CURABLE HYDROPHILIC COMPOSITIONS

• US 20070275042A1
• Filed: 05/23/2006
• Published: 11/29/2007
• Est. Priority Date: 05/23/2006
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: PLAUT, David J., ANDERSON, Kelly S., LEWANDOWSKI, Kevin M., GADDAM, Babu N., THOMPSON, Wendy L.
• Granted Patent: US 7,981,949 B2
• Time in Patent Office: Days
• US Class Current: 424/445
• 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: C08J 3/245 Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
• CPC Class Codes: C08L 71/02 Polyalkylene oxides

Abstract

A curable composition is described, including a gel material derived from the curable composition, and medical articles including such material, wherein the transparent gel material includes a polymerized monofunctional poly(alkylene oxide) macromonomer component and a surface modified nanoparticle component.

Claims

1. A curable composition comprising

a) 1 to 20 parts by weight of a surface modified nanoparticle component having ethylenically unsaturated groups, wherein the average particle size is 20 nanometers or less;

and

b) 80 to 99 parts by weight of a monomer component comprising;

a monofunctional poly(alkylene oxide) free-radically polymerizable macromonomer having a poly(alkylene oxide) moiety.

2. The curable composition of claim 1 wherein monofunctional poly(alkylene oxide) free-radically polymerizable macromonomer is of the formula:

R⁶-Q-(CH(R¹)—

CH₂—

O—

)_m—

(CH₂—

CH₂—

O—

)_n—

R²

wherein

R⁶ is a an ethylenically unsaturated polymerizable group;

R¹ is a (C₁-C₄) alkyl group,

R² is H or R¹,

Q is —

O—

, —

S—

or —

NR²—

,

n is at least 5, m may be 0, n+m is at least 5, and the mole ratio of n;

m is at least 2;

1.

3. The curable composition of claim 2, wherein m is at least 1 and the mole ratio of n to m (n:

m) is greater than 2;

1.

4. The curable composition of claim 2 where R⁶ is selected from:

wherein R¹ is a C₁ to C₄ alkyl,

R² is H or R¹,

R⁵ is an aromatic group, aliphatic group, alicylic group, or combinations thereof,

W is an alkylene or poly(alkylene oxide) group, and r=2-10.

5. The composition of claim 1 wherein the monomer component further comprises a multifunctional poly(alkylene oxide) free-radically polymerizable macromonomer having a poly(alkylene oxide) moiety.

6. The composition of claim 5 wherein the multifunctional macromer is of the formula:

R⁶-Q-(CH(R¹)—

CH₂—

O—

)_m—

(CH₂—

CH₂—

O)_n—

R⁷

wherein;

R⁶ and R⁷ are each independently an ethylenically unsaturated polymerizable group,

R¹ is a (C₁-C₄) alkyl group,

R² is H or R¹,

Q is —

O—

, —

S—

or —

NR²—

,

n is at least 5, m may be 0, n+m is at least 5, and the mole ratio of n;

m is at least 2;

1.

7. The composition of claim 1 wherein the monomer component comprises:

a) 30 to 80 wt. % of a monofunctional poly(alkylene oxide) free-radically polymerizable macromonomer having a poly(alkylene oxide) moiety;

b) 5 to 40 wt. % of a polar monomer;

c) 0 to 20 wt. % of a hydrophobic monomer;

d) 0 to 20 wt. % of a multifunctional poly(alkylene oxide) free-radically polymerizable macromonomer having a poly(alkylene oxide) moiety.

8. The composition of claim 7 comprising 0. 1 to 20 wt. % of said multifunctional poly(alkylene oxide) free-radically polymerizable macromonomer.

9. The composition of claim 1, wherein said surface modified nanoparticles further comprise hydrophilic poly(alkylene oxide) groups.

10. The curable composition of claim 9 wherein the surface modified nanoparticles comprise inorganic nanoparticles modified by a first surface modifying agent having an ethylenically unsaturated group and a second surface modifying agent having poly(alkylene oxide) groups.

11. The curable composition of claim 1 wherein the nanoparticles are selected from silica, alumina, tin oxide, iron oxide, zirconia, vanadia, and titania;

combinations thereof.

12. The curable composition of claim 1 wherein said particles of said nanoparticle phase are less than 10 nanometers average particle size, prior to surface modification.

13. The curable composition of claim 10 wherein said first surface modifying agent of the formula Y—

R³—

Si—

(OR⁴)_b(R⁴)_3-b, wherein;

R³ is a covalent bond or a polyvalent hydrocarbon bridging group.

Y is an ethylenically unsaturated polymerizable group,

R⁴is independently an alkyl, aryl, or aralkyl group of 1 to 8 carbon atoms optionally substituted in available positions by oxygen, nitrogen and/or sulfur atoms; and

b is 1 to 3.

14. The curable composition of claim 13, wherein R³ is a poly(alkylene oxide) group.

15. The curable composition of claim 10 wherein said second surface modifying agent is of the formula R²—

(OCH₂CH₂—

)_n(OCH₂CH(R¹)_m-Q′

-R³—

Si—

(OR⁴)_{bl (R}⁴)_3-b, wherein

Q′

is a divalent linking group;

R¹ is a C₁ to C₄ alkyl group,

R² is a R¹ or H,

R³ is a covalent bond or a divalent hydrocarbon bridging group;

R⁴ is independently an alkyl, aryl, or aralkyl group of 1 to 8 carbon atoms optionally substituted by catenary oxygen, nitrogen and/or sulfur atoms;

n is at least 5, m may be 0, and the mole ratio of n;

m is at least 2;

1; and

b is 1 to 3.

16. The curable composition of claim 10 wherein the ratio of hydrophilic poly(alkylene oxide) groups to ethylenically unsaturated groups on the surface of the inorganic nanoparticles is 1:

10 to 10;

1.

17. The curable composition of claim 10 wherein said first surface modifying agent is used in amounts sufficient to react with 10 to 90% of the available functional groups on the surface of the inorganic nanoparticles.

18. The curable composition of claim 7 wherein the polar monomer is selected from the group consisting of 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, N-vinyl caprolactam, N-vinyl acetamide, N-vinyl pyrrolidone, acrylamide, mono- or di-N-alkyl substituted acrylamide, (meth)acrylic acid, itaconic acid, beta-carboxyethyl acrylate, glycerol methacrylate, [2-(meth)(acryloyloxy)ethyl]trimethylammonium chloride, [2-(meth)(acryloyloxy)ethyl]trimethylammonium methyl sulfate, and combinations thereof.

19. The curable composition of claim 7 comprising a copolymer of the multifunctional macromonomer, a polar monomer, a monofunctional poly(alkylene oxide) monomer, and a hydrophobic monomer.

20. The cured composition of claim 1.

21. The cured composition of claim 1 having an absorbency of at least 100%.

22. The cured composition of claim 22 having a light transmittance of greater than 85% by A.S.T.M. D1003-00.