Amphiphilic polysiloxane prepolymers and uses thereof

• US 9,341,744 B2
• Filed: 02/09/2015
• Issued: 05/17/2016
• Est. Priority Date: 07/30/2010
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Chang, Frank, Scott, Robert, Huang, Jinyu, Medina, Arturo N., Smith, Dawn A., Sanders, Laura A., Pruitt, John Dallas
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US14/617,310
• Publication Number:
  US 20150153482A1
• Time in Patent Office: 463 Days
• US Class Current: 1/1
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 220/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 230/085 the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 77/388 containing nitrogen
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: C08L 101/14 the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The present invention provides an amphiphilic polysiloxane prepolymer which comprises hydrophilic monomeric units derived from at least one hydrophilic vinylic monomer, polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having at least two terminal ethylenically-unsaturated groups, dangling polysiloxane chains each of which is terminated with one ethylenically unsaturated group, and chain-transfer units derived from a chain transfer agent other than a RAFT agent. A prepolymer of the invention is suitable for making hydrogel contact lenses. The present invention is also related to hydrogel contact lenses made from an amphiphilic polysiloxane prepolymer of the invention and to processes for preparing an amphiphilic polysiloxane prepolymer of the invention and for making silicone hydrogel contact lenses.

Claims

1. A silicone hydrogel contact lens comprising a polymeric material which is a polymerization product of a lens-forming composition including:

(1) an amphiphilic branched polysiloxane prepolymer, wherein the amphiphilic branched polysiloxane prepolymer is obtained by

(i) polymerizing a polymerizable composition to obtain a mixture of amphiphilic branched polysiloxane copolymer, wherein the polymerizable composition comprises

(a) a partially ethylenically-functionalized polysiloxane, wherein the partially ethylenically-functionalized polysiloxane is a mixture of reaction products obtained by reacting a first ethylenically functionalizing vinylic monomer having a first reactive functional group with a functional polysiloxane compound having two or more second reactive functional groups at a molar equivalent ratio, R_Equivalent, of from about 40% to about 95%, wherein each first reactive functional group reacts with one second reactive functional group in the presence or absence of a coupling agent to form a covalent bond or linkage, wherein the mixture of reaction product comprises at least one polysiloxane crosslinkers having at least two ethylenically unsaturated groups and at least one polysiloxane vinylic monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group,

(b) at least one hydrophilic vinylic monomer,

(c) optionally a hydrophobic vinylic monomer,

(d) a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally including a third reactive functional group, and

(e) a free-radical initiator, and

(ii) ethylenically functionalizing the amphiphilic branched polysiloxane copolymer by reacting it with a second ethylenically functionalizing vinylic monomer having a fourth reactive functional group which reacts with one second or third reactive functional group in the presence or absence of a coupling agent to form a covalent linkage, thereby forming the amphiphilic branched polysiloxane prepolymer; and

(2) less than 20% by weight of one or more vinylic monomers relative to the total amount of all polymerizable components in the lens-forming composition; and

(3) optionally a hydrophobic vinylic monomer.

2. The silicone hydrogel contact lens of claim 1, wherein the lens-forming composition comprises:

from about 75% to about 97% by weight of the amphiphilic branched polysiloxane prepolymer;

from about 0.1% to about 5% by weight of a free-radical initiator; and

from about 2% to about 16% by weight of said one or more vinylic monomers,

wherein the percentages by weight of the components listed above are relative to the total amount of all polymerizable components including those not listed above in the lens-forming composition.

3. The silicone hydrogel contact lens of claim 2, wherein the polymerizable composition comprising:

(a) from about 20% to about 80% by weight of the partially ethylenically-functionalized polysiloxane;

(b) from about 5% to about 75% by weight of at least one hydrophilic vinylic monomer;

(c) from 0 to about 55% by weight of a bulky hydrophobic vinylic monomer;

(d) from about 0.25% to about 5% by weight of a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally including a reactive functional group;

(e) from 0 to 5% by weight by weight of a polymerizable UV-absorbing compound; and

(f) from about 0.1% to about 5% by weight of a free radical initiator,

wherein the percentages by weight of the above-listed components are relative to the combined weight of all polymerizable components.

4. The silicone hydrogel contact lens of claim 3, wherein the hydrophilic vinylic monomer in the polymerizable composition is free of reactive functional group capable of participating in a coupling reaction with the second ethylenically functionalizing vinylic monomer.

