MXPA97010041A - Macromonomeros de siloxano polimerizab - Google Patents

Abstract

A macromonomer of formula I is described: wherein n is zero or at least 1.0, Q is a polymerizable group, B may be the same or different, and is a difunctional block of a molecular weight on the scale of 100 to 8,000, and wherein at least one B is a residue of a difunctional polymer or copolymer wherein B has a molecular weight of 248 to 8,000, in which it comprises silicone repeat units of the formula II: wherein R1 and R2 may be the same or different , and are selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, heterocyclyl, and haloheterocyclyl, L is a difunctional linking group, and T is a terminal group. The macromonomer can be used preferably in the production of contact lenses.

Description

OXANO POLYMERIZABLE SI MACROMONOMERS The invention relates to macromonomers, to polymers, and to polymeric articles particularly suitable for ocular applications, and as cell growth substrates. More specifically, this invention relates to polymers that are suitable for use in contact lenses, and to ophthalmic devices such as epiqueratoprostheses. A wide variety of research has been conducted in the field of biocompatible polymers. The definition of biocompatible depends on the particular application for which the polymer is designed. In order to function properly * as a contact lens, a material must have a variety of properties, including biological and chemical inertness, mechanical stability, optical transparency, oxygen permeability, and wettability by tears. It is particularly convenient that a contact lens can transmit oxygen to the cornea, and that it be soft and comfortable to allow use for prolonged periods. In order to function properly as a corneal implant, such as an epitheratoprosthesis, the polymer, in addition, must allow adhesion and growth of the corneal epithelium, and must be highly biostable as an implant. Contact lenses can be classified into lenses hard and rigid contacts, such as those made from poly (methyl methacrylate), and soft flexible contact lenses, such as those made from poly (2-hydroxyethyl methacrylate). Both of these basic types of contact lenses suffer from several limitations. Hard and rigid contact lenses are uncomfortable to use, and therefore, are not well tolerated by some patients. Although poly (methyl methacrylate) hard lenses do not allow virtually the transmission of oxygen through the lens to support the cornea, there are some kinds of rigid lenses that do allow a good oxygen passage, for example, materials based on silicon. Regardless of this, they suffer from the aforementioned limitation of poor comfort due to their lack of softness. For optimum comfort and handling, the modulus of elasticity of the lens material would be 0.5 to 5.0 MPa, preferably 1.0 to 2.5 MPa. Conventional soft contact lenses suffer from the drawback that there is insufficient transmissibility of oxygen through the lens to support normal corneal physiology. According to the above, they can not be used continuously for prolonged periods. Clinical symptoms of this lens-induced hypoxia include limbal redness and corneal swelling. An ocular infection of an extended hypoxia induced by the use of the contact lens may result. A minimum oxygen transmissibility would be greater than 50 Sweep, preferably greater than 70 Sweep, and more preferably greater than 87 Sweep for continuous use. There is a long-felt need for durable contact lens materials that combine the comfort of a soft contact lens with sufficient oxygen transmissibility to maintain normal corneal physiology. In one aspect, the present invention provides materials that meet this need. Contact lenses should be comfortable and suitable for long-term use. In order to achieve comfort for prolonged periods, a lens must have a low modulus of elasticity (ie, it must be soft). In addition, it is desirable that it be resistant to contamination by proteins, lipids, mucoids, and the like. However, contact lenses must also be of sufficient durability to allow normal handling and use. Accordingly, a polymer having the combination of high oxygen permeability and a low modulus is required. We have now discovered a macromonomer that is suitable for use in the manufacture of these polymers. According to the above, in its main aspect, this invention provides a macromonomer of the formula I: -B (L-B) nT (I) wherein n is zero or at least 1.0, preferably at least 1.0; Q is a polymerizable group; B may be the same or different, and is a difunctional block of a molecular weight in the range of 100 to 8,000, and wherein at least one B is a residue of a difunctional polymer or copolymer wherein B has a molecular weight of 248 a 8,000, which comprises repeat units of silicone of formula II: wherein Rj and R2 may be the same or different, and are selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, heterocyclyl, and haloheterocyclyl; preferably from alkyl, aryl, and alkyl substituted by halogen; L is a difunctional link group; and T is a terminal group.

Preferably n is on the scale of 1 to 5, and still more preferably on a scale of 1 to 4, for example 1 to 3 or 2 to 4. Q is a polymerizable group which preferably comprises an ethylenically unsaturated fraction which can enter a polymerization reaction. Preferably Q is a group of the formula A: lxl - (Y) m- (R < -Xl) p- (A) wherein P i is a free radical polymerizable group; Y is -C0NHC00-, -CONHCONH-, -OCO HCO-, -NHCONHCO-, -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -NHCOO-, OR -OCONH-. m and p, independently of one another, are 0 or 1; R 'is a bivalent radical of an organic compound having up to 20 carbon atoms; Xj is -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -NHCOO-, or -OCONH-. A free radical polymerizable group j is, for example, alkenyl, alkenylaryl, or alkenylarylenealkyl having up to 20 carbon atoms. Examples of alkenyl are vinyl, allyl, l-propen-2-yl, l-buten-2-, -3-, and -4-yl, 2-buten-3-yl, and the isomers of pentenyl, hexenyl, octenyl, decenyl, and undecenyl. The examples of alkenylaryl are vinylphenyl, vinylnaphthyl, or allylphenyl. An example of alkenylarylenealkyl is o-, m-, or p-vinylbenzyl. Pj is preferably alkenyl or alkenylaryl having up to 12 carbon atoms, particularly preferably alkenyl having up to 8 carbon atoms, in particular alkenyl having up to 4 carbon atoms. And it is preferably -COO-, -OCO-, -NHCONH-, NHCOO-, -OCONH-, -NHCO-, or -CONH-, in a particularly preferable manner -COO-, -OCO-, NHCO-, or- CONH-, and in particular, -COO- or -OCO-. Xj is preferably -NHCONH-, -NHCOO-, or -OCONH-, in a particularly preferable manner -NHCOO- or -OCONH. In a preferred embodiment, the indices m and p are not simultaneously zero, if p is zero, m is preferably 1. R 'is preferably alkylene, arylene, a saturated bivalent cycloaliphatic group having from 6 to 20 carbon atoms, ary 1 e n 1 qu i 1 ene, a 1 qu i 1 e na ri 1 ene, alkylenealkylenealkylene, or arylenenalkylenearylene. Preferably, R 'is a bivalent radical having up to 12 carbon atoms, particularly preferably a bivalent radical having up to 8 carbon atoms. In a preferred embodiment, R 'is further alkylene or arylene having up to 12 carbon atoms. A particularly preferred embodiment of R 'is lower alkylene, in particular lower alkylene having up to 4 carbon atoms.

