REACTIVE HYDROPHILIC OLIGOMERS

• US 20060292209A1
• Filed: 08/08/2006
• Published: 12/28/2006
• Est. Priority Date: 09/26/2003
• 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.
• Granted Patent: US 7,459,489 B2
• Time in Patent Office: Days
• US Class Current: 424/445
• CPC Class Codes: A61L 15/22 containing macromolecular materials
• CPC Class Codes: A61P 17/02 for treating wounds, ulcers, burns, scars, keloids, or the like
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 283/06 on to polyethers, polyoxymethylenes or polyacetals C08F283/004 takes precedence
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08G 65/329 with organic compounds
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 51/006 grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
• 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 71/02 Polyalkylene oxides
• CPC Class Codes: C09D 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09D151/04, C09D151/06 take precedence
• CPC Class Codes: C09D 151/006 grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 151/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

Hydrophilic compositions are described, which are prepared from a first oligomer containing pendent polymerizable groups and pendent hydrophilic groups, crosslinked with a co-reactive second component oligomer possessing photoinitiator groups. The compositions may be used as in preparation of hydrophilic gel coatings or layers for medical devices.

Claims

1. A hydrophilic, crosslinkable oligomer composition comprising

(a) a first component oligomer comprising a plurality of polymerized monomer units having pendent, free-radically polymerizable functional groups, and a plurality of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups;

and

(b) a second component oligomer comprising a plurality of polymerized monomer units having pendent, photoinitiator groups.

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 2 weight %.

4. The composition of claim 1, wherein said oligomers a) and b) have an average degree of polymerization of less than 300.

5. The composition of claim 1 wherein each of said oligomers a) and b) have a degree of polymerization of less than 300.

6. The composition of claim 1, wherein said pendent polyalkylene oxide groups of said first component oligomer is of the formula:

—

(CH(R¹)—

CH₂—

O)_m—

R² wherein R¹ is a H or a C₁ to C₄alkyl group, R² is H, a C₁ to C₄ alkyl group, aryl, or combinations thereof, and m is from 2 to 100.

7. The composition of claim 1, wherein said pendent poly(alkylene oxide) group is a poly(ethylene oxide) (co)polymer.

8. The composition of claim 1, wherein said pendent poly(alkylene oxide) group is a poly(ethylene oxide-co-propylene oxide) copolymer.

9. The composition of claim 1, wherein said second component oligomer further comprises a plurality of polymerized monomer units having pendent, hydrophilic poly(alkylene oxide) groups.

10. The composition of claim 1 wherein said first oligomer having pendent unsaturated polymerizable groups is prepared by the reaction of an oligomer having a plurality of pendent reactive functional groups with an unsaturated compounds having co-reactive functional groups.

11. The composition of claim 10 wherein said pendent reactive functional groups are selected from hydroxyl, amino, oxazolinyl, oxazolonyl, acetyl acetonyl, carboxyl, isocyanato, epoxy, aziridinyl, acyloyl halide, and cyclic anhydride groups.

12. The composition of claim 1 wherein the second component oligomer is prepared by the reaction of an oligomer having a plurality of pendent reactive functional groups with co-reactive compounds having a photoinitator group.

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

14. The composition of claim 1 which comprises:

(a) from 0.01 to 99.9 parts by weight of said first component oligomer, and

(b) from 99.9 to 0.1 parts by weight of said second component oligomer,

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

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

(a) from 20 to 99 parts by weight of polymerized monomer units derived from an ethylenically-unsaturated monomer having a pendent poly(alkylene oxide) group;

(b) from 0.1 to 35 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent polymerizable functional group;

(c) from 0 to 50 parts by weight of polymerized monomer units derived from a polar monomer;

(d) from 0 to 20 parts by weight of polymerized monomer units derived from a hydrophobic monomer;

(e) from 0 to 10 parts by weight of at least one other monomer.

16. The oligomer composition of claim 15 wherein said polar monomer c), when present, is selected from the group consisting of substituted (meth)acrylamides, N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile, N-vinyl acetamide, tetrahydrofurfuryl acrylate, acrylamides, and mixtures thereof.

17. The composition of claim 1 wherein the second oligomer component comprises:

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

(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;

(d) from 0 to 20 parts by weight of hydrophobic monomers;

(e) from 0 to 50 parts by weight of polymerized monomer units derived from a polar monomer; and

(f) from 0 to 40 parts by weight, preferably less than 25 parts by weight, of at least one other monomer.

18. A crosslinked composition comprising the composition of claim 1, having an average molecular weight between crosslinks of ≧

1000.

19. A process for making a substrate bearing 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 crosslinking said first component oligomer and second component oligomer, in the presence of a photoinitiator, by forming covalent bonds between said pendent, free-radically polymerizable functional groups of said first component oligomer said second component oligomer.

20. The process of claim 19 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.

21. The process of claim 19 wherein said oligomer composition comprises

(a) per 100 parts by weight of said first component, an amount of said second component sufficient to provide more than two crosslinks per first component oligomer chain;

(b) less than 2 parts by weight residuals content.

22. The process of claim 19 wherein the molecular weight (M_n) 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 oligomers is ≦

300.

24. An absorbent dressing comprising a crosslinked hydrophilic gel absorbent layer of claim 1.

25. The absorbent dressing of claim 24 comprising:

a permeable facing layer,

a backing layer bonded to said facing layer at the periphery, and

a hydrophilic gel absorbent layer disposed between the backing and facing layer.

26. The absorbent dressing of claim 25 having a layer of pressure sensitive adhesive on at least a portion of the front surface of the facing layer.

27. The absorbent dressing of claim 25 wherein the gel layer further comprises a pharmacologically active agent.

28. The absorbent dressing of claim 25 wherein the gel layer further comprises a hydrocolloid.

29. The absorbent dressing of claim 25 wherein the gel layer further comprises a patterned surface.