5. The silicone hydrogel contact lens of claim 3, wherein the polymerizable composition comprises a first hydrophilic vinylic monomer free of any reactive functional group capable of participating in a coupling reaction with the second ethylenically functionalizing vinylic monomer and a second hydrophilic vinylic monomer having a reactive functional group capable of participating the coupling reaction with the second ethylenically functionalizing vinylic monomer, wherein the first and second hydrophilic vinylic monomers are present in the polymerizable composition at a ratio of from about 5:

1 to about 30;

1.

6. The silicone hydrogel contact lens of claim 5, wherein the first hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethyl (meth)acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, dimethylaminoethyl (meth)acrylate, N-vinyl-2-pyrrolidone, a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, and mixtures thereof;

and wherein the second hydrophilic vinylic monomer is selected from the group consisting of hydroxyl-substituted C₁-C₄ alkyl (meth)acrylate, hydroxyl-substituted C₁-C₄ alkyl (meth)acrylamide, amino-substituted C₁-C₄ alkyl (meth)acrylate, amino-substituted C₁-C₄ alkyl (meth)acrylamide, allyl alcohol, allyl amine, and mixture thereof.

7. The silicone hydrogel contact lens of claim 6, wherein the partially ethylenically functionalized polysiloxane is obtained by reacting the first ethylenically functionalized vinylic monomer with the functional polysiloxane compound at a molar equivalent ratio of from about 70% to about 90%.

8. The silicone hydrogel contact lens of claim 7, wherein the polymerizable composition comprises a bulky hydrophobic vinylic monomer selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide;

N-[tris(dimethylpropylsiloxy)-silylpropyl](meth)acrylamide;

N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide;

N-[tris(dimethylethylsiloxy)silylpropyl](meth)acrylamide;

N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl acrylamide;

N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide;

N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide;

N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide;

N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide;

N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide;

N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide;

N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide;

N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide;

N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;

N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide;

N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;

3-methacryloxy propylpentamethyldisiloxane;

tris(trimethylsilyloxy)silylpropyl methacrylate (TRIS);

(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane);

(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane;

3-methacryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane;

N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate;

3-(trimethylsilyl)propylvinyl carbonate;

3-(vinyloxycarbonylthio)propyl-tris(trimethyl-siloxy)silane;

3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate;

3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate;

3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate;

t-butyldimethyl-siloxyethyl vinyl carbonate;

trimethylsilylethyl vinyl carbonate;

trimethylsilylmethyl vinyl carbonate;

t-butyl (meth)acrylate, cyclohexylacrylate, isobornyl methacrylate, a polysiloxane-containing vinylic monomer having 3 to 8 silicone atoms, and combinations thereof.

9. The silicone hydrogel contact lens of claim 8, wherein the first reactive functional group, the second reactive functional groups of the functional polysiloxane compound, the third reactive functional group of the chain transfer agent, and the fourth reactive functional group, independently of each other, are selected from the group consisting of amino group, hydroxyl group, carboxylic acid group, acid halide groups of —

COX in which X=Cl, Br or I, acid anhydrate group, aldehyde group, azlactone group, isocyanate group, epoxy group, aziridine group, amide groups, and combinations thereof, provided that one first or fourth reactive functional group can react with one second or third reactive functional group in the presence or absence of a coupling agent to form a covalent linkage.

10. The silicone hydrogel contact lens of claim 9, wherein the first and second ethylenically functionalizing vinylic monomers independently of each other are selected from the group consisting of C₁ to C₆ hydroxylalkyl (meth)acrylate, C₁ to C₆ hydroxyalkyl(meth)acrylamide, C₁ to C₆ aminoalkyl (meth)acrylate, allylalcohol, allylamine, C₁ to C₆ aminoalkyl (meth)acrylamide, aziridinyl C₁-C₁₂ alkyl (meth)acrylate (e.g., 2-(1-aziridinyl) ethyl (meth)acrylate, 3-(1-aziridinyl) propyl (meth)acrylate, 4-(1-aziridinyl) butyl (meth)acrylate, 6-(1-aziridinyl) hexyl (meth)acrylate, or 8-(1-axiridinyl) octyl (meth)acrylate), glycidyl (meth)acrylate, C₁ to C₆ alkly (meth)acrylic acid, (meth)acrylic acid halide (—

COX, X=Cl, Br, or I), C₁ to C₆ isocyanatoalkyl (meth)acrylate, 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-ethyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one, 2-vinyl-4,4-dibutyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one, 2-isopropenyl-4,4-tetramethylene -1,3-oxazolin-5-one, 2-vinyl-4,4-diethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-nonyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one, 2-vinyl-4,4-pentamethylene-1,3-oxazolin-5-one, and 2-vinyl-4,4-dimethyl-1,3-oxazolin-6-one, with 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDMO), 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one (IPDMO), and combinations thereof.

