Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same

• US 9,815,979 B2
• Filed: 11/04/2016
• Issued: 11/14/2017
• Est. Priority Date: 05/06/2010
• Status: Active Grant

• Current Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Original Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Inventors: Scales, Charles, Venkatasubban, Kunisi, Mahadevan, Shivkumar, Fadli, Zohra, Healy, Brent Matthew
• Primary Examiner(s): PEPITONE, MICHAEL F
• Application Number:
  US15/343,663
• Publication Number:
  US 20170051145A1
• Time in Patent Office: 375 Days
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 39/08 Homopolymers or copolymers of vinyl-pyridine
• 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 51/085 on to polysiloxanes
• CPC Class Codes: G02B 1/04 made of organic materials, e.g. plastics G02B1/08 takes precedence
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 7/049 Contact lenses having special fitting or structural features achieved by special materials or material structures

Abstract

The present invention relates to compositions comprising at least one stable, near-monodisperse, non-reactive hydrophilic polymer comprising in said polymer'"'"'s backbone, a hydrophilic segment having a degree of polymerization of about 10 to about 1000, and a linear silicone segment at at least one terminal end of said non-reactive hydrophilic polymer, wherein said silicone segment comprises between about 6 and about 200 siloxy units, and said non-reactive hydrophilic polymer is associated, via the linear silicone block with a silicone hydrogel. The non-reactive hydrophilic polymers may be incorporated into the formulation from which the silicone hydrogel is made or may be contacted with the silicone hydrogel post formation.

Claims

1. A composition comprising at least one stable, near-monodisperse, non-reactive hydrophilic polymer comprising in said polymer'"'"'s backbone, a hydrophilic segment having a degree of polymerization of about 300 to about 10,000, and a linear silicone segment on at least one terminal end of said non-reactive hydrophilic polymer, wherein said silicone segment comprises between about 6 and about 200 siloxy units, and said non-reactive hydrophilic polymer is associated, via the linear silicone block with a silicone hydrogel, wherein said polymer has a polydispersity of less than about 1.5.

2. The composition of claim 1 wherein said hydrophilic segment of said non-reactive hydrophilic polymer has a degree of polymerization between about 500 and about 10,000.

3. The composition of claim 1 wherein said hydrophilic segment of said non-reactive hydrophilic polymer has a degree of polymerization between about 500 and about 5000.

4. The composition of claim 1 wherein said hydrophilic segment of said non-reactive hydrophilic polymer has a degree of polymerization between about 500 and about 2000.

5. The composition of claim 1 wherein hydrophilic segment and linear silicone segment are present in said non-reactive hydrophilic polymer in a ratio, based upon the degree of polymerization, between 13:

1 and 500;

1.

6. The composition of claim 5 wherein the ratio of hydrophilic segment to linear silicone segment, based upon degree of polymerization, is between 30:

1 and 200;

1.

7. The composition of claim 5 wherein the ratio of hydrophilic segment to linear silicone segment, based upon degree of polymerization is between 70:

1 and 200;

1.

8. The composition of claim 1 wherein said hydrophilic segment is linear or branched.

9. The composition of claim 1 wherein said silicone segment comprises polydialkylsiloxane, polydiarylsiloxane and mixtures thereof.

10. The composition of claim 9 wherein said alkyl is selected from C₁-C₄ alkyl.

11. The composition of claim 9 wherein said polydialkylsiloxane comprises polydimethylsiloxane or polydiethylsiloxane.

12. The composition of claim 1 wherein said hydrophilic segment is formed from monomers selected from the group consisting of vinyl amides, vinyl lactones, vinylimides, vinyl lactams, hydrophilic (meth)acrylates, (meth)acrylamides and mixtures thereof.

13. The composition of claim 1 wherein said non-reactive hydrophilic polymer is formed by

(a) Reacting a hydroxyl alkyl terminated polydialkylsiloxane with 4-(bromomethyl)benzoyl bromide in the presence of at least one hindered non-nucleophilic amine and subsequently reacting a thiocarbonylthio anion to form a polysiloxane-functional RAFT agent having a silicone segment and a dithio compound on one terminus of said silicone segment;

(b) Contacting the polysiloxane-functional RAFT agent with at least one hydrophilic monomer, a free radical initiator, and an optional solvent; and

(c) Polymerizing said at least one hydrophilic monomer in the presence of the polysiloxane-functional RAFT agent to form a hydrophilic segment on the polysiloxane-functional RAFT agent, such that the dithio compound is on a terminal end of said hydrophilic segment and the silicone segment is on an opposite terminus.

14. The composition of claim 1 wherein said non-reactive hydrophilic polymer is formed by

(a) Reacting a silane-terminated polydialkylsiloxane with 1-(chloromethyl)-4-vinylbenzene in the presence of a catalyst and subsequently reacting a thiocarbonylthio anion to form a polysiloxane-functional RAFT agent having a silicone segment and a dithio compound on one terminus of said silicone segment;

(b) Contacting the polysiloxane-functional RAFT agent with at least one hydrophilic monomer, a free radical initiator, and an optional solvent; and

(c) Polymerizing at least one hydrophilic monomer in the presence of the polysiloxane-functional RAFT agent to form a hydrophilic segment on the polysiloxane-function RAFT agent, such that the dithio compound is on a terminal end of said hydrophilic segment and the silicone segment is on the opposite terminus.

15. A composition comprising at least one stable, near-monodisperse, non-reactive hydrophilic polymer comprising in said polymer'"'"'s backbone, a hydrophilic segment having a degree of polymerization of about 300 to about 10,000, and a linear silicone segment on at least one terminal end of said non-reactive hydrophilic polymer, wherein said silicone segment comprises between about 6 and about 200 siloxy units, and said non-reactive hydrophilic polymer is associated, via the linear silicone block with a silicone hydrogel, wherein said polymer is a polymer of Formula I:

16. The composition of claim 15 wherein

R₁ is selected from the group consisting of substituted and unsubstituted C_1-10 alkyl;

R₂-R₅ are independently selected from C₁-C₄ alkyl,

R₆ is selected from the group consisting aromatic groups of the following formulae;

17. The composition of claim 15 wherein R₁ is selected from the group consisting of substituted and unsubstituted C_1-4 alkyl and R₂-R₅ are methyl.

18. The composition of claim 15 wherein n is 6-12.

19. The composition of claim 15 wherein

R₁ is selected from the group consisting of substituted and unsubstituted alkyl;

R₂-R₅ are independently selected from C₁-C₄ alkyl,

R₆ is selected from the group consisting of alkylenes;

20. The composition of claim 15 wherein Z is selected from optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryl, and optionally substituted benzyl.