Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate

• US 4,786,657 A
• Filed: 07/02/1987
• Issued: 11/22/1988
• Est. Priority Date: 07/02/1987
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Staral, John S., Hammar, W. James
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US07/069,428
• Time in Patent Office: 509 Days
• Field of Search: 528/75, 528/26, 528/28, 522/90, 522/148, 522/149, 522/164, 526/301, 526/302, 526/303.1
• US Class Current: 522/90
• CPC Class Codes: A61F 2/06 Blood vessels
• CPC Class Codes: A61F 2/14 Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
• CPC Class Codes: A61F 2/16 Intraocular lenses
• CPC Class Codes: A61L 15/26 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof A61L15/225 takes precedence
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: B01D 71/54 Polyureas; Polyurethanes
• CPC Class Codes: C08G 18/675 Low-molecular-weight compounds
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G11B 5/7021 containing a polyurethane or a polyisocyanate

Abstract

A crosslinkable polyurethane or polyurethane/polyurea comprises the reaction product of a composition comprising a macrodiol or macrodiamine, 2-gl;yceryl acrylate or 2-glyceryl methacrylate, a diisocyanate, and optionally a small glycol or small diamine as chain extender. The performance properties of the polyurethanes and polyurethane/polyureas can be controlled by adjustment of the crosslink level and/or curing parameters.

Claims

1. A crosslinkable polyurethane or polyurethane/polyurea comprising the reaction product of a composition comprising a macrodiol having a number average molecular weight of at least 400 or macrodiamine having a number average molecular weight of at least 400, 2-glyceryl acrylate or 2-glyceryl methacrylate, and a diisocyanate.

2. The crosslinkable polyurethane or polyurethane/polyurea according to claim 1 further comprising a small glycol having a number average molecular weight of less than 400 or small diamine having a number average molecular weight of less than 400 in the reaction composition.

3. The crosslinkable polyurethane or polyurethane/polyurea according to claim 1 wherein said composition further comprises at least one ethylenically-unsaturated monomer.

4. The crosslinkable polyurethane or polyurethane/polyurea according to claim 3 wherein said ethylenically-unsaturated monomer is an acrylate or methacrylate monomer.

5. The polyurethane or polyurethane/polyurea according to claim 1 which has been crosslinked by means of at least one of thermal energy, ultraviolet radiation, gamma radiation, or electron beam radiation.

6. The polyurethane or polyurethane/polyurea according to claim 1 wherein said macrodiamine in said composition is a polyether diamine or a polydimethylsiloxane diamine.

7. The polyurethane or polyurethane/polyurea according to claim 2 wherein said small glycol is an aliphatic, aromatic, or ether glycol containing 2 to 20 carbon atoms.

8. The polyurethane or polyurethane/polyurea according to claim 2 wherein said small diamine is an aliphatic, aromatic, or ether diamine containing 2 to 20 carbon atoms.

9. The polyurethane or polyurethane/polyurea according to claim 4 wherein the acrylate or methacrylate monomer is a mono-, di-, tri-, or oligomeric acrylate or methacrylate which is the reaction product of acrylic or methacrylic acid and an oligomeric alcohol, diol, or triol.

10. The polyurethane or polyurethane/polyurea according to claim 9 wherein said oligomeric alcohol or diol is a polyether, polyester, or polydimethylsiloxane moiety.

17. The polyurethane or polyurethane/polyurea according to claim 1 wherein said macrodiol in said composition is a polyether diol, polyester diol, or silicone carbinol having the formula ##STR11## where n is 2 to 800, and

x=3 to 11.

18. The crosslinkable polyurethane or polyurethane/polyurea according to claim 2 wherein said composition further comprises at least one ethylenically-unsaturated monomer.

20. The crosslinkable polyurethane or polyurethane/polyurea according to claim 17 wherein said composition further comprises at least one ethylenically-unsaturated monomer.

21. The polyurethane or polyurethane/polyurea according to claim 2 which has been crosslinked by means of at least one of thermal energy, ultraviolet radiation, gamma radiation, or election beam radiation.

22. The polyurethane or polyurethane/polyurea according to claim 3 which has been crosslinked by means of at least one of thermal energy, ultraviolet radiation, gamma radiation, or electron beam radiation.

11. A crosslinkable polyurethane or polyurethane/polyurea having randomly disposed units of the formula ##STR9## wherein:

X is --NH-- or --O--,

R¹ is a polyether, a polyester, or a polydimethylsiloxane segment,

R² and R⁴ independently are selected from the class consisting of alkylene, cycloalkylene, and arylene groups and combinations thereof

R³ is H or CH₃, and

A, B, D=total number of OH and NH equivalents and the total molecular weight of the A, B, and D units is in the range of 10,000 to 400,000.

12. A method comprising the step of

(a) reacting a macrodiol having a number average molecular weight of at least 400 or macrodiamine having a number average molecular weight of at least 400, a diisocyanate, and 2-glyceryl acrylate or 2-glyceryl methacrylate to provide a crosslinkable polyurethane or polyurethane/polyurea.

13. The method according to claim 12 further comprising also reacting a small glycol having a number average molecular weight of less than 400 or small diamine having a number average molecular weight of less than 400 with the other three components.

14. The method according to claim 12 further comprising reacting said polyurethane or polyurethane/polyurea with an ethylenically-unsaturated monomer.

15. The method according to claims 12, 13, or 14 further comprising the step of

(b) effecting crosslinking of said polyurethane or polyurethane/polyurea by means of at least one of thermal energy, ultraviolet radiation, gamma radiation, and electron beam radiation.

19. The method according to claim 13 further comprising reacting said polyurethane or polyurethane/polyurea with an ethylenically-unsaturated monomer.

23. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a flexible magnetic recording media binder, a biomaterial, a membrane, a fabric treatment, or a protective coating.

24. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a flexible magnetic recording media binder.

25. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a biomaterial.

26. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a wound dressing, a vascular graft, or an ophthalmic device.

27. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is an intraocular lens, a contact lens or a corneal implant.

28. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a membrane.

29. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a waterproof, breathable fabric treatment.

30. The crosslinked polyurethane or polyurethane/polyurea according to claims 5, 19 or 20 which is a protective coating.

16. A method for adjusting the crosslinking of polyurethanes or polyurethane/polyureas comprising the steps of:

(a) providing a crosslinkable polyurethane or polyurethane/polyurea having chain extender units of the formula ##STR10## wherein R is hydrogen or methyl, and (b) crosslinking said polyurethane via at least one of thermal energy, ultraviolet radiation, gamma radiation or electron beam radiation.