Silicone contact lens-forming prepolymer and silicone contact lens formed therefrom

Abstract

A silicone contact lens-forming prepolymer includes a reaction product of (a) a copolymerization product of a polymerization composition containing (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

Description

SILICONE CONTACT LENS-FORMING PREPOLYMER AND SILICONE CONTACT LENS FORMED THEREFROMPRIORITY CLAIM

[0001] The present application claims priority to U.S. Provisional Patent Application Serial No. 63 / 632,639, entitled “Silicone Contact Lens-Forming Prepolymer and Silicone Contact Lens Formed Therefrom,” filed April 11, 2024, the content of which is incorporated by reference herein in its entirety.BACKGROUND

[0002] Contact lenses made from, for example, silicone-containing materials, have been investigated for a number of years. Such materials can generally be subdivided into two major classes, namely hydrogels and non-hydrogels. Hydrogels can absorb and retain water in an equilibrium state, whereas non-hydrogels do not absorb appreciable amounts of water. Regardless of their water content, both hydrogel and non-hydrogel silicone medical devices tend to have relatively hydrophobic, non-wettable surfaces that have a high affinity for lipids. This problem is of particular concern with contact lenses.

[0003] It is well known that sunlight may damage the human eye, especially in connection with the formation of cataracts and age-related macular degeneration which can lead to loss of vision. To minimize ultraviolet (UV) light damage to the eyes, a subject can wear eye glasses or contact lenses that are protective against peripheral radiation. The degree of blocking however depends on the type of lens and the design of the sunglasses. Most styles of sunglasses do not offer complete protection from UV radiation, thereby allowing UV light to reach the eyes around the frames of the eyeglasses. By wearing UV blocking contact lenses, which cover the entire cornea, UV protection from all angles can be obtained.

[0004] In the fraction of sunlight, the long wave and near ultraviolet (UVA and UVB) range are most concerned, which are characterized by wavelengths of 280 to 380 nanometers (nm). The U.S. Food and Drug administration (FDA) has established standards for UV blocking contact lenses based on American National Standards Institute (ANSI) standards. In particular, the FDA classifies UV blocking contact lenses into two categories, Class I and Class II, depending on the extent of the protection. Class I contact lenses must block more than 90% of UVA i.e., 316 to 380 nm for UVA, and 99% of UVB, i.e., 280 to 315 nm, radiation. Class II lenses must block more than 50% of UVA and 95% of UVB radiation. Although UVAradiation corresponds to the wavelength range of 316 to 400 nm, only wavelengths from 316 to 380 nm are considered for classification of a contact lens.SUMMARY

[0005] In accordance with an illustrative embodiment, a silicone contact lens-forming prepolymer comprises a reaction product of (a) a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0006] In accordance with another illustrative embodiment, a silicone contact lens comprises a polymerization product of a silicone contact lens-forming mixture comprising a silicone contact lens-forming prepolymer comprising a reaction product of (a) a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0007] In accordance with yet another illustrative embodiment, a method for making a silicone contact lens comprises:

[0008] (a) subjecting a silicone contact lens-forming mixture comprising a silicone contact lens-forming prepolymer comprising a reaction product of (i) a copolymerization product of a polymerization composition comprising (1) an alkylacrylamide monomer, (2) a hydroxyethyl acrylate monomer, (3) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (4) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (ii) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group to polymerization conditions to provide a polymerized silicone contact lens, and

[0009] (b) hydrating the polymerized silicone contact lens.DETAILED DESCRIPTION

[0010] Various illustrative embodiments described herein include a silicone contact lens-forming prepolymer and silicone contact lenses made therefrom.

[0011] DEFINITIONS

[0012] To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.

[0013] A “prepolymer” refers to a starting polymer which can be cured (e.g., crosslinked and / or polymerized) actinically or thermally or chemically to obtain a crosslinked and / or polymerized polymer having a molecular weight higher than the molecular weight of the starting polymer.

[0014] A “crosslinkable prepolymer” refers to a starting polymer which can be crosslinked to obtain a crosslinked polymer having a molecular weight higher than the molecular weight of the starting polymer.

[0015] While compositions and processes are described in terms of “comprising” various components or steps, the compositions and processes can also “consist essentially of’ or “consist of’ the various components or steps, unless stated otherwise.

[0016] The terms “a,” “an,” and “the” are intended to include plural alternatives, e.g., at least one. The terms “including,” “with,” and “having,” as used herein, are defined as comprising (i.e., open language), unless specified otherwise.

[0017] Various numerical ranges are disclosed herein. When Applicant discloses or claims a range of any type, Applicant’s intent is to disclose or claim individually each possible number that such a range could reasonably encompass, including end points of the range as well as any sub-ranges and combinations of sub-ranges encompassed therein, unless otherwise specified. For example, all numerical end points of ranges disclosed herein are approximate, unless excluded by proviso.

[0018] Values or ranges may be expressed herein as “about,” from “about” one particular value, and / or to “about” another particular value. When such values or ranges are expressed, other embodiments disclosed include the specific value recited, from the one particular value, and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that there are a number of values disclosed therein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. In another aspect, use of the term “about” means ±20% of the stated value, ±15% of the stated value, ±10% of the stated value, ±5% of the stated value, ±3% of the stated value, or ±1% of the stated value.

[0019] Applicant reserves the right to proviso out or exclude any individual members of any such group of values or ranges, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed according to a range or in any similar manner, if for any reason Applicant chooses to claim less than the full measure of the disclosure, for example, to account for a reference that Applicant may be unaware of at the time of the filing of the application. Further, Applicant reserves the right to proviso out or exclude any members of a claimed group.

[0020] In the field of contact lenses, various physical and chemical properties such as, for example, oxygen permeability, wettability, material strength and stability, are but a few of the factors that must be carefully balanced in order to provide a useable contact lens. For example, oxygen permeability is a desirable property for contact lens materials since the human cornea will be damaged if it is deprived of oxygen for an extended period. Oxygen permeability is conventionally expressed in units of Barrer, and also called Dk. Oxygen transmissibility is a property of contact lens materials related to oxygen permeability where oxygen permeability is divided by lens thickness, or Dk / t. Wettability also is important in that, if the lens is not sufficiently wettable, it does not remain lubricated and therefore cannot be worn comfortably in the eye. A challenge in developing improved silicone contact lenses is that attempting to increase oxygen permeability can compromise other desired properties of the material, such as machinability or optical clarity.

[0021] In addition, as mentioned above, it is well known that sunlight may damage the human eye, especially in connection with the formation of cataracts and age-related macular degeneration which can lead to loss of vision. To minimize UV damage to the eyes, a subject can wear eyeglasses or contact lenses that are protective against peripheral radiation. Bywearing UV blocking contact lenses, which cover the entire cornea, UV protection from all angles can be obtained.

[0022] The major challenges in preparing a contact lens loaded with a UV blocker include, for example, preparing the lens with short curing times at reasonable light intensities to avoid any undesired side reactions, maintaining the optical clarity and uniformity of the lens and the UV blocker over the entire area of the lens, and avoiding any leaching of the UV blocker from the lens.

[0023] The non-limiting illustrative embodiments disclosed herein overcome the foregoing drawbacks by providing a silicone contact lens-forming prepolymer for making silicone contact lenses that are optically clear and exhibit suitable physical and chemical properties, e.g., oxygen permeability, lubriciousness and wettability, for prolonged contact with the body. In addition, the silicone contact lens-forming prepolymer can further include monomeric units derived from a UV blocker and optionally a blue light blocker such that the silicone contact lenses contain the UV blocker covalently attached over the entire area of the contact lens thereby avoiding any leaching of the UV blocker from the lens.

[0024] As used herein, the term “contact lens” refers to contact lenses that reside in or on the eye. These lenses can provide optical correction, wound care, drug delivery, diagnostic functionality or cosmetic enhancement or effect or a combination of these properties. Suitable contact lenses include, for example, contact lenses such as soft contact lenses, e.g., a soft, hydrogel lens; soft, non-hydrogel lens and the like, hard contact lenses, e.g., a hard, gas permeable lens material, a hybrid lens and the like. A contact lens can be in a dry state or a wet state. A “dry state” refers to a soft contact lens in a state prior to hydration or the state of a hard lens under storage or use conditions. A “wet state” refers to a soft contact lens in a hydrated state. As is understood by one skilled in the art, a contact lens is considered to be “soft” if it can be folded back upon itself without breaking.

[0025] In non-limiting illustrative embodiments, a silicone contact lens-forming prepolymer comprises a reaction product of (a) a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0026] In some embodiments, an alkylacrylamide monomer for use in the polymerization composition includes, for example, N,N-dimethylacrylamide, N,N- dimethylmethacrylamide, and the like.

[0027] In some embodiments, the polymerization composition can contain from about 20 wt. % to about 60 wt. %, based on the total weight of the polymerization composition, of the alkylacrylamide monomer. In some embodiments, the polymerization composition can contain from about 40 wt. % to about 45 wt. %, based on the total weight of the polymerization composition, of the alkylacrylamide monomer.

[0028] In some embodiments, a hydroxyethyl acrylate monomer for use in the polymerization composition is represented by the following structure:

[0029] In some embodiments, the polymerization composition can contain from about 0.01 wt. % to about 40 wt. %, based on the total weight of the polymerization composition, of the hydroxyethyl acrylate monomer. In some embodiments, the polymerization composition can contain from about 20 wt. % to about 30 wt. %, based on the total weight of the polymerization composition, of the hydroxyethyl acrylate monomer.

[0030] The polymerization composition further includes a non-bulky organosilicon- containing monomer having an ethylenically unsaturated reactive end group. An “organosilicon-containing monomer” as used herein contains at least one [siloxanyl] or at least one [silyl-alkyl-siloxanyl] repeating unit, in a monomer, macromer or prepolymer. In an illustrative embodiment, an example of a non-bulky organosilicon-containing monomers is represented by a structure of Formula la:

[0031] wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9are independently hydrogen, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenylgroup, or an aryl group; R10and R11are independently hydrogen or an alkyl group wherein at least one of R10and R11is hydrogen; y is 2 to 7 and n is 1 to 100 or from 1 to 20.

