| Title of Invention | WETTABLE HYDROGELS COMPRISING REACTIVE, HYDROPHILIC, POLYMERIC INTERNAL WETTING AGENTS |
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| Abstract | The present invention relates to wettable silicone hydrogels comprising the reaction production of at least one siloxane containing component and at least one reactive, hydrophilic polymeric internal wetting agent. The present invention further relates to silicone hydrogel contact lenses comprising at least one oxygen permeable component, and an amount of reactive, hydrophilic polymeric internal wetting agent sufficient to impart wettability to said device. |
| Full Text | WO 2006/039466 PCT/US2005/035149 In another example, reactive, hydrophilic polymeric IWAs can be made by initiating the polymerization of a monomer (such as, for example, DMA) with a 5 lesser molar amount of an aroine-functionalized azo initiator (such as, for example, 2,2'-Azobis(2-mcthylpropionamide)dihydrochloride) and then reacting the amine groups of the resulting low molecular weight polymers with materials containing free radical polymerizable groups, such as 2-isocyanatoethyl methaerylate, 3- isopropenyl-alpha, alpha-dimcthylbenzyl isocyanate, methacrylic anhydride, acrylic 10 acid, methacrylic acid, acryloyl chloride, or methacryloyl chloride. Examples of the above compounds include low molecular weight hydrophilic polymers of Formulae III and reactive, hydrophilic polymeric IWAs of Formulae IV. WO 2006/039466 PCT/US2005/035149 In yet a further example, reactive, hydrophilic polymeric IWAs can also be 5 made by initiating the polymerization of a monomer (such as, for example, DMA) with a lesser molar amount of a carboxylic acid-functionalized azo initiator (such as, for example, 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate) and then reacting the carboxylic acid groups of the resulting low molecular weight hydrophilic polymer with materials containing free radical polymcrizable groups, 10 such as, for example, 2-arninoethyl methacrylate or 3-aminopropyl methacrylamide. A person skilled in the art will recognize that incomplete reaction between the low molecular weight hydrophilic polymer and the free radical polymerizable WO 2006/039466 PCT/US2005/035149 - 10 - compound results in a mixture of products which include, in part, the starting low molecular weight hydrophilic polymer, the reactive hydrophilic polymeric IWA, and unreacted free radical polymerizable compounds. If low molecular weight hydrophilic polymer is present in the final product mixture, it is not essential to 5 remove it from the product mixture. Instead, the low molecular weight hydrophilic polymer may remain, serve as a diluent in the contact lens formulation and be removed later during the purification of the lenses. Those of skill in the art will also recognize that molecular weights of the reactive, hydrophilic polymeric IWAs will vary depending on the reaction parameters, such as amount of initiator present, 10 reaction temperature, and monomer concentration. In addition, the presence of chain transfer agents such thioglycolic acid and thiolactic acid can also be used to control the molecular weights of the reactive, hydrophilic polymeric IWAs. Examples of the above compounds include low molecular weight hydrophilic polymers of Formulae V and reactive, hydrophilic polymeric internal 15 wetting agents of Formulae VI and VII. WO 2006/039466 PCT/US2005/035149 One preferred class of reactive, hydrophilic polymeric IWAs include those that contain a cyclic moiety in their backbone, more preferably, a cyclic amide or 5 cyclic imide. Reactive, hydrophilic polymeric IWAs include but are not limited to macromers derived from poly-N-vinyl pyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactarn, poly-N-vmyl-3-methyl-2- caprolactam, poly-N-vinyl- 3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2- piperidone, poly-N-vinyl-4- methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2~ pyrrolidone, and poly-N-vinyl-4,5- 10 dimethyl-2- pyrrolidone, polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, poly-2-(ethyl-oxa/,oline), WO 2006/039466 PCT/US2005/035149 - 12 - heparin polysaceharides, polysaccharides, mixtures and copolymers (including block or random, branched, mullichain, comb-shaped or star shaped) thereof where poly- N-vinylpyrrolidonc (PVP) is particularly preferred. Copolymers might also be used such as graft copolymers of PVP. These lactam containing polymers may also be made reactive by treatment with alkali and transition metal borohydrides, such as sodium borohydride (NaBH4), zinc borohydride, sodium triacetoxyborohydride, bis(isopropoxytitanium) borohydride in solution, followed by reaction with suitable polymerizable groups. Another class of preferred reactive, hydrophilic polymeric IWAs include reactive polymers and copolymers comprising pendant acyclic amide groups capable of association with hydroxyl groups. Examples of suitable reactive, hydrophilic polymeric IWAs include polymers and copolymers comprising, in tire backbone, repeating units of Formula VIII wherein Rc is a Cl to C3 alkyl group; Ra is selected from H, straight or branched, substituted or unsubstituted Cl to C4 alkyl groups, WO 2006/039466 PCT/US2005/035149 - 13 - R is selected from H, straight or branched, substituted or unsubstituted Cl to C4 alkyl groups, amino groups having up to two carbons, amide groups having up to 4 carbon atoms and alkoxy groups having up to two carbons and wherein the number of carbon atoms in Ra and Rb taken together is 8, preferably 6 or less. As 5 used herein substituted alkyl groups include alkyl groups substituted with an aminc, amide, ether or carboxy group. In one preferred embodiment Ra and Rb are independently selected from H, and substituted or unsubstituted Cl to C2 alkyl groups and preferably unsubstituted Cl to C2 alkyl groups. 10 In another preferred embodiment Q is a direct bond, Ra and Rb are independently selected from H, substituted or unsubstituted Cl to C2 alkyl groups. Preferably the reactive, hydrophilic polymeric IWAs of the present invention comprise a majority of the repeating unit of Formula Vlll, and more preferably at least about 80 mole% of the repeating unit of Formula Vlll. 15 Specific examples of repeating units of Formula Vlll include repeating units derived from N-vmyl-N-methylacetamide, N-vinylacetamide, N-vinyl-N- methylpropionamido, N-vinyl-N-methyl-2-mcthylpropionamide, N-vinyl-2- methylpropionamide, N-vinyl-N,N'-dhnethylurea, and the following acyclic polyamides: 20 Additional repeating units may be formed from monomers selected from N- vinyl amides, acrylamides, hydroxyalkyl (mcth) acrylates, alkyl (meth)aerylates or 25 other hydrophilic monomers and siloxane substituted acrylates or mcthacrylates. WO 2006/039466 PCT/US2005/035149 - 14 - ' Specific examples of monomers which may be used to form reactive, hydrophilic polymeric IWAs include as N-vinylpyrrolidone, NJsf-dimethylacrylamide, 2- hydroxyethylmethacrylatc, vinyl acetate, acrylonitrile, methyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and butyl methacrylate, 5 methacryloxypropyl tristrimethylsiloxysilane and the like and mixtures thereof. Preferred additional repeating units monomers include of N-vinylpyrrolidone, N,N- dimethylacrylamide, 2-hydroxyethylmcthacrylate and mixtures thereof. in one embodiment the reactive, hydrophilic polymeric IWA comprises poly(N-vmyl-N-methylacetainide). 10 In yet another embodiment the reactive, hydrophilic polymeric IWA comprises a reactive high molecular weight copoiymcr derived from monomers comprising vinyllactam monomers and vinyl carboxylate monomers. Preferably the reactive high molecular weight copolymers have molecular weights (weight average) of at least about 60,000 Daltons, more preferably between about 60,000 to 15 about 750,000 Daltons, more preferably still between about 100,000 to about 600,000 Daltons, and most preferably between about 180,000 to about 500,000 Daltons. In one embodiment these reactive high molecular weight copolymers may be synthesized in 3 steps. In the first step, a vinyllactam monomer and a vinyl 20 carboxylate monomer are copolymerized using a free radical initiator, resulting in a high molecular weight hydrophilic copolymer. In the second step, the carboxylate groups of the resultant copolymer are partially or completely hydrolyzed under appropriate reaction conditions, resulting in a "modified" high molecular weight copolymer that is capable of further reacting with one or more photo-polymerizable 25 compounds via hydroxyl groups on the polymer backbone. Partial hydrolysis gives terpolymers comprising the units vinyllactam, vinyl alcohol, and vinyl carboxylate, for example a terpolymer of vinylpyrrolidone, vinyl acetate, and vinyl alcohol. In the third step, the modified high molecular weight hydrophilic copolymer is treated WO 2006/039466 PCT/US2005/035149 - 15 - with a reactive group, as defined above, to generate the reactive, hydrophilic polymeric IWA. Suitable N-vinyllactams include N-vinyl-2-pyrrolidone, N-vinyl-2- piperidone, N-vinyl-2-caprolactam, M-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3- 5 methyl-2-piperidonc, N-vinyl-3-methyl-2-capralactam, N-vinyl-4-methyl-2- pyrrolidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl-2- pyrrolidone, N- vinyl-5-melhyl-2-piperidone, N-vinyl-5,5-dimethyl-2- pyrrolidone, N-vinyl-3,3,5- trimethyl-2-pyrrolidone, N-vinyl-5-mcthyl-5- cthyl-2-pyrrolidone, N-vinyl-3,4,5- trimethyl-3-ethyl-2-pyrrolidone, N- vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2- 10 piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vi nyl-4,4-dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5- diraethyl-2-caprolactam, N-vinyl4,6-dimethyl-2-caprolactarn, N-vinyl-3,5,7- trimethyl-2-caprolactaxn, N-vinylmaleimidc, vinylsuccinimide, mixtures thereof and the like. 15 Preferred