Novel Polymers

• US 20080015315A1
• Filed: 07/10/2007
• Published: 01/17/2008
• Est. Priority Date: 07/12/2006
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Medina, Norberto Arturo, Chang, Frank
• Granted Patent: US 8,404,783 B2
• Time in Patent Office: Days
• US Class Current: 525/326.9
• CPC Class Codes: C07C 231/12 by reactions not involving the formation of carboxamide groups
• CPC Class Codes: C07C 67/00 Preparation of carboxylic acid esters
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/26 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08F 220/286 and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 2800/20 as weight or mass percentages
• CPC Class Codes: C08F 2810/20 leading to a crosslinking, either explicitly or inherently
• CPC Class Codes: C08F 2810/30 leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• CPC Class Codes: C08F 285/00 Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08J 2433/04 esters
• CPC Class Codes: C08J 2483/04 Polysiloxanes
• CPC Class Codes: C08J 3/075 Macromolecular gels
• CPC Class Codes: C08J 3/28 Treatment by wave energy or particle radiation
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The invention relates to novel crosslinkable copolymers which are obtainable by (a) copolymerizing at least two different hydrophilic monomers selected from the group consisting of N,N-dimethyl acrylamide (DMA), 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), N-vinylpyrrolidone (NVP), acrylic acid (AA) and a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500, and at least one crosslinker comprising two or more ethylenically unsaturated double bonds in the presence of a chain transfer agent having a functional group; and (b) reacting one or more functional groups of the resulting copolymer with an organic compound having an ethylenically unsaturated group.

Claims

1. An actinically crosslinkable prepolymer that is obtained by:

(a) copolymerizing a polymerizable mixture to obtain a copolymer with first functional groups, wherein the polymerizable mixture comprises a first hydrophilic monomer, at least one polysiloxane-containing crosslinker, a chain transfer agent having a first functional group, a second hydrophilic monomer; and

(b) reacting an organic compound with the copolymerization product to form the crosslinkable prepolymer having ethylenically unsaturated groups, wherein the organic compound comprises an ethylenically unsaturated group and a second functional group, wherein the second functional group of the organic compound reacts with one of the first functional groups of the copolymerization product, wherein the second hydrophilic monomer is present in an amount sufficient to produce the resultant prepolymer which, after purification, can be crosslined actinically or thermally to form a silicone hydrogel material, wherein the silicone hydrogel material having a reduced amount of non-volatile extractables.

2. A prepolymer according to claim 1, wherein the silicone hydrogel material having about 10% or less of non-volatile extractables, wherein the second hydrophilic monomer selected from the group consisting of 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), N-vinylpyrrolidone (NVP), acrylic acid (AA), and a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500.

3. A prepolymer according to claim 2, wherein the silicone hydrogel material having about 5% or less of non-volatile extractables.

4. A prepolymer according to claim 2, wherein the first hydrophilic monomer is (C₁-C₄-alkyl)acrylamide, N,N-di-(C₁-C₄-alkyl)acrylamide, or mixture thereof.

5. A prepolymer according to claim 2, wherein the first hydrophilic monomer is DMA and the second hydrophilic monomer is a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 300 to 1000.

6. A prepolymer according to claim 2, wherein the first hydrophilic monomer is DMA and the second hydrophilic monomer is HEA.

7. A prepolymer according to claim 2, wherein the first hydrophilic monomer is DMA and the second hydrophilic monomer is a mixture of HEA and AA.

8. A prepolymer according to claim 2, wherein the polysiloxane-containing crosslinker is a polysiloxane of formula

in which (alk) is alkylene having up to 20 carbon atoms which may be interrupted by —

O—

;

X is —

O—

or —

NR₈—

, R₈ is hydrogen or C₁-C₆-alkyl, Q is an organic radical comprising a crosslinkable or polymerizable group, 80-100% of the radicals R₆, R₆′

, R₆″

, R₆′

″

, R₆*, R₇, R₇′ and

R₇″

, independently of one another, are C₁-C₈-alkyl and 0-20% of the radicals R₆, R₆′

, R₆″

, R₆′

″

, R₆*, R₇, R₇′ and

R₇″

, independently of one another, are unsubstituted or C₁-C₄ alkyl- or C₁-C₄—

alkoxy-substituted phenyl, fluoro(C₁-C₁₈-alkyl), cyano(C₁-C₁₂-alkyl), hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl, x is the number 0 or 1, d₁ is an integer of from 5 to 700, d₂ is an integer from 0 to 8 if x is 0, and is 2 to 10 if x is 1, and the sum of (d₁+d₂) is from 5 to 700.