[0032] Ethylenically unsaturated polymerizable groups are well known to those skilled in the art. Suitable ethylenically unsaturated polymerizable groups include, for example, (meth)acrylates, vinyl carbonates, O-vinyl carbamates, N-vinyl carbamates, and (meth)acrylamides.

[0033] Linking groups can be any divalent radical or moiety and include, for example, a substituted or unsubstituted Ci to C12 alkyl group, an alkyl ether group, an alkenyl group, an alkenyl ether group, a halo alkyl group, a substituted or unsubstituted siloxane group, and monomers capable of propagating ring opening.

[0034] In one embodiment, V is a (meth)acrylate, L is a Ci to C12 alkylene group, R1,R2, R3, R4, R5, R6, R7, R8, and R9are independently a Ci to C12 alkyl group, R10and R11are independently H or a Ci to C12 alkyl group, y is 2 to 7 and n is 3 to 8.

[0035] In one embodiment, V is a (meth)acrylate, L is a Ci to Ce alkyl group, R1, R2,R3, R4, R5, R6, R7, R8, and R9are independently a Ci to Ce alkyl group, R10and R11are independently H or a Ci to Ce alkyl group, y is 2 to 7 and n is 1 to 20.

[0036] Non-bulky organosilicon-containing monomers represented by a structure of Formula la are known in the art, see, e.g., U.S. Patent Nos. 7,915,323, 7,994,356, 8,420,711, 8,827,447 and 9,039,174, the contents of which are incorporated by reference herein.

[0037] In an illustrative embodiment, as may be combined with one or more of the preceding paragraphs, an example of a non-bulky organosilicon-containing monomer is represented by a structure of Formula lb:

[0038] wherein R12is H or methyl; X is O or NR16; wherein R16is selected from H, or Ci to C4 alkyl, which may be further substituted with one or more hydroxyl groups, and in some embodiments is H or methyl; R13is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of ether groups, hydroxyl groups, carbamate groups and combinations thereof, and in another embodiment a Ci to Ce alkylene group which may be substituted with ether, hydroxyl and combinations thereof, and in yet another embodiment a Ci or C3 to C4 alkylene group which may be substituted withether, hydroxyl and combinations thereof; each R14is independently a phenyl or a Ci to C4 alkyl group which may be substituted with fluorine, hydroxyl or ether, and in another embodiment each R14is independently selected from ethyl and methyl groups, and in yet another embodiment, each R14is methyl; R15is a Ci to C4 alkyl group; a is 2 to 50, and in some embodiments 5 to 15.

[0039] Non-bulky organosilicon-containing monomers represented by a structure of Formula lb are known in the art, see, e.g., U.S. Patent Nos. 8,703,891, 8,937,110, 8,937,111, 9,156,934 and 9,244,197, the contents of which are incorporated by reference herein.

[0040] Representative examples of non-bulky organosilicon-containing monomers for use herein include:

[0041] M1EDS6: a compound having the structure and available from Gelest:

[0042] MCR-M1 1 : a compound having the structure:

[0043] M1-MCR-C12: a compound having the structure:wherein n is an average of 12.

[0044] In some embodiments, the polymerization composition can contain from about 0.10 wt. % to about 30 wt. %, based on the total weight of the polymerization composition, of a non-bulky organosilicon-containing monomer. In some embodiments, the polymerizationcomposition can contain from about 5 wt. % to about 15 wt. %, based on the total weight of the polymerization composition, of a non-bulky organosilicon-containing monomer.

[0045] The polymerization composition further includes a bulky siloxane monomer having an ethylenically unsaturated reactive end group. The term “bulky” refers to groups on the siloxane monomer that are sterically and / or electronically encumbering, i.e., sterically hindering. In a non-limiting illustrative embodiment, suitable bulky siloxane monomers include, for example, a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof. In one embodiment, a representative example of a bulky siloxane monomer is represented by a structure of Formula II:

[0046] wherein X denotes -O- or -NR19-, where each R19is hydrogen or a C1-C4 alkyl group; R17independently denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical such as a Ci-Ce group, a phenyl radical or a group represented by the following structure:R18— Si— R18R18'

[0047] wherein each R18' independently denotes a lower alkyl radical such as a Ci-Ce group or a phenyl radical; and h is 1 to 10; or is represented by a structure of Formula III:

[0048] wherein X denotes -NR19- wherein R19denotes hydrogen or a C1-C4 alkyl; R17denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical such as a Ci-Ce group, a phenyl radical or a group represented by the following structure:R18— Si— R18R18'

[0049] wherein each R18' independently denotes a lower alkyl radical such as a Ci-Ce group or a phenyl radical; and h is 1 to 10.

[0050] Representative examples of bulky siloxane monomers include 3- methacryloyloxypropyltris(trimethylsiloxy)silane or tris(trimethylsiloxy)silylpropyl methacrylate, sometimes referred to as TRIS and tris(trimethylsiloxy)silylpropyl vinyl carbamate, sometimes referred to as TRIS-VC, pentamethyldisiloxanyl methylmethacrylate, phenyltetramethyl-disiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane, (3 -methacryloxy -2 -hydroxy propoxy )propyl bis(trimethyl siloxy)methyl silane, sometimes referred to as Sigma and the like and mixtures thereof. In one embodiment, the bulky siloxane monomer is a tris(trialkylsiloxy)silylalkyl methacrylate-containing monomer such as a tris(trimethylsiloxy)silylpropyl methacrylate-containing monomer.

[0051] Such bulky monomers may be copolymerized with a silicone macromonomer, which is a poly(organosiloxane) capped with an unsaturated group at two or more ends of the molecule. U.S. Patent No. 4,153,641 discloses, for example, various unsaturated groups such as acryloxy or methacryloxy groups.

[0052] In some embodiments, the polymerization composition can contain from about 5 wt. % to about 30 wt. %, based on the total weight of the polymerization composition, of abulky siloxane monomer. In some embodiments, the polymerization composition can contain from about 15 wt. % to about 25 wt. %, based on the total weight of the polymerization composition, of a bulky siloxane monomer.

[0053] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the polymerization composition can further include an ultraviolet (UV) blocker having an ethylenically unsaturated reactive group. Suitable UV blockers having an ethylenically unsaturated reactive group can be any known UV blocker having an ethylenically unsaturated reactive group. In some embodiments, a UV blocker for use herein can include a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups. In a non-limiting illustrative embodiment, a UV blocker comprising a phenolic group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups can be represented by a benzotriazole compound having a structure of Formula IV:wherein each R is independently hydrogen, a halogen, an -O- group, a nitro group, a nitrile group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted carbonyl group, and a substituted or unsubstituted hydrocarbyl group, R* is hydrogen or a substituted or unsubstituted hydrocarbyl group, and R** is an ethylenically unsaturated reactive group.

[0054] As used herein, recitations of “substituted” group, means a group such as an alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, and / or heteroaryl group, in which at least one hydrogen atom thereof has been optionally replaced or substituted with a group that is other than hydrogen, such as, for example, halo groups (e.g., F, Cl, I, and Br), hydroxyl groups, ether groups, thiol groups, thio ether groups, carboxylic acid groups, carboxylic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g., alkyl; alkenyl; alkynyl; cycloalkyl, including poly-fused-ring cycloalkyl and polycyclocalkyl; heterocycloalkyl; aryl, including hydroxyl substituted aryl, such as phenol, and including poly-fused-ring aryl; heteroaryl, including poly-fused-ring heteroaryl; and aralkyl groups), and amine groups.

[0055] As used herein, recitations of “linear or branched” groups, such as linear or branched alkyl, are herein understood to include, for example, groups that are linear, such as linear C2 to C30 alkyl groups; and groups that are appropriately branched, such as branched C3 to C30 alkyl groups.

[0056] Representative examples of halogen groups include, by way of example, Cl, I, F, and Br.

[0057] Representative examples of hydrocarbyl groups include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups (including polycyclic aryl groups), heteroaryl groups (having at least one hetero atom in the aromatic ring); and aralkyl groups as defined herein.

[0058] Representative examples of alkoxy groups for use herein include, by way of example, an alkyl group as defined herein attached via oxygen linkage to the rest of the molecule, i.e., of the general formula -OR1, wherein R1is an alkyl, cycloalkyl, or aromatic group as defined herein, e.g., -OCH3, -OC2H5, or -OCeHs which may be substituted or unsubstituted, and the like.

[0059] Representative examples of alkyl groups for use herein include, by way of example, a linear or branched hydrocarbon chain radical containing carbon and hydrogen atoms of from 1 to about 30 carbon atoms or from 1 to 12 carbon atoms or from 1 to 6 carbon atoms with or without unsaturation, to the rest of the molecule, e.g., methyl, ethyl, n-propyl, 1- methylethyl (isopropyl), n-butyl, n-pentyl, etc., and the like.

[0060] Representative examples of alkenyl groups for use herein include, by way of example, a straight or branched hydrocarbon chain radical containing from about 3 to about 30 carbon atoms with at least one carbon-carbon double bond such as, for example, propenyl, butenyl, pentenyl and the like.

[0061] Representative examples of alkynyl groups for use herein include, by way of example, a straight or branched hydrocarbon chain radical containing from about 3 to about 30 carbon atoms with at least one carbon-carbon triple bond such as, for example, propynyl, butynyl, pentynyl and the like.

[0062] Representative examples of cycloalkyl groups for use herein include, by way of example, a substituted or unsubstituted non-aromatic mono or multicyclic ring system of about3 to about 30 carbon atoms or from 3 to 12 carbon atoms or from 3 to 6 carbon atoms such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronapththyl, adamantyl and norbornyl groups bridged cyclic group or sprirobicyclic groups, e.g., sprio-(4, 4)-non-2-yl and the like, optionally containing one or more heteroatoms, e.g., O and N, and the like.

