Thermoplastic polyurethanes comprising polytrimethylene ether soft segments

• US 20070129524A1
• Filed: 12/06/2005
• Published: 06/07/2007
• Est. Priority Date: 12/06/2005
• Status: Abandoned Application

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Sunkara, Hari
• Application Number:
  US11/294,850
• Publication Number:
  US 20070129524A1
• Time in Patent Office: Days
• US Class Current: 528/44
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/2815 Monohydroxy compounds
• CPC Class Codes: C08G 18/32 Polyhydroxy compounds; Polyamines; Hydroxyamines
• CPC Class Codes: C08G 18/4825 Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: D01F 6/70 from polyurethanes

Abstract

Thermoplastic polyurethane prepared from reactants comprising: (a) polytrimethylene ether glycol; (b) diisocyanate; (c) diol chain extender; and (d) monofunctional alcohol chain terminator or monofunctional amine chain terminator; and manufacture and use thereof.

Claims

1. A thermoplastic polyurethane prepared from reactants comprising:

(a) polytrimethylene ether glycol;

(b) diisocyanate;

(c) diol chain extender; and

(d) monofunctional alcohol chain terminator or monofunctional amine chain terminator.

2. The thermoplastic polyurethane of claim 1 wherein the monofunctional alcohol or amine chain terminator is a monofunctional alcohol selected from the group consisting of n-butanol, n-hexanol, n-octanol, n-decanol, n-dodecanol and mixtures thereof.

3. The thermoplastic polyurethane-urea of claim 1 wherein the monofunctional alcohol or amine chain terminator is a monofunctional amine selected from the group consisting of ethyl amine, propylamine, butyl amine, octyl amine, stearyl amine and mixtures thereof.

4. The thermoplastic polyurethane of claim 1 wherein the monofunctional alcohol selected from the group consisting of n-butanol, n-hexanol, n-octanol, n-decanol, n-dodecanol and mixtures thereof;

the monofunctional amine selected from the group consisting of ethyl amine, propylamine, butyl amine, octyl amine, stearyl amine and mixtures thereof;

the diol chain extender is selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 1,4-bis(hydroxyethoxy)benzene, bis(hydroxyethylene)terephthalate, hydroquinone bis(2-hydroxyethyl) ether, and mixtures thereof; and

the diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′

-diphenylmethane diisocyanate, 4,4′

-dicyclohexylmethane diisocyanate, 3,3′

-dimethyl-4,4′

-biphenyl diisocyanate, 1,4-benzene diisocyanate, cyclohexane-1,4-diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, 4,6-xylyene diisocyanate, isophorone diisocyanate, and mixtures thereof.

5. The thermoplastic polyurethane of claim 1 wherein the ratio of total hydroxyl and amine groups contained in the polytrimethylene ether glycol, diol chain extenders and monofunctional alcohol or amine chain terminators to isocyanate groups in the diisocyanate is about 1:

0.95 to about 1;

1.1.

6. The thermoplastic polyurethane of claim 1 wherein the ratio of total hydroxyl and amine groups contained in the polytrimethylene ether glycol, diol chain extenders and monofunctional alcohol or amine chain terminators to isocyanate groups in the diisocyanate is from about 1:

0.98 to about 1;

1.05.

7. The thermoplastic polyurethane of claim 1 wherein the polytrimethylene ether glycol is blended with up to about 50 wt. % of other polymeric glycols selected from the group consisting of hydroxyl terminated polyether glycols, polyester glycols, polycarbonate glycols and silicone glycols.

8. The thermoplastic polyurethane of claim 1 wherein the polytrimethylene ether glycol is blended with up to about 25 weight % of other polymeric glycols selected from the group consisting of hydroxyl terminated polyether glycols, polyester glycols, polycarbonate glycols and silicone glycols.

9. The thermoplastic polyurethane of claim 1 wherein the polytrimethylene ether glycol is not blended with other polymeric glycols.

10. The thermoplastic polyurethane of claim 4 wherein the ratio of total hydroxyl and amine groups contained in the polytrimethylene ether glycol, diol chain extenders and monofunctional alcohol or amine chain terminators to isocyanate groups in the diisocyanate is about 1:

0.95 to about 1;

1.1, and wherein the polytrimethylene ether glycol is blended with 0 to about 25 weight % of other polymeric glycols.

