Prepolymers with dangling polysiloxane-containing polymer chains

• US 20080231798A1
• Filed: 03/21/2008
• Published: 09/25/2008
• Est. Priority Date: 03/22/2007
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Zhou, Jian S., Smith, Dawn A.
• Granted Patent: US 8,071,658 B2
• Time in Patent Office: Days
• US Class Current: 351/160H
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/18 to alkoxy or aryloxy groups
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The invention provide a new class of silicone-containing prepolymers containing dangling polysiloxane-containing polymer chains. This class of silicone-containing prepolymer is capable of being actinically crosslinked to form a silicone hydrogel material with a relatively high oxygen permeability, a reduced elastic modulus, and a relatively high ion permeability. The present invention is also related to silicone hydrogel contact lenses made from this class of silicone-containing prepolymers and to methods for making the silicone hydrogel contact lenses.

Claims

1. An actinically crosslinkable prepolymer, comprising:

(1) dangling polysiloxane units derived from one or more monoethylenically functionalized polysiloxane-containing monomers and/or one or more monoethylenically-functionalized polysiloxane-containing macromers, wherein the dangling polysiloxane units is free of ethylenically unsaturated group;

(2) hydrophilic units derived from one or more hydrophilic vinylic monomers;

(3) crosslinking units derived from at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker; and

(4) optionally hydrophobic units derived from at least one hydrophobic vinylic monomer, wherein the prepolymer comprises multiple ethylenically unsaturated groups and is capable of being actinically crosslinked, in the absence of one or more monomers, to form a silicone hydrogel material.

2. The prepolymer of claim 1, wherein the dangling polysiloxane units is present in the prepolymer in an amount sufficient to provide the silicone hydrogel lens with a reduction in modulus of at least about 10% or more and/or with an increase in ion permeability of at least about 20% or more.

3. The prepolymer of claim 1, wherein the dangling polysiloxane units is present in the prepolymer in an amount sufficient to provide the silicone hydrogel lens with a reduction in modulus of at least about 30% or more and/or with an increase in ion permeability of at least about 60% or more.

4. The prepolymer of claim 2, wherein the prepolymer is obtained from an intermediary copolymer with pendant or terminal functional groups and dangling hydrophilic polymer chains by covalently attaching actinically crosslinkable groups to the intermediary copolymer through the pendant or terminal functional groups, wherein the pendant or terminal functional groups are selected from the group consisting of hydroxy groups, amino groups (—

NH₂), carboxyl groups (—

COOH), epoxy groups, aldehyde groups (—

CHO), amide groups (—

CONH₂), acid halide groups (—

COX, X═

Cl, Br, or I), isothiocyanate groups, isocyanate groups, halide groups (—

X, X═

Cl, Br, or I), acid anhydride groups, and combinations thereof.

5. The prepolymer of claim 4, wherein the intermediary copolymer is obtained by copolymerization of an actinically polymerizable composition A or B, wherein the composition A comprises the components of:

(1) at least one monoethylenically functionalized polysiloxane-containing monomer and/or at least one monoethylenically unsaturated polysiloxane-containing macromer,

(2) at least one hydrophilic vinylic monomer,

(3) at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker, and

(4) optionally at least one hydrophobic vinylic monomer, provided that at least one of components (2)-(4) further comprises at least one functional group through which an ethylenically unsaturated group can be covalently linked to the obtained intermediary copolymer,

wherein the composition B comprises the components of;

(1) at least one monoethylenically functionalized polysiloxane-containing monomer and/or at least one monoethylenically unsaturated polysiloxane-containing macromer,

(2) at least one hydrophilic vinylic monomer,

(3) at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker,

(4) optionally at least one hydrophobic vinylic monomer, and

(5) at least one chain transfer agent having a functional group through which an ethylenically unsaturated group can be covalently linked to the obtained intermediary copolymer.

6. The prepolymer of claim 5, wherein the at least one monoethylenically functionalized polysiloxane-containing monomer and the at least one monoethylenically unsaturated polysiloxane-containing macromer independently of each other are defined by

7. The prepolymer of claim 6, wherein the at least one hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, allyl alcohol, vinylpyridine, N-(1,1dimethyl-3-oxobutyl)acrylamide, 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 combinations thereof.

8. The prepolymer of claim 7, wherein the polymerizable composition A or B further comprises at least one silicone-containing vinylic monomer.

9. The prepolymer of claim 6, wherein the at least one silicone-containing vinylic monomer is selected from the group consisting of 3-methacryloxy propylpentamethyldisiloxane, bis(methacryloxypropyl)tetramethyl-disiloxane, N-[tris(trimethylsiloxy)silylpropyl]-acrylamide, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, and tris(trimethylsilyloxy)silylpropylmethacrylate, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, (3-methacryloxy-2-hydroxypropyloxy)-propylbis(trimethylsiloxy)methylsilane, (3-methacryloxy-2-hydroxypropyloxy)propyl-tris(trimethylsiloxy)silane, (3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propyl-bis(trimethylsiloxy)methylsilane, N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane, 3-(trimethylsilyl)propyl vinyl 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-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

10. The prepolymer of claim 8, wherein intermediary copolymer comprises:

(1) from about 2% to about 70% by weight of dangling polysiloxane units derived from one or more monoethylenically functionalized polysiloxane-containing monomers and/or macromers;

(2) from about 10% to about 70% by weight of hydrophilic units derived from one or more hydrophilic monomers;

(3) from 0 to about 70% by weight of crosslinking polysiloxane units derived from a polysiloxane-containing crosslinker;

(4) from 0 to about 5% by weight of silicone-free crosslinker; and

(5) from about 0 to about 35% by weight of silicone-containing units derived from one or more silicone-containing vinylic monomers.