It is particularly preferred that Q be selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, urethane methacrylate, or any substituted derivatives thereof. Preferably, Q is a compound of the formula A wherein Pj is alkenyl of up to 4 carbon atoms. Y is -COO-, R 'is alkylene of up to 4 carbon atoms, Xj is -NHCOO-, yiyp are each, one. Groups of substituents suitable for Q can be selected from: alkyl, alkenyl, alkynyl, aryl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, amino, alkylamino, alkenylamino, alkynylamino, alkylamino, acylamino, aroyl, alkenylacyl, arylacyl, acylamino, alkylsulfonyloxy, arylsulfonyloxy, heterocyclyl, heterocyclyloxy, heterocyclylamino, haloheterocyclyl, alkoxycarbonyl, thioalkyl, alkylsulfonyl, thioaryl, arylsulfonyl, aminosulfonyl , dialkylamino, and dialkylsulfonyl, having up to 10 carbon atoms. Blocks B can be monomeric, oligomeric, or polymeric. The molecular weights and chemical composition of each block B may be the same or different, provided that they fall within the scale of molecular weight specified above, and that at least one block B is a residue comprising units of the formula II. B blocks can be hydrophobic or hydrophilic. When B is a hydrophobic block, difunctional residues derived from perfluorinated polysiloxanes and polyethers are particularly preferred; when B is hydrophilic, difunctional residues derived from poly (alkylene oxides), such as polyethylene glycols or poly (cyclic ethers) are particularly preferred. In one embodiment, it is preferred that the macromonomer of the present invention have at least two B blocks that are polysiloxanes. At least one block B is a residue of a difunctional polymer or copolymer, wherein B has a molecular weight of 248 to 8,000, preferably 248 to 6,000, comprising silicone repeat units of formula II as defined above in present, and preferably with an end functionality as described below. It is preferred that Rj and R2 have both 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. In particular, it is preferred that the silicone repeat units are as described herein, and wherein Rj and R2 are both alkyl of 1 to 6 carbon atoms, more preferably methyl. A difunctional polymer or copolymer from which B is derived, contains a terminal functionality independently selected at each end, which reacts with the precursor of the linking group L, such that a covalent bond is formed. The preferred terminal functionality is hydroxyl or amino. This functionality can be linked to the siloxane units in B by means of an alkylene group or other non-reactive separator. Preferred terminal fractions are hydroxyalkyl, hydroxyalkoxyalkyl, and alkylamino. Especially preferred hydroxyalkyls are hydroxypropyl and hydroxybutyl; Particularly preferred hydroxyalkyls are hydroxyethoxyethyl and hydroxyethoxypropyl. Preferred B blocks in formula I as specified above, are of the formula M: where Q is an integer from 5 to 100; Alk is alkylene having up to 20 carbon atoms, uninterrupted or interrupted by oxygen; the radicals R1 # R2, R3, and R4, independently of one another, are alkyl, aryl, or alkyl substituted by halogen; and X3 is -0- or -NH-. In a preferred meaning, Q is an integer from 5 to 70, particularly preferable from 8 to 50, in particular to 28. In a preferred sense, the radicals R j, R 2, R 3, and R are, independently of one another, lower alkyl having up to 8 carbon atoms, particularly preferably lower alkyl having up to 4 carbon atoms. carbon, especially lower alkyl having up to 2 carbon atoms. A further particularly preferred unit of Rlf R2, R3, and R4 is methyl. Alkylene interrupted by oxygen is preferably lower alkylene-lower oxy-alkylene having up to 6 carbon atoms in each of the two lower alkylene fractions, more preferably lower alkylene-lower oxy-alkylene having up to 4 carbon atoms in each one of the two lower alkylene fractions, the examples being ethylene-oxy-ethylene or ethylene-oxy-propylene. Alkyl substituted by halogen is preferably lower alkyl substituted by one or more, especially up to 3 halogen atoms such as fluorine, chlorine, or bromine, the examples being trifluoromethyl, chloromethyl, heptafluorobutyl, or bromoethyl. When B is derived from a perfluorinated polyether, it is preferably of the formula N: -COH2CF20 (CF2CF20)? (CF20) andCF2CH20 (N) wherein the CF2CF20 and CF20 units can be randomly distributed, or they can be distributed as blocks throughout the chain, and where x and y can be the same or different, such that the molecular weight of the perfluorinated polyether is on the scale of 242 to 4,000. Preferably, x in the formula N is on the scale of 0 to 20, more preferably on the scale of 8 to 12, e and is on the scale of 0 to 25, more preferably on the scale of 10 to 14. When one or more of the B blocks is hydrophilic, these blocks are derived in a particularly preferable manner from poly (alkylene oxides) , more preferably from poly (lower alkylene oxide), and most preferably from polyethylene glycols. It is more preferred that blocks B be selected from blocks of formula II (or M) and poly (alkylene oxides), provided that at least one of the blocks is of formula II (or M). In two highly preferred embodiments of the invention, there are two B blocks in a macromonomer of the formula I which are both of the formula II (or M), or one of which is of formula II (or M), while the other is derived from a poly (alkylene oxide), preferably from a poly (lower alkylene oxide) , more preferably from polyethylene glycols. "Derivative from a poly (alkylene oxide)", in the context of the definition of B-blocks, means that this B-block differs from a poly (alkylene oxide) in that the two hydrogens terminals have been abstracted from this poly (alkylene oxide). For the purpose of exemplifying this, B denotes, if derived from a polyethylene glycol, - (OCH2CH2) aO-, where a is the index indicating the repeating ethyleneoxy number or groups, hereinafter referred to as " PEG. " The linking group L can be any difunctional fraction that can react with hydroxyl. Suitable precursors for L are a,? - diepoxides, cc,? - diisocyanates, a,? -diisothiocyanates, halides,? -diacyl, halides of a,? -dithioacyl, at,? - dicarboxylic acids, a acids, ? -dithiocarboxylic, a,? - dianhydrides, Qf,? - dilactones, a,? - dialkyl esters, a,? - dihalides, c *,? - dialkyl ethers, amide a,? - dihydroxymethyl. It is preferred that the linking group be a bivalent