11. The thermoplastic polyurethane of claim 10, wherein the other polymeric glycols are polyether glycols selected from the group consisting of homo or copolyethers of polyethylene glycol, poly(1,2-propylene glycol), polytetramethylene ether glycol and mixtures thereof.

12. The thermoplastic polyurethane of claim 1 wherein about 75 to 100 mole percent of the repeat units of the polytrimethylene ether glycol are trimethylene ether units.

13. The thermoplastic polyurethane of claim 10 wherein about 90 to 100 mole percent of the repeat units of the polytrimethylene ether glycol are trimethylene ether units.

15. A shaped article comprising the thermoplastic polyurethane of claim 1.

16. The shaped article of claim 15 selected from the group consisting of fibers, films, sheets, hoses, tubing, wire and cable jackets, shoe soles, air bag bladders and medical devices.

17. A melt spun fiber comprising the thermoplastic polyurethane of claim 1.

18. The melt spun fiber of claim 17 wherein the fiber is a monofilament or multifilament fiber.

19. A woven or knit fabric comprising the fiber of claim 18.

20. A film comprising the thermoplastic polyurethane of claim 1.

21. A film as claimed in claim 20 wherein the thickness of the film is from about 5 μ

m to 500 μ

m.

22. A water vapor permeable membrane comprising the films of claim 20.

23. The water vapor permeable membrane according to claim 22 wherein said polyurethane film has a water vapor permeability rate of at least about 2500 mil-gm/m²/day

24. A water impermeable, water vapor permeable fabric comprising a substrate and a polyurethane film according to claim 22.

30. A process of forming a shaped article comprising providing the thermoplastic polyurethane of claim 1 and melt processing the thermoplastic polyurethane to form a shaped article.

31. A process of forming a fiber comprising providing the thermoplastic polyurethane of claim 1 and melt spinning the thermoplastic polyurethane into a fiber.

14. A thermoplastic polyurethane comprising:

(a) 80 to 20 weight %, by weight of the thermoplastic polyurethane, soft segment containing repeat units from polytrimethylene ether glycol;

(b) 20 to 80 weight %, by weight of the thermoplastic polyurethane, hard segment comprising repeating units from diisocyanate and from diol chain extender; and

(c) chain termination units from monofunctional alcohol chain terminator or monofunctional amine chain terminator;

wherein the ratio of total hydroxyl and amine groups contained in the polytrimethylene ether glycol, diol chain extenders and monofunctional alcohol or amine chain terminators to isocyanate groups in the diisocyanate is from about 1;

0.95 to about 1;

1.1.

25. A process of producing thermoplastic polyurethane comprising:

(a) reacting diisocyanate and polytrimethylene ether glycol to form diisocyanate-terminated polytrimethylene ether-urethane prepolymer; and

(b) reacting the diisocyanate-terminated polytrimethylene ether-urethane prepolymer with diol chain extender and monofunctional alcohol or amine chain terminator.

26. The process of claim 25 wherein the reacting the diisocyanate and polytrimethylene ether glycol is carried out while maintaining an NCO:

OH equivalent ratio of about 1.1;

1 to about 10;

1, and wherein the ratio of total hydroxyl and amine groups contained in the polytrimethylene ether glycol, diol chain extenders and monofunctional alcohol or amine chain terminators to isocyanate groups in the diisocyanate is about 1;

0.95 to about 1;

1.1.

27. The process of claim 26 that is performed in an extruder at a temperature of from about 100°

C. to about 220°

C.

28. A process of producing thermoplastic polyurethane comprising:

(a) providing (i) diisocyanate, (ii) polytrimethylene ether glycol, (iii) diol chain extender; and

(iv) monofunctional alcohol or amine chain terminator; and

(b) reacting the diisocyanate, the polytrimethylene ether glycol, the diol chain extender and the monofunctional alcohol or amine chain terminator.

29. The process of claim 29 wherein the ratio of total hydroxyl and amine groups contained in the polytrimethylene ether glycol, diol chain extenders and monofunctional alcohol or amine chain terminators to isocyanate groups in the diisocyanate is about 1:

0.95 to about 1;

1.1.