Actinically-crosslinkable siloxane-containing copolymers

• US 8,383,744 B2
• Filed: 05/20/2010
• Issued: 02/26/2013
• Est. Priority Date: 05/22/2009
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Justynska, Justyna, Seiferling, Bernhard
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US12/783,591
• Publication Number:
  US 20100296049A1
• Time in Patent Office: 1,013 Days
• Field of Search: 526/279, 351/160.R
• US Class Current: 526/279
• CPC Class Codes: B29D 11/00038 Production of contact lenses
• 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 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 290/068 Polysiloxanes
• 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 invention provide a class of actinically-crosslinkable silicone-containing prepolymers which comprise dangling polysiloxane chains each having a terminal ethylenically-unsaturated group and are obtained in a one-step of RAFT polymerization of a reactive mixture comprising a polysiloxane crosslinker, a hydrophilic vinylic monomer, a RAFT agent, and a free-radical initiator. The present invention is also related to silicone hydrogel contact lenses made from a prepolymer of the invention and methods for making the contact lenses in a cost-effective way and with high consistency and high fidelity to the original lens design.

Claims

1. An actinically crosslinkable prepolymer, which is a RAFT polymerization product of a reactive mixture comprising a polysiloxane crosslinker with two terminal vinyl-groups, a hydrophilic vinylic monomer, a RAFT agent, and a free-radical initiator, wherein the prepolymer comprises:

(1) polysiloxane crosslinking units derived from the polysiloxane crosslinker both the two terminal vinyl-groups of which undergo the RAFT polymerization;

(2) hydrophilic units derived from a hydrophilic vinylic monomer;

(3) dangling polysiloxane chains each with one terminal vinyl group, wherein the dangling polysiloxane chains are derived from the polysiloxane crosslinker one of the two terminal vinyl-groups of which undergoes the RAFT polymerization while the other remains unreacted, wherein the molar ratio of the RAFT agent to the polysiloxane crosslinker in the reactive mixture is from about 0.005 to about 0.1, wherein the prepolymer is capable of being actinically crosslinked, in the absence of one or more vinylic monomers, to form a silicone hydrogel material.

2. The prepolymer of claim 1, wherein the free-radical initiator is a peroxide initiator or an azo initiator.

3. The prepolymer of claim 1, wherein the RAFT agent is selected from the group consisting of 4-Cyano-4-(dodecyl-sulfanylthiocarbonyl)sulfanylpentanoic acid, S-Cyanomethyl-5-dodecyltrithiocarbonate, S-(2-Cyano-2-propyl)-S-dodecyltrithiocarbonate, 3-benzylsulfanylthiocarbonylsulfanyl-propionic acid, cumyl dithiobenzoate, 2-cyanoprop-2-yl dithiobenzoate (i.e., cyanoisopropyl dithiobenzoate), 4-thiobenzoylsulfanyl-4-cyanopentanoic acid (TCA), S,S′

-bis(α

,α

′

-dimethyl-α

″

-acetic acid)-trithiocarbonate (BATC), and mixtures thereof.

4. The prepolymer of claim 1, wherein the hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid monohydrate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 2-hydroxyethylmethacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinyl caprolactam, and mixtures thereof.

5. The prepolymer of claim 1, wherein the polysiloxane crosslinker is represented by formula (1)

Q-X₁-A₁-PDMS-A₂-X₂-Q 

 

(1)

in which

A₁ and A₂ independent of each other is a linear or branched C₁-C₁₀ alkyl diradical which optionally comprises one or more hydroxyl or amino groups;

X₁ and X₂ independent of each other are a linkage selected from the group consisting of a direct bond,

6. The prepolymer of claim 1, wherein the reactive mixture can further comprises a siloxane-containing vinylic monomer of formula (5)

7. The prepolymer of claim 6, wherein the siloxane-containing vinylic monomer is selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, 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)propyl-tris(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, and trimethylsilylmethyl vinyl carbonate), and mixtures thereof.

8. The prepolymer of claim 1, wherein the reactive mixture can further comprises a monoethylenically functionalized polysiloxane vinylic monomer or macromer of formula (7)

9. The prepolymer of claim 1, wherein the reactive mixture comprises a polymerizable UV absorber.

10. The prepolymer of claim 9, wherein the polymerizable UV absorber is selected from the group consisting of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl)benzotriazole, 2-(2′

-hydroxy-5′

-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2′

-hydroxy-5′

-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2′

-hydroxy-5′

-methacryloxypropyl-3′

-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2′

-hydroxy-5′

-methacryloxyethylphenyl)benzotriazole, 2-(2′

-hydroxy-5′

-methacryloxypropylphenyl)benzotriazole, 2-hydroxy-4-acryloxy alkoxy benzophenone, 2-hydroxy-4-methacryloxy alkoxy benzophenone, allyl-2-hydroxybenzophenone, 2-hydroxy-4-methacryloxy benzophenone, and mixture thereof.