residue (-C (O) -NH-R-NH-C (O) -) of a diisocyanate, wherein R is a bivalent organic radical having up to 20 carbon atoms. The bivalent radical R is, for example, alkylene, arylene, alkylenearylene, arylenealkylene, or arylenenalkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having from 6 to 20 carbon atoms, or cycloalkylenealkylenecycloalkylene having 7 to 20 carbon atoms. at 20 carbon atoms. In a preferred embodiment, R is alkylene, arylene, alkylenearylene, arylenealkylene, or arylenenalkylenearylene having up to 14 carbon atoms, or a cycloaliphatic group saturated bivalent having 6 to 14 carbon atoms. In a particularly preferred embodiment, R is alkylene or arylene having up to 12 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms. In a preferred embodiment, R is alkylene or arylene having up to 10 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 10 carbon atoms. In a particularly preferred meaning, R is a radical derived from a diisocyanate, for example from 1,6-hexane diisocyanate, 1,6-diisocyanate of 2,2,4-trimethylhexane, tetramethylene diisocyanate, 1, 4-phenylene diisocyanate, toluene 2,4-diisocyanate, 2,6-toluene diisocyanate, m- or p-tetramethylxylene diisocyanate, isophorone diisocyanate, or 1,4-cyclohexane diisocyanate. Aryl is a carbocyclic aromatic radical that is unsubstituted or is preferably substituted by lower alkyl or lower alkoxy. Examples are phenyl, tolyl, xylyl, methoxyphenyl, t-butoxyphenyl, naphthyl, and phenanthryl. Arylene is preferably phenylene or naphthylene, which is unsubstituted or substituted by lower alkyl or lower alkoxy, in particular 1, 3-phenylene, 1,4-phenylene, omethyl-1,4-phenylene, 1,5-naphthylene, or 1 , 8-naphthylene. A saturated bivalent cycloaliphatic group is preferably cycloalkylene, for example cyclohexylene or cyclohexylene (lower alkylene), for example cyclohexylenemethylene, which is unsubstituted or substituted by one or more lower alkyl groups, for example methyl groups, for example trimethylcyclohexylenemethylene, for example the bivalent isophorone radical. For the purposes of the present invention, the term "lower" in relation to radicals and compounds, unless defined otherwise, denotes, in particular, radicals or compounds having up to 8 carbon atoms, preferably having They have up to 4 carbon atoms. Lower alkyl has, in particular, up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methyl, ethyl, propyl, butyl, tertiary butyl, pentyl, hexyl, or isohexyl. Alkylene has up to 12 carbon atoms, and can be straight or branched chain. Suitable examples are decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene, 3-pentylene, and the like. Lower alkylene is alkylene having up to 8 carbon atoms, particularly preferably up to 4 carbon atoms. Particularly preferred meanings of lower alkylene are propylene, ethylene, and methylene. The arylene unit in alkylenearylene or arylenealkylene is preferably phenylene, unsubstituted or substituted by lower alkyl or lower alkoxy, and the unit of alkylene in it is preferably lower alkylene, such as methylene or ethylene, in particular methylene. Accordingly, these radicals are preferably phenylenemethylene or methylenephenylene. Lower alkoxy has in particular up to 8 carbon atoms, preferably up to 4 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tertiary butoxy, or hexyloxy. Ailelene-alkylenearylene is preferably phenylene (lower alkylene) phenylene having up to 8, in particular up to 4 carbon atoms in the alkylene unit, for example phenylene-ethylene-phenylene or phenylene-methylene-phenylene. Some examples of highly preferred diisocyanates from which bivalent residues are derived include trimethylhexamethylene diisocyanate diisocyanate (TMHMDI), isophorone diisocyanate (IPDI), methylenediphenyl diisocyanate (MDI), and 1,6-hexamethylene diisocyanate (HMDI). In formula I, T is a univalent terminal group that can not be polymerized by free radicals, but may contain other functionality. In a particular manner, the preferred terminal groups are hydrogen, alkyl, substituted alkyl, aryl, or substituted aryl. The most preferred T groups are hydrogen, lower alkyl, and phenyl. Suitable groups or substituents for T can be selected from the same groups and substituents given previously known herein in the context of Q. In the preferred embodiments of the present invention, macromonomers of the formulas IIIA, IVA, and VIA are provided: CH2 = C (CH3) COOC2H4NHCO-PDMS-CONH-R-NHCO-PDMS-R? (IIIA) CH2 = C (CH3) COOC2H4NHCO-PDMS-R? (VAT) CH2 = C (CH3) COOC2H4NHCO-PDMS-CONH-R-NHCO-PEG-R, (VIA) wherein PDMS is of the formula M as defined hereinabove, R is alkylene or arylene having up to 12 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms, and Rx is hydrogen or lower alkyl. Of these compounds, those of the formulas IIIA and VIA, especially those of the formula IIIA, are preferred. In the further preferred embodiments of the present invention, macromonomers of the formulas III to VI are provided: CH2 = C (CH3) COOC2H4NHCO-PDMS-CONH-R-NHCO-PDMS-H (III) CH2 = C (C) COOC2H4NHCO-PDMS-CH3 (IV) CH2 = C (CH3) COOC2H4NHCO-PDMS-H (V) CH2 = C (CH3) COOC2H4NHCO-PDMS-CONH-R-NHCO-PEG-CH3 (VI) wherein PDMS is the residue of bishydroxyalkoxyalkylpolydimethylsiloxane of a molecular weight in the range of 800 to 3,000, and R is the trimethylhexamethylene component of TMHMDI. We have discovered that, in general, an appropriate modulus of elasticity and proper oxygen permeability can be obtained in polymers and copolymers derived from these macromonomers. This makes these polymers and copolymers particularly useful in the manufacture of comfortable long-wearing soft contact lenses. The macromonomers of the present invention can be conveniently prepared from commercially available bis-hydroxyalkyl-terminated poly (dimethylsiloxanes) or bis-hydroxyalkoxyalkyl (such as Shin-Etsu KF-6001 or Shin-Etsu X-22-160AS) by methods well known in the art of polymer synthesis. These methods typically involve mixing the bis-hydroxyalkyl or alkoxyalkyl-terminated polydimethylsiloxane with a precursor for the polymerizable group (such as isocyanatoethyl methacrylate or methacryloyl chloride), and with a precursor (such as trimethylhexamethylene diisocyanate) for the linking group ( in your case). Optionally, catalysts (such as dibutyl tin dilaurate) and solvents can be used. Other reactive polymer blocks (such as poly (ethylene