[0063] Representative examples of heterocyclic groups for use herein include, by way of example, a substituted or unsubstituted stable 3 to about 15 membered ring radical, containing carbon atoms and from one to five heteroatoms, e.g., nitrogen, phosphorus, oxygen, sulfur and mixtures thereof. Suitable heterocyclic ring radicals for use herein may be a monocyclic, bicyclic or tricyclic ring system, which may include fused, bridged or spiro ring systems, and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in the heterocyclic ring radical may be optionally oxidized to various oxidation states. Examples of such heterocyclic groups include, but are not limited to, azetidinyl, acridinyl, benzodi oxolyl, benzodi oxanyl, benzofurnyl, carbazolyl, cinnolinyl, dioxolanyl, indolizinyl, naphthyridinyl, perhydroazepinyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pyridyl, pteridinyl, purinyl, quinazolinyl, quinoxalinyl, quinolinyl, isoquinolinyl, tetrazoyl, imidazolyl, tetrahydroisouinolyl, piperidinyl, piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2- oxopyrrolidinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolinyl, oxasolidinyl, triazolyl, indanyl, isoxazolyl, isoxasolidinyl, morpholinyl, thiazolyl, thiazolinyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, isoindolyl, indolinyl, isoindolinyl, octahydroindolyl, octahydroisoindolyl, quinolyl, isoquinolyl, decahydroisoquinolyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, benzooxazolyl, furyl, tetrahydrofurtyl, tetrahydropyranyl, thienyl, benzothienyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfone, dioxaphospholanyl, oxadiazolyl, chromanyl, isochromanyl and the like and mixtures thereof.

[0064] Representative examples of aryl groups for use herein include, by way of example, a substituted or unsubstituted monoaromatic or polyaromatic radical containing from about 5 to about 30 carbon atoms or from 5 to 12 carbon atoms or from 5 to 8 carbon atoms such as, for example, phenyl, naphthyl, tetrahydronapthyl, indenyl, biphenyl and the like, optionally containing one or more heteroatoms, e.g., O and N, and the like.

[0065] Representative examples of heteroaryl groups for use herein include, by way of example, a substituted or unsubstituted stable 5 to about 30 membered monoaromatic orpolyaromatic radical, containing carbon atoms and from one to five heteroatoms, e.g., nitrogen, phosphorus, oxygen, sulfur and mixtures thereof.

[0066] Representative examples of fused ring polycyclic-aryl-alkyl groups and similar terms such as, fused ring polycyclic-alkyl-aryl groups, fused ring polycyclo-aryl-alkyl groups, and fused ring polycyclo-alkyl-aryl groups means a fused ring polycyclic group that includes at least one aryl ring and at least one cycloalkyl ring that are fused together to form a fused ring structure. For purposes of non-limiting illustration, examples of fused ring polycyclic-aryl- alkyl groups include, but are not limited to indenyl, 9H-flourenyl, cyclopentanaphthenyl, and indacenyl.

[0067] Representative examples of aralkyl groups as used herein, and in accordance with some embodiments, include, but are not limited to, Ce to C24 aralkyl, such as a Ce to C10 aralkyl, and means an aryl group substituted with an alkyl group.

[0068] Representative examples of amine groups for use herein include, by way of example, an amine of the general formula -R2NR3R4wherein R2, R3and R4are independently hydrogen or a C1-C30 hydrocarbon such as, for example, alkyl groups, aromatic groups, or cycloalkyl groups as defined herein, and the like.

[0069] The term “carbonyl group” as used herein is a divalent group of the formula - C(=O).

[0070] Representative examples of ethylenically unsaturated reactive groups for use herein include, by way of example, a (meth)acrylate-containing reactive end group, a (meth)acrylamide-containing reactive end group, an allyl-containing reactive end group, a vinyl-containing reactive end group, a vinylcarbonate-containing reactive end group, a vinylcarbamate-containing reactive end group, a styrene-containing reactive end group, an itaconate-containing reactive end group, a vinyloxy-containing reactive end group, a fumarate- containing reactive end group, a maleimide-containing reactive end group, a vinylsulfonyl reactive end group and the like.

[0071] In a non-limiting illustrative embodiment, a (meth)acrylate-containing reactive end group can be represented by the structure:wherein L is a linking group or bond. Suitable linking groups include, for example, a heteroatom such as O, any divalent hydrocarbon radical or moiety such as independently astraight or branched, substituted or unsubstituted Ci-Ce alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C4-C12 cycloalkylalkyl group, a substituted or unsubstituted C3-C12 cycloalkenyl group, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C7-C12 arylalkyl group and substituted and unsubstituted ether-containing groups.

[0072] In an illustrative embodiment, R and R* are each hydrogen and R** is a (meth)acrylate-containing reactive end group.

[0073] In another illustrative embodiment, as may be combined with one or more of the preceding paragraphs, R** is positioned on the aromatic ring in the para position relative to the OH moiety.

[0074] The foregoing UV blockers for use herein are known and either commercially available from such sources as, for example, Aldrich, Polysciences, Gelest, and Melrob, or can be made by methods within the purview of one skilled in the art.

[0075] Representative examples of suitable UV blockers include 2-(2 ’-hydroxy-3 methallyl-5’-methylphenyl)benzotriazole, commercially available as o-Methallyl Tinuvin P (“oMTP”) from Polysciences, Inc., Warrington, Pa., 3-(2H-benzo[d][l,2,3]triazol-2-yl)-4- hydroxyphenylethyl methacrylate, and 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H- benzo[d][l,2,3]triazol-2-yl)phenoxy)ethyl methacrylate.

[0076] In one illustrative embodiment, suitable UV blockers include, for example, one or more compounds of the following formulae:(2-Propenoic acid, 2-m ethyl, 2-(4-benzoyl-3 -hydroxyphenoxy)- l-[(4-benzoyl3- hydroxyphenoxy)methyl ester),

[0077] The foregoing UV blockers are merely illustrative and not intended to be limiting. Any known UV blocker comprising a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups or later developed UV blocker comprising a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups are contemplated for use herein.

[0078] In some embodiments, the polymerization composition can contain from about 0.1 wt. % to about 5 wt. %, based on the total weight of the polymerization composition, of a UV blocker. In some embodiments, the polymerization composition can contain from about 0.5 wt. % to about 1.5 wt. %, based on the total weight of the polymerization composition, of a UV blocker.

[0079] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the polymerization composition can further include one or more blue-light blockers having an ethylenically unsaturated reactive group. Many reactive bluelight absorbing compounds are known, see, e.g., the reactive blue-light absorbing compounds described in U.S. Pat. Nos. 5,470,932; 8,207,244; and 8,329,775, the contents of which are hereby incorporated by reference.

[0080] In non-limiting illustrative embodiments, a class of blue light blockers can include a phenolic group comprising a hydroxyl moiety and one or more ethylenically unsaturated reactive groups represented by an acridone compound having a structure of Formula V:wherein R* and R** are as defined above.

[0081] In an illustrative embodiment, R* is hydrogen and R** is a (meth)acrylate- containing reactive end group as defined above.

[0082] In some embodiments, R** is positioned on the aromatic ring in the para position relative to the OH moiety.

[0083] The foregoing blue light blockers for use herein are known and either commercially available from such sources as, for example, Vishwa-Syntharo PharmaCompany, or can be made by methods within the purview of one skilled in the art.

[0084] The foregoing one or more blue light blockers comprising a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups are merely illustrative and not intended to be limiting. Any known blue light blockers comprising a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups or later developed blue light blockers comprising a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups are contemplated for use herein.

[0085] In some embodiments, a blue-light blocker is N-2-[3-(2’-methylphenylazo)-4- hy dr oxy phenyl ] ethyl methacryl ami de .

[0086] In some embodiments, the blue-light absorbers can be present in the polymerization composition in an amount ranging from about 0.005 to about 1 wt. %, based on the total weight of the polymerization composition. In another illustrative embodiment, the blue-light absorbers can be present in the polymerization composition in an amount ranging from about 0.01 wt. % to about 1 wt. %, based on the total weight of the polymerization composition.

[0087] In an illustrative embodiment, as may be combined with one or more of the preceding paragraphs, a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and optionally (v) an ultraviolet blocker having an ethylenically unsaturated reactive group and / or (vi) a blue-light blocker having an ethylenically unsaturated reactive group can be prepared using free radical polymerization techniques with the structure of the polymer being completely random or controlled by the reactivity ratios of the respective monomers.

[0088] In some embodiments, a random copolymer can be obtained by (1) mixing the components to obtain a polymerization composition, (2) adding a polymerization initiator to the polymerization composition, and (3) subjecting the monomer / initiator mixture to a source of heat or radiation such as ultraviolet light, visible light, or high energy radiation to obtain a copolymerization product as discussed below. Suitable free radical thermal polymerization initiators include acetyl peroxide, lauroyl peroxide, decanoyl peroxide, coprylyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, sodium percarbonate, tertiary butyl peroctoate, and azobis-isobutyronitrile (AIBN), and the like. Representative UV initiators are those known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocure® 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure® 651 and 184 (Ciba-Geigy), 2,2’Azobis(2- methylpropionitrile) (Vazo 64) and the like. Generally, the initiator will be employed in the mixture at a concentration of about 0.01 to about 5 percent by weight of the total mixture.

[0089] Suitable polymerization conditions include, for example, a temperature of between about 60°C to about 100°C for a time period of about 30 minutes to about 48 hours. If desired, the reaction can be carried out in the presence of a suitable solvent. Suitable solvents are in principle all solvents which dissolve the monomers used including, for example, 1,4- dioxane, hexanol, dimethylformamide; acetone, cyclohexanone, toluene, and the like and mixtures thereof.

[0090] The copolymerization product disclosed herein can also be prepared using techniques of controlled radical polymerization, e.g., by reversible addition-fragmentation chain transfer (RAFT) polymerization or atom-transfer radical polymerization (ATRP) employing a chain transfer agent that allows construction of copolymers with a well-defined molecular weight distribution and narrow polydispersity. RAFT polymerization is particularly preferred because it is compatible with a wide variety of vinyl monomers.