11. The prepolymer of claim 1, wherein the reactive mixture comprises:

(1) from about 5% to about 60% by weight of one or more hydrophilic vinylic monomers;

(2) from about 5% to about 75% by weight of one or more polysiloxane crosslinkers; and

(3) from zero to about 50% by weight of a siloxane-containing vinylic monomer and/or a monoethylenically functionalized polysiloxane vinylic monomer or macromer, provided that components (1) to (3) and any additional polymerizable components add up to 100% by weight.

12. A soft contact lens, comprising:

a silicone hydrogel material that is obtained by curing a lens-forming material in a mold, wherein the lens-forming material comprises an actinically crosslinkable prepolymer which is a RAFT polymerization product of a reactive mixture comprising a polysiloxane crosslinker with two terminal vinyl-groups, a hydrophilic vinylic monomer, a RAFT agent, and a free-radical initiator, wherein the molar ratio of the RAFT agent to the polysiloxane crosslinker in the reactive mixture is from about 0.005 to about 0.1, wherein the prepolymer comprises;

(1) polysiloxane crosslinking units derived from the polysiloxane crosslinker both the two terminal vinyl-groups of which undergo the RAFT polymerization;

(2) hydrophilic units derived from a hydrophilic vinylic monomer;

(3) dangling polysiloxane chains each with one terminal vinyl group, wherein the dangling polysiloxane chains are derived from the polysiloxane crosslinker one of the two terminal vinyl-groups of which undergoes the RAFT polymerization while the other remains unreacted, wherein the contact lens has at least one property selected from the group consisting of an oxygen permeability of at least about 40 barrers, an elastic modulus of about 1.5 MPa or less, an Ionoflux Diffusion Coefficient, D, of at least about 1.5×

10<sup>−

6</sup> mm²/min, and a water content of from about 15% to about 70%.

13. The soft contact lens of claim 12, wherein the RAFT agent is selected from the group consisting of 4-Cyano-4-(dodecyl-sulfanylthiocarbonyl)sulfanylpentanoic acid, S-Cyanomethyl-5-dodecyltrithiocarbonate, S-(2-Cyano-2-propyl)-S-dodecyltrithiocarbonate, 3-benzylsulfanylthiocarbonylsulfanyl-propionic acid, cumyl dithiobenzoate, 2-cyanoprop-2-yl dithiobenzoate (i.e., cyanoisopropyl dithiobenzoate), 4-thiobenzoylsulfanyl-4-cyanopentanoic acid (TCA), S,S′

-bis(α

,α

′

-dimethyl-α

″

-acetic acid)-trithiocarbonate (BATC), and mixtures thereof.

14. The soft contact lens of claim 12, wherein the hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid monohydrate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 2-hydroxyethylmethacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of from 200 to 1500, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinyl caprolactam, and mixtures thereof.

15. The soft contact lens of claim 12, wherein the polysiloxane crosslinker is represented by formula (1)

Q-X₁-A₁-PDMS-A₂-X₂-Q 

 

(1)

in which

A₁ and A₂ independent of each other is a linear or branched C₁-C₁₀ alkyl diradical which optionally comprises one or more hydroxyl or amino groups;

X₁ and X₂ independent of each other are a linkage selected from the group consisting of a direct bond,

16. The soft contact lens of claim 12, wherein the reactive mixture further comprises a siloxane-containing vinylic monomer of formula (5)

17. The soft contact lens of claim 12, wherein the siloxane-containing vinylic monomer is selected from the group consisting of N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl]methacrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl]methacrylamide, 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, and trimethylsilylmethyl vinyl carbonate), and mixtures thereof.

18. The soft contact lens of claim 12, wherein the reactive mixture further comprises a monoethylenically functionalized polysiloxane vinylic monomer or macromer of formula (7)

19. A method for producing soft contact lenses, comprising the steps of:

providing a mold for making a soft contact lens, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens and a second mold half with a second molding surface defining the posterior surface of the contact lens, wherein said first and second mold halves are configured to receive each other such that a cavity is formed between said first and second molding surfaces;

introduce a lens-forming material into the cavity, wherein the lens-forming material comprises an actinically crosslinkable prepolymer which is a RAFT polymerization product of a reactive mixture comprising a polysiloxane crosslinker with two terminal vinyl-groups, a hydrophilic vinylic monomer, a RAFT agent, and a free-radical initiator, wherein the molar ratio of the RAFT agent to the polysiloxane crosslinker in the reactive mixture is from about 0.005 to about 0.1, wherein the prepolymer comprises (1) polysiloxane crosslinking units derived from the polysiloxane crosslinker both the two terminal vinyl-groups of which undergo the RAFT polymerization, (2) hydrophilic units derived from a hydrophilic vinylic monomer, and (3) dangling polysiloxane chains each with one terminal vinyl group, wherein the dangling polysiloxane chains are derived from the polysiloxane crosslinker one of the two terminal vinyl-groups of which undergoes the RAFT polymerization while the other remains unreacted; and

actinically irradiating the lens forming material in the cavity to form a contact lens.