glycol)) may be present. Although the reagents can be mixed at the same time, preferably they are added in sequence to the polymerization mixture. It is particularly preferred that the precursor for the polymerizable group is slowly added to the precursor of the B groups before the precursor of the linking groups is added to the reaction mixture. It will be appreciated that the above procedure can result in a monofunctionalized macromonomer mixture of the present invention, and a proportion of difunctionalized and non-functionalized material. We have discovered that it is also possible to prepare the macromonomer of the present invention from a preformed monofunctional block. This monofunctional block, by way of example, may be a monofunctional siloxane or a monofunctional poly (ethylene oxide), such as poly (ethylene oxide) terminated in monomethyl. In another aspect, this invention provides a process for the production of polymers. The macromonomers of the present invention can be copolymerized or homopolymerized to provide a clear polymer in the presence of a suitable initiator. Conventional methods well known in the art can be used to effect polymerization, with free radical polymerization being preferred. The polymerization with free radicals can simply be done by radiating (using ultraviolet light) monomer mixtures containing an ultraviolet initiator, such as methyl ether benzoin, in an appropriate container. The mixture is irradiated for a sufficient time to enable the polymerization to take place between the monomers. Alternatively, thermal initiation may be employed using a thermal initiator, such as azobisisobutyronitr The macromonomer can be converted to a clean polymer, or in the presence of one or more solvents and / or comonomers. Although the structure of the macromonomer has the most significant effect on the resulting module, the choice of the solvent and the comonomer also has an effect. Useful solvents include those selected from the following classes: esters, alcohols, ethers, and halogenated solvents. Solvent concentrations of between 0 and 70 weight percent / weight, particularly from 10 to 50 weight percent / weight in the polymerization mixture are desirable. Preferred solvents include acetates, particularly isopropyl acetate and tertiary butyl acetate. Other useful solvents include chlorofluoroalkanes, such as trichlorotrifluoroethane, and perfluorinated alkanes, such as perfluoro-1,3-dimethylcyclohexane, and the like. Comonomers comprising one or more ethylenically unsaturated groups that can enter a reaction to form a copolymer can be incorporated. It is preferred that the ethylenically unsaturated group is selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, urethane methacrylate, or any substituted derivatives thereof. A comonomer present in the novel polymer can be hydrophilic or hydrophobic, or a mixture thereof. Suitable comonomers are, in particular, those that are commonly used in the production of contact lenses and biomedical materials. A hydrophobic comonomer means a monomer that typically gives a homopolymer that is insoluble in water, and that can absorb less than 10 weight percent water. Analogously, a hydrophilic comonomer means a monomer that typically gives a homopolymer that is soluble in water, or that can absorb at least 10 percent by weight of water. Suitable hydrophobic comonomers are, without limitation, alkyl acrylates and methacrylates of 1 to 18 carbon atoms and cycloalkyl of 3 to 18 carbon atoms, acrylamides and methacrylamides of 3 to 18 carbon atoms, acrylonitr methacrylonitr alkanoates of 1 to 18 carbon atoms of vinyl, alkenes of 2 to 18 carbon atoms, haloalkenes of 2 to 18 carbon atoms, styrene, (lower alkyl) styrene, vinyl lower alkyl ether, acrylates and perfluoroalkyl methacrylates of 2 to 10 atoms carbon, and the corresponding partially fluorinated acrylates and methacrylates, perfluoroalkylethylcarbonylaminoethyl acrylates and methacrylates of 3 to 12 carbon atoms carbon, acryloxy- and methacryloxy-alkylsiloxanes, N-vinylcarbazole, alkyl esters of 1 to 12 carbon atoms of maleic acid, fumaric acid, itaconic acid, mesaconic acid, and the like. Preference is given, for example, to acrylonitr to alkyl esters of 1 to 4 carbon atoms of vinyl unsaturated carboxylic acids having from 3 to 5 carbon atoms, or vinyl esters of carboxylic acids having up to 5 carbon atoms. Examples of suitable hydrophobic comonomers are methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitr 1-butene, butadiene, methacrylonitr vinyltoluene, vinylethyl ether, perfluorohexylethylcarbonylaminoethyl methacrylate, isobornyl methacrylate , trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, tristrimethylsilyloxysilylpropyl methacrylate (hereinafter: Tris methacrylate), tristrimethylsilyloxysilylpropyl acrylate (hereinafter: Tris acrylate), 3-methacryloxypropylpentamethyldisiloxane, and bis (methacryloxypropyl) tetramethyldisiloxane. Preferred examples of hydrophilic comonomers are ethyl methacrylate, tris acrylate, tris methacrylate, and acrylonitrile. Suitable hydrophilic comonomers are, without this being an exhaustive list, lower alkyl acrylates and methacrylates substituted by hydroxyl, acrylamide, methacrylamide, acrylamides and methacrylamides of lower alkyl, ethoxylated acrylates and methacrylates, acrylamides and lower alkyl methacrylamides substituted. by hydroxyl, vinyl ether of lower alkyl substituted by hydroxyl, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyl oxazoline, 2-vinyl-4 , 41-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinyl unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, amino acrylates and methacrylates (lower alkyl) (wherein the term "amino" also includes quaternary ammonium), mono (lower alkyl-amino) (lower alkyl) and di (lower alkyl-amino) (lower alkyl), allyl alcohol, and the like. Preference is given, for example, to N-vinyl-2-pyrrolidone, acrylamide, methacrylamide, hydroxy-substituted lower alkyl acrylates and methacrylates, hydroxy-substituted acrylamides and methacrylamides of (lower alkyl), and vinyl unsaturated carboxylic acids having an total of 3 to 5 carbon atoms. Examples of suitable hydrophilic comonomers are hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl acrylate, trimethyl ammonium 2-hydroxypropylmethacrylate hydrochloride (Blemer® QA, for example from Nippon Oil), dimethylaminoethyl methacrylate.