vinyllactams include heterocyclic monomers containing 4 carbon atoms in the heterocyclic ring. A highly preferred vinyllactam is N-vinyl-2- pyrrolidone. Suitable vinyl carboxylate include compounds having both vinyl and carboxylate functionality, preferably having up to 10 carbon atoms. Specific 20 examples of suitable vinyl carboxylates include vinyl heptanoate, vinyl hexanoatc, vinyl pentanoate, vinyl butanoate, vinyl propanoate (vinyl propionate), vinyl ethanoate (vinyl acetate), vinyl trifluoroacetate, mixtures thereof and the like. A preferred vinyl carboxylate is vinyl acetate. The high molecular weight copolymers may further comprise repeat units 25 derived from vinyl alcohols. Suitable vinyl alcohols include 2-hydroxyethyl 2- methyl-2-propenoate, p-hydroxystyrene, 4-vinylbenzyl alcohol, dicthylene glycol monomethacrylate, 2-[2-(2-hydroxyethoxy)ethoxy] ethyl 2-methyl-2-propenoate, 2,3-Dihydroxypropyl methacrylate, 2-hydroxy-l-(hydroxymethyl)ethyl 2-methyl-2- WO 2006/039466 PCT/US2005/035149 - 16 - propenoatc, 2-hydroxyethyl aciylate, 2-hydroxypropyl acrylate, butanediol monoacrylatc, butanediol monoinethacrylate, 3-[(4-ethenylphenyl)methoxy]-l ,2- propanediol, 3-(etheiry]phenyi)mcthoxy-l,2-propanediol mix of ra-and p-isomers, 2- (ethenylphenyl)methoxyacetic acid mixture of m- and p-isomers, xylitol 1- 5 methacrylate and xylitol 3-methacrylate, N-2-hydroxyethyl methacrylamide, N-2- hydroxyethyl acryl amide. A class of reactive, hydrophilic polymeric IWAs of this embodiment comprise units in their polymer chain derived from the following monomer units (all numbers are preceded by the word "about"): 10 Concentration (mole%) Vinyllactam vinyl alcohol vinyl carboxylate Reactivegroup 85-99.9 0.1-15 0-15 0.1-15 85-99 0.1-10 0-10 0.1-10 85-99 0.1-10 0-5 0.1-5 The reactive, hydrophilic polymeric IWAs formed from high molecular weight copolymers may also be formed from copolymers derived from polyamides, polylactones, polyimides, polylactams and functionalized polyamides, polylactones, 15 polyimides, polylactams, polycarboxylates, such as N-vinyl-2-pyrrolidone (NVF) and vinyl acetate (VA) functionalized by initiating the polymerization of NVP and VA with a lesser molar amount of an azo initiator, hydrolyzing or partially hydrolyzing the carboxylate groups, and then reacting the hydroxyl groups of the resulting high molecular weight hydrophilic copolymcr with materials containing 20 radical polymerizable groups, such as 2-isocyanatoeth3'l methacrylate, methacrylic anhydride, acryloyl chloride, or methacryloyl chloride to form the high molecular WO 2006/039466 PCT/US2005/035149 - 17 - weight photo-polymerizable hydrophilic copolymer (HMWPPHC). Suitable azo catalysts are known in the art and include AIBN, 2,2'-azobis{2-[l-(2-hydroxyethyl)~ 2-imida/.olin-2-yl]propanc}dihydrochloride, 2,2'-azobis{2-methyl-N-[ 1,1 - bis(hydroxymcthyl)-2-hydroxyethyl] propionamide, 2,2'-azobis[2~melhyl-N-(2- 5 hydroxyethyl)propionamide], 2,2'-azobis{2-methyl-N-[2-(l- hydroxybutyl)|propionarnide}, 2,2'-azobis(2-methylpropionamide)dihydrochloride, or 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine|tetrahydrate). Reactive, hydrophilic polymeric IWAs made with glycidyl methacrylate may also be used. The glycidyl methacrylate ring can be opened to give a diol that may be used in 10 conjunction with another hydrophilic polymer in a mixed system to increase the compatibility of the reactive, hydrophilic polymeric IWAs, compatibilizing components and any other groups that impart compatibility. Examples of the above described reactive, hydrophilic polymeric IWAs include compounds Formulae IX and X 15 WO 2006/039466 PCT/US2005/035149 The reactive, hydrophilic polymeric IWAs may be used in amounts from about 1 to about 15 weight percent, more preferably about 3 to about 15 percent, 5 most preferably about 5 to about 12 percent, all based upon the total of all reactive components. In some embodiments it is preferred that the reactive, hydrophilic polymeric IWA be soluble in the diluent at processing temperatures. Manufacturing processes that use water or water-soluble diluents may be preferred due to their simplicity and WO 2006/039466 PCT/US2005/035149 - 19 - reduced cost. In these embodiments reactive, hydrophilic polymeric IWAs that are water soluble at processing temperatures are preferred. In addition to the reactive, hydrophilic polymeric IWAs, the hydrogels of the present invention further comprise one or more silicone-contaimng components and, 5 optionally one or more hydrophilic components. The silicone-containing and hydrophilic components used to make the polymer of this invention can be any of the known components used in the prior art to make siliconc hydrogels. These terms silicone-containing component and hydrophilic component are not mutually exclusive, in that, the silicone-containing component can be somewhat hydrophilic 10 and the hydrophilic component can comprise some silicone, because the silicone- containing component can have hydrophilic groups and the hydrophilic components can have siliconc groups. Further, silicone-containing componcnt(s) and hydrophilic components) can be reacted prior to polymerization to form a prepolyrner which is later polymerized 15 in the presence of a diluent to form the polymer of this invention. When prepolymers or macromers are used, it is preferred to polymerize at least one silicone-containing monomer and at least one hydrophilic monomer in the presence of the diluent, wherein the silicone-containing monomers and the hydrophilic monomers differ. The term "monomer" used herein refers to low molecular weight 20 compounds (i.e. typically having number average molecular weights less than 700) that can be polymerized. Thus, it is understood that the terms "silicone-containing components" and "hydrophilic components" include monomers, macromonomers and prepolymers. A silicone-containing component is one thai contains at least one [—Si—O— 25 Si] group, in a monomer, rnacromer or prepolymer. Preferably, the Si and attached O are present in the silicone-containing component in an amount greater than 20 weight percent, and more preferably greater than 30 weight percent of the total molecular weight of the silicone-containing component. Useful silicone-contaimng components WO 2006/039466 PCT/US2005/035149 - 20 - preferably comprise polyrnerizable functional groups such as acrylatc, methacrylate, acrylamide, rnethaerylamide, N-vinyl lactam, N-vinylamide, and styryl functional groups. Examples of xilicone-containing components which are useful in this invention may be found in U.S. Pat. Nos. 3,808,178; 4,120,570; 4,136,250; 4,153,641; 5 4,740,533; 5,034,461 and 5,070,215, and EP080539. All of the patents cited herein are hereby incorporated in their entireties by reference. These references disclose many examples of olefinic silicone-containing components. Further examples of suitable silicone-containing monomers are polysiloxanylalkyl(ineth)acrylic monomers represented by the following formula: 10 Formula XI wherein: Z denotes II or lower alkyl and preferably II or methyl; X denotes O or 15 NR ; each R independently denotes hydrogen or methyl, each R1-R3 independently denotes a lower alkyl radical or a phenyl radical, and j is 1 or 3 to 10. Examples of these polysiloxanylalkyl (meth)acrylic monomers include methacryloxypropyl tris(trimcthylsiloxy) silane, pentamethyldisiloxanyl 20 methylmethacrylate, and inethyldi(trimethylsiloxy)methacryloxymethyl silane. Methacryloxypropyl tris(trimethylsiloxy)silane is the most preferred. One preferred class of silicone-containing components is a poly(organosiloxane) prepolymer represented by Formula XII: Formula XII WO 2006/039466 PCT/US2005/035149 wherein each A independently denotes an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid or an alkyl or aryl group (providing that at least one A comprises an activated unsaturated group capable of 5 undergoing radical polymerization); each of R5, R6, R7 and R8 are independently selected from the group consisting of a monovalent hydrocarbon radical or a halogen substituted monovalent hydrocarbon radical having 1 to 18 carbon atoms which may have ether linkages between carbon atoms; R denotes a divalent hydrocarbon radical having from 1 to 22 carbon atoms, 10 and m is 0 or an integer greater than or equal to 1, and preferable 5 to 400, and more preferably 10 to 300. One specific example is a, co-bismcthacryloxypropyl poly-dimethylsiloxane. Another preferred example is mPDMS (monomethacryloxypropyl terminated mono-n-butyl terminated is polydimethylsiloxane). Another useful class of silicone containing components includes silicone- containing vinyl carbonate or vinyl carbamate monomers of the following formula: Formula XIII 2 o wherein: Y denotes O, S or Nil; RSi denotes a silicone-containing organic radical; R denotes hydrogen or lower alkyl, and preferably H or methyl; d is 1, 2, 3 or 4; and q is 0 or 1. Suitable silicone-containing organic radicals RSi| include the following: WO 2006/039466 PCT/US2005/035149 Wherein p is 1 to 6; or an alkyl radical or a fluoroalkyl radical having 1 to 6 carbon atoms; e is 1 to 200; q is 1, 2, 3 or 4; and s is 0, 1, 2, 3, 4 or 5. The siliconc-contain ing vinyl carbonate or vinyl carbamate monomers specifically include: 1,3-bis[4-(vinyloxycarbonyloxy)but-l-yl]tetramethyl-isiloxane 3-(vmyloxycarbonylthio) propyl-[tris (trimethykiloxysilane]; 3- [tris(trimethylsiloxy)silyl] propyl allyl carbamate; 3-[tris(trimeth)'lsiloxy)wilyl] propyl vinyl carbamate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate, and WO 2006/039466 PCT/US2005/035149 Another class of silicone-containing components includes compounds of the following formulae: Formulae XIV-XV 5 (*D*A*D*G)fl *D*D*EI; E(*D*G*D*A)a *D*G*D*E1 or; E(*D*A*D*G)n *D*A*D*E1 wherein: D denotes an alkyi diradical, an alkyl cycloalkyl diradical, a cycloalkyl 10 diradical, an