[0091] In non-limiting illustrative embodiments, the RAFT agents suitable for use herein can be based upon thio carbonyl thio chemistry which is well known to those of ordinary skill in the art. The thio carbonyl thio fragment can be derived from a RAFT agent such as, for example, a xanthate-containing compound, trithiocarbonate-containing compound, dithiocarbamate-containing compound, a dithiobenzoate-containing compound or dithio ester- containing compound, wherein each compound contains a thio carbonyl thio group. One class of RAFT agents that can be used herein is of the general formula:wherein x is 1 or 2, Z is a substituted oxygen (e.g., xanthates (-O-R)), a substituted nitrogen (e.g., dithiocarbamates (-NRR)), a substituted sulfur (e.g., trithiocarbonates (-S-R)), a dithiobenzoate, a substituted or unsubstituted C1-C20 alkyl or C3-C25 unsaturated, or partially or fully saturated ring (e.g., dithioesters (-R)) or carboxylic acid-containing group; and R is independently a straight or branched, substituted or unsubstituted C1-C30 alkyl cyano group, a straight or branched, substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkylalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C5-C30 aryl group, a substituted or unsubstituted C5-C30 arylalkyl group, a C1-C20 ester group; an ether or polyether-containing group; an alkyl- or arylamide group; an alkyl- or arylamine group; a substituted or unsubstituted C5-C30 heteroaryl group; a substituted or unsubstituted C3- C30 heterocyclic ring; a substituted or unsubstituted C4-C30 heterocycloalkyl group; a substituted or unsubstituted C6-C30 heteroarylalkyl group; and combinations thereof.

[0092] The substituents in the ‘substituted oxygen’, ‘substituted nitrogen’, ‘substituted sulfur’, ‘substituted alkyl’, ‘substituted alkylene, ‘substituted cycloalkyl’, ‘substituted cycloalkylalkyl’, ‘substituted cycloalkenyl’, ‘substituted arylalkyl’, ‘substituted aryl’, ‘substituted heterocyclic ring’, ‘substituted heteroaryl ring,’ ‘substituted heteroarylalkyl’, ‘substituted heterocycloalkyl ring’, ‘substituted cyclic ring’ may be the same or different and include one or more substituents such as hydrogen, hydroxy, halogen, carboxyl, cyano, nitro, oxo (=0), thio(=S), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted amino, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted heterocycloalkyl ring, substituted or unsubstituted heteroarylalkyl, substituted or unsubstituted heterocyclic ring, and the like.

[0093] Representative examples of RAFT agents for use herein include, but are not limited to, 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(a,a’-dimethyl-alpha”-acetic acid)-trithiocarbonate (BATC), benzyl dodecyl trithiocarbonate, ethyl-2-dodecyl trithiocarbony) proprionate, S-sec propionic acid O- ethyl xanthate, a-ethyl xanthylphenylacetic acid, ethyl a-(o-ethyl xanthyl) proprionate, ethyl a-(ethyl xanthyl) phenyl acetate, ethyl 2-(dodecyl trithiocarbonyl) phenyl acetate, ethyl 2- (dodecyl trithiocarbonyl) propionate, 2-(dodecylthiocarbonylthiol)propanoic acid, and the like and mixtures thereof.

[0094] There is no particular limitation on the organic chemistry used to form the RAFT agent and is within the purview of one skilled in the art.

[0095] The copolymerization product disclosed herein can be obtained in by (1) mixing an alkylacrylamide monomer, a hydroxyethyl acrylate monomer, a non-bulky organosilicon- containing monomer having an ethylenically unsaturated reactive end group, a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and an ultraviolet blocker having an ethylenically unsaturated reactive group with a RAFT agent and a polymerization initiator, and (2) subjecting the monomer / RAFT agent / initiator mixture to a source of heat. Suitable initiators include, for example, free-radical-generating polymerization initiators of the type illustrated by acetyl peroxide, lauroyl peroxide, decanoyl peroxide, coprylyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, sodium percarbonate, tertiary butyl peroctoate, and azobisisobutyronitrile (AIBN).

[0096] The reaction can be carried out at a temperature of between about 50°C to about 80°C for a time period of about 30 minutes to about 48 hours. If desired, the reaction can be carried out in the presence of a suitable solvent. Suitable solvents are in principle all solvents which dissolve the monomer used, for example, 1,4-di oxane, hexanol, dimethylformamide; acetone, cyclohexanone, toluene, and the like and mixtures thereof.

[0097] In an illustrative embodiment, the RAFT procedure is carried using a mixture including (i) from about 2 wt. % to about 40 wt. %, based on the total weight of the mixture, of an alkylacrylamide monomer, (ii) from about 10 wt. % to about 20 wt. %, based on the total weight of the mixture, of a hydroxy ethyl acrylate monomer, (iii) from about 10 wt. % to about 60 wt. %, based on the total weight of the mixture, of a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, (iv) from about 20 wt. % to about 60 wt. %, based on the total weight of the mixture, of a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and (v) from about 0.05 wt. % to about 2 wt.%, based on the total weight of the mixture, of the RAFT agent. The level of initiator employed will vary within the range of 0.01 wt. % to 2 wt. % of the mixture of monomers. In some embodiments, the mixture for the RAFT procedure further includes from about 0.1 wt. % to about 5 wt. %, based on the total weight of the mixture, of an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0098] A non-limiting schematic representation of a synthetic method for making a copolymerization product with a RAFT agent is set forth below in Scheme I below.

[0099] In the case where the copolymerization product disclosed herein is obtained from ATRP polymerization, the ethylenically unsaturated groups may be introduced by appropriate selection of a suitable ATRP initiator or by displacement reactions of the terminal halogen atom. Suitable ATRP groups for use herein include any standard monofunctional or difunctional ATRP group as is well known to those of ordinary skill in the art. A comprehensive review on the use of ATRP initiators or displacement of the terminal halogen using electrophilic, nucleophilic, and radical reactions to produce telechelic polymers is disclosed in, for example, Matyjaszewski, K.; Xia, J. Chem. Rev., 101, 2921-2990 (2001).

[0100] In one embodiment, a useful ATRP group includes an ethylenically unsaturated ATRP initiator such as, for example, vinyl functionalized ATRP initiators, e.g., prop-2-enyl- 2’ -bromoisobutyrate, vinyl chloroacetate, allyl chloroacetate, allyl bromide and the like.

[0101] In another embodiment, a useful ATRP group includes a non-ethylenically unsaturated ATRP initiator that can be converted to an ethylenically unsaturated initiator by a subsequent step. Examples of such initiators include a-bromo-isobutyric acid, hydroxyethyl 2-bromopropionate, glycidol 2-bromopropionate, tert-butyl 2-bromopropionate, and 4- bromobenzyl bromide, and the like.

[0102] In an illustrative embodiment, the copolymerization product is obtained from ATRP polymerization by (1) mixing an alkylacrylamide monomer, a hydroxy ethyl acrylate monomer, a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and optionally an ultraviolet blocker having an ethylenically unsaturated reactive group and / or a blue-light blocker having an ethylenically unsaturated reactive group with, for example, an ATRP initiator and suitable ATRP catalyst such as a copper(I) bromide and (2) subjecting the monomer / ATRP agent / initiator mixture to a source of heat.

[0103] The reaction can be carried out at a temperature of between about 60°C to about 100°C for a time period of about 30 minutes to about 48 hours. If desired, the reaction can be carried out in the presence of a suitable solvent. Suitable solvents are in principle all solvents which dissolve the monomer used, for example, 1,4-di oxane, hexanol, dimethylformamide; acetone, cyclohexanone, toluene, and the like and mixtures thereof.

[0104] In an illustrative embodiment, the ATRP procedure is carried using a mixture including (i) from about 0.1 wt. % to about 20 wt. %, based on the total weight of the mixture, of an alkylacrylamide monomer, (ii) from about 5 wt. % to about 20 wt. %, based on the total weight of the mixture, of a hydroxy ethyl acrylate monomer, (iii) from about 10 wt. % to about 20 wt. %, based on the total weight of the mixture, of a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, (iv) from about 20 wt. % to about 60 wt. %, based on the total weight of the mixture, of a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and (v) from about 0.05 wt. % to about 5 wt. %, based on the total weight of the mixture, of the ATRP initiator. The level of catalyst employed will vary within the range of 0.01 wt. % to 2 wt. % of the mixture of monomers. In some embodiments, the mixture for the ATRP procedure further includes from about 20 to about 40 wt. %, based on the total weight of the mixture, of an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0105] As one skilled in the art will readily appreciate, the copolymerization product disclosed herein can contain a balance of monomeric units derived from an alkylacrylamide monomer, monomeric units derived from a hydroxyethyl acrylate monomer, monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0106] In some embodiments, a copolymerization product can include from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer, from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer, from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group, and optionally from about 1 to about 25 repeating units of monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0107] In one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the copolymerization product is thereafter reacted with a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group to obtain a silicone contact lens-forming prepolymer. The foregoing reaction will result in additional monomeric units derived from the hydroxyethyl acrylate monomer with the hydroxy moiety being reacted with the reactive functionality of the monomer such that the hydroxyethyl acrylate monomer contains an end functionalized group, i.e., a polymerizable ethylenically unsaturated reactive end group which can be complementary to an ethylenically unsaturated reactive group of a contact lens-forming comonomer as discussed below. Suitable polymerizable ethylenically unsaturated reactive end groups can be any of those discussed above.

[0108] In an illustrative embodiment, a polymerizable ethylenically unsaturated reactive end group can be one or more of an acrylate end group and a methacrylate end group.

[0109] Suitable monomers having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group include, for example, 2-isocyanatoethyl acrylate, 3- isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, l-methyl-2-isocyanatoethyl methacrylate, 1,1-dimethy 1 -2-isocyanatoethyl acrylate, (meth)acryloyl chloride, vinyl chloroformate and the like.

[0110] In an illustrative embodiment, the copolymerization product is present in the reaction mixture in an amount ranging from about 10 wt. % to about 90 wt. %, based on the total weight of the reaction mixture. In an illustrative embodiment, the copolymerizationproduct is present in the reaction mixture in an amount ranging from about 50 wt. % to about 80 wt. %, based on the total weight of the reaction mixture.

