Polyurethane films prepared from polyurethane dispersions

• US 6,451,908 B1
• Filed: 04/13/2000
• Issued: 09/17/2002
• Est. Priority Date: 04/14/1999
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Parks, Franklin E., Bhattacharjee, Debkumar, Koonce, William A.
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US09/548,823
• Time in Patent Office: 887 Days
• Field of Search: 524/591, 524/839, 524/840, 524/589, 524/590, 528/44, 528/49, 528/45, 428/423.1, 427/385.5, 427/372.2, 604/328, 604/327, 604/347, 216/17, 216/8
• US Class Current: 524/591
• CPC Class Codes: C08G 18/0866 the dispersing or dispersed phase being an aqueous medium
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/302 Water
• CPC Class Codes: C08G 18/4808 Mixtures of two or more polyetherdiols
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

A process for preparing a polyurethane film comprising two steps is disclosed. The first step comprises preparing a nonionic prepolymer formulation, the prepolymer formulation comprising a diisocyanate, an active hydrogen containing material, and a monol. The second step comprises preparing an aqueous dispersion of the prepolymer, in the presence of a surfactant. Both steps occur in the substantial absence of an organic solvent. Also disclosed is a polyurethane film and an aqueous dispersion useful for preparing such films. The present invention has the advantage of having increased shear stability. The dispersions of the present invention do not settle or coagulate prematurely. Moreover, the films of the present invention do not include the dermal irritants which occur in natural rubber latex. The films and dispersions of the present invention are thus suitable for use in applications such as, for example, medical applications.

Claims

1. A process for preparing a polyurethane film comprising the steps of:

preparing a nonionic prepolymer formulation, the prepolymer formulation comprising a diisocyanate, an active hydrogen containing material, and a polyether monol, the monol comprising polyoxyethylene and being present in an amount effective for improving shear stability of a dispersion prepared from the prepolymer formulation but no more than 0.99 percent by weight of prepolymer formulation;

dispersing the prepolymer formulation in water in the presence of a surfactant to prepare a coagulatable dispersion, the coagulatable dispersion having improved shear stability over a dispersion prepared without a polyether monol; and

forming a film by coagulating or electrodepositing the coagulatable dispersion onto a substrate,

wherein the three steps occur in the substantial absence of an organic solvent.

2. The process according to claim 1, wherein the diisocyanate is either:

(1) an aliphatic diisocyanate;

or

(2) an aromatic diisocyanate selected from the group consisting of MDI, TDI and mixtures thereof.

3. The process according to claim 1, wherein the active hydrogen containing material is either:

(a) a mixture of a high molecular weight diol and a low molecular weight diol;

or

(b) a high molecular weight diol, wherein when the active hydrogen containing material does not include a low molecular weight diol, the prepolymer is dispersed in water which includes a difunctional amine chain extender.

4. The process according to claim 1 wherein the monol has a molecular weight of from 500 to 1500.

5. The process according to claim 1 wherein the monol is a polyoxyethylene polyether monol.

6. The process according to claim 1, wherein the resulting film has a shape of a glove, a condom, an angioplasty balloon, a medical bag or a catheter.

17. The process of claim 1, wherein the polyether monol is present in an amount of between 0.1 and 0.99 percent by weight of prepolymer formulation.

18. The process of claim 1, wherein the polyether monol is present in an amount of between 0.3 and 0.99 percent by weight of prepolymer formulation.

7. A polyurethane film comprising a film prepared with a process which includes (1) preparing a coagulatable polyurethane dispersion from a prepolymer formulation including a polyether monol comprising polyoxyethylene and being present in an amount effective for improving shear stability of a dispersion prepared from the prepolymer formulation but no more than 0.99 weight percent, the shear stability being improved over shear stability of a dispersion prepared without a polyether monol, and (2) coagulating or electrodepositing the dispersion onto a substrate to form a film.

8. The polyurethane film according to claim 7 wherein the monol is a polyoxyethylene polyether monol.

9. A coagulatable aqueous polyurethane dispersion useful for preparing polyurethane films comprising the product of dispersing in water a nonionic polyurethane prepolymer prepared from a prepolymer formulation including a diisocyanate, one or more diols and a polyether monol, the monol comprising polyoxyethylene and being present in an amount effective for improving shear stability of a dispersion prepared from the prepolymer formulation but no more than 0.99 percent by weight of prepolymer formulation wherein:

the dispersion is formed in a two or more step process wherein,

(1) in a first step the prepolymer is formed and, in a subsequent step,

(2) an aqueous dispersion of the prepolymer is formed, in the presence of a surfactant, both steps occurring in the substantial absence of an organic solvent; and

the dispersion has improved shear stability over a dispersion prepared without a polyether monol and the dispersion coagulates in the presence of calcium nitrate.

10. The dispersion of claim 9 wherein the monol has a molecular weight of from 500 to 1500.

21. The dispersion of claim 9, wherein the polyether monol is present in an amount of between 0.1 and 0.99 percent by weight of prepolymer formulation.

22. The dispersion of claim 9, wherein the polyether monol is present in an amount of between 0.3 and 0.99 percent by weight of prepolymer formulation.

11. A process for preparing a coagulatable polyurethane dispersion comprising the steps of:

preparing a nonionic prepolymer formulation comprising a diisocyanate, an active hydrogen-containing material, and a polyether monol, the monol comprising polyoxyethylene and being present in an amount effective for improving shear stability of a dispersion prepared from the prepolymer formulation but no more than 0.99 percent by weight of prepolymer formulation; and

dispersing the prepolymer formulation in water in the presence of a surfactant to prepare a coagulatable polyurethane dispersion, the coagulatable dispersion having improved shear stability over a dispersion prepared without a polyether monol;

wherein both steps occur in the substantial absence of organic solvent and the dispersion coagulates in the presence of calcium nitrate.

12. The process according to claim 11, wherein the diisocyanate is either:

(1) an aliphatic diisocyanate or

(2) an aromatic diisocyanate selected from the group consisting of MDI, TDI, and mixtures thereof.

13. The process according to claim 11, wherein the active hydrogen containing material is either:

(a) a mixture of a high molecular weight diol and a low molecular weight diol;

or

(b) a high molecular weight diol, wherein when the active hydrogen containing material does not include a low molecular weight diol, the prepolymer is dispersed in water which includes a difunctional amine chain extender.

14. The process according to claim 11, wherein the monol has a molecular weight of from 500 to 1500.

15. The process according to claim 11, wherein the monol is a polyoxyethylene polyether monol.

16. The process according to claim 11, wherein the coagulatable polyurethane dispersion is coagulated onto a substrate to prepare a film having a shape of a glove, a condom, an angioplasty balloon, a medical bag, or a catheter.

19. The process of claim 11, wherein the polyether monol is present in an amount of between 0.1 and 0.99 percent by weight of prepolymer formulation.

20. The process of claim 11, wherein the polyether monol is present in an amount of between 0.3 and 0.99 percent by weight of prepolymer formulation.

23. A shear-stable polyurethane dispersion comprising a nonionic polyurethane prepolymer dispersed in water, the prepolymer comprising a diisocyanate, at least one diol, and a polyether monol comprising polyoxyethylene, wherein the dispersion has improved shear stability over a dispersion prepared without a polyether monol and the dispersion is coagulatable.

24. A shear-stable polyurethane dispersion comprising a nonionic polyurethane prepolymer dispersed in water, the prepolymer comprising a diisocyanate, at least one diol, and a polyether monol comprising polyoxyethylene, wherein the dispersion has improved shear stability over a dispersion prepared without a polyether monol and the dispersion is coagulatable.