(DMAEMA), dimethylaminoethyl (meth) acrylamide, acrylamide, methacrylamide, N, N-dimethylacrylamide (DMA), allyl alcohol, vinylpyridine, glycerol methacrylate, N- (1, l-dimethyl-3-oxobutyl) acrylamide, N- vinyl-2-pyrrolidone (NVP), acrylic acid, methacrylic acid, and the like. Preferred hydrophilic comonomers are trimethyl ammonium 2-hydroxypropyl methacrylate hydrochloride, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, trimethyl ammonium 2-hydroxypropylmethacrylate hydrochloride, N, N-dimethylacrylamide, and N-vinyl-2-pyrrolidone. As previously reported herein, suitable comonomers include alkyl acrylates containing fluorine and silicon and hydrophilic comonomers, which may be selected from a wide range of commercially available materials, and mixtures thereof. Particularly preferred comonomers include dihydroperfluoroalkyl acrylates, such as dihydroperfluorooctyl acrylate and 1,1-dihydroperfluorobutyl acrylate, trihydroperfluoroalkyl acrylates, tetrahydroperfluoroalkyl, methacrylate or tris (trimethylsilyloxy) propyl acrylate, and amine-containing comonomers such as N, N-dimethylaminoethyl methacrylate, N, N-dimethylacrylamide, and N, N-dimethylaminoethylacrylamide. The preferred scale for the addition of the individual comonomers in the formulation is from 0 to 60 weight percent, and more preferably from 0 to 40 weight percent of the formulation. Mixtures of macromonomers of the formula I can also be used to make suitable copolymers with or without other comonomers. Other macromonomers (monofunctional or difunctional) can also be incorporated with or without other comonomers. The difunctional macromonomers or comonomers can optionally be incorporated to control the degree of crosslinking in the polymer. Other macromonomers suitable for incorporation into the polymers of the present invention include those described in our pending Australian provisional applications numbers PN2159, PN2160, PN2161, and PN2162. If desired, a polymer network can be reinforced by the addition of a crosslinking agent, for example a polyunsaturated crosslinking comonomer. In this case, the term "cross-linked polymers" is used. Accordingly, the invention further relates to a crosslinked polymer comprising the polymerization product of a macromer of the formula (I), if desired with at least one vinyl comonomer, and with when minus a crosslinking comonomer. Examples of typical crosslinking comonomers are allyl (meth) acrylate, lower alkylene glycol di (meth) acrylate, poly (lower alkylene) glycol di (meth) acrylate, lower alkylene di (meth) acrylate, ether divinyl, divinyl sulfone, di- and tri-vinylbenzene, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, methylenebis (meth) acrylamide, triallyl phthalate, and diallyl phthalate . If a crosslinking comonomer is used, the amount used is on the scale of 0.05 to 20 percent of the total expected weight of the polymer, preferably the comonomer is on the scale of 0.1 to 10 percent, and more preferably on the scale of 0.1 to 2 percent. A preferred class of silicone-containing monomers that can function either as crosslinking agents or as comonomers is a poly (organosiloxane) polymer as described below: CH2 = C (CH3) COOC2HNHCO-PDMS-OCNHC2H4OOCC (CH3) = CH2 wherein PDMS is of the formula M as defined hereinabove, or is the residue of a bis-hydroxyalkoxyalkylpolydimethylsiloxane of a molecular weight in the scale from 248 to 3,000. According to a further aspect of the present invention, there is provided a polymer produced by the process defined herein, wherein the polymer is formed from at least one macromonomer as defined herein. We have discovered that, in general, an appropriate modulus of elasticity and oxygen permeability can be obtained for use as soft contact lenses, in polymers and copolymers derived from the macromonomers defined herein. According to a further aspect of the present invention, a soft contact lens manufactured from polymers or copolymers as described hereinabove is provided. Soft contact lenses are reticulated polymer discs with surfaces of different radii of curvature. The spokes are selected in combination with the refractive index of the polymer, in such a way that the desired optical correction is obtained, and that the inner surface of the lens matches the contour of the user's cornea. Normally they are sold swollen by sterile serum. By way of example, in the manufacture of these lenses, the appropriate amounts of polymerizable monomers, solvent (if required), and photoinitiator, are mixed together to form a polymerization mixture. Then the mixture of The polymerization is flooded with nitrogen, and the amount required in the concave half of a polypropylene mold is dosed. The mold is closed and fastened, and the assembly is placed in an ultraviolet irradiation cabinet equipped with ultraviolet lamps. The irradiation is carried out for the required time, and then the halves of the mold are separated. The polymerized lens is extracted in a suitable solvent (for example, a mixture of isopropyl or tertiary butyl acetate / fluorinated solvent). The solvent is then exchanged extensively with an alcohol (eg, isopropyl alcohol), and subsequently with serum, to give the lens product. We have also discovered that in certain embodiments of the present invention, polymers and polymeric materials may be suitable for use as corneal or superimposed implants (which may be referred to as "artificial corneas"), cell growth substrates, materials for bonding and growth of cells in vi tro or in vivo, medical implants (such as implantable semi-permeable membrane materials, tissue implants in cosmetic surgery, implants containing hormone-secreting cells such as pancreatic islet cells, breast implants, artificial joints, and similar), and the like. In accordance with another aspect of this invention, an ophthalmic device manufactured from polymers or copolymers as described herein is provided. HE they can produce artificial corneas according to the procedures already described for the production of soft contact lenses. Artificial corneas can be placed by conventional surgical techniques under, in, or through the corneal epithelial tissue, or inside the corneal stroma or other layers of corneal tissue. These implants can change the optical properties of the cornea (such as to correct visual deficiencies), and / or can change the appearance of the eye, such as the placement of the pupil. A corneal implant may comprise a region of an optical axis that, over the implant, covers the pupil and provides visual acuity, and a region surrounding the periphery of the region of the optical axis. The implant can have the same visual acuity through its dimensions. It has been discovered that the flow of fluid components of high molecular tissue, such as proteins and glycoproteins (e.g., growth factors, peptides and protein hormones, and proteins associated with the transport of essential metals), and the like, to Through a corneal implant, that is, between the epithelial cells and the stromal cells, and even the endothelial layer and beyond, it is important for the long-term maintenance and viability of the anterior and posterior tissues to a corneal implant. In accordance with the foregoing, a corneal implant is conveniently prepared with sufficient porosity to allow passage through the same. fluid tissue components having a molecular weight of greater than about 10,000 Daltons, thereby providing a flow of the fluid components of tissue in addition to the small molecular weight nutrients and the respiratory gases between the cells prior to the implant, and the cells subsequent to it. The porosity of the corneal implant can be provided by virtue of the material from which the implant is formed, that is, by the inherent porosity of the material. Alternatively, pores may be introduced into the polymers or copolymers according to this invention, from which the implant is formed, by various methods well known in the art, such as those described in International Publication Number WO 90 / 07575, in International Publication Number WO 91/07687, in U.S. Patent Number 5,244,799, U.S. Patent Number 5,238,613, U.S. Patent Number 4,799,931, and in U.S. Patent Number 5,213,721. Regardless of the methods of formation of the required porosity of the implant of the invention, the implant preferably has a porosity sufficient to admit proteins and other biological macromolecules of a molecular weight up to, and greater than, 10,000 Daltons, such as 10,000 1,000,000 Daltons, but not enough to admit cells, and for consequently, invasion of tissue in the region of the optic axis of the superimposed cornea. Where the porosity of the implant is provided by pores, the region of the optical axis comprises a plurality of pores, the number of which is by no means limiting, but which is sufficient to provide the flow of the tissue components between the anterior and posterior regions of the implant. an implant The polymers and polymeric materials of this invention can withstand colonization with tissue cells (eg, vascular endothelial cells, fibroblasts, bone derived cells, etc.) without the need for specific surface modifications in order to stimulate cell adhesion and growth. This is convenient, since processing costs can be minimized. Alternatively, the polymers and polymeric materials according to this invention can be surface modified by techniques well known in the art., such as modification with radiofrequency brightness discharge plasma (see U.S. Patent No. 4,919,659 and Patent Number PCT / AU89 / 00220), or radiation grafting or chemical treatment. The polymers and polymeric materials of this invention can be surface coated with one or more components that promote tissue growth. For example, these materials include fibronectin, chondroitin sulfate, collagen, laminin, cell binding proteins, antigelatin factor, cold insoluble globulin, condronectin epidermal growth factor, mussel adhesive protein, and the like, and / or derivatives thereof, and mixtures thereof. Fibronectin, the epidermal growth factor, and / or its derivatives, its active fragments, or mixtures thereof, are particularly useful. This surface coating can be applied after surface modification, as described above, if necessary. The polymers and polymeric materials of this invention can also be used as cell growth substrates, such as tissue culture apparatuses (such as plates, bottles, trays, and the like), in biological reactors (such as in the production of proteins). valuable and other components by cell culture), in optical instruments, in microscope slides, and the like. The polymers produced according to the present invention can be formed into other useful articles, employing conventional molding and processing techniques, as are well known in the art. The polymers can also find use in soft membrane materials, controlled release of drugs, gas separation membranes, and ion transport membranes. Through all this specification and in the following claims, unless otherwise required by the context, the word "comprise" or variations such as "comprises" or "comprising" shall be construed to imply the inclusion of an integer or group of integers mentioned, but not with the exclusion of any other integer or group of integers. The present is further described in the following non-limiting examples. If not specified otherwise, all parts are by weight. The temperatures are in degrees Celsius. The molecular weights of the macromers or polymers are number average molecular weights if not otherwise specified.