[0111] In an illustrative embodiment, the monomers having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group is present in the reaction mixture in an amount ranging from about 5 wt. % to about 60 wt. %, based on the total weight of the reaction mixture. In an illustrative embodiment, the monomer having a reactive functionality complementary to one of the one or more reactive functionalities of the hydrophilic monomer and a polymerizable ethylenically unsaturated reactive end group is present in the reaction mixture in an amount ranging from about 10 wt. % to about 20 wt. %, based on the total weight of the reaction mixture.

[0112] The reaction of the copolymerization product and the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group can be carried out in the presence of a catalyst. Suitable catalysts include, for example, the stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, stannous acetate, and stannous laurate, dialkyltin dicarboxylates, such as dibutyltin dilaurate and dibutyltin diacetate which are known in the art as urethane catalysts, as are tertiary amines and tin mercaptides. The amount of catalyst employed is generally between about 0.01 wt. % to about 5 wt. % of the mixture catalyzed.

[0113] The reaction can be carried out at a temperature of between about 60°C to about 100°C for about 2 hours to about 24 hours. The reaction can be carried out in the presence of a suitable solvent as discussed above.

[0114] Accordingly, in a non-limiting illustrative embodiment, a silicone contact lensforming prepolymer disclosed herein comprises:

[0115] (i) monomeric units derived from an alkylacrylamide monomer,

[0116] (ii) monomeric units derived from a hydroxy ethyl acrylate monomer,

[0117] (iii) monomeric units derived from a hydroxy ethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxy ethyl acrylate and a polymerizable ethylenically unsaturated reactive end group,

[0118] (iv) monomeric units derived from a bulky siloxane monomer,

[0119] (v) monomeric units derived from a non-bulky siloxane monomer, and optionally

[0120] (vi) monomeric units derived from an ultraviolet blocker having one or more reactive functionalities.

[0121] In some embodiments, a silicone contact lens-forming prepolymer is a silicone contact lens-forming random copolymer.

[0122] In some embodiments, a silicone contact lens-forming prepolymer disclosed herein includes:

[0123] from about 50 to about 400 repeating units of monomeric units derived from an alkylacrylamide monomer,

[0124] from about 50 to about 200 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer,

[0125] from about 5 to about 20 repeating units of monomeric units derived from a hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group,

[0126] from about 20 to about 300 repeating units of monomeric units derived from a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and

[0127] from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0128] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, a silicone contact lens-forming prepolymer disclosed herein further includes from about 1 to about 25 repeating units of monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0129] In some embodiments, a silicone contact lens-forming prepolymer disclosed herein can have a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons. The weight average molecular weight of the silicone contact lens-forming prepolymer is determined by Gel Permeation Chromatography (GPC).

[0130] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, a silicone contact lens disclosed herein is formed from apolymerization product of a silicone contact lens-forming mixture comprising one or more of the silicone contact lens-forming prepolymer disclosed herein.

[0131] In a non-limiting illustrative embodiment, a silicone contact lens disclosed herein can have an oxygen permeability of at least about 50 Barrers. In some embodiments, a silicone contact lens disclosed herein can have an oxygen permeability of from about 75 Barrers to about 175 Barrers.

[0132] In a non-limiting illustrative embodiment, a silicone contact lens disclosed herein can have an equilibrium water content of at least about 20 wt. %. In another illustrative embodiment, a silicone contact lens can have an equilibrium water content of from about 20 wt. % to about 60 wt. %.

[0133] In some embodiments, a silicone contact lens disclosed herein demonstrates sufficient blocking of UV light to meet both FDA Class I and II specifications for UV blocking. As stated above, Class I contact lenses must block more than 90% of UVA i.e., 316 to 380 nm, radiation and 99% of UVB, i.e., 280 to 315 nm, radiation. Class II contact lenses must block more than 50% of UVA and 95% of UVB radiation.

[0134] In some embodiments, a silicone contact lens-forming prepolymer disclosed herein is present in the silicone contact lens-forming mixture in an amount ranging from about 50 wt. % to about 100 wt. %, based on the total weight of the silicone contact lens-forming mixture. In some embodiments, a silicone contact lens-forming prepolymer disclosed herein is present in the silicone contact lens-forming mixture in an amount ranging from about 60 wt. % to about 80 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0135] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming mixture for forming the silicone contact lens disclosed herein can further contain one or more silicone contact lens-forming monomers. In some embodiments, the one or more silicone contact lens-forming monomers include one or more hydrophilic comonomers. Suitable one or more hydrophilic comonomers include, for example, unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl- containing-(meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups and the like and mixtures thereof.

[0136] As used herein, the term “(meth)” denotes an optional methyl substituent. Thus, terms such as “(meth)acrylate” denotes either methacrylate or acrylate, and“(meth)acrylamide” denotes either methacrylamide or acrylamide.

[0137] Representative examples of unsaturated carboxylic acids include, but are not limited to, methacrylic acid, acrylic acid and the like and mixtures thereof. Representative examples of acrylamides include, but are not limited to, alkylamides such as N,N- dimethylacrylamide, N,N-dimethylmethacrylamide and the like and mixtures thereof. Representative examples of cyclic lactams include, but are not limited to, N-vinyl-2- pyrrolidone, N-vinyl caprolactam, N-vinyl-2-piperidone and the like and mixtures thereof. Representative examples of hydroxyl-containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate and the like and mixtures thereof. Additional device-forming hydrophilic comonomers include, for example, the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Patent No. 5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Patent No. 4,910,277. Other suitable device-forming hydrophilic comonomers will be apparent to one skilled in the art. Mixtures of the foregoing device-forming hydrophilic comonomers can also be used in the monomeric mixtures herein.

[0138] In accordance with one or more additional non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more silicone contact lens-forming monomers such as one or more hydrophilic comonomers can be present in the silicone contact lens-forming mixture in an amount ranging from about 10 wt. % to about 50 wt. %, based on the total weight of the silicone contact lens-forming mixture. In another illustrative embodiment, the one or more silicone contact lens-forming monomers can be present in the silicone contact lens-forming mixture in an amount ranging from about 20 wt. % to about 60 wt. %, based on the total weight of the silicone contact lensforming mixture.

[0139] The silicone contact lens-forming mixture may further include a second silicone contact lens-forming monomer including, for example, a copolymerizable group and a reactive functional group. The copolymerizable group is preferably an ethylenically unsaturated group, such that this silicone contact lens-forming monomer copolymerizes with the hydrophilic monomer and any other silicone contact lens-forming monomers in the initial silicone contact lens-forming mixture. Additionally, the second monomer can include a reactive functional group that reacts with a complementary reactive group of the silicone contact lens-forming prepolymer.

[0140] In an embodiment, reactive groups of the second silicone contact lens-forming monomers include epoxide groups. Accordingly, second silicone contact lens-formingmonomers are those that include both an ethylenically unsaturated group (that permits the monomer to copolymerize with the hydrophilic monomer) and the epoxide group (that does not react with the hydrophilic monomers but remains to react with the silicone contact lensforming prepolymer, e.g., the reaction product of one or more polymerizable polyhydric alcohols and one or more polymerizable fluorine-containing monomers). Suitable second ophthalmic device-forming monomers include, for example, glycidyl methacrylate, glycidyl acrylate, glycidyl vinylcarbonate, glycidyl vinylcarbamate, and 4-vinyl- 1 -cyclohexene- 1,2- epoxide.

[0141] The silicone contact lens-forming mixtures disclosed herein may further contain, as necessary and within limits not to impair the purpose and effect of the illustrative embodiments disclosed herein, various additives such as an antioxidant, coloring agent, toughening agents and the like and other constituents as is well known in the art.

[0142] The silicone contact lenses of the illustrative embodiments can be prepared by polymerizing the foregoing silicone contact lens-forming mixtures to form a product that can be subsequently formed into the appropriate shape by, for example, lathing, injection molding, compression molding, cutting and the like. For example, in producing contact lenses, the initial mixture may be polymerized in tubes to provide rod-shaped articles, which are then cut into buttons. The buttons may then be lathed into contact lenses.

[0143] Alternately, the silicone contact lenses may be cast directly in molds, e.g., polypropylene molds, from the mixtures, e.g., by spincasting and static casting methods. Spincasting methods are disclosed in U.S. Patent Nos. 3,408,429 and 3,660,545, and static casting methods are disclosed in U.S. Patent Nos. 4,113,224, 4,197,266, and 5,271,875. Spincasting methods involve charging the mixtures to be polymerized to a mold, and spinning the mold in a controlled manner while exposing the mixture to a radiation source such as UV light. Static casting methods involve charging the monomeric mixture between two mold sections, one mold section shaped to form the anterior lens surface and the other mold section shaped to form the posterior lens surface, and curing the mixture while retained in the mold assembly to form a lens, for example, by free radical polymerization of the mixture.

[0144] Examples of free radical reaction techniques to cure the lens material include thermal radiation, infrared radiation, electron beam radiation, gamma radiation, ultraviolet (UV) radiation, and the like; or combinations of such techniques may be used. U.S. Patent No. 5,271,875 describes a static cast molding method that permits molding of a finished lens in a mold cavity defined by a posterior mold and an anterior mold. As an additional method, U.S.Patent No. 4,555,732 discloses a process where an excess of a mixture is cured by spincasting in a mold to form a shaped article having an anterior lens surface and a relatively large thickness, and the posterior surface of the cured spincast article is subsequently lathed to provide a contact lens having the desired thickness and posterior lens surface.

[0145] Polymerization may be facilitated by exposing the mixture to heat and / or radiation, such as ultraviolet light, visible light, or high energy radiation. A polymerization initiator may be included in the mixture to facilitate the polymerization step. Representative examples of free radical thermal polymerization initiators include organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, terti arylbutyl peroxypivalate, peroxydicarbonate, and the like. Representative UV initiators are those known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocure® 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure® 651, 184 and 2959 (Ciba- Geigy), 2,2’Azobis(2-methylpropionitrile) (VAZO 64) and the like. Generally, the initiator will be employed in the mixture at a concentration of about 0.01 to about 5 percent by weight of the total mixture.

[0146] Polymerization is generally performed in a reaction medium, such as, for example, a solution or dispersion using a solvent, e.g., water or an alkanol containing from 1 to 4 carbon atoms such as methanol, ethanol or propan-2-ol. Alternatively, a mixture of any of the above solvents may be used.

