to react 0.1-200% by mol of at least one of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A), followed by thermally-kneading.

37. A polyester block copolymer composition (R) as claimed in claim 36, wherein at least one kind of said multifunctional compound (D) contains at least one of carboxylic group (i) or an ester-formable group therefrom.

38. A polyester block copolymer composition (R) as claimed in claim 36 or 37, wherein said epoxy compound (C) contains at least one kind of a bifunctional epoxy compound.

39. A polyester block copolymer composition (R) as claimed in any one of claims 36-38, wherein said polyester block copolymer composition (R) has an acid value of not more than 0.5 mgKOH/g and, moreover, a melting point Tm(R) is not less than 5°

C.-lower than a melting point Tm(P) of said polyester block copolymer (P) before adding said epoxy compound, and Tm(R)≧

Tm(P)−

5°

C.

40. A polyester block copolymer composition as claimed in any one of claims 36-39, wherein a melt viscosity stability (MI-B)/(MI-A) is 0.5-2.0 which is calculated from an MI value (MI-A) in said polyester block copolymer composition (R) and an MI value (MI-B) after heating for 10 minutes at a temperature selected so as to be a lower temperature of the temperature described in JIS K7210.

41. A polyester block copolymer composition as claimed in any one of claims 36-40, which is a composition for blow molding.

42. A method for the preparation of a polyester block copolymer composition (R) characterized in that in obtaining the polyester block copolymer composition by allowing to react said crystalline aromatic polyester (A) with lactones (B), there is heated a polyester block copolymer composition (Q) at a solid phase, and said composition (Q) is obtained by formulating 0.1-5.0 parts by weight of at least one kind of an epoxy compound (C) having one or more pieces of epoxy groups and 0-2.0 parts by weight of a carbodiimide compound (E) with 100 parts by weight of a polyester block copolymer (P) obtained by allowing to react 0.1-200% by mol of at least one kind of a multifunctional compound (D) having at least three pieces of carboxylic group (i), hydroxyl group (ii), and/or an ester-formable group therefrom (iii) with 100% by mol of a crystalline aromatic polyester (A), followed by thermally-kneading.

43. A method for the preparation of a polyester block copolymer as claimed in claim 42, wherein heating is conducted in a solid phase at conditions from a temperature lower than a melting point of said polyester block copolymer composition (R) to a temperature higher than a glass transition temperature thereof in a solid phase under an inert gas atmosphere and, moreover, heating is conducted at a higher temperature (Ta) than 120°

C.,

Tg<

Ta<

Tm (R), and

120°

C.<

Ta.

44. A method for the preparation of a polyester block copolymer as claimed in claim 42, wherein the temperature heating in a solid phase is 100- to 5C°

-lower than a melting point of said polyester block copolymer composition (R) in a solid phase and, moreover, a temperature (Ta) higher than 150°

C.,

Tm(R)-100°

C.≦

Ta≦

Tm(R)−

5°

C., and

150°

C.≦

Ta.

45. A method for the preparation of a polyester block copolymer as claimed in any one of claims 42-44, wherein heating is conducted in a solid phase at conditions of,

(1) a temperature ranges from a temperature lower than a melting point of the polymer to a temperature higher than a glass transition temperature of the polymer in a solid phase and, moreover, preheating is conducted at a temperature lower than 150°

C. and a temperature (Tb) lower than Ta, and then,

(2) a temperature ranges from a temperature lower than a melting point of the polymer to a temperature higher than a glass transition temperature of the polymer in a solid phase and, moreover, heating is conducted at a temperature higher than 120°

C.,

Preheating temperature Tb

Tg<

Tb<

Tm(R),

Tb<

150°

C., and

Tb<

Ta

Heating temperature Ta

Tg<

Ta<

Tm(R), and

120°

C.<

Ta.