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

Patent metadata

Field	Value
Publication number	US-9815979-B2
Application number	US-201615343663-A
Country	US
Kind code	B2
Filing date	Nov 4, 2016
Priority date	May 6, 2010
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

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.

First claim

We claim:

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 C 1 -C 4 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:

wherein R 1 is selected from substituted and unsubstituted C 1-24 alkyl;
R 2 -R 5 are independently selected from H, C 1 -C 4 alkyl and C 6-10 aryl;
n is 6-20;
R 9 is selected from a direct bond and C 1-12 alkylene;
X is selected from the group consisting of —O—(CO)—, —(CO)O—, —NR 8 —(CO)—, —(CO)NR 8 —, —O—, or a direct bond;
R 8 is selected from H, methyl, ethyl or propyl;

R 6 is selected from the group consisting of alkylenes of the following formulae:

and aromatic groups of the following formulae:

Q is the hydrophilic segment,
Z is selected from the group consisting of hydrogen, chlorine, fluorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxy, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl (—COOR″), carboxy (—COOH), optionally substituted acyloxy (—O 2 CR″), optionally substituted carbamoyl (—CONR″ 2 ), cyano (—CN), dialkyl- or diaryl-phosphonato [—P(═O)(OR″) 2 ], dialkyl- or diaryl-phosphinato [—P(═O)(OR″) 2 ];
t is 1 or an integer greater than 1 and p is an integer of 1-5.

16. The composition of claim 15 wherein
R 1 is selected from the group consisting of substituted and unsubstituted C 1-10 alkyl;
R 2 -R 5 are independently selected from C 1 -C 4 alkyl,
R 6 is selected from the group consisting aromatic groups of the following formulae:

and n is 6-15.

17. The composition of claim 15 wherein R 1 is selected from the group consisting of substituted and unsubstituted C 1-4 alkyl and R 2 -R 5 are methyl.

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

19. The composition of claim 15 wherein
R 1 is selected from the group consisting of substituted and unsubstituted alkyl;
R 2 -R 5 are independently selected from C 1 -C 4 alkyl,

R 6 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.

Assignees

• Johnson & Johnson Vision Care

Inventors

• Scales Charles
• Venkatasubban Kunisi
• Mahadevan Shivkumar
• Fadli Zohra
• Healy Brent Matthew

Classifications

• C08F226/10

  N-Vinyl-pyrrolidone · CPC title

• C08L51/085 Primary

  on to polysiloxanes · CPC title

• C08G77/442 Primary

  containing vinyl polymer sequences · CPC title

• G02B1/043

  Contact lenses · CPC title

• C08L51/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds · CPC title