[0147] Generally, polymerization can be carried out for about 15 minutes to about 72 hours, and under an inert atmosphere of, for example, nitrogen or argon. If desired, the resulting polymerization product can be dried under vacuum, e.g., for about 5 to about 72 hours or left in an aqueous solution prior to use.

[0148] Polymerization of the silicone contact lens-forming mixtures will yield a polymerization product, that when hydrated, preferably forms a hydrogel. When producing a hydrogel lens, the silicone contact lens-forming mixture may further include at least a diluent that is ultimately replaced with water when the polymerization product is hydrated to form a hydrogel. The amount of diluent used should be less than about 50 wt. %, and in most cases, the diluent content will be less than about 30 wt. %. However, in a particular polymer system, the actual limit will be dictated by the solubility of the various monomers in the diluent. In order to produce an optically clear copolymer, it is important that a phase separation leading to visual opacity does not occur between the comonomers and the diluent, or the diluent and the final copolymer.

[0149] Furthermore, the maximum amount of diluent which may be used will depend on the amount of swelling the diluent causes the final polymers. Excessive swelling will or may cause the copolymer to collapse when the diluent is replaced with water upon hydration. Suitable diluents include, but are not limited to, ethylene glycol, glycerine, liquid polyethylene glycol), alcohols, alcohol / water mixtures, ethylene oxide / propylene oxide block copolymers, low molecular weight linear poly(2 -hydroxyethyl methacrylate), glycol esters of lactic acid, formamides, ketones, dialkylsulfoxides, butyl carbitol, and the like and mixtures thereof.

[0150] If necessary, it may be desirable to remove residual diluent from the contact lens before edge-finishing operations which can be accomplished by evaporation at or near ambient pressure or under vacuum. An elevated temperature can be employed to shorten the time necessary to evaporate the diluent. The time, temperature and pressure conditions for the solvent removal step will vary depending on such factors as the volatility of the diluent and the specific monomeric components, as can be readily determined by one skilled in the art. If desired, the mixture used to produce the hydrogel lens may further include crosslinking and wetting agents known in the prior art for making hydrogel materials.

[0151] The silicone contact lenses obtained herein may be subjected to optional machining operations. For example, the optional machining steps may include buffing or polishing a lens edge and / or surface. Generally, such machining processes may be performed before or after the product is released from a mold part, e.g., the lens is dry released from the mold by employing vacuum tweezers to lift the lens from the mold, after which the lens is transferred by means of mechanical tweezers to a second set of vacuum tweezers and placed against a rotating surface to smooth the surface or edges. The lens may then be turned over in order to machine the other side of the lens.

[0152] The lens may then be transferred to individual lens packages containing a buffered saline solution. The saline solution may be added to the package either before or after transfer of the lens. Appropriate packaging designs and materials are known in the art. A plastic package is releasably sealed with a film. Suitable sealing films are known in the art and include foils, polymer films and mixtures thereof. The sealed packages containing the lenses are then sterilized to ensure a sterile product. Suitable sterilization means and conditions are known in the art and include, for example, autoclaving.

[0153] As one skilled in the art will readily appreciate other steps may be included in the molding and packaging process described above. Such other steps can include, for example, coating the formed lens, surface treating the lens during formation (e.g., via moldtransfer), inspecting the lens, discarding defective lenses, cleaning the mold halves, reusing the mold halves, and the like and combinations thereof.

[0154] The following examples are provided to enable one skilled in the art to practice the invention and are merely illustrative of the invention. The examples should not be read as limiting the scope of the invention as defined in the claims.

[0155] In the examples, the following abbreviations are used.

[0156] DMA: N,N-dimethylacrylamide.

[0157] HEA: hydroxyethyl acrylate.

[0158] HEMA: 2-hydroxyethyl methacrylate.

[0159] IEM: -isocyanatoethyl methacrylate.

[0160] DBTDL: dibutyltin dilaurate.

[0161] TrisMA: tris(trimethylsiloxy)silylpropyl methacrylate.

[0162] CTA: Chain transfer agent.

[0163] M1EDS: A compound having the following structure and available from Gelest:

[0164] MCR-M1 1 : A compound having the structure:

[0165] MCRM07: A compound having the following structure and available fromGelest:

[0166] SA monomer: A compound having the structure:

[0167] AIBN: azo bis-isobutylnitrile (Vazo™ 64).EXAMPLE 1

[0168] Preparation and functionalization of copolymer P(DMA-HEA-TRISMA- MCRM11-SA) to obtain a silicone contact lens forming prepolymer by the general reaction scheme.

[0169] Experiment detail: 16g of DMA, 12g of HEA, 30.30g of TRIS-MA, 40.32g of MCRM1 1, 1.38g of SA monomer, 0.099g of mercaptoethanol, 200 ml of toluene, and 0.0238g of AIBN were added to a 500mL airfree flask. The flask was sealed and then purged by a needle with nitrogen for 1 hour at room temperature. The oil bath was preheated to 65°C. The nitrogen purge was removed, closed the stopcock, dropped the flask in the oil bath and stirred at 65°C. The oil bath was allowed to react overnight. A sample was removed after 24 hours. The conversion was 95%. The values of a, b, c, d and e are as follows: a is 126, b is 81, c is 57, d is 33 and e is 3.

[0170] The flask from the oil bath was allowed to cool to room temperature before adding in 0.14g of DBTDL and 1.35g of IEM. The mixture was allowed to react overnight in the sealed flask. Next, the reaction mixture was poured into a 2L media bottle and precipitated a polymer with 1600mL of acetonitrile. The media bottle was placed in a refrigerator to settle out overnight. The top layer of acetonitrile was decanted off the dissolved polymer. Theremaining polymer was poured into a Teflon bucket and started to dry the polymer. After 4 days when all solvents were removed and analyzed by NMR and GC, the polymer was removed from the bucket, chopped into smaller pieces and put back in a vacuum oven to complete drying. Total yield was 88g of polymer = 88% yield. The values of n, m, o, x, y and z are as follows: n is 126, m is 8, o is 73, x is 57, y is 33 and z is 3.EXAMPLE 2

[0171] Preparation and functionalization of copolymer P(DMA-HEA-TRISMA- MCRM11-SA) using a RAFT agent to obtain a silicone contact lens forming prepolymer by the general reaction scheme.

[0172] 16g of DMA, 12g of HEA, 30.30g of TRIS-MA, 40.32g of MCRM11, 1.38g ofSA monomer, 0.3135g of 4-cyano-4-((ethoxycarbonothioyl)thio)pentanoic acid, 200 ml of toluene, and 0.0238g of AIBN were added to a 500mL airfree flask. The flask was sealed and then purged by a needle with nitrogen for 1 hour. The oil bath was preheated to 65°C. The nitrogen purge was removed, closed the stopcock, dropped the flask in the oil bath and stirred at 65°C. The oil bath was allowed to react overnight. A sample was removed after 24 hours. The conversion was 90%. The values of a, b, c, d and e are as follows: a is 113, b is 73, c is51, d is 30 and e is 3.

[0173] The flask from the oil bath was allowed to cool to room temperature before adding in 0.14g of DBTDL and 1.35g of IEM. The mixture was allowed to react overnight in the sealed flask. Next, the reaction mixture was poured into a 2L media bottle and precipitated a polymer with 1600mL of acetonitrile. The media bottle was placed in a refrigerator to settle out overnight. The top layer of acetonitrile was decanted off the dissolved polymer. The remaining polymer was poured into a Teflon bucket and started to dry the polymer. After 4 days when all solvents were removed and analyzed by NMR and GC, the polymer was removed from the bucket, chopped into smaller pieces and put back in a vacuum oven to completedrying. Total yield was 75g of polymer=75% yield. The values of n, m, o, x, y and z are as follows: n is 113, m is 5, o is 68, x is 51, y is 30 and z is 3.EXAMPLE 3

[0174] Preparation and functionalization of copolymer P(DMA-HEA-TRISMA- MCRM07-SA) to obtain a silicone contact lens forming prepolymer by the general reaction scheme.

[0175] 16g of DMA, 12g of HEA, 30.30g of TRIS-MA, 40.32g of MCRM07, 1.38g ofSA monomer, 0.099g of mercaptoethanol, 200 ml of toluene, and 0.0238g of AIBN were added to a 500mL airfree flask. The flask was sealed and then purged by a needle with nitrogen for 1 hour. The oil bath was preheated to 65°C. The nitrogen purge was removed, closed the stopcock, dropped the flask in the oil bath and stirred at 65°C. The oil bath was allowed to react overnight. A sample was removed after 24 hours. The conversion was 90%. The values of a, b, c, d and e are as follows: a is 113, b is 73, c is 51, d is 30 and e is 3.

[0176] The flask from the oil bath was allowed to cool to room temperature before adding in 0.14g of DBTDL and 1 ,35g of IEM. The mixture was allowed to react overnight in the sealed flask. Next, the reaction mixture was poured into a 2L media bottle and precipitated a polymer with 1600mL of acetonitrile. The media bottle was placed in a refrigerator to settle out overnight. The top layer of acetonitrile was decanted off the dissolved polymer. The remaining polymer was poured into a Teflon bucket and started to dry the polymer. After 4 days till all solvents get removed and analyzed by NMR and GC, the polymer was removed from the bucket, chopped into smaller pieces and put back in a vacuum oven to complete drying. Total yield was 80g of polymer=80% yield. The values of n, m, o, x, y and z are as follows: n is 113, m is 5, o is 68, x is 51, y is 30 and z is 3.EXAMPLES 4-6

[0177] Preparation of Contact Lenses.