aryl diradical or an alkylaryl diradical having 6 to 30 carbon atoms, G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 1 to 40 carbon atoms and which may contain ether, thio or arnine linkages in the main chain; * denotes a urethanc or ureido linkage; 15 a is at least 1; A denotes a divalent polymeric radical of formula: Formula XVI WO 2006/039466 PCT/US20O5/035149 - 24 - R independently denotes an alkyl or fluoro-substituted alkyl group having 1 to 10 carbon atoms which may contain ether linkages between carbon atoms; r is at least 1; and p provides a moiety weight of 400 to 10,000; each of E and E1 independently denotes a polymcrizable unsaturated organic radical represented by formula: 5 Formula XVII wherein: R12 is hydrogen or methyl; R13 is hydrogen, an alkyl radical having 1 to 6 10 carbon atoms, or a - CO -Y-R15 radical wherein Y is —O—,Y—S— or —Nil—; R14 is a divalent radical having 1 to 12 carbon atoms; X denotes —CO— or — OCO—; Z denotes —O— or —NH—; Ar denotes an aromatic radical having 6 to 30 carbon atoms; a is 0 to 6; b is 0 or 1; e is 0 or 1; and c is 0 or 1. A preferred silicone-containing component is represented by the following 15 formula: Formula XVIII wherein R16 is a diradical of a diisocyanate after removal of the isocyanate group, such as the diradical of isophorone diisocyanate. Another preferred silicone 20 containing macromer is compound of formula X (in which x + y is a number in the range of 10 to 30) formed by the reaction of fluoroether, hydroxy-tenninated polydimethylsiloxane, isophorone diisocyanate and isocyanatoethylmethacrylate. Formula XIX WO 2006/039466 PCT/US2005/035149 Other silicone-containing components suitable for use in this invention include those described is WO 96/31792 such as macromers containing polysiloxane, polyalkylene ether, diisocyanate, polyfluorinated hydrocarbon, 5 polyfluorinated ether and polysaccharide groups. U.S. Pat. Nos. 5,321,108; 5,387,662 and 5,539,016 describe polysiloxancs with a polar fluorinated graft or side group having a hydrogen atom attached to a terminal difluoro-substitutcd carbon atom. Such polysiloxancs can also be used as the siliconc monomer in this invention. 10 The hydrogels may further comprise hydrophilic components, such as those which are capable of providing at least about 20% and preferably at least about 25% water content to the resulting lens when combined with the remaining reactive components. When present, suitable hydrophilic components may be present in amounts up to about 60 weight %, preferably between about 10 to about 60 15 weight%, more preferably between about 15 to about 50 weight % and more preferably still between about 20 to about 40 weight %, all based upon the weight of all reactive components. The hydrophilic monomers that may be used to make the polymers of this invention have at least one polymerizable double bond and at least one hydrophilic functional group. Examples of functional groups with 20 polymerizable double bonds include acrylic, methacrylic, acrylamido, rnethacrylarnido, fumaric, maleic, styryl, isopropenylphenyl, O-vinylcarbonate, O- vinylcarbamate, allylic, O-vinylacetyl and N-vinyllactam and N-vinylamido double bonds. Such hydrophilic monomers may themselves be used as crosslinking agents. WO 2006/039466 PCT/US2005/035149 - 26 - "Acrylic-type" or "acrylic-containing" monomers arc those monomers containing the acrylic group (CR'H=CRCOX) wherein R is H or CH3, R" is II, alkyl or carbonyl, and X is 0 or N, which are also known to polymerize readily, such as N,N-dimethylacrylarnide (DMA), 2- 5 hydroxyethyl acrylate , glycerol methacryiate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, rnethacrylie acid, acrylic acid and mixtures thereof. Hydrophilic vinyl-containing monomers which may be incorporated into the hydrogels of the present invention include monomers such as N-vinyl lactams (e.g. 10 N-vinyl pyrrolidone (N VP)), N-vinyl-N-methyl acctamide, N-vinyl-N-ethyl acetamidc, N-vinyl-N-ethyl fonnamide, N-vinyl formamide, N-2-hydroxyethyl vinyl carbamate, N-carboxy-B-alanine N-vinyl ester, with NVP being preferred. Other hydrophilic monomers that can be employed in the invention include polyoxyethylene polyols having one or more of the terminal hydroxyl groups 15 replaced with a functional group containing a polymerizable double bond. Examples include polyethylene glycol with one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizable double bond. lixamples include polyethylene glycol reacted with one or more molar equivalents of an end-capping group such as isocyanatoethyl methacryiate ("1EM"), methacrylic 20 anhydride, methacryloyl chloride, vinylbenzoyl chloride, or the like, to produce a polyethylene polyol having one or more terminal polymerizable olefinic groups bonded to the polyethylene polyol through linking moieties such as carbamate or ester groups. Still further examples are the hydrophilic vinyl carbonate or vinyl carbamate 25 monomers disclosed in U.S. Pat. No.5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277. Other suitable hydrophilic monomers will be apparent to one skilled in the art. WO 2006/039466 PCT/US2005/035149 - 27 - More preferred hydrophilic monomers which may be incorporated into the polymer of the present invention include hydrophilic monomers such as N,N- dimethyl acrylamide (DMA), 2-hydroxyethyl acrylate, glycerol methacrylate, 2- hydroxyetliyl methacrylamide, N-vinylpyrrolidonc (NVP), and polyethyleneglycol 5 monomethacrylate. Most preferred hydrophilic monomers include DMA, NVP and mixtures thereof. When the reactive, hydrophilic polymeric IWAs of the present invention are incorporated into a silicono hydrogel formulation, it may be desirable to include at 10 least one a hydroxyl containing component to help compatibilize the reactive, hydrophilic polymeric 1WA of the present invention and the silicone containing components. The hydroxyl containing component that may be used to make the polymers of this invention have at least one polymerizable double bond and at least one hydrophilic functional group. Examples of polymerizable double bonds include 15 acrylic, methacrylic, acrylamido, methacrylamido, fumaric, maleic, styryl, isopropenylphcnyl, O-vinylcarbonate, O-vinylcarbamate, allylic, O-vinylacetyl and N-vinyllactam and N-vinylamido double bonds. The hydroxyl containing component may also act as a crosslinking agent. In addition the hydroxyl containing component comprises a hydroxyl group. This hydroxyl group may be a primary, 20 secondary or tertiary alcohol group, and may be located on an allcyl or aryl group. Examples of hydroxyl containing monomers that may be used include but are not limited to 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylamide, 2-hydroxyethyl acrylamide, N-2-hydroxyethyl vinyl carbamate, 2- hydroxyethyl vinyl carbonate, 2-hydroxypropyl methacrylate, hydroxyhexyl 25 methacrylate, hydroxyoctyl methacrylate and other hydroxyl functional monomers as disclosed in U.S. Patents 5,006,622; 5,070,215; 5,256,751 and 5,311,223. Preferred hydroxyl containining monomers include 2~hydroxyethyl methacrylate, and hydroxyl functional monomers including silicone or siloxane functionalities, WO 2006/039466 PC 17US2005/035149 28 such as the hydroxyl-functionalized siliconc containing monomers disclosed in WO03/022321, and the compatibilizing components comprising at least one active hydrogen and at least one siloxane group as disclosed in WO03/022322, the disclosure of which is incorporated herein by reference. Specific examples of 5 include 2-propenoic acid, 2- methyl-2-hydroxy-3-[3-| 1,3,3,3- tetramcthyl-1- [trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (which can also be named (3- methaciyloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane), 3- methacryloxy-2- hydroxypropyloxy)propyltris(trimethylsiloxy)silane, bis-3- methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, 3-methacryloxy-2- l0 (2-hydroxyethoxy)propyloxy) propylbis(trimethylsiloxy)methylsilane, N-2- methacryloxyethyl-0-(methyl-bis-trimcthylsiloxy-3-propyl)silyl carbamate and N,N,N',N'-tetrakis(3-mcthacryloxy-2-hydroxypropyl)-a,co-bis-3-aminopropyl- polydimethylsiloxane and mixtures thereof include 2-hydroxyethyl methacrylate, 3 -mcthacryloxy-2-hydroxypropyloxy)propyIbis(trimethylsiloxy)methylsilane), 3 - 15 methacryloxy-2- hydroxypropyloxy)propyltris(trimethylsiloxy)silane and mixtures thereof are preferred. When a compatibilizing component is used, effective amounts of compatibilizing component in the polymer formulation include about 5 percent (weight percent, based on the total weight of the reactive components) to about 90 20 percent, preferably about 10 percent to about 80 percent, most preferably, about 20 percent to about 50 percent. Alternatively the reactive, hydrophilic polymeric IWAs may be included in hydrophilic hydrogels. Generally these hydrogels arc made from the hydrophilic monomers listed above. Commercially available hydrogel formulations include, but 25 are not limited to etafilcon, polymacon, vifilcon, genfilcon A and lenefilcon A. Generally the reactive components arc mixed in a diluent to form a reaction mixture. Suitable diluents are known in the art. WO 2006/039466 PCT/US2005/035149 29 - Classes of suitable diluents for silicone hydrogel reaction mixtures include ethers, esters, alkanes, alkyl balides, silanes, amides, alcohols and combinations thereof. Amides and alcohols are preferred diluents with alcohols having 2 to 20 carhons, amides having 10 to 20 carbon atoms derived from primary amines and 5 carboxylic acids having 8 to 20 carbon atoms. In some embodiments primary and tertiary alcohols are preferred. Preferred classes include alcohols having 5 to 20 carhons and carboxylic acids having 10 to 20 carbon atoms. Specific diluents which may be used include 1 -ethoxy-2-propanol, diisopropylaminoethanol, isopropanol, 3,7-dimethyl-3-oetanol, 