EXAMPLE 1: The example illustrates the synthesis of a macromonomer of formula III: in a 20 milliliter bottle, 4,999 grams of bis-hydroxyalkoxyalkyl-terminated PDMS of a molecular weight of 2.158 are placed (commercially available as Shin-Etsu KF-6001 ), and 0.357 grams of freshly distilled isocyanatoethyl methacrylate. After stirring the mixture vigorously for several minutes, 0.025 grams of dibutyl tin dilaurate are added. Then the mixture is stirred overnight. An infrared spectrum is recorded to confirm the disappearance of the isocyanate peak. To the reaction mixture are then added 0.486 grams of distilled trimethylhexamethylene diisocyanate, and 0.010 grams of dibutyl tin dilaurate. Again the mixture is stirred overnight. Then add another 5,000 grams of PDMS finished in bis-hydroxyalkoxyalkyl to the mixture, with 0.040 grams of dibutyl tin dilaurate. The flask is shaken vigorously overnight. Again an infrared spectrum is recorded to confirm the disappearance of the isocyanate. This process produces a macromonomer with a high component of formula III.

EXAMPLE 2: This example illustrates the synthesis of a macromonomer of formula IV: in a 100 milliliter conical flask, 27,505 grams of a commercially available monocarbinol-terminated polydimethylsiloxane, having an approximate molecular weight of 1420 (commercially available from United Chemical, are placed. Technologies, Petrarch Silanes and Silicones), and 3,009 grams of freshly distilled isocyanatoethyl methacrylate. After stirring vigorously for several minutes, 0.015 grams of dibutyl tin dilaurate are added. Then the mixture is stirred overnight. An infrared spectrum is recorded to confirm the disappearance of the isocyanate peak.