[0178] Contact lenses were prepared using the reaction components listed in Table 1 below, as amounts per weight percent.TABLE 1

[0179] The mixtures were made in ambient conditions with no nitrogen or oxygen mitigation. The copolymer was dissolved in HEMA and DMA. The mixtures were speed mixed for 10 minutes at 2500RPM, repeated twice until fully dissolved. Next, Irgacure 819 and tint were added to the mixtures and speed mixed for 10 minutes at 2500RPM. A syringe was then centrifuged to remove bubbles for 15 minutes at speed 8. The mixtures were cast in ultra molds, and cured in 420nm LED 4mW light for 10 minutes to produce optically clear lenses.COMPARATIVE EXAMPLE A

[0180] HEMA was used to prepare and functionalize a copolymer P(DMA-HEMA- TRISMA-MCRM1 1-SA) with a RAFT agent to obtain a silicone contact lens forming

[0181] 16g of DMA, 12g of HEMA, 30.30g of TRIS-MA, 40.32g of MCRM11, 1.38g of SA monomer, 0.3135g of 4-cyano-4-((ethoxycarbonothioyl)thio)pentanoic acid, 200 ml of toluene, and 0.0238g of AIBN were added to a 500mL airfree flask. The flask was sealed and then purged by a needle with nitrogen for 1 hour. The oil bath was preheated to 65°C. The nitrogen purge was removed, closed the stopcock, dropped the flask in the oil bath and stirred at 65°C. After 2 hours the precipitation of a whitish polymer showed up in the reactor. A sample from the reaction showed that the precipitated polymer had high percentage of HEMA versus the other monomers due to the higher reactivity of HEMA versus DMA and silicon monomers. An NMR experiment showed that 90 mole% of HEMA consumed in the reaction after 13 mole% of whole monomers conversion. The high percentage of HEMA in the polymer chain made the polymer insoluble in the reaction mixture due to high hydrophilicity of the polymer chains.

[0182] According to an aspect of the present disclosure, a silicone contact lens-forming prepolymer comprises a reaction product of (a) a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0183] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the alkylacrylamide monomer is N,N-dimethylacrylamide.

[0184] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the non-bulky organosilicon-containing monomer is represented by the following structure:

[0185] wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R10and R11are independently hydrogen or alkyl wherein at least one of R10and R11is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon- containing monomer is represented by the following structure:

[0186] wherein R12is H or methyl; X is O or NR16; wherein R16is hydrogen or Ci to C4 alkyl, which may be further substituted with one or more hydroxyl groups; R13is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R14is independently a phenyl or Ci to C4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R15is a Ci to C4 alkyl; and a is 2 to 50.

[0187] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is selected from the group consisting of a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof.

[0188] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is represented by the following structure:

[0189] wherein X denotes -O- or -NR19- where each R19is hydrogen or a C1-C4 alkyl; R17independently denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18'

[0190] wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:

[0191] wherein X denotes -NR19-; wherein R19denotes hydrogen or a C1-C4 alkyl; R17denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18'

[0192] wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10.

[0193] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, l-methyl-2- isocyanatoethyl methacrylate, 1, 1-dimethy 1 -2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

[0194] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer comprises:

[0195] from about 50 to about 400 repeating units of monomeric units derived from the alkylacrylamide monomer,

[0196] from about 50 to about 200 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer,

[0197] from about 5 to about 20 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group,

[0198] from about 20 to about 300 repeating units of monomeric units derived from the non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and

[0199] from about 1 to about 400 repeating units of monomeric units derived from the bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0200] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the polymerization composition further comprises (v) an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0201] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the ultraviolet blocker having an ethylenically unsaturated reactive group comprises a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

[0202] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the ultraviolet blocker having an ethylenically unsaturated reactive group comprises a benzotriazole compound represented by the following structure:

[0203] wherein each R is independently hydrogen, a halogen, an -O- group, a nitro group, a nitrile group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted carbonyl group, and a substituted or unsubstituted hydrocarbyl group, R* is hydrogen or a substituted or unsubstituted hydrocarbyl group, and R** is an ethylenically unsaturated reactive group.

[0204] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, R and R* are each hydrogen and R** is a (meth)acrylate-containing reactive end group.

[0205] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, R** is positioned on the aromatic ring in the para position relative to the OH moiety.

[0206] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer further comprises from about 1 to about 25 repeating units of monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0207] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the polymerization composition further comprises a blue light blocker having an ethylenically unsaturated reactive group.

[0208] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

[0209] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer is a silicone contact lens-forming random copolymer.

[0210] According to another aspect of the present disclosure, a silicone contact lens comprising a polymerization product of a silicone contact lens-forming mixture comprising a silicone contact lens-forming prepolymer comprising a reaction product of (a) a copolymerization product of a polymerization composition comprising (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

[0211] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the alkylacrylamide monomer is N,N-dimethylacrylamide.

[0212] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the non-bulky organosilicon-containing monomer is represented by the following structure:

[0213] wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R10and R11are independently hydrogen or alkyl wherein at least one of R10and R11is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon- containing monomer is represented by the following structure:

[0214] wherein R12is H or methyl; X is O or NR16; wherein R16is hydrogen or Ci to C4 alkyl, which may be further substituted with one or more hydroxyl groups; R13is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R14is independently a phenyl or Ci to C4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R15is a Ci to C4 alkyl; and a is 2 to 50.

[0215] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is selected from the group consisting of a bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof.

[0216] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the bulky siloxane monomer is represented by the following structure:

[0217] wherein X denotes -O- or -NR19- where each R19is hydrogen or a C1-C4 alkyl; R17independently denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18'

[0218] wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:

[0219] wherein X denotes -NR19-; wherein R19denotes hydrogen or a C1-C4 alkyl; R17denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18'

[0220] wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10.

[0221] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, l-methyl-2- isocyanatoethyl methacrylate, 1, 1-dimethy 1 -2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

[0222] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer comprises:

[0223] from about 50 to about 400 repeating units of monomeric units derived from the alkylacrylamide monomer,

[0224] from about 50 to about 200 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer,

[0225] from about 5 to about 20 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with monomer having a reactivefunctionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group,

[0226] from about 20 to about 300 repeating units of monomeric units derived from the non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and

[0227] from about 1 to about 400 repeating units of monomeric units derived from the bulky siloxane monomer having an ethylenically unsaturated reactive end group.

[0228] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the polymerization composition further comprises (v) an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0229] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the ultraviolet blocker having an ethylenically unsaturated reactive group comprises a phenolic group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

[0230] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the ultraviolet blocker having an ethylenically unsaturated reactive group comprises a benzotriazole compound represented by the following structure:

[0231] wherein each R is independently hydrogen, a halogen, an -O- group, a nitro group, a nitrile group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted carbonyl group, and a substituted or unsubstituted hydrocarbyl group, R* is hydrogen or a substituted or unsubstituted hydrocarbyl group, and R** is an ethylenically unsaturated reactive group.

[0232] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, R and R* are each hydrogen and R** is a (meth)acrylate-containing reactive end group.

[0233] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, R** is positioned on the aromatic ring in the para position relative to the OH moiety.

[0234] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer further comprises from about 1 to about 25 repeating units of monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

[0235] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the polymerization composition further comprises a blue light blocker having an ethylenically unsaturated reactive group.

[0236] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

[0237] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer is a silicone contact lens-forming random copolymer.

[0238] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer is present in the silicone contact lens-forming mixture in an amount ranging from about 50 wt. % to about 100 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0239] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer is present in the silicone contact lens-forming mixture in an amount ranging from about 60 wt. % to about 80 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0240] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming mixture further comprises one or more silicone contact lens-forming monomers.

[0241] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more silicone contact lens-forming monomers are present in the silicone contact lens-forming mixture in an amount ranging from about 10 wt. % to about 50 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0242] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming mixture further comprises one or more hydrophilic monomers.

[0243] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic monomers include one or more of an unsaturated carboxylic acid, an acrylamide, a vinyl lactam, a hydroxyl-containing- (meth)acrylate, a hydrophilic vinyl carbonate, a hydrophilic vinyl carbamate, a hydrophilic oxazolone, and a poly(alkene glycols) functionalized with polymerizable groups and mixtures thereof.

[0244] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic monomers are present in the silicone contact lens-forming mixture in an amount ranging from about 10 wt. % to about 50 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0245] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming mixture further comprises one or more blue light blockers having an ethylenically unsaturated reactive group.

[0246] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more blue light blockers are represented by an acridone compound represented by the following structure:

[0247] wherein R* is hydrogen or a substituted or unsubstituted hydrocarbyl group, and R** is an ethylenically unsaturated reactive group.

[0248] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens has an oxygen permeability of at least about 50 Barrers.

[0249] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens has an oxygen permeability of from about 75 Barrers to about 175 Barrers.

[0250] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens demonstrates sufficient blocking of UV light to meet at least FDA Class I specifications for UV blocking.

[0251] According to yet another aspect of the present disclosure, a method for making a silicone contact lens comprises:

[0252] (a) subjecting a silicone contact lens-forming mixture comprising a silicone contact lens-forming prepolymer according to the aspect of the present disclosure discussed above to polymerization conditions to provide a polymerized silicone contact lens, and

[0253] (b) hydrating the polymerized silicone contact lens.

[0254] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer is present in the silicone contact lens-forming mixture in an amount ranging from about 50 wt. % to about 100 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0255] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming prepolymer is present in the silicone contact lens-forming mixture in an amount ranging from about 60 wt. % to about 80 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0256] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming mixture further comprises one or more silicone contact lens-forming monomers.

[0257] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more silicone contact lens-forming monomers are present in the silicone contact lens-forming mixture in an amount ranging from about 10 wt. % to about 50 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0258] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens-forming mixture further comprises one or more hydrophilic monomers.

[0259] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic monomers include one or more of an unsaturated carboxylic acid, an acrylamide, a vinyl lactam, a hydroxyl-containing- (meth)acrylate, a hydrophilic vinyl carbonate, a hydrophilic vinyl carbamate, a hydrophilic oxazolone, and a poly(alkene glycols) functionalized with polymerizable groups and mixtures thereof.

[0260] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the one or more hydrophilic monomers are present in the silicone contact lens-forming mixture in an amount ranging from about 10 wt. % to about 50 wt. %, based on the total weight of the silicone contact lens-forming mixture.

[0261] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens has an oxygen permeability of at least about 50 Barrers.

[0262] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens has an oxygen permeability of from about 75 Barrers to about 175 Barrers.

[0263] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the silicone contact lens demonstrates sufficient blocking of UV light to meet at least FDA Class I specifications for UV blocking.

