Silicone hydrogel contact lens modified using lanthanide or transition metal oxidants

1. A process for modifying the surface of a silicon-containing polymer, the process comprising the steps of:

forming a reaction mixture comprising the silicon-containing polymer, a polymerization monomer, a free radical redox initiator system and a solvent system, the polymerization monomer comprising a zwitterionic monomer and the free radical redox initiator system comprising a Lanthanide or Transition metal oxidant; and

polymerizing the monomer in the reaction mixture to form a surface modification polymer on the surface of the silicon-containing polymer.

2. The process of claim 1 wherein the silicon-containing polymer contains at least 1 wt. % silicon.

3. The process of claim 1 wherein the silicon-containing polymer contains at least 25 wt. % silicon.

4. The process of claim 1 wherein the Lanthanide or Transition metal oxidant is a cerium (IV) salt.

5. The process of claim 1 wherein the Lanthanide or Transition metal oxidant is selected from the following: Fe 2+ , Cr 2+ , V 2+ , Ti 3+ , Co 2+ , and Cu + .

6. The process of claim 1 wherein the surface modification comprises a carboxyammonium polymer or a sulfoammonium polymer.

7. The process of claim 1 wherein the surface modification comprises a zwitterionic polymer.

8. The process of claim 1 wherein the surface modification comprises a carboxybetaine polymer or a sulfobetaine polymer.

9. The process of claim 1 wherein the surface modification polymer comprises repeat units corresponding to Formula 1

wherein

X 1 and X 2 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocyclo, or substituted carbonyl, provided, however, X 1 and X 2 are not each selected from the group consisting of aryl, heteroaryl, and heterosubstituted carbonyl,

X 3 is hydrogen, alkyl or substituted alkyl,

X 4 is —OX 40 , —NX 41 X 42 , —N + X 41 X 42 X 43 , —SX 40 , aryl, heteroaryl or acyl,

X 40 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocyclo or acyl, and

X 41 , X 42 and X 43 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo.

10. The process of claim 1 wherein the surface modification polymer comprises at least one repeat unit corresponding to Formula 2:

wherein

X 3 is hydrogen, alkyl or substituted alkyl, and

X 4 is a pendant group comprising an oxylated alkylene moiety, a zwitterionic moiety, an anionic moiety, or a cationic moiety.

11. The process of claim 1 wherein the surface modification polymer polymer comprises repeat units corresponding to Formula 3:

wherein X 44 comprises an oxylated alkylene moiety, a zwitterionic moiety, an anionic moiety, or a cationic moiety.

12. The process of claim 11 wherein X 44 is —OX 45 , —NHX 45 , or —SX 45 , and X 45 is a substituted hydrocarbyl or heterocyclo moiety comprising an oxylated alkylene moiety, a zwitterionic moiety, an anionic moiety, or a cationic moiety.

13. The process of claim 11 wherein X 3 is hydrogen or methyl and X 44 comprises an oxylated alkylene moiety corresponding to Formula POA-1 or a zwitterionic moiety corresponding to Formula ZI-1, ZI-2, ZI-3, ZI-4, ZI-5, ZI-6A, ZI-6B, or ZI-7.

14. The process of claim 11 wherein X 44 is —O(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) n SO 3 − , —O(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) n CO 2 − , —NH(CH 2 ) 3 N + (CH 3 ) 2 (CH 2 ) n CO 2 − , or —NH(CH 2 ) 3 N + (CH 3 ) 2 (CH 2 ) n SO 3 − , and n is 1-8.

15. The process of claim 11 wherein X 44 is —NH(CH 2 ) m N(CH 2 ) n CH 3 (CH 2 ) p SO 3 , —NH(CH 2 ) m N(CH 2 ) n CH 3 (CH 2 ) p CO 2 , —NH(CH 2 ) m N + [(CH 2 ) n CH 3 ] 2 (CH 2 ) p SO 3 , —NH(CH 2 )N + [(CH 2 ) n CH 3 ] 2 (CH 2 ) p CO 2 , —NH(CH 2 ) m Ncyclo-(CH 2 ) p CO 2 , or —NH(CH 2 ) m Ncyclo-(CH 2 ) p SO 3 , Ncyclo- is a heterocyclic structure or a heterocyclic derivative containing at least one nitrogen atom, m is 1-8; n is 0-5; and p is 1-8.