EXAMPLE 3: This example illustrates the synthesis of a macromonomer of formula VI: in a 20 milliliter bottle, 1,263 grams of a commercially available polyethylene glycol monomethyl ether of a molecular weight of 350 (obtained from Polysciences, Ine) are placed. , in Warrington, PA). This is they add 0.760 grams of freshly distilled trimethylhexamethylene diisocyanate, and the mixture is stirred for several minutes. Then a catalyst, dibutyl tin dilaurate (0.006 grams) is added, and the mixture is stirred overnight. To this is then added 7,624 grams of commercially available hydroxyalkoxy-terminated polydimethylsiloxane, with a molecular weight of 2.158 (Shin-Etsu KF-6001), and another 0.009 grams of dibutyl tin dilaurate. After stirring overnight, an infrared spectrum is recorded to confirm the disappearance of the isocyanate peak, and freshly distilled isocyanatoethyl methacrylate (0.563 grams) is added to the mixture. The mixture is stirred again overnight, and the disappearance of the isocyanate peak is confirmed by infrared spectrometry. This procedure produces a macromonomer with a high component of Figure VI.

EXAMPLE 4: In a 20 milliliter flask, 5,007 grams of commercially available bis-hydroxyalkoxy-terminated polydimethylsiloxane, of a molecular weight of 987 (commercially available as Shin-Etsu X-22-160AS), and 1,574 grams of methacrylate of methacrylate are placed. freshly distilled isocyanatoethyl. After stirring vigorously for several minutes, 0.033 grams of dibutyl tin dilaurate are added. Then the mixture is stirred overnight. An infrared spectrum is recorded to confirm the disappearance of the isocyanate peak.

EXAMPLE 5: In a 20 milliliter flask, 10,000 grams of a commercially available bis-hydroxyalkoxy-terminated polydimethylsiloxane, of a molecular weight of 2.158 (commercially available as Shin-Etsu KF-6001), and 1438 grams of isocyanatoethyl methacrylate are placed. freshly distilled After stirring vigorously for several minutes, 0.011 grams of dibutyl tin dilaurate are added. Then the mixture is stirred overnight. An infrared spectrum is recorded to confirm the disappearance of the isocyanate peak.

EXAMPLE 6: The following composition is placed in a polypropylene lens mold, and polymerized for 3 hours under irradiation of 365 nanometer ultraviolet lamps. (All parts are parts by weight).

Macromonomer of Example 1 55.6 parts N, N-dimethylacrylamide 15.9 parts Dihydroperfluorooctyl acrylate 8.0 parts Benzoin methyl ether 0.3 parts Isopropyl acetate 20.6 parts The polymer lenses were extracted at room temperature in PF5060 (a commercially available perfluorinated solvent) for 3 hours, then placed in isopropyl acetate (IPAc) overnight, then in a mixture of 50/50 (volume / volume) of IPAc-isopropyl alcohol (IPA) for three hours, and in fresh IPA for another three hours. The lenses were dried overnight in a vacuum oven on filter paper before being hydrated in serum for several days. After extraction and hydration, the transmissibility of oxygen in the resulting transparent polymer lens is measured, and it was shown to be 104 Barrers. The module is 1.0 MPa. These values are suitable for a soft contact lens for prolonged use. The water content is 19 percent. The extraction procedure of this example was used in the following examples: EXAMPLE 7: The following composition is placed in a polypropylene lens mold, and polymerized for three hours under irradiation of 365 nanometer ultraviolet lamps. (All parts are parts by weight).

Macromonomer of Example 1 67.8 parts N, N-dimethylaminoethyl methacrylate 12.1 parts Benzoin methyl ether 0.3 parts Isopropyl acetate 20.1 parts After extraction and hydration using the procedure of Example 6, the water content in transparent polymer lenses is measured and found to be 17 percent.

EXAMPLE 8: The following composition is placed in a polypropylene mold lens, and polymerized for 3 hours under irradiation of 365 nanometer ultraviolet lamps. (All parts are parts by weight). Macromonomer of Example 2 55.7 parts Dimethylacrylamide 16.1 parts Dihydroperfluorooctyl acrylate 8.1 parts Isopropyl acetate 20.1 parts Darocur 1173 0.3 parts The resulting lenses were extracted in PF5060 at 37 ° C for 3 hours, then in isopropyl acetate, also at 37 ° C overnight. They were then exchanged in isopropyl alcohol for 3 hours at 37 ° C before being dried overnight in a vacuum oven. Then the lenses were hydrated in a saline solution for several days. The transmissibility of oxygen in the resulting transparent polymer lenses is measured, and it was shown to be 117 Barrers. The module is 0.55 MPa. It was found that the water content was 22.5 percent.

EXAMPLE 9: The following composition is placed in a mold of polypropylene, and polymerized for 3 hours under irradiation of 365-nanometer ultraviolet lamps. (All parts are parts by weight).

Macromonomer of Example 1 45.2 parts Macromonomer of Example 4 3.4 parts Dimethylacrylamide 13.9 parts Dihydroperfluorooctyl acrylate 7.3 parts Isopropyl acetate 30.2 parts Benzoin methyl ether 0.3 parts After extraction and hydration using the procedure of Example 6, the transmissibility of oxygen in transparent polymer lenses is measured, and it was shown to be 103 Barrers. The module is 1.22 MPa. It was found that the water content was 20 percent.

EXAMPLE 10: The following composition is placed in a polypropylene lens mold, and polymerized for 3 hours under irradiation of 365 nanometer ultraviolet lamps. (All parts are parts by weight).