[0264] Various features disclosed herein are, for brevity, described in the context of a single embodiment, but may also be provided separately or in any suitable sub-combination. All combinations of the embodiments are specifically embraced by the illustrative embodiments disclosed herein just as if each and every combination was individually and explicitly disclosed. In addition, all sub-combinations listed in the embodiments describing such variables are also specifically embraced by the present compositions and are disclosed herein just as if each and every such sub-combination was individually and explicitly disclosed herein.

[0265] It will be understood that various modifications may be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the present invention are for illustration purposes only. Other arrangements and methods may be implemented by those skilled in the art without departing from the scope and spirit of this invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the features and advantages appended hereto.

Claims

CLAIMS1. A silicone contact lens-forming prepolymer comprising a reaction product of (a) a copolymerization product of a polymerization composition comprises (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

2. The silicone contact lens-forming prepolymer according to claim 1, wherein the alkylacrylamide monomer is N,N-dimethylacrylamide.

3. The silicone contact lens-forming prepolymer according to claim 1 or 2, wherein the non-bulky organosilicon-containing monomer is represented by the following structure:wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R10and R11are independently hydrogen or alkyl wherein at least one of R10and R11is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure:wherein R12is H or methyl; X is O or NR16; wherein R16is hydrogen or Ci to C4 alkyl, which may be further substituted with one or more hydroxyl groups; R13is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of anether group, a hydroxyl group, a carbamate group and combinations thereof; each R14is independently a phenyl or Ci to C4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R15is a Ci to C4 alkyl; and a is 2 to 50.

4. The silicone contact lens-forming prepolymer according to any one of claims 1-3, wherein the bulky siloxane monomer is represented by the following structure:wherein X denotes -0- or -NR19- where each R19is hydrogen or a C1-C4 alkyl; R17independently denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:wherein X denotes -NR19-; wherein R19denotes hydrogen or a C1-C4 alkyl; R17denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18' wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10.

5. The silicone contact lens-forming prepolymer according to any one of claims 1-4, wherein the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxy ethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3- isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, l-methyl-2-isocyanatoethyl methacrylate, 1, 1-dimethy 1 -2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

6. The silicone contact lens-forming prepolymer according to any one of claims 1-5, wherein the silicone contact lens-forming prepolymer comprises: from about 50 to about 400 repeating units of monomeric units derived from the alkylacrylamide monomer; from about 50 to about 200 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer; from about 5 to about 20 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of the copolymer and the hydroxy moiety is end functionalized with monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group; from about 20 to about 300 repeating units of monomeric units derived from the non- bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group; andfrom about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

7. The silicone contact lens-forming prepolymer according to any one of claims 1-6, wherein the polymerization composition further comprises (v) an ultraviolet blocker having an ethylenically unsaturated reactive group.

8. The silicone contact lens-forming prepolymer according to claim 7, wherein the ultraviolet blocker having an ethylenically unsaturated reactive group comprises a benzotriazole compound represented by the following structure:wherein each R is independently hydrogen, a halogen, an -O- group, a nitro group, a nitrile group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted carbonyl group, and a substituted or unsubstituted hydrocarbyl group, R* is hydrogen or a substituted or unsubstituted hydrocarbyl group, and R** is an ethylenically unsaturated reactive group.

9. The silicone contact lens-forming prepolymer according to any one of claims 1-6, wherein the silicone contact lens-forming prepolymer further comprises from about 1 to about 25 repeating units of monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

10. The silicone contact lens-forming prepolymer according to any one of claims 1-9, wherein the polymerization composition further comprises a blue light blocker having an ethylenically unsaturated reactive group.

11. The silicone contact lens-forming prepolymer according to any one of claims 1-10, wherein the silicone contact lens-forming prepolymer has a weight average molecular weight ranging from about 10,000 to about 300,000 Daltons.

12. A silicone contact lens comprising a polymerization product of a silicone contact lens-forming mixture comprising a silicone contact lens-forming prepolymer comprising a reaction product of (a) a copolymerization product of a polymerization composition comprises (i) an alkylacrylamide monomer, (ii) a hydroxyethyl acrylate monomer, (iii) a non-bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group, and (iv) a bulky siloxane monomer having an ethylenically unsaturated reactive end group, with (b) a monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group.

13. The silicone contact lens according to claim 12, wherein the alkylacrylamide monomer is N,N-dimethylacrylamide.

14. The silicone contact lens according to claim 12 or 13, wherein the non-bulky organosilicon-containing monomer is represented by the following structure:wherein V is ethylenically unsaturated polymerizable group, L is a linker group or a bond; R1, R2, R3, R4, R5, R6, R7, R8, and R9are independently hydrogen an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a halo alkenyl group, or an aromatic group; R10and R11are independently hydrogen or alkyl wherein at least one of R10and R11is hydrogen; y is 2 to 7 and n is 1 to 100, or the non-bulky organosilicon-containing monomer is represented by the following structure:wherein R12is H or methyl; X is O or NR16; wherein R16is hydrogen or Ci to C4 alkyl, which may be further substituted with one or more hydroxyl groups; R13is a divalent alkyl group, which may further be functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof; each R14is independently a phenyl or Ci to C4 alkyl which may be substituted with fluorine, hydroxyl or an ether; R15is a Ci to C4 alkyl; and a is 2 to 50.

15. The silicone contact lens according to any one of claims 12-14, wherein the bulky siloxane monomer is represented by the following structure:wherein X denotes -O- or -NR19- where each R19is hydrogen or a C1-C4 alkyl; R17independently denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18' wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10; or the following structure:wherein X denotes -NR19-; wherein R19denotes hydrogen or a C1-C4 alkyl; R17denotes hydrogen or methyl; each R18independently denotes a lower alkyl radical, a phenyl radical or a group represented by the following structure:R18'— Si— R18'R18' wherein each R18' independently denotes a lower alkyl radical or a phenyl radical; and h is 1 to 10.

16. The silicone contact lens according to any one of claims 12-15, wherein the monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate monomer and a polymerizable ethylenically unsaturated reactive end group is selected from the group consisting of 2-isocyanatoethyl acrylate, 3-isocyanatopropyl acrylate, 2-isocyanatoethyl methacrylate, l-methyl-2-isocyanatoethyl methacrylate, 1, 1- dimethy 1 -2-isocyanatoethyl acrylate, (meth)acryloyl chloride and vinyl chloroformate.

17. The silicone contact lens according to any one of claims 12-16, wherein the silicone contact lens-forming prepolymer comprises: from about 50 to about 400 repeating units of monomeric units derived from the alkylacrylamide monomer; from about 50 to about 200 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer; from about 5 to about 20 repeating units of monomeric units derived from the hydroxyethyl acrylate monomer where the acrylate moiety is attached to the backbone of thecopolymer and the hydroxy moiety is end functionalized with monomer having a reactive functionality complementary to the hydroxyl moiety of the hydroxyethyl acrylate and a polymerizable ethylenically unsaturated reactive end group; from about 20 to about 300 repeating units of monomeric units derived from the non- bulky organosilicon-containing monomer having an ethylenically unsaturated reactive end group; and from about 1 to about 400 repeating units of monomeric units derived from a bulky siloxane monomer having an ethylenically unsaturated reactive end group.

18. The silicone contact lens according to any one of claims 12-17, wherein the polymerization composition further comprises (v) an ultraviolet blocker having an ethylenically unsaturated reactive group.

19. The silicone contact lens according to claim 18, wherein the ultraviolet blocker having an ethylenically unsaturated reactive group comprises a benzotriazole compound represented by the following structure:wherein each R is independently hydrogen, a halogen, an -O- group, a nitro group, a nitrile group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted carbonyl group, and a substituted or unsubstituted hydrocarbyl group, R* is hydrogen or a substituted or unsubstituted hydrocarbyl group, and R** is an ethylenically unsaturated reactive group.

20. The silicone contact lens according to any one of claims 12-17, wherein the silicone contact lens-forming prepolymer further comprises from about 1 to about 25 repeating units of monomeric units derived from an ultraviolet blocker having an ethylenically unsaturated reactive group.

21. The silicone contact lens according to any one of claims 12-20, wherein the polymerization composition further comprises a blue light blocker having an ethylenically unsaturated reactive group.

22. The silicone contact lens according to any one of claims 12-21, wherein the silicone contact lens-forming prepolymer is present in the silicone contact lens-forming mixture in an amount ranging from about 50 wt. % to about 100 wt. %, based on the total weight of the silicone contact lens-forming mixture.

23. The silicone contact lens according to any one of claims 12-22, wherein the silicone contact lens-forming prepolymer is present in the silicone contact lens-forming mixture in an amount ranging from about 60 wt. % to about 80 wt. %, based on the total weight of the silicone contact lens-forming mixture.

24. The silicone contact lens according to any one of claims 12-23, wherein the silicone contact lens-forming mixture further comprises one or more silicone contact lens-forming monomers.

25. The silicone contact lens according to claim 24, wherein the one or more silicone contact lens-forming monomers are present in the silicone contact lens-forming mixture in an amount ranging from about 10 wt. % to about 50 wt. %, based on the total weight of the silicone contact lens-forming mixture.

26. The silicone contact lens according to any one of claims 12-25, wherein the silicone contact lens-forming mixture further comprises one or more hydrophilic monomers.

27. The silicone contact lens according to any one of claims 12-26, having an oxygen permeability of at least about 50 Barrers.

28. The silicone contact lens according to any one of claims 18-20, demonstrating sufficient blocking of UV light to meet at least FDA Class I specifications for UV blocking.

29. A method for making a silicone contact lens, comprising:(a) subjecting a silicone contact lens-forming mixture comprising a silicone contact lens-forming prepolymer according to any one of claims 1-11 to polymerization conditions to provide a polymerized silicone contact lens, and(b) hydrating the polymerized silicone contact lens.

30. The method according to claim 29, wherein the silicone contact lens-forming prepolymer is present in the method-forming mixture in an amount ranging from about 50 wt. % to about 100 wt. %, based on the total weight of the silicone contact lens-forming mixture.

31. The method according to claims 29 or 30, wherein the silicone contact lens-forming mixture further comprises one or more one or more hydrophilic monomers.

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