1-decanol, 1- 10 dodecanol, 1-octanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hcxanol, 2-octanol, 3- methyl-3-pentanol, fert-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2- pentanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-l-butanol, SiGMA acetate, l-lert- butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol, 2-octyl-l- dodecanol, decanoic acid, octanoic acid, dodecanoic acid, 2- 15 (diisopropylamino)ethanol mixtures thereof and the like. Preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2- pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2- ethyl-1 -butanol, ethanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic 20 acid, octanoic acid, dodecanoic acid, mixtures thereof and the like. More preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1- decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 1-dodecanol, 3- methyl-3-pentanol, 1-pentanol, 2-pentanol, tert-amyl alcohol, tert-butanol, 2- butanol, 1-butanol, 2-rnethyl-2-pentanol, 2-ethyl-l-butanol, 3,3-dimethyl-2-butanol, 25 2-octyl-1 -dodecanol, mixtures thereof and the like. Suitable diluents for non-siliconc containing reaction mixtures include glycerin, cthylene glycol, ethanol, rncthanol, ethyl acetate, methylene chloride, polyethylene glycol, polypropylene glycol, low molecular weight PVP, such as WO 2006/039466 PCT/US2005/035149 3 0 disclosed in US 4,018,853, US 4,680,336 and US 5,039,459, including, but not limited to boric acid esters of dihydric alcohols, combinations thereof and the like. Mixtures of diluents may be used. The diluents may be used in amounts up to about 50% by weight of the total of all components in the reaction mixture. More 5 preferably the diluent is used in amounts less than about 45% and more preferably in amounts between about 15 and about 40% by weight of the total of all components in the reaction mixture. In another embodiment, the diluent comprises a low molecular weight hydrophilic polymer without photo-polymerizable reactive groups. The diluent may 10 also comprise additional components such as release agents. Suitable release agents are water soluble and aid in lens deblocking. It is generally necessary to add one or more cross-linking agents, also referred to as cross-linking monomers, to the reaction mixture, such as ethylene glycol dimcthacrylate ("EGDMA"), trimethylolpropane trimethacrylate 15 ("TMPTMA"), glycerol trimethacrylate, polyethylene glycol dimethacrylatc (wherein the polyethylene glycol preferably has a molecular weight up to, e.g., about 5000), and other polyacrylate and polymethacrylate esters, such as the end-capped polyoxyethylene polyols described above containing two or more terminal methacrylate moieties. The cross-linking agents are used in the usual amounts, e.g., 20 from about 0.000415 to about 0.0156 mole per 100 grams of reactive components in the reaction mixture. (The reactive components are everything in the reaction mixture except the diluent and any additional processing aids which do not become part of the structure of the polymer.) Alternatively, if the hydrophilic monomers and/or the silicone-containing monomers act as the cross-linking agent, the addition 25 of a crosslinking agent to the reaction mixture is optional. Examples of hydrophilic monomers which can act as the crosslinking agent and when present do not require the addition of an additional crosslinking agent to the reaction mixture include WO 2006/039466 PCT/US2005/035149 31 - polyoxyethylenc polyols described above containing two or more terminal methacrylatc moieties. An example of a silicone-containing monomer which can act as a crosslinking agent and, when present, does not require the addition of a crosslinking 5 monomer to the reaction mixture includes a, avbismethacryloxypropyl polydimethylsiloxanc. The reaction mixture may contain additional components such as, but not limited to, UV absorbers, medicinal agents, antimicrobial compounds, reactive tints, pigments, copolymerizable and nonpolymerizable dyes, release agents and 10 combinations thereof. A polymerization catalyst or initiator is preferably included in the reaction mixture. The polymerization initiators includes compounds such as lauryl peroxide, bcnzoyl peroxide, isopropyl percarbonale, azobisisobutyronitrile, and the like, that generate free radicals at moderately elevated temperatures, and photoinitiator 15 systems such as aromatic alpha-hydroxy ketones, alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphine oxides, and a tertiary aminc plus a diketone, mixtures thereof and the like. Illustrative examples of photoinitiators are 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-l- phenyl propan-1-onc, bi.s(2,6-dimethoxybcnzoyl)-2,4-4-trimethylpentyl phosphine 20 oxide (DMBAPO), bis(2,4,6~trimethylberizoyl)-phenyl phosphineoxidc (Irgacure 819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide and 2,4,6-trimcthylbenzoyl diphenylphosphine oxide, benzoin methyl ether and a combination of camphorquinone and ethyl 4-(N,N-dimethylamino)bcnzoate. Commercially available visible light initiator systems include Irgacure 819, Irgacure 1700, Irgacure 25 1800, Irgacure 819, Irgacure 1850 (all from Ciba Specialty Chemicals) and Lucirin TPO initiator (available from BASF). Commercially available UV photoinitiators include Darocur 1173 and Darocur 2959 (Ciba Specialty Chemicals). These and other photoinitators which may be used are disclosed in Volume III, Photoinitiators WO 2006/039466 PCT/US2005/035149 - 32 - for Free Radical Cationic & Anionic Photopolymerization, 2nd Edition by J.V. Crivcllo & K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998, which is incorporated herein by reference. The initiator is used in the reaction mixture in effective amounts to initiate photopolymerization of the reaction mixture, 5 e.g., from about 0.1 to about 2 parts by weight per 100 parts of reactive monomer. Polymerization of the reaction mixture can be initiated using the appropriate choice of heat or visible or ultraviolet light or other means depending on the polymerization initiator used. Alternatively, initiation can be conducted without a photoinitiator using, for example, e-beam. However, when a photoinitiator is used, the preferred 10 initiators are bisacylphosphine oxides, such as bis(2,4,6-trimethylbenz,oyl)-phenyl phosphinc oxide (Irgacure 819®) or a combination of l-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide (DMBAPO), and the preferred method of polymerization initiation is visible light. The most preferred is bis(2,4,6-trimethylbeiizoyl)-phenyl phosphine oxide (Irgacure 15 81909). The invention further comprises, consists and consists essentially of a silicone hydrogel containing a covalently attached reactive, hydrophilic, polymeric IWA and biomedical device, ophthalmic device and contact lenses formed from the formulations shown below: (all numbers are preceded by the word "about") 20 Wt% RHP1WA OPC HM OC 1-15 5-75, or5-60, or10-50 0-70, or5-60, or10-50 0-90, or10-80, or20-50 3-15 5-75, or5-60, or10-50 0-70, or5-60, or10-50 0-90, or10-80, or20-50 5-12 5-75, or5-60, or10-50 0-70, or5-60, or10-50 0-90, or10-80, or20-50 WO 2006/039466 PCT/US2005/035149 33 - RHHWA is reactive, hydrophilic polymeric internal wetting agent OPC is oxygen permeable component HM is hydrophilic monomer CC is compatibilizirig component 5 The reaction mixtures of the present invention can be formed by any of the methods know to those skilled in the art, such as shaking or stirring, and used to form polymeric articles or devices by known methods. For example, the biomedical devices of the invention may be prepared by 10 mixing reactive components and the diluent(s) with a polymerization initator and curing by appropriate conditions to form a product that can be subsequently formed into the appropriate shape by lathing, cutting and the like. Alternatively, the reaction mixture may be placed in a mold and subsequently cured into the appropriate article. 15 Various processes are known for processing the reaction mixture in the production of contact lenses, including spincasting and static casting. Spincasting methods are disclosed in U.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting methods are disclosed in U.S. Pat. Nos. 4,113,224 and 4,197,266. The preferred method for producing contact lenses comprising the polymer of this invention is by 20 the molding of the silicone hydrogels, which is economical, and enables precise control over the final shape of the hydrated lens. For this method, the reaction mixture is placed in a mold having the shape of the final desired silicone hydrogel, i.e., water-swollen polymer, and the reaction mixture is subjected to conditions whereby the monomers polymerize, to thereby produce a polymer/diluent mixture in 25 the shape of the final desired product. Then, this polymer/diluent mixture is treated with a solvent to remove the diluent and ultimately replace it with water, producing a silicone hydrogel having a final size and shape which are quite similar to the size and shape of the original molded polymer/diluent article. This method can be used WO 2006/039466 PCT7US2005/035149 - 34 - to form contact lenses and is further described in U.S. Pat. Nos. 4,495,313; 4,680,336; 4,889,664; and 5,039,459, incorporated herein by reference. The biomedical devices, and particularly ophthalmic lenses of the present invention have a balance of properties which makes them particularly useful. Such 5 properties include clarity, water content, oxygen permeability and contact angle. Thus, in one embodiment, the biomedical devices are contact lenses having a water content of greater than about 17%, preferably greater than about 20% and more preferably greater than about 25%. As used herein clarity means substantially free from visible haze. Preferably 10 clear lenses have a haze value of less than about 150%, more preferably less than about 100%. Suitable oxygen permeabilities are preferably greater than about 40 barrer and more preferably greater than about 60 barrer. Also, the biomedical devices, and particularly ophthalmic devices and 15 contact lenses have contact angles (advancing) which are less than about 80°, preferably less than about 70° and more preferably less than about 65°. In some preferred embodiments the articles of the present invention have combinations of the above described oxygen permeability, water content and contact angle. All combinations of the above ranges are deemed to be within the present invention. 