Macromonomer of Example 1 45.2 parts Macromonomer of Example 5 4.0 parts Dimethylacrylamide 16.0 parts Dihydroperfluorooctyl acrylate 8.0 parts Isopropyl acetate 20.0 parts Darocur 1173 0.3 parts After extraction and hydration using the procedure of Example 6, the transmissibility of oxygen in the resulting transparent polymer lenses is measured, and it was shown to be 100 Barrers. The module is 1.72 MPa. It was found that the water content is 19.6 percent.

EXAMPLE 11: The following composition is placed in a polypropylene lens mold, and polymerized for 3 hours under irradiation of 365 nanometer ultraviolet lamps. (All parts are parts by weight).

Macromonomer of Example 3 68.0 parts Dimethylacrylamide 12.1 parts Isopropyl acetate 20.0 parts Benzoin methyl ether 0.3 parts After extraction and hydration using the procedure of Example 6, it was found that the water content is 19.4 percent.

EXAMPLE 12: This example illustrates the synthesis of a macromonomer of formula V: in a 200 milliliter bottle, 10,004 grams of bis-hydroxyalkoxyalkyl-terminated polydimethylsiloxane (Shinetsu KF-6001), and 0.7193 grams of freshly distilled isocyanatoethyl methacrylate are placed. After stirring the mixture vigorously for several minutes, 0.042 grams of dibutyl tin dilaurate are added. Then the mixture is stirred overnight. An infrared spectrum is then recorded to confirm the disappearance of the isocyanate peak.

EXAMPLE 13: The following composition is placed in a polypropylene lens mold, and polymerized for 3 hours under irradiation of 365 nanometer ultraviolet lamps. (All parts are parts by weight).

Macromonomer of Example 12 55.9 parts Dimethylacrylamide 16.3 parts Dihydroperfluorooctyl acrylate 8.0 parts Isopropyl acetate 19.8 parts Darocur 1173 0.3 parts After extraction and hydration using the procedure of Example 8, the oxygen transmissibility in the resulting transparent polymer lenses is measured, and found to be 93 Barrers. The module is 1.92 MPa. It was found that the water content is 15.5 percent.

EXAMPLE 14: The following procedure was used to evaluate the cell attachment and the growth of corneal epithelial cells and stromal fibroblast cells on the polymers: Bovine corneal epithelial cells (BCE_) and bovine horny stromal fibroblasts (BCF) were used. the culture passage numbers 2 and 4, to determine the relative cell binding and the growth performance of each copolymer. Test polymers were cut into 6-millimeter diameter disks using a sterile Dermapunch (Registered Trade Mark), each sample being prepared in triplicate. The replicated polymer samples were transferred to individual wells of a tissue culture polystyrene tray in 96-well format (TCPS), and left overnight at room temperature in a phosphate-buffered saline containing 60 micrograms / milliliter of penicillin, and 100 micrograms / milliliter of streptomycin. Cells were seeded on the surface of each sample, including polystyrene replicas of tissue culture alone, at a density of 5x103 cells / well, and cultured for 7 days in a culture medium containing Dulbecco's Minimum Essential Medium and Ham's F12 (50:50, volume / volume) supplemented with 5 micrograms / milliliter of insulin, 5 micrograms / milliliter of transferrin, 5 nanograms / milliliter of selenium acid, 60 micrograms / milliliter of penicillin, and 100 micrograms / milliliter of streptomycin, and fetal bovine serum was used (with cells BCEP, 20 percent (volume / volume, but with BCF cells, 10 percent (volume / volume)). These cultures were maintained at 37 ° C in a humidified atmosphere of C02 at 5 percent in air. The culture medium was changed every second day. To determine the relative cell numbers present in each sample at the end of the seven-day culture period, the cells were fixed with formalin-serum, and then stained with methylene blue (1 weight percent / volume in borate buffer). , pH of 8.4). The relative number of cells was determined from the dye adsorbed, colorimetrically in an ELISA plate reader, and the adsorbences were expressed as an average percentage (+ Standard Deviation) of the absorbance value obtained for the cells grown on the control surface of polystyrene tissue culture after the same period of time. The following results were found. Bovine corneal epithelial cells bound and grew on the polymeric formulations of Example 6, indicating that these polymers are suitable for the binding and growth of corneal and tissue epithelial cells. The bovine horn stromal fibroblasts were joined and grown on the polymer formulations of Example 6, and the number of cells present on the polymeric surfaces was 63 percent of that which is seen on the tissue culture polystyrene surface, after 7 days. days of cultivation. These data indicate that the polymers in accordance with This invention is suitable for application in artificial cornea and other implants, as well as in binding and growth substrates. Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications different from those specifically described. It should be understood that the invention includes all variations and modifications that fall within its spirit and scope. The invention also includes all steps, features, compositions, and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of any two or more of these steps or features.

Claims (45)

NOVELTY OF THE INVENTION Having described the above invention, it is considered as a novelty, and therefore, the content of the following is claimed as property: CLAIMS

1. A macromonomer of formula I Q-B (L-B) nT (I) where n is zero or at least 1.0; Q is a polymerizable group; B may be the same or different, and is a difunctional block of a molecular weight in the range of 100 to 8,000, and wherein at least one B is a residue of a difunctional polymer or copolymer wherein B has a molecular weight of 248 a 8,000, which comprises repeat units of silicone of formula II: (II) wherein Rj and R2 may be the same or different, and are selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, heterocyclyl, and haloheterocyclyl; L is a difunctional link group; and T is a terminal group.

2. A macromonomer according to claim 1, wherein n is in the scale from 1 to 5.

3. A macromonomer according to claim 1 or with claim 2, wherein n is in the scale from 2 to 4.

4. A macromonomer according to any of claims 1 to 3, wherein Q is a polymerizable group comprising an ethylenically unsaturated moiety.

5. A macromonomer according to any of claims 1 to 4, wherein Q is selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, or urethane methacrylate, or any substituted derivatives thereof