16. The process of claim 11 wherein X 44 is —O(CH 2 ) m N(CH 2 ) n CH 3 (CH 2 ) p SO 3 , —O(CH 2 ) m N(CH 2 ) n CH 3 (CH 2 ) p CO 2 , —O(CH 2 ) m N + [(CH 2 ) n CH 3 ] 2 (CH 2 ) p SO 3 , —O(CH 2 )N + [(CH 2 ) n CH 3 ] 2 (CH 2 ) p CO 2 , —O(CH 2 ) m Ncyclo-(CH 2 ) p CO 2 , or —O(CH 2 ) m Ncyclo-(CH 2 ) p SO 3 , Ncyclo- is a heterocyclic structure or a heterocyclic derivative containing at least one nitrogen atom, m is 1-8; n is 0-5; and p is 1-8.

17. The process of claim 11 X 44 is —O(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 , —O(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 2 CO 2 , —NH(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 , —NH(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 2 CO 2 , —NH(CH 2 ) 3 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 , —NH(CH 2 ) 3 N + (CH 3 ) 2 (CH 2 ) 2 CO 2 , —O(CH 2 ) 2 N + (CH 2 CH 3 ) 2 (CH 2 ) 3 SO 3 , —O(CH 2 ) 2 N + (CH 2 CH 3 ) 2 (CH 2 ) 2 CO 2 , —O(CH 2 ) 2 N + (CH 2 CH 2 CH 2 CH 3 ) 2 (CH 2 ) 3 SO 3 , —O(CH 2 ) 2 N + (CH 2 CH 2 CH 2 CH 3 ) 2 (CH 2 ) 2 CO 2 or —NH(CH 2 ) 3 Ncyclo-(CH 2 ) 3 SO 3 , and Ncyclo- is a heterocyclic structure or a heterocyclic derivative containing at least one nitrogen atom.

18. The process of claim 1 wherein the surface modification polymer comprises repeat units corresponding to Formula 4:

wherein

a is 0-1;

b is 0-1;

c is 0-1;

d is 0-1;

m is 1-20

n and o are independently 0-11;

p and q are independently 0-11;

X 3 is hydrogen, alkyl or substituted alkyl,

X 4 is —OX 40 , —NX 41 X 42 , —SX 40 , aryl, heteroaryl or acyl;

X 40 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocyclo or acyl;

X 41 and X 42 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo; and

X 49 is hydrogen, hydrocarbyl or substituted hydrocarbyl,

provided the sum of a, b, c and d is greater than 0 and X 4 of repeat unit D differs from the corresponding pendant group of repeat units A, B and C.

19. The process of claim 1 wherein the surface modification polymer comprises repeat units corresponding to Formula 5, Formula 6, Formula 7, Formula 8, or Formula 9:

wherein

HET is part of a heterocyclic structure,

X 3 is hydrogen, alkyl or substituted alkyl,

X 4 is —OX 40 , —NX 41 X 42 , —SX 40 , aryl, heteroaryl or acyl,

X 5 is ester, anhydride, imide, amide, ether, thioether, thioester, hydrocarbylene, substituted hydrocarbylene, heterocyclo, urethane, or urea;

X 6 is hydrocarbylene, substituted hydrocarbylene, heterocyclo, amide, anhydride, ester, imide, thioester, thioether, urethane, or urea;

X 7 is hydrogen, alkyl or substituted alkyl;

X 8 is an anionic moiety;

X 9 is hydrocarbylene, substituted hydrocarbylene, heterocyclo, amide, anhydride, ester, imide, thioester, thioether, urethane, or urea;

X 10 is hydrogen, alkyl or substituted alkyl;

X 11 is a cationic moiety;

X 12 is hydrocarbylene, substituted hydrocarbylene, heterocyclo, amide, anhydride, ester, imide, thioester, thioether, urethane, or urea;

X 13 is hydrogen, alkyl or substituted alkyl;

X 14 is an anionic moiety;

L 1 and L 2 are independently hydrocarbylene, substituted hydrocarbylene, heterocyclo, amide, anhydride, ester, imide, thioester, thioether, urethane, or urea; and

X 40 is hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocyclo or acyl, and

X 41 and X 42 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo.

20. The process of claim 1 wherein the silicon-containing polymer is comprised by a contact lens.

21. A contact lens formed by the process of claim 1 .