11. The silicone hydrogel contact lens of claim 7, wherein the functional polysiloxane compound is defined by formula (1) or (2)

FG-G₁-PDMS-G₂-FG 

 

(1)

CR(-G₁-PDMS-G₂-FG)_a1 

 

(2)

in which

G₁ and G₂ independent of each other are a linear or branched C₁-C₁₀ alkylene divalent radical, a divalent radical of

12. The silicone hydrogel contact lens of claim 11, wherein the polymerizable composition comprises a bulky hydrophobic vinylic monomer selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide;

N-[tris(dimethylpropylsiloxy)-silylpropyl](meth)acrylamide;

N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide;

N-[tris(dimethylethylsiloxy)silylpropyl](meth)acrylamide;

N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl acrylamide;

N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide;

N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide;

N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide;

N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methyl acrylamide;

N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide;

N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl acrylamide;

N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide;

N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide;

N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;

N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl acrylamide;

N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;

3-methacryloxy propylpentamethyldisiloxane;

tris(trimethylsilyloxy)silylpropyl methacrylate (TRIS);

(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane);

(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane;

3-methacryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane;

N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate;

3-(trimethylsilyl)propylvinyl carbonate;

3-(vinyloxycarbonylthio)propyl-tris(trimethyl-siloxy)silane;

3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate;

3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate;

3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate;

t-butyldimethyl-siloxyethyl vinyl carbonate;

trimethylsilylethyl vinyl carbonate;

trimethylsilylmethyl vinyl carbonate;

t-butyl (meth)acrylate, cyclohexylacrylate, isobornyl methacrylate, a polysiloxane-containing vinylic monomer having 3 to 8 silicone atoms, and combinations thereof.

13. The silicone hydrogel contact lens of claim 12, wherein the first reactive functional group, the second reactive functional groups of the functional polysiloxane compound, the third reactive functional group of the chain transfer agent, and the fourth reactive functional group, independently of each other, are selected from the group consisting of amino group, hydroxyl group, carboxylic acid group, acid halide groups of —

COX in which X=Cl, Br or I, acid anhydrate group, aldehyde group, azlactone group, isocyanate group, epoxy group, aziridine group, amide groups, and combinations thereof, provided that one first or fourth reactive functional group can react with one second or third reactive functional group in the presence or absence of a coupling agent to form a covalent linkage.

14. The silicone hydrogel contact lens of claim 13, wherein the first and second ethylenically functionalizing vinylic monomers independently of each other are selected from the group consisting of C₁ to C₆ hydroxylalkyl (meth)acrylate, C₁ to C₆ hydroxyalkyl (meth)acrylamide, C₁ to C₆ aminoalkyl (meth)acrylate, allylalcohol, allylamine, C₁ to C₆ aminoalkyl (meth)acrylamide, aziridinyl C₁-C₁₂ alkyl (meth)acrylate (e.g., 2-(1-aziridinyl) ethyl (meth)acrylate, 3-(1-aziridinyl) propyl (meth)acrylate, 4-(1-aziridinyl) butyl (meth)acrylate, 6-(1-aziridinyl) hexyl (meth)acrylate, or 8-(1-axiridinyl) octyl (meth)acrylate), glycidyl (meth)acrylate, C₁ to C₆ alkly (meth)acrylic acid, (meth)acrylic acid halide (—

COX, X=Cl, Br, or I), C₁ to C₆ isocyanatoalkyl (meth)acrylate, 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-ethyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one, 2-vinyl-4,4-dibutyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one, 2-isopropenyl-4,4-tetramethylene-1,3-oxazolin-5-one, 2-vinyl-4,4-diethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-nonyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one, 2-vinyl-4,4-pentamethylene-1,3-oxazolin-5-one, and 2-vinyl-4,4-dimethyl-1,3-oxazolin-6-one, with 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDMO), 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one (IPDMO), and combinations thereof.

15. The silicone hydrogel contact lens of claim 7, wherein the first and second ethylenically-functionalizing vinylic monomers are identical to each other.

16. The silicone hydrogel contact lens of claim 7, wherein the molar equivalent ratio of the second ethylenically functionalizing vinylic monomer to the amphiphilic polysiloxane copolymer is from about 1 to about 1.2.