20 The non-limiting examples below further describe this invention. The dynamic contact angle or DCA, was measured at 23°C, with borate buffered saline, using a Wilhelmy balance. The wetting force between the lens surface and borate buffered saline is measured using a Wilhelmy microbalance while the sample strip cut from the center portion of the lens is being immersed into the 25 saline at a rate of 100 microns/sec . The following equation is used F = 2γpcosθ or θ = cos-1(F/2γp) where F is the wetting force, γ is the surface tension of the probe liquid, p is the perimeter of the sample at the meniscus and 0 is the contact angle. Typically, two WO 2006/039466 PCT/US2005/035149 - 35 - contact angles are obtained from a dynamic wetting experiment - advancing contact angle and receding contact angle. Advancing contact angle is obtained from the portion of the wetting experiment where the sample is being immersed into the probe liquid, and these are the values reported herein. At least four lenses of each 5 composition are measured and the average is reported. The water content was measured as follows: lenses to be tested were allowed to sit in packing solution for 24 hours. Each of three test lens were removed from packing solution using a sponge tipped swab and placed on blotting wipes which have been dampened with packing solution. Both sides of the lens were contacted 10 with the wipe. Using tweezers, the test lens were placed in a weighing pan and weighed. The two more sets of samples were prepared and weighed as above. The pan was weighed three times and the average is the wet weight. The dry weight was measured by placing the sample pans in a vacuum oven which has been preheated to 60°C for 30 minutes. Vacuum was applied until 15 at least 0.4 inches Hg is attained. The vacuum valve and pump were turned off and the lenses were dried for four hours. The purge valve was opened and the oven was allowed reach atmospheric pressure. The pans were removed and weighed. The water content was calculated as follows: 20 Wet weight = combined wet weight of pan and lenses - weight of weighing pan Dry weight = combined dry weight of pan and lens - weight of weighing pan % water content = (wet weight - dry weights x 100 wet weight 25 The average and standard deviation of the water content are calculated for the samples are reported. Modulus was measured by using the crosshead of a constant rate of movement type tensile testing machine equipped with a load cell that is lowered to the initial gauge height. A suitable testing machine includes an Instron model 1122. 3 0 A dog-bone shaped sample having a 0.522 inch length, 0.276 inch "ear" width and WO 2006/039466 PCT/US2005/035149 - 36 - 0.213 inch "neck" width was loaded into the grips and elongated at a constant rate of strain of 2 in/min. until it broke. The initial gauge length of the sample (Lo) and sample length at break (Lf) were measured. Twelve specimens of each composition were measured and the average is reported. Tensile modulus was measured at the 5 initial linear portion of the stress/strain curve. Haze is measured by placing a hydrated test lens in borate buffered saline in a clear 20 x 40 x 10 mm glass cell at ambient temperature above a flat black background, illuminating from below with a fiber optic lamp (Titan Tool Supply Co. fiber optic light with 0.5" diameter light guide set at a power setting of 4-5.4) at an 10 angle 66° normal to the lens cell, and capturing an image of the lens from above, normal to the lens cell with a video camera (DVC 1300C: 19130 RGB camera with Navitar TV Zoom 7000 zoom lens) placed 14 mm above the lens platform. The background scatter is subtracted from the scatter of the lens by subtracting an image of a blank cell using EPIX XCAP V 1.0 software. The subtracted scattered light 15 image is quantitatively analyzed, by integrating over the central 10 mm of the lens, and then comparing to a -1.00 diopter CSI Thin Lens®, which is arbitrarily set at a haze value of 100, with no lens set as a haze value of 0. Five lenses are analyzed and the results are averaged to generate a haze value as a percentage of the standard CSI lens. 20 Oxygen permeability (Dk) may be determined by the polarographic method generally described in ISO 9913-1: 1996(E), but with the following variations. The measurement is conducted at an environment containing 2.1% oxygen. This environment is created by equipping the test chamber with nitrogen and air inputs set at the appropriate ratio, for example 1800 ml/min of nitrogen and 200 ml/min of 25 air. The t/Dk is calculated using the adjusted po2- Borate buffered saline was used. The dark current was measured by using a pure humidified nitrogen environment instead of applying MMA lenses. The lenses were not blotted before measuring. Four lenses were stacked instead of using lenses of varied thickness. A curved WO 2006/039466 PCT/US2005/035149 - 37 - sensor was used in place of a flat sensor. The resulting Dk value is reported in barrers. The following abbreviations are used throughout the Examples and have the 5 following meanings. SiGMA 2-propenoic acid, 2-methyl-2-hydroxy-3- [3-[l,3,3,3- tetramethyl-1 - [trimethylsilyl)oxy]disiloxanyl]propoxy] propyl ester DMA N,N-dimethylacrylamide 10 HEMA 2-hydroxyethyl methacrylate mPDMS 800-1000 MW (Mn) monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane Norbloc 2-(2'-hydroxy-5-memacrylyloxyethylphenyl)-2H- benzotriazole 15 CGI 1850 1:1 (weight) blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)- 2,4-4-trimethylpentyl phosphine oxide CGI 819 2,4,6-trimethylbenzyldiphenyl phosphine oxide LMWHP low molecular weight hydrophilic polymer comprised of a 20 poly(N-vinyl pyrrolidone) backbone with either hydroxyl, amine, carboxylic acid, or carboxylate end groups HMWHC high molecular weight hydrophilic copolymer comprised of poly(N-vinyl pyrrolidone)-co-(9-vinylcarbazole) (97.5/2.5) RHPIWA reactive, hydrophilic polymeric IWA comprised of a poly(N- 25 vinyl pyrrolidone) backbone with covalently attached photo- polymerizable end groups IPA isopropyl alcohol D3O 3,7-dimethyl-3-octanol WO 2006/039466 PCTYUS2005/035149 - 38 - TEGDMA tetraethyleneglycol dimethacrylate EGDMA ethyleneglycol dimethacrylate MMA methyl methaciylate THF tetrahydrofiiran 5 Dioxane 1,4-dioxane DMF N,N-dimethylfonnamide DMAc N,N-dimethylacetamide PVPlow Poly(N-vinyl pyrrolidone), -2500 MW 10 Example 1 9-Vinylcarbazole (0.79 gm, 4.1 mmol) (Aldrich, Milwaukee, WI), 2,2'- Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate (0.16 gm, 0.46 mmol) (Wako Chemicals USA, St. Louis, MO) and freshly distilled N-vinyl-2- pyrrolidone (NVP) (15.1 gm, 136 mmol) were added to a 250 mL round bottom 15 flask equipped with magnetic stirrer and nitrogen inlet. Methyl alcohol (19.2 gm) and distilled water (23.4 gm) were added to the reaction mixture. The mixture was degassed using 3 freeze-pump-thaw cycles and then allowed to warm to ambient temperature. The reaction mixture was heated at 60°C for 16 hours, then precipitated three times using acetone as asolvent to yield a white polymer with Mn, Mw, and 20 polydispersity values of 166,000,420,000, and 2.6, respectively. Molecular weights were measured by gel permeation chromatography (GPC) using poly(2- vinylpyridine) standards and hexafluoroisopropanol as mobile phase. 1H NMR (D2O): A= 7.0-8.2 (bm, 8H, carbazole aromatic H), 3.4-3.8 (bm, 1H, -CH2CH-), 2.8- 3.3 (bm, 2H, -C[O]NCH2-), 2.0-2.4 (bm, 2H, -C[O]CH2-), 1.8-2.0 (bm, 2H, - 25 CH2CH2CH2-), 1.4-1.7 (bm, 2H, -CH2CH-). Example 2 WO 2006/039466 PCT/US2005/035149 - 39 - 9-Vinylcarbazole (Aldrich, Milwaukee, WI) (1.9 gm, 9.6 mmol), 2,2'- azobis[N-(2-carboxyethyl)-2-methylpropionatnidine]tetrahydrate(Wako Chemicals USA, St Louis, MO) (0.56 gm, 1.4 mmol) and freshly distilled N-vinyl-2- pyrrolidone (NVP) (52.8 gm, 475 mmol) were added to a 1 L round bottom flask 5 equipped with magnetic stirrer and nitrogen inlet. Methyl alcohol (231.4 gm) was added to the reaction mixture. The mixture was degassed using 3 freeze-pump-thaw cycles and then allowed to warm to ambient temperature. The reaction mixture was heated at 60°C for 4 hours, then isolated by precipitation (3 times) into diisopropyl ether to yield a white polymer with Mn, Mw, and polydispersity values of 30,000, 10 110,000, and 3.7, respectively, using poly(2-vinylpyridine) standards and hexafluoroisopropanol as mobile phase. Example 3 Polymer from Example 2 (27.0 gm, 239 mmol), DMAC (173 gm), 4- 15 dimethylaminopyridine (DMAP, Avocado Research Chemicals, Heysham, England) (1.2 gm, 9.6 mmol), pyridine (20 mL), methacrylic anhydride (Aldrich, Milwaukee, WI) (7.43 g, 48.2 mmol) and hydroquinone (50 mg, 0.5 mmol, Aldrich, Milwaukee, WI) were charged to a 500 mL round bottom flask equipped with magnetic stirrer and nitrogen inlet. The reaction mixture was heated at 70°C for 6 hours and then 2 o isolated by precipitation into diisopropyl ether (three times) to afford a white solid with Mn, Mw, and polydispersity values of 33,000,109,000, and 3.3, respectively, using poly(2-vinylpyridine) standards and hexafluoroisopropanol as mobile phase. Example 4 25 N-vinylpyrrolidone (50.0 gm, 450 mmol), 2-mercaptopropionic acid (Aldrich, Milwaukee, WI) (0.97 g, 9.2 mmol), 9-vinylcarbazole (1.8 g, 9.2 