9. A prepolymer according to claim 2, wherein the polysiloxane-containing crosslinker is a polysiloxane of formula

wherein R₆, R₆′

, R₇ and R₇′

are each methyl, d₁ is an integer from 10 to 300, (alk) is linear or branched C₂-C₆ alkylene or a radical —

(CH₂)_1-3—

O—

(CH₂)_1-3—

, X is —

O—

or —

NH— and

Q is a radical of the formula

10. A prepolymer according to claim 1, wherein the chain transfer agent is an organic primary thiol having a hydroxy, amino, N—

C₁-C₆-alkylamino or carboxy group.

11. A prepolymer according claim 1, wherein the components in step (a) are used in a molar ratio of from 0.5 to 5 equivalents of chain transfer agent:

1 equivalent of polysiloxane-containing crosslinker;

5 to 60 of equivalents hydrophilic monomer(s).

12. A prepolymer according to claim 1, wherein the copolymer of step (a) is reacted in step (b) with a compound of formula

wherein R₁₃ is halogen, hydroxy, unsubstituted or hydroxy-substituted C₁-C₆-alkoxy or phenoxy, R₁₄, and R₁₅ are each independently of the other hydrogen, C₁-C₄-alkyl, phenyl, carboxy or halogen, R₁₆ is hydrogen, C₁-C₄-alkyl or halogen, R₁₇ and R₁₇′

are each an ethylenically unsaturated radical having from 2 to 6 C-atoms, or R₁₇ and R₁₇′

together form a bivalent radical —

C(R₁₄)═

C(R₁₆)—

wherein R₁₄ and R₁₆ are as defined above, and (Alk*) is C₁-C₆-alkylene, and (Alk**) is C₂-C₁₂-alkylene.

13. A soft contact lens, comprising a silicon hydrogel material that is obtained by curing a lens-forming material in a mold, wherein the lens-forming material comprises an actinically crosslinkable or polymerizable prepolymer, wherein the prepolymer is obtained by:

(a) copolymerizing a polymerizable mixture to obtain a copolymer with first functional groups, wherein the polymerizable mixture comprises a first hydrophilic monomer, at least one polysiloxane-containing crosslinker, a chain transfer agent having a first functional group, a second hydrophilic monomer; and

(b) reacting an organic compound with the copolymerization product to form the crosslinkable prepolymer having ethylenically unsaturated groups, wherein the organic compound comprises an ethylenically unsaturated group and a second functional group, wherein the second functional group of the organic compound reacts with one of the first functional groups of the copolymerization product, wherein the second hydrophilic monomer is present in an amount sufficient to produce the resultant prepolymer which, after purification, can be crosslinked actinically or thermally to form a silicone hydrogel material, wherein the silicone hydrogel material having a reduced amount of non-volatile extractables.

14. A soft contact lens of claim 13, wherein the silicone hydrogel material having about 10% or less of non-volatile extractables, wherein second hydrophilic monomer selected from the group consisting of 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), N-vinylpyrrolidone (NVP), acrylic acid (AA), and a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500.

15. A soft contact lens of claim 14, wherein the silicone hydrogel material having about 5% or less of non-volatile extractables.

16. A soft contact lens of claim 14, wherein the first hydrophilic monomer is (C₁-C₄-alkyl)acrylamide, N,N-di-(C₁-C₄-alkyl)acrylamide, or mixture thereof.

17. A soft contact lens of claim 14, wherein the first hydrophilic monomer is DMA and the second hydrophilic monomer is a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 300 to 1000.

18. A soft contact lens of claim 14, wherein the first hydrophilic monomer is DMA and the second hydrophilic monomer is HEA.

19. A soft contact lens of claim 14, wherein the first hydrophilic monomer is DMA and the second hydrophilic monomer is a mixture of HEA and AA.

20. A soft contact lens of claim 14, wherein the polysiloxane-containing crosslinker is a polysiloxane of formula

in which (alk) is alkylene having up to 20 carbon atoms which may be interrupted by —

O—

;

X is —

O—

or —

NR₈—

, R₈ is hydrogen or C₁-C₆-alkyl, Q is an organic radical comprising a crosslinkable or polymerizable group, 80-100% of the radicals R₆, R₆′

, R₆′

″

, R₆′

″

, R₆*, R₇, R₇′ and

R₇″

, independently of one another, are C₁-C₈-alkyl and 0-20% of the radicals R₆, R₆′

, R₆″

, R₆′

″

, R_6*, R₇, R₇′ and

R₇″

, independently of one another, are unsubstituted or C₁-C₄ alkyl- or C₁-C₄—

alkoxy-substituted phenyl, fluoro(C₁-C₁₈-alkyl), cyano(C₁-C₁₂-alkyl), hydroxy-C₁-C₆-alkyl or amino-C₁-C₆-alkyl, x is the number 0 or 1, d₁ is an integer of from 5 to 700, d₂ is an integer from 0 to 8 if x is 0, and is 2 to 10 if x is 1, and the sum of (d₁+d₂) is from 5 to 700.

