Crosslinkable hydrophilic materials from reactive oligomers having pendent photoinitiator groups

• US 7,074,839 B2
• Filed: 03/01/2004
• Issued: 07/11/2006
• Est. Priority Date: 03/01/2004
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Gaddam, Babu N., Heilmann, Steven M., Lewandowski, Kevin M., Wendland, Michael S., Fansler, Duane D.
• Primary Examiner(s): BERMAN, SUSAN W
• Application Number:
  US10/790,902
• Publication Number:
  US 20050192370A1
• Time in Patent Office: 862 Days
• Field of Search: 522/34, 522/35, 522/181, 522/173
• US Class Current: 522/35
• 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 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: A61P 17/02 for treating wounds, ulcers, burns, scars, keloids, or the like
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]

Abstract

The present invention provides crosslinkable compositions useful in the preparation of hydrophilic gels, and are prepared from oligomers having pendent hydrophilic, poly(alkylene oxide) groups, pendent photoinitiator groups, and optionally polymerizable functional groups, and crosslinked by polyfunctional poly(alkylene oxides).

Claims

1. A hydrophilic, crosslinkable oligomer composition comprising

a) a first component oligomer comprising a plurality of polymerized monomer units having pendent hydrophilic poly(alkylene oxide) groups, and pendent photoinitiator groups;

and

b) a hydrophilic poly(alkylene oxide) crosslinking agent haying polymerizable, ethylenically unsaturated terminal groups of the formula

Z—

Q-CH(R¹)—

CH₂—

O—

(CH(R¹)—

CH₂—

O)_m—

CH(R¹)—

CH₂-Q-Z,

wherein Z is a polymerizable ethylenically unsaturated moiety, R¹ is a H or a C₁ to C₄ alkyl group, and m is from 20 to 500, and Q is a divalent linking group selected from —

O—

, —

NR¹—

, —

CO₂— and

—

CONR¹—

.

2. The oligomer composition of claim 1 wherein the composition is melt-processible at temperatures of 100°

C. or less.

3. The composition of claim 1 wherein said composition has a residual content of less than two weight %.

4. The composition of claim 1, wherein said oligomer has an average degree of polymerization of less than 300.

5. The composition of claim 1 wherein said oligomer has a degree of polymerization of less than 300.

6. The composition of claim 1, wherein said crosslinking agent is a poly(ethylene oxide)(co)polymer.

7. The composition of claim 1, wherein said crosslinking agent is a poly(ethylene oxide-co-propylene oxide) copolymer.

8. The composition of claim 1 wherein said first component oligomer comprises:

a) from 20 to 99 parts by weight of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups, and

b) from 0.1 to 25 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent photoinitiator group;

c) from 0 to 25 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable group; and

d) from 0 to 30 parts by weight of polymerized monomer units derived from acrylic acid esters, preferably of non-tertiary alkyl alcohols containing 1–

14 carbon atoms; and

e) from 0 to 40 parts by weight of at least one other monomer.

9. The composition of claim 8, wherein the composition comprises both polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent photoinitiator group;

and polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable group, and the total of such monomer units is 0.1 to 25 parts by weight.

10. The composition of claim 8 wherein said first component oligomer comprises a plurality of polymerized monomer units having pendent photoinitiator groups, wherein said pendent photoinitiator groups are of the formula:

11. The composition of claim 1 wherein oligomer having pendent photoinitiator groups is prepared by the reaction of a polymer having a plurality op pendent reactive functional groups with an co-reactive compounds having photoinitiator group.

12. The composition of claim 11 wherein said pendant reactive functional groups are selected from hydroxyl, amino, oxazolinyl, oxazolonyl, acetyl acetonyl, carboxyl, isocyanato, epoxy, aziridinyl, acyloyl halide, and eyelic anhydride groups.

13. The composition of claim 1 which comprises an amount of said crosslinking agent is sufficient to provide more than two crosslinks per first component oligomer chain.

14. The composition of claim 1 which comprises:

a) from 50 to 99.9 parts by weight of said first component oiligomer, and

b) from 0.1 to 50 parts by weight of said cross linking agent.

wherein the composition, when crosslinked, can absorb at least 50 wt. % water.

15. A crosslinked composition comprising the composition of claim 1 having an average molecular weight between crosslinks of at least 1000.

16. The composition of claim 1, wherein said Z of said crosslinking agent is

17. The composition of claim 1 wherein said first component oligomer comprises both pendent free-radically polymerizable functional groups and pendent photoinitiator groups.

18. A process for making a substrate hearing a coating of a crosslinked polymer composition on at least one surface thereof, comprising the steps of:

a) coating onto said substrate the oligomer composition of claim 1; and

b) photochemically cross linking said first component oligomer and crosslinking agent.

19. The process of claim 18 wherein said oligomer composition has been partially converted to a coatable viscosity of from 750 to 7,500 cPs at 22°

C. prior to step a.

20. The process of claim 18 wherein said oligomer composition comprises

a) per 100 parts by weight of said first component, an amount of said crosslinking agent sufficient to provide more than two cross links per first component oligomer chain;

b) less than 2 parts by weight residuals content; and

c) from 0.01 to about 5.0 parts by weight of a photoinitiator.

21. The process of claim 18 wherein said first component oligomer comprises:

a) from 20 to 99 parts by weight of polymerized monomer units having pendent, hydrophilic poly(alkyllene oxide) groups, and

b) from 0.1 to 25 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent photoinitiator group;

c) from 0 to 25 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable group; and

d) from 0 to 30 parts by weight of polymerized monomer units derived from acrylic acid esters, preferably of non-tertiary alkyl alcohols containing 1–

14 carbon atoms; and

e) from 0 to 40 parts by weight of at least one other monomer.

22. The process of claim 18 wherein the molecular weight (M₅) of said first oligomer is less than the entanglement molecular weight.

23. The process of claim 19 wherein the average degree of polymerization of the first and second component ollgomers is ≦

300.