mmol), and 2,2,'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate(Wako Chemicals USA, St. Louis, MO) (0.53 gm, 1.3 mmol), DMAC (143 gm), and WO 2006/039466 PCT/US2005/035149 - 40 - distilled water (40 mL) were charged to a 500 mL round bottom flask equipped with a nitrogen inlet and magnetic stirrer. The reaction mixture was frozen using an external CCVacetone bath and then placed under vacuum. The solution was backfilled with nitrogen, thawed, and frozen again under vacuum for a total of 3 5 freeze-pump-thaw cycles. The solution was heated to 60°C under nitrogen for 6 hours. Hydroquinone (50 mg, 0.5 mmol, Aldrich, Milwaukee, WI) was added to the reaction mixture, which was then cooled to 5°C. 1 -Hydroxybenzotriazole (Aldrich, Milwaukee, WI) (3.7 gm, 28 mmol), 2-aminoethyl methacrylate hydrochloride (Aldrich, Milwaukee, WI) (4.6 gm, 28 mmol), and l-[3-(dimethylamino)propyl]-3- 10 ethylcarbodiimide hydrochloride (EDC) (Aldrich, Milwaukee, WI) (5.3 gm, 28 mmol) were added and the mixture was stirred for 1 hour at 5°C, followed by an additional 20 hours at room temperature. The reaction mixture was diluted with DMAC (250 mL) and then poured slowly into 70:30 f-butyl methyl ether/hexanes to precipitate out the white solid (90 percent). The polymer was dissolved in 2- 15 propanol and re-precipitated an additional 2 times. The resultant PVP macromer had Mn, Mw, and polydispersity values of 41,000,155,000, and 3.7, respectively. Example 5 N-vinylpyrrolidone (42.6 gm, 384 mmol), 9-vinylcarbazole (0.59 gm, 3.0 20 mmol), 2,2'-azobis{2-[l-(2-hydroxyethyl)-2-imidazolin-2- yl]propane}dihydrochloride (Wako Chemicals USA, St. Louis, MO) (2.67 gm, 7.89 mmol), and methyl alcohol (160 gm) were charged to a 500 mL round bottom flask equipped with a nitrogen inlet and magnetic stirrer. The reaction mixture was subjected to 3 freeze-pump-thaw cycles and then heated to 60°C under nitrogen for 25 6 hours. The polymer was isolated as a white solid (85 percent) by precipitation into diisopropyl ether 3 times and then dried. The resultant polymer (15.8 gm, 141 mmol) was dissolved in anhydrous 1,4- dioxane (Aldrich, Milwaukee, WI) (400 mL). Hydroquinone (50 mg, 0.5 mmol) was WO 2006/039466 PCT/US2005/035149 - 41 - added to the reaction mixture, followed by 2-isocyanatoethyl methacrylate (Aldrich, Milwaukee, WI) (2.2 gm, 14 mmol) and 100 microL of 0.33M stannous octoate (made by dissolving stannous octoate (Aldrich, Milwaukee, WI) in anhydrous toluene). The reaction mixture was heated to 70°C for 8 hours and then poured 5 slowly into diisopropyl ether to yield a white solid (88 percent). The polymer was re-dissolved in 2-propanol and precipitated 2 additional times. The resultant PVP macromer had Mn, Mw, and polydispersity values of 8,000,46,000, and 6.0, , respectively. 10 Example 6 N-vinylpyrrolidone (50.4 gm, 453 mmol), 2-mercaptopropionic acid (Aldrich, Milwaukee, WI) (1.0 gm, 9.2 mmol), 9-vinylcarbazole (1.78 gm, 9.4 mmol), and 2,2'-azobis(2-methylpropionamide)dihydrochloride (Wako Chemicals USA, St. Louis, MO) (2.5 gm, 9.3 mmol), DMAC (150 gm), and distilled water (100 15 mL) were charged to a 500 mL round bottom flask equipped with a nitrogen inlet and magnetic stirrer. The reaction mixture was frozen using an external CC2/acetone bath and then placed under vacuum. The solution was backfilled with nitrogen, thawed, and frozen again under vacuum for a total of 3 freeze-pump-thaw cycles. The solution was heated to 60°C under nitrogen for 6 hours. Hydroquinone (50 mg, 20 0.5 mmol) was added to the reaction mixture, which was then cooled to 10°C. 1- Hydroxybenzotriazole (3.9 gm, 30 mmol), 2-aminoethyl methacrylate hydrochloride (4.6 gm, 28 mmol), and EDC (5.7 gm, 30 mmol) were added and the mixture was stirred for 1 hour at 5°C, followed by an additional 40 hours at room temperature. The reaction mixture was diluted with DMAC (200 mL) and then poured slowly into 25 70:30 The polymer was dissolved in 2-propanol and re-precipitated an additional 2 times. The resultant PVP macromer had Mn, Mw, and polydispersity values of 9,800, 44,000, and 4.5, respectively. WO 2006/039466 PCT/US2005/035149 - 42 - Example 7: Contact Lens Formation The reaction components and diluent (tert-amyl alcohol) listed in Table 2 were mixed together with stirring, shaking, or rolling for at least about 3 hours at 5 23°C, until all components were dissolved. The reactive components are reported as weight percent of all reactive components and the diluent and low molecular weight PVP (PVP low) are weight percents of reaction mixture. The reactive components were purged for approximately 15 minutes using N2. Approximately 40-50 microliters of the reaction formulations were pipetted onto 10 clean polypropylene concave mold halves and covered with the complementary polypropylene convex mold halves. The mold halves were compressed and the mixtures were cured at 55°C for about 30 minutes in the presence of visible light (0.4 mW/cm2 using Philips TL 20W/03T fluorescent bulbs, as measured by an International Light radiometer/photometer). The molds were allowed to cool to room 15 temperature. The top mold halves were removed and the lenses gently removed using tweezers. The lenses were released in water at 90°C for about 20 minutes and then placed in vials containing borate buffered packing solution. 20 Table 2 Example 7A 7B 7C 7D 7E 7F Component SiGMA 30.5 30.5 30.5 30.5 30 30 Ex l 6.1 0 0 0 0 0 Ex 2 0 6.1 0 0 0 0 Ex 3 0 0 6.1 0 0 0 Ex 4 0 0 0 6.1 0 0 Ex 5 0 0 0 0 6 0 Ex 6 0 0 0 0 0 6 DMA 31.5 31.5 31.5 31.5 31 31 mPDMS 22.3 22.3 22.3 22.3 22 22 WO 2006/039466 PCT/US2005/035149 -43 - HEMA 8.6 8.6 8.6 8.6 8.5 8.5 Norbloc 0 0 0 0 1.5 1.5 CGI 1850 0 0 0 0 0 0 CGI 819 0.23 0.23 0.23 0.23 0.23 0.23 TEGDMA 0 0 0 0 0 0 EGDMA 0.76 0.76 0.76 0.76 0.75 0.75 PVPlow 11 11 11 11 11 11 t-amyl 29 29 29 29 29 29 alcohol percent The reactive, hydrophilic polymeric IWAs (RHPIWA) were synthesized in the presence of small amounts (~ 1 mol percent) of fluorescent vinyl monomers. 5 Covalently attached fluorescent "probes", or fluorophores, were used to detect the diffusion of unreacted monomers from the production of the reactive, hydrophilic polymeric IWAs from the contact lenses. The concentration of fluorescent probe in the RHPIWA is low enough so that the physical properties of the labeled RHPIWA are similar to that of unlabeled RHPIWA. 10 The fluorescent probes and fluorescently labeled macromers were first tested to determine whether conditions necessary to make lenses, such as for example, light intensity and heat, affect the emission of fluorescence of the fluorophore. The resultant fluorescently labeled macromers were then combined with reactive components and diluents to make contact lenses. The release of PVP macromers 15 labeled with fluorescent carbazole groups was measured from the extraction media using a Shimadzu RF5301-PC spectrofluorometer (excitation λ = 343 nm, emission λ - 348 nm, slit width = 3 nm). A standard calibration curve of PVP macromer standards was used to correlate the amount of PVP macromer release from lenses. As a control, a high molecular weight hydrophilic copolymer (HMWHC) was used 20 based on PVP (containing 2.5 mol percent carbazole groups) with Mn, Mw, and PD values of 94,800, 511,000, and 5.4, respectively. The molecular weight of the internal wetting agent (Mn), and amount of internal wetting agent extracted after 50- WO 2006/039466 PCT/US2005/035149 - 44 - 100 hrs are shown in Table 3. Table 3 Ex.# 7A 7B 7C 7D 7E 7F Mn 166,000 30,000 33,000 41,000 8,000 9,800 Extraction 100 104 96 52 102 99 Time (hrs) Internal 420 (2.6) 110 109 155 46 (6.0) 44 (4.5) wetting agent (3.7) (3.3) (3.7) Mwx 10-3 (PDI) Percent 12 50 35 5 25 20 wetting agent released The results of Examples 7A through 7F show that the reaction mixture s components and their amounts may be varied. All lenses showed low haze. The reactive, hydrophilic polymeric internal wetting agents in Examples 7C through 7F) were comparable or lower in molecular weight than the low molecular weight hydrophilic polymer of Example 2 (used in formulation 7B) having no photo-polymerizable groups. The percent release of the reactive, hydrophilic 10 polymeric IWAs (Examples 7C-F) from contact lenses was lower (5-35%) as compared to polymers without photo-polymerizable groups (Example 7B, 50%). Example 7A used a non-reactive high molecular weight hydrophilic copolymers. Figure 1 shows the percent of internal wetting agent loss in IPA as a function of time. Example 7D, which comprises a reactive, hydrophilic polymeric IWA lost less 15 than about 5% of the IWA, while Example 7A (which contained a non-reactive hydrophilic, polymeric IWA) lost about 12% of the IWA. Based on Example 4, comparable and even slower release rates can be achieved using lower molecular hydrophilic polymeric IWAs with photo-polymerizable end group(s). The Examples also show that reactive, hydrophilic polymeric IWAs may be 20 synthesized using several synthetic routes, and resulting in resulting in reactive, WO 2006/039466 PCT/US2005/035149 - 45 - hydrophilic polymeric IWAs with different structures, particularly at the end groups. The lenses from Example 7F were analyzed to determine contact angle, water content and mechanical properties. The results are shown in Table 4, below. Table 4 Advancing contact angle 52° Water content 45.2% Modulus ll0psi Elongation at break 124% 5 Thus the reactive, hydrophilic polymeric IWAs produce contact lenses with desirable properties. Example 8 10 Reactive, hydrophilic polymeric IWA was synthesized as in Example 3, except without the use of 9-vinylcarbazole to yield a white polymer with Mn, Mw, and polydispersity values of 38,000,113,000, and 3.0, respectively. Example 9 15 Reactive, hydrophilic polymeric IWA was synthesized as in Example 4, except without the use of 9-vinylcarbazole to yield a white polymer with Mn, Mw, and polydispersity values of 34,500,138,000, and 4.0, respectively. Example 10 20 Reactive, hydrophilic polymeric IWA was synthesized as in Example 5, except without the use of 9-vinylcarbazole to yield a white polymer with Mn, Mw, and polydispersity values of 8,500,42,000, and 4.9, respectively. Example 11 WO 2006/039466 PCT/US2005/035149 - 46 - Reactive, hydrophilic polymeric IWA was synthesized as in Example 6, except without the use of 9-vinylcarbazole to yield a white polymer with Mn, Mw, and polydispersity values of 10,000,40,000, and 4.0, respectively. 