21. A soft contact lens of claim 14, wherein the polysiloxane-containing crosslinker is a polysiloxane of formula

wherein R₆, R₆′

, R₇ and R₇′

are each methyl, d₁ is an integer from 10 to 300, (alk) is linear or branched C₂-C₆ alkylene or a radical —

(CH₂)_1-3—

O—

(CH₂)_1-3—

, X is —

O—

or —

NH— and

Q is a radical of the formula

22. A soft contact lens of claim 14, wherein the chain transfer agent is an organic primary thiol having a hydroxy, amino, N—

C₁-C₆-alkylamino or carboxy group.

23. A soft contact lens of claim 14, wherein the components in step (a) are used in a molar ratio of from 0.5 to 5 equivalents of chain transfer agent:

1 equivalent of polysiloxane-containing crosslinker;

5 to 60 of equivalents hydrophilic monomer(s).

24. A soft contact lens of claim 14, wherein the copolymer of step (a) is reacted in step (b) with a compound of formula

wherein R₁₃ is halogen, hydroxy, unsubstituted or hydroxy-substituted C₁-C₆-alkoxy or phenoxy, R₁₄, and R₁₅ are each independently of the other hydrogen, C₁-C₄-alkyl, phenyl, carboxy or halogen, R₁₆ is hydrogen, C₁-C₄-alkyl or halogen, R₁₇ and R₁₇′

are each an ethylenically unsaturated radical having from 2 to 6 C-atoms, or R₁₇ and R₁₇′

together form a bivalent radical —

C(R₁₄)═

C(R₁₆)—

wherein R₁₄ and R₁₆ are as defined above, and (Alk*) is C₁-C₆-alkylene, and (Alk**) is C₂-C₁₂-alkylene.

25. A process for manufacturing an actinically crosslinkable prepolymer, comprising:

(1) obtaining a reaction mixture comprising a first hydrophilic monomer, at least one polysiloxane-containing crosslinker, a second hydrophilic monomer, and a chain transfer agent having a first functional group and present in an amount to have a desired initial concentration;

(2) adjusting the temperature of the reaction mixture in order to start the polymerization reaction;

(3) dosing the chain transfer agent to the reaction mixture at a rate sufficient to have a concentration comparable to the desired initial concentration until a desired total amount of the chain transfer agent is added;

(4) following the completion of the chain transfer agent dosing maintaining the reaction mixture at the reaction temperature in order to complete the reaction so as to obtain a copolymerization product with first functional groups; and

(5) reacting an organic compound with the copolymerization product to form the crosslinkable prepolymer having ethylenically unsaturated groups, wherein the organic compound comprises an ethylenically unsaturated group and a second functional group, wherein the second functional group of the organic compound reacts with one of the first functional groups of the copolymerization product, wherein said crosslinkable prepolymer can be crosslinked to form a silicone hydrogel material.

26. A process according to claim 25, wherein the portion of chain transfer agent being present in the initial reaction mixture according to (1) is from 10 to 40% by weight of the total weight of chain transfer agent, and the remaining 60 to 90% by weight are dosed in step (3), wherein the second hydrophilic monomer selected from the group consisting of 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), N-vinylpyrrolidone (NVP), acrylic acid (AA), and a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500.

27. A process according to claim 26, wherein the temperature of the reaction mixture is adjusted to a temperature between 35 to 80°

C. in step (2) and is maintained in steps (3) and (4).

28. A process for the manufacture of an actinically crosslinkable or polymerizable prepolymer, comprising:

(a) copolymerizing a polymerizable mixture to obtain a copolymerization product with first functional groups, wherein the polymerizable mixture comprises a first hydrophilic monomer, at least one polysiloxane-containing crosslinker, a chain transfer agent having a first functional group, a second hydrophilic monomer selected from the group consisting of 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), N-vinylpyrrolidone (NVP), acrylic acid (AA), and a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500; and

(b) reacting an organic compound with the copolymerization product to form the crosslinkable prepolymer having ethylenically unsaturated groups, wherein the organic compound comprises an ethylenically unsaturated group and a second functional group, wherein the second functional group of the organic compound reacts with one of the first functional groups of the copolymerization product, wherein the second hydrophilic monomer is present in an amount sufficient to produce the resultant prepolymer which, after purification, can be crosslined actinically or thermally to form a silicone hydrogel material.