11. 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 at least one actinically crosslinkable prepolymer and is substantially free of vinylic monomers and crosslinking agent with molecular weight of less than 1500 dalton, wherein the prepolymer comprises (1) dangling polysiloxane units derived from one or more monoethylenically functionalized polysiloxane-containing monomers and/or one or more monoethylenically-functionalized polysiloxane-containing macromers, wherein the dangling polysiloxane units is free of ethylenically unsaturated groups;

(2) hydrophilic units derived from one or more hydrophilic vinylic monomers;

(3) crosslinking units derived from at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker;

(4) multiple ethylenically unsaturated groups; and

(5) optionally hydrophobic units derived from at least one hydrophobic vinylic monomer.

12. The contact lens of claim 11, wherein the soft contact lens has at least one of lens property selected from the group consisting of:

an elastic modulus of about 1.2 MPa or less;

an oxygen permeability of at least about 40 barrers;

an Ionoflux Diffusion Coefficient, D, of at least about 1.5×

10<sup>−

6</sup> mm²/min;

a water content of from about 15% to about 55% when fully hydrated, and a combination thereof.

13. The contact lens of claim 12, wherein the at least one actinically crosslinkable prepolymer is previously purified by precipitation with organic solvents, filtration and washing, extraction in a suitable solvent, dialysis, or ultrafiltration.

14. The contact lens of claim 12, wherein the dangling polysiloxane units is present in the prepolymer in an amount sufficient to provide the contact lens with a reduction in modulus of at least about 10% or more and/or with an increase in ion permeability of at least about 20% or more.

15. The contact lens of claim 14, wherein the intermediary copolymer is obtained by copolymerization of an actinically polymerizable composition A or B, wherein the composition A comprises the components of:

(1) at least one monoethylenically functionalized polysiloxane-containing monomer and/or at least one monoethylenically unsaturated polysiloxane-containing macromer,

(2) at least one hydrophilic vinylic monomer,

(3) at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker, and

(4) optionally at least one hydrophobic vinylic monomer, provided that at least one of components (2)-(4) further comprises at least one functional group through which an ethylenically unsaturated group can be covalently linked to the obtained intermediary copolymer,

wherein the composition B comprises the components of;

(1) at least one monoethylenically functionalized polysiloxane-containing monomer and/or at least one monoethylenically unsaturated polysiloxane-containing macromer,

(2) at least one hydrophilic vinylic monomer,

(3) at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker,

(4) optionally at least one hydrophobic vinylic monomer, and

(5) at least one chain transfer agent having a functional group through which an ethylenically unsaturated group can be covalently linked to the obtained intermediary copolymer.

16. The contact lens of claim 15, wherein the at least one monoethylenically functionalized polysiloxane-containing monomer and the at least one monoethylenically unsaturated polysiloxane-containing macromer independently of each other are defined by

17. The contact lens of claim 16, wherein the at least one hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, Aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, allyl alcohol, vinylpyridine, N-(1,1dimethyl-3-oxobutyl)acrylamide, 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 combinations thereof.

18. The contact lens of claim 17, wherein the polymerizable composition A or B further comprises at least one silicone-containing vinylic monomer selected from the group consisting of 3-methacryloxy propylpentamethyidisiloxane, bis(methacryloxypropyl)-tetramethyldisiloxane, N-[tris(trimethylsiloxy)silylpropyl]-acrylamide, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, and tris(trimethylsilyloxy)silylpropyl-methacrylate, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, (3-methacryloxy-2-hydroxypropyloxy)-propylbis(trimethylsiloxy)methylsilane, (3-methacryloxy-2-hydroxypropyloxy)propyl-tris(trimethylsiloxy)silane, (3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propyl-bis(trimethylsiloxy)methylsilane, N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane, 3-(trimethylsilyl)propyl vinyl 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-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

19. The contact lens of claim 18, wherein intermediary copolymer comprises:

(1) from about 2% to about 70% by weight of dangling polysiloxane units derived from one or more monoethylenically functionalized polysiloxane-containing monomers and/or macromers;

(2) from about 10% to about 70% by weight of hydrophilic units derived from one or more hydrophilic monomers;

(3) from 0 to about 70% by weight of crosslinking polysiloxane units derived from a polysiloxane-containing crosslinker;

(4) from 0 to about 5% by weight of silicone-free crosslinker; and

(5) from 0 to about 35% by weight of silicone-containing units derived from one or more silicone-containing vinylic monomers.

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

a). 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;

b). introduce a lens-forming material into the cavity, wherein the lens-forming material comprises one or more actinically crosslinkable prepolymers and is substantially free of vinylic monomer and/or crosslinking agent, wherein each of said one or more prepolymers comprises in the branched copolymer chains

(1) dangling polysiloxane units derived from one or more monoethylenically functionalized polysiloxane-containing monomers and/or one or more monoethylenically-functionalized polysiloxane-containing macromers, wherein the dangling polysiloxane units is free of ethylenically unsaturated groups,

(2) hydrophilic units derived from one or more hydrophilic vinylic monomers,

(3) crosslinking units derived from at least one polysiloxane-containing crosslinker and/or at least one silicone-free crosslinker,

(4) multiple ethylenically unsaturated groups, and

(5) optionally hydrophobic units derived from at least one hydrophobic vinylic monomer; and

c). actinically irradiating the composition in the mold to crosslink said one or more crosslinkable prepolymers to form the contact lens.