5 Example 12: Contact Lens Formation Lenses containing the reactive, hydrophilic polymeric internal wetting agents of Examples 8-11 (no fluorophore) were made as in Example 7. The cure intensity, temperature, and time were maintained 4.0 mW/cm2,55°C, and 12 minutes, respectively. Again, low haze was observed in all lenses. 10 Example 13 NVP (50.5 gm, 454 mmol), vinyl acetate (6.7 gm, 78 mmol), 9- Vinylcarbazole (1.0 gm, 5.4 mmol), 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]tetrahydrate (0.578 gm, 1.39 mmol), methyl alcohol (170 15 gm), and distilled water (27 gm) were added to a 500 mL round bottom flask equipped with magnetic stirrer and nitrogen inlet. The mixture was degassed using 3 freeze-pump-thaw cycles and then allowed to warm to ambient temperature. The reaction mixture was heated at 60°C for 6 hours, and then isolated by precipitation (3 times) into diisopropyl ether to yield a white polymer. The polymer was 20 redissolved in distilled water (1 L) and NaOH was added (3.6 gm, 89 mmol). The reaction mixture was heated to 70°C for 4 hours and then concentrated by rotary evaporation of the solvent. The polymer was precipitated from cold acetone, redissolved in 2 L distilled water, and dialyzed for 72 hours against water and 48 hours against isopropyl alcohol using 3500 molecular weight cut-off Spectra/Por® 25 dialysis membrane (purchased from VWR). The polymer was isolated by removal of solvent to yield an off-white solid with Mn, Mw, and polydispersity values of 49,000,191,000, and 3.9, respectively. WO 2006/039466 PCT/US2005/035149 - 47 - Example 14 The high molecular weight polymer product from Example 13 (21 gin, 200 mmol), anhydrous triethylamine (11.6 gm, 115 mmol), 4-(dimethylamino)pyridine (Aldrich, Milwaukee, WI) (6.1 gm, 50 mmol), hydroquinone (Aldrich, Milwaukee, 5 WI) (50 mg, 0.5 mmol) and anhydrous 1,4-dioxane (300 mL) were charged to a 500 mL round bottom flask equipped with a nitrogen inlet and magnetic stirrer. Methacryloyl chloride (Aldrich, Milwaukee, WI) (6.0 gm, 57 mmol) was added dropwise to the reaction mixture. The mixture was subsequently heated at 60°C for 4 hours. The polymer was isolated by precipitation into 50/50 t-butyl methyl 10 ether/hexanes to yield an off-white solid with Mn, Mw, and polydispersity values of 54,000, 200,000, and 3.7, respectively. Example 15 NVP (50.7 gm, 457 mmol), vinyl acetate (3.7 gm, 43 mmol), 9- 15 vinylcarbazole (0.90 gm, 4.9 mmol), 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]tetrahydrate (0.38 gm, 0.91 mmol), methyl alcohol (75 gm), and distilled water (75 gm) were added to a 500 mL round bottom flask equipped with magnetic stirrer and nitrogen inlet The mixture was degassed using 3 freeze- pump-thaw cycles and then allowed to warm to ambient temperature. The reaction 20 mixture was heated at 60°C for 18 hours, and then isolated by precipitation (3 times) into 50/50 diisopropyl ether/hexanes to yield a white polymer. The polymer was redissolved in distilled water (1 L) and NaOH was added (1.7 gm, 43 mmol). The reaction mixture was heated to 60°C for 6 hours and then concentrated by rotary evaporation of the solvent at 60°C. The polymer was precipitated from 70/30 25 acetone/hexanes, redissolved in 2 L distilled water, and dialyzed for 72 hours against water and 48 hours against isopropyl alcohol using 3500 molecular weight cut-off Spectra/Por® dialysis membrane (purchased from VWR). The polymer was isolated WO 2006/039466 PCT/US2005/035149 - 48 - by removal of solvent to yield an off-white solid with Mn, Mw, and polydispersity values of 86,000,310,000, and 3.6, respectively. Example 16 5 The high molecular weight polymer product from Example 15 (25 gm, 240 mmol), hydroquinone (Aldrich, Milwaukee, WI) (50 mg, 0.5 mmol), 2- isocyanatoethyl methacrylate (Aldrich, Milwaukee, WI) (3.21 gm, 20.4 mmol) and 100 millililters of 0.33M stannous octoate [made by dissolving stannous octoate (Aldrich, Milwaukee, WI) in anhydrous toluene], and anhydrous 1,4-dioxane (300 10 mL) were charged to a 500 mL round bottom flask equipped with a nitrogen inlet and magnetic stirrer. The reaction mixture was heated to 70°C for 8 hours and then poured slowly into diisopropyl ether to yield a white solid (92 percent). The polymer was dissolved in 2-propanol and precipitated 2 additional times affording an off- white solid with Mn, Mw, and polydispersity values of 86,000, 320,000, and 3.7, 15 respectively. Example 17 The reaction components and diluent (tert-amyl alcohol) listed in Table 3 were mixed together and processed to make lenses in accordance with the procedure 20 described in Example 7, above. In one embodiment, reactive, hydrophilic polymeric IWAs were synthesized in the presence of small amounts (~ 1 mol percent) of fluorescent vinyl monomers. The general structure is shown in Formulae XIX, where 9-vinylcarbazole units are present between 0.1 and 2 mol percent. 25 WO 2006/039466 PCT/US2005/035149 Small amounts of covalently attached fluorescent "probes", or fluorophores, were used to detect the diffusion of the polymers listed in Table 3 from contact 5 lenses, as described in Example 7. The lens compositions, molecular weight of the internal wetting agent, and amount of internal wetting agent extracted after 50-100 hrs are shown in Table 5, below. WO 2006/039466 PCT/US2005/035149 - 50 - Table 5 Component 17A 17B 17C 17D 17E 17F SiGMA 30.5 30.5 30.5 30.5 30 30 Ex l 6.1 0 0 0 0 0 Ex 2 0 6.1 0 0 0 0 Ex 13 0 0 6.1 0 0 0 Ex 14 0 0 0 6.1 0 0 Ex 15 0 0 0 0 6.1 0 Ex 16 0 0 0 0 0 6.1 DMA 31.5 31.5 31.5 31.5 31.5 31.5 MPDMS 22.3 22.3 22.3 22.3 22.3 22.3 HEMA 8.6 8.6 8.6 8.6 8.6 8.6 Norbloc 0 0 0 0 0 0 CGI 819 0.23 0.23 0.23 0.23 0.23 0.23 TEGDMA 0 0 0 0 0 0 EGDMA 0.76 0.76 0.76 0.76 0.76 0.76 PVPlow 11 11 11 11 11 11 t-amyl 29 29 29 29 29 29 alcohol % Percent PVP macromer released from lens after extraction in 2-propanol Extraction 100 104 98 96 100 99 Time (hrs) IWA Mwx 420 110 191 200 310 320 (3.7) 10-3 (PDI) (2.6) (3.7) (3.9) (3.7) (3.6) Weight % 12 50 26 0.3 18 0.4 release of IWA The results of Examples 17A through F show that the reaction mixture 5 components and their amounts may be varied. All lenses showed low haze. As shown in Table 5, the rate of release of the polymers without reactive groups (Examples 17C and 17E) was faster than that of the high molecular weight control (Example 17A) and slower than that of the low molecular weight control (Example 17B) after ~100 hours in isopropanol. Examples 17D and 17F, which 10 contained reactive, hydrophilic polymeric IWAs of the present invention, displayed WO 2006/039466 PCT/US2005/035149 - 51 - insignificant release of the internal wetting agents. This is significant since preservation of the internal wetting agent helps maintain lens wettability in addition to other previously described lens properties since the initial weight percent of components in the reaction mixture remains relatively constant after curing and 5 extraction in organic solvents. Example 18 Synthesis was carried out as in Example 13 without the use of 9- vinylcarbazole. In addition, methyl alcohol in the reaction mixture was replaced by 10 an equal weight of distilled water. Polymer Mn, Mw, and polydispersity was: 45,000,225,000, and 5.0. Example 19 Synthesis was carried out as in Example 14 without the use of 9- 15 vinylcarbazole. In addition, methyl alcohol in the reaction mixture was replaced by an equal weight of distilled water. Polymer Mn, Mw, and polydispersity were: 49,000,230,000, and 4.7. Examples 20 20 Lenses containing the low molecular weight hydrophilic polymer of Example 18 and the reactive, hydrophilic polymer IWA of Example 19 were made as in Example 17 using similar amounts of reaction components, but without the addition of fluorophore. The cure intensity, temperature, and time were similarly held at 4.0 mW/cm2, 55°C, and 12 minutes, respectively. Low haze was observed in all lenses. 25 WO 2006/039466 PCT7US2005/035149 - 52 - What is claimed is: 1. A silicone hydrogel formed from a reaction mixture comprising at least one oxygen permeable component and at least one reactive, hydrophilic polymeric 5 internal wetting agent. 2. The hydrogel of claim 1 wherein said internal wetting agent has a Mw of about 5,000 to about 2,000,000 Daltons. 3. The hydrogel of claim 1 wherein said internal wetting agent has a Mw of about 5,000 to about 180,000 Daltons. 10 4. The hydrogel of claim 1 wherein said internal wetting agent has a Mw of about 5,000 to about 150,000 Daltons. 5. The hydrogel of claim 1 wherein said internal wetting agent has a Mw of about 60,000 to about 2,000,000 Daltons. 6. The hydrogel of claim 1 wherein said internal wetting agent has a Mw of is about 1800,000 to about 1,500,000 Daltons 7. The hydrogel of claim 1 comprising a mixture of reactive, hydrophilic polymeric IWAs. 8. The hydrogel of claim 1 wherein said internal wetting agent is derived from at least one polymer selected from the group consisting of polyamides, polylactones, 20 polyimides, polytectams and functionalized polyamides, polylactones, polyimides, polylactams and copolymers and mixtures thereof. 