Crosslinkable hydrophilic materials from polymers having pendent Michael donor groups

• US 20060167180A1
• Filed: 01/25/2005
• Published: 07/27/2006
• Est. Priority Date: 01/25/2005
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Gaddam, Babu N., Lewandowski, Kevin M., Fansler, Duane D., Plaut, David J.
• Granted Patent: US 7,335,690 B2
• Time in Patent Office: Days
• US Class Current: 525/187
• CPC Class Codes: C08F 290/12 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C09D 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Abstract

The present invention provides crosslinkable compositions useful in the preparation of hydrophilic gels, and are prepared from polymers having pendent hydrophilic groups, and pendant Michael donor groups, and crosslinked by polyacryl Michael acceptor compounds.

Claims

1. A hydrophilic, crosslinkable composition comprising

a) a first component polymer comprising a plurality of polymerized monomer units having pendent hydrophilic groups, and pendent Michael donor groups;

and

b) a crosslinking agent comprising at least two Michael acceptor groups, and

c) optionally a monoacryl component.

2. The composition of claim 1 wherein the pendent hydrophilic group of the first component polymer is a poly(alkylene oxide) group.

3. The composition of claim 1 wherein said crosslinking agent comprises a polyacryl compound.

4. The composition of claim 1 wherein said crosslinking agent comprises a hydrophilic poly(alkylene oxide) crosslinking agent having acryl terminal groups.

5. The composition of claim 1 wherein said crosslinking agent is of the formula

CH₂═

CH—

C(O)-Q-CH(R¹)—

CH₂—

O—

(CH(R¹)—

CH₂—

O)_m—

CH(R¹)—

CH₂-Q-C(O)—

CH═

CH₂,

wherein R¹ is a H or a C₁ to C₄ alkyl group, and m is from 1 to 500, and Q is a divalent linking group selected from alkylene, —

O—

, —

NR¹—

, —

S— and

combinations thereof.

6. The composition of claim 1, wherein said polymer a) is an oligomer having an average degree of polymerization of less than 300.

7. The composition of claim 1, wherein said crosslinking agent is a poly(ethylene oxide) (co)polymer having terminal acryl groups.

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

9. The composition of claim 1 wherein said first component polymer comprises:

a) from 25 to 75 parts by weight of polymerized monomer units having pendent, hydrophilic groups,

b) from 25 to 75 parts by weight of polymerized monomer units derived from of an ethylenically-unsaturated monomer having a pendent Michael donor groups;

c) from 0 to 25 parts by weight of polymerized monomer units derived from acrylic acid esters, preferably of non-tertiary alkyl alcohols containing 1-14 carbon atoms.

10. The composition of claim 1 wherein said first polymer having pendent Michael donor groups is prepared by the reaction of a polymer having a plurality of pendent reactive functional groups with Michael donor 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 said first polymer having pendent Michael donor groups is prepared by the reaction of a polymer having a plurality of pendent nucleophilic functional groups with diketene.

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

14. The composition of claim 1 which comprises:

a) from 80 to 99.9 parts by weight of said first component polymer, and

b) from 0.1 to 50 parts by weight of said crosslinking agent,

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

15. The composition of claim 1 wherein the ratio of said Michael donor group equivalents to said Michael acceptor group equivalents of the crosslinking agent is less than 5:

1.

16. The composition of claim 1 wherein the ratio of Michael donor equivalents to total Michael acceptor group equivalents (of the crosslinking agent plus monoacryl compounds) is 1.2:

1 to 1;

1.2.

17. The composition of claim 1, wherein said monomer units having Michael donor groups are of the formula:

W¹—

CHR⁴—

C(O)-Q-Z  

 

(II) or
W¹—

NH—

C(O)-Q-Z  

 

(III)

wherein

R⁴ represents hydrogen, an alkyl group or an aryl group;

W¹ is selected from a cyano group, a nitro group, an alkyl carbonyl group, an alkoxy carbonyl group, an aryl carbonyl group, an aryloxy carbonyl group, an amido group, and a sulphonyl group,

Z is a polymerizable ethylenically unsaturated moiety, and

Q is a divalent linking group selected from alkylene, —

O—

, —

NR¹—

, —

S—

, and combinations thereof.

18. The composition of claim 2, wherein said monomer units having pendent hydrophilic poly(alkylene oxide) groups is of the formula:

Z-Q-(CH(R¹)—

CH₂—

O)_n—

R²,  

 

(I)

wherein Z is a polymerizable ethylenically unsaturated moiety, R¹ is a H or a C₁ to C₄ alkyl group, R² is a H, a C₁ to C₄ alkyl group, aryl group, or combinations thereof and n is from 2 to 100, and Q is a divalent linking group.

19. The composition of claim 1, wherein the composition is transparent.

20. A crosslinked composition comprising the composition of claim 1, wherein the composition is transparent.

21. 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 polymer composition of claim 1;

and

b) crosslinking said first component polymer and crosslinking agent, in the presence of a basic, catalyst.

22. The process of claim 21 wherein the ratio of said Michael donor group equivalents to said Michael acceptor group equivalents is less than 2:

1, wherein the crosslinked polymer has pendent, unreacted Michael donor groups.

23. The process of claim 22 further comprising the step of reacting the pendent, unreacted Michael donor groups with a monoacryl component.

24. The process of claim 21 wherein the step of crosslinking is in the presence of a basic catalyst and a monoacryl component.

25. The process of claim 21 wherein said polymer composition comprises

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

and

b) less than 2 parts by weight residuals content.

26. The process of claim 21 wherein the average degree of polymerization of the first and second component oligomers is ≦

300.