9. The hydrogel of claim 1 wherein said internal wetting agent is derived from at least one polymer selected from the group consisting of polymers of Formulae of II, IV, VI and VH 25 Formula II WO 2006/039466 PCT/US2005/035149 WO 2006/039466 PCT7US2005/035149 10. The hydrogel of claim 1 wherein said internal wetting agent is derived from at least one polymer comprising repeating units of Formula VIII 5 wherein Q is a direct bond, 10 wherein Rc is a Cl to C3 alkyl group; Ra is selected from H, straight or branched, substituted or unsubstituted Cl to C4 alkyl groups, Rb is selected from H, straight or branched, substituted or unsubstituted Cl to C4 alkyl groups, amino groups having up to two carbons, amide groups having up to 15 4 carbon atoms and alkoxy groups having up to two carbons and wherein the WO 2006/039466 PCT/US2005/035149 - 55 - number of carbon atoms in Ra and Rb taken together is 8, preferably 6 or less. As used herein substituted alkyl groups include alkyl groups substituted with an amine, amide, ether or carboxy group. 5 11. The hydrogel of claim 1 wherein said reactive, hydrophilic polymeric internal wetting agent is present in an amounts from about 1 to about 15 weight percent, based upon total weight of all reactive components. 12. The hydrogel of claim 1 wherein said internal wetting agent is present in an amounts from about 3 to about 15 percent, based upon total weight of all reactive 10 components. 13. The hydrogel of claim 1 wherein said internal wetting agent is present in an amounts from about 5 to about 12 percent, based upon total weight of all reactive components. 15 14. The hydrogel of claim 10 wherein said internal wetting agent further comprises repeating units selected from the group consisting of N-vinylpyrrolidone, N,N-dimethylacrylamide, 2-hydroxyethylmethacrylate, vinyl acetate, acrylonitrile, methyl methacrylate, siloxane substituted acrylates or methacrylates, alkyl 20 (meth)acrylates and mixtures thereof. 15. The hydrogel of claim 10 wherein said internal wetting agent further comprises repeating units selected from the group consisting of N-vinylpyrrolidone, N,N-dimethylacrylamide, 2-hydroxyethylmethacrylate and mixtures thereof. 25 16. The hydrogel of claim 10 wherein said repeating unit comprises N-vinyl- N-methylacetamide. WO 2006/039466 PCT/US2005/035149 - 56 - 17. The hydrogel of claim 1 wherein said oxygen permeable component comprises at least one silicone containing component. 18. The hydrogel of claim 17 wherein said at least one silicone containing 5 component is selected from the group consisting of silicone containing monomers, silicone containing macromers and mixtures thereof. 19. The hydrogel of claim 17 wherein said at least one silicone containing component is selected from the group consisting of polysiloxyalkyl(meth)acrylic 10 monomers, poly(organosiloxane) prepolymers, silicone containing vinyl carbonate monomers, silicone containing vinyl carbamate monomers, and mixtures thereof. 20. The hydrogel of claim 1 further comprising at least one hydrophilic monomer. 15 21. The hydrogel of claim 20 wherein said hydrophilic monomer is present in amounts up to about 60 weight % based upon weight of all reactive components. 22. The hydrogel of claim 20 wherein said hydrophilic monomer is present 20 in amounts between about 10 to about 60 weight%, based upon weight of all reactive components. 23. The hydrogel of claim 20 wherein said hydrophilic monomer is present in amounts between about 20 to about 40 weight %, based upon weight of all 25 reactive components. 24. The hydrogel of claim 20 wherein said hydrophilic monomer is selected from the group consisting of N,N-dimethyl acrylamide (DMA), 2-hydroxyethyl WO 2006/039466 PCT/US2005/035149 - 57 - acrylate, 2-hydroxyethyl methactylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone, polyethyleneglycol monomethacrylate, and mixtures thereof. 5 25. The hydrogel of claim 1 further comprising at least one compatibilizing component. 26. The hydrogel of claim 25 wherein said compatibilizing component is selected from hydroxyl containing monomers and macromers. 10 27. The hydrogel of claim 25 wherein said compatibilizing component is selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylamide, 2-hydroxyethyl acrylamide, N-2- hydroxyethyl vinyl carbamate, 2-hydroxyethyl vinyl carbonate, 2-hydroxypropyl 15 methacrylate, hydroxyhexyl methacrylate, hydroxyoctyl methacrylate and hydroxyl functional monomers comprising silicone or siloxane groups and mixtures thereof. 28. The hydrogel of claim 25 wherein said compatibilizing component is selected from the group consisting of 2-hydroxyethyl methacrylate, 3-methacryloxy- 20 2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, 3-methacryloxy-2- hydroxypropyloxy)propyltris(trimethylsiloxy)silane, bis-3-methacryloxy-2- hydroxypropyloxypropyl polydimethylsiloxane, 3-methacryloxy-2-(2- hydroxyethoxy)propyloxy) propylbis(trimethylsiloxy)methylsilane, N-2- methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate and 25 N,N,N',N'-tetrakis(3-methacryloxy-2-hydroxypropyl)-α,ω-bis-3-aminopropyl- polydimethylsiloxane and mixtures thereof. 29. The hydrogel of claim 25 wherein said compatibilizing component is selected from the group consisting of 2-hydroxyethyl methacrylate, 3-methacryloxy- WO 2006/039466 PCT/US2005/035149 - 58 - 2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane), 3-methacryloxy-2- hydroxypropyloxy)propyltris(trimethylsiloxy)silane and mixtures thereof. 30. The hydrogel of claim 25 wherein said compatibilizing component is 5 present in amounts between about 5 to about 90 weight percent, based on total weight of the reactive components. 31. The hydrogel of claim 25 wherein said compatibilizing component is present in amounts between about 10 to about 80 weight percent based on total weight of the reactive components. 10 32. The hydrogel of claim 25 wherein said compatibilizing component is present in amounts between about 20 to about 50 weight percent, based on total weight of the reactive components. 15 33. A contact lens formed from the hydrogel of claim 1. 34. The hydrogel of claim 1 wherein said reactive, hydrophilic polymeric IWA comprises a reactive high molecular weight copolymer derived from monomers comprising vinyllactam monomers and vinyl carboxylate monomers. 20 35. The hydrogel of claim 34 wherein said reactive, hydrophilic polymeric IWA has a molecular weight (weight average) of at least about 60,000 Daltons. 36. The hydrogel of claim 34 wherein said reactive, hydrophilic polymeric IWA has a molecular weight (weight average) of between about 60,000 to about 750,000 Daltons. 25 37. The hydrogel of claim 34 wherein said reactive, hydrophilic polymeric IWA has a molecular weights (weight average) of between about 180,000 to about 500,000 Daltons. WO 2006/039466 PCT/US2005/035149 - 59 - 38. The hydrogel of claim 34 wherein said vinyllactams monomers are selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3-methyl-2- piperidone, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2- pyrrolidone, N- 5 vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl-2- pyrrolidone, N-vinyl-5-methyl- 2-piperidone, N-vinyl-5,5-dimethyl-2- pyrrolidone, N-vinyl-3,3,5-trimethyl-2- pyrrolidone, N-vinyl-5-methyl-5- ethyl-2-pyrrolidone, N-vinyl-3,4,5-trirnethyl-3- ethyl-2-pyrrolidone, N- vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vi nyl-4,4-dimethyl-2-piperidone, N-vinyl-7- 10 methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5- dimethyl-2- caprolactam, N-vinyl4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2- caprolactam, N-vinylmaleimide, vinylsuccinimide and mixtures thereof. 39. The hydrogel of claim 34 wherein said vinyllactam monomers are selected from the group consisting of heterocyclic monomers containing 4 carbon 15 atoms in the heterocyclic ring. 40. The hydrogel of claim 34 wherein said vinyllactams monomer comprises N-vinyl-2-pyrrolidone. 41. The hydrogel of claim 34 wherein said vinyl carboxylate monomers are selected from the group consisting of compounds having 1 to 10 carbon atoms and 20 bom vinyl and carboxylate functionality. 42. The hydrogel of claim 34 wherein said vinyl carboxylate monomers are selected from the group consisting of vinyl heptanoate, vinyl hexanoate, vinyl pentanoate, vinyl butanoate, vinyl propanoate (vinyl propionate), vinyl ethanoate (vinyl acetate) and mixtures thereof. 25 43. The hydrogel of claim 34 wherein said vinyl carboxylate monomer comprises vinyl acetate. 44. The hydrogel of claim 34, wherein said reactive, hydrophilic polymeric IWA is selected from the group consisting of compounds of Formula DC, X WO 2006/039466 PCT/US2005/035149 and mixtures thereof. The present invention relates to wettable silicone hydrogels comprising the reaction production of at least one siloxane containing component and at least one reactive, hydrophilic polymeric internal wetting agent. The present invention further relates to silicone hydrogel contact lenses comprising at least one oxygen permeable component, and an amount of reactive, hydrophilic polymeric internal wetting agent sufficient to impart wettability to said device. |
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| Patent Number | 271381 | ||||||||||||||||||
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| Indian Patent Application Number | 1084/KOLNP/2007 | ||||||||||||||||||
| PG Journal Number | 08/2016 | ||||||||||||||||||
| Publication Date | 19-Feb-2016 | ||||||||||||||||||
| Grant Date | 18-Feb-2016 | ||||||||||||||||||
| Date of Filing | 28-Mar-2007 | ||||||||||||||||||
| Name of Patentee | JOHNSON & JOHNSON VISION CARE, INC | ||||||||||||||||||
| Applicant Address | 7500 CENTURION PARKWAY, SUIT 100 JACKSONVILLE, FL 32256 U.S.A. | ||||||||||||||||||
Inventors:
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| PCT International Classification Number | G02B 1/04 | ||||||||||||||||||
| PCT International Application Number | PCT/US2005/035149 | ||||||||||||||||||
| PCT International Filing date | 2005-09-28 | ||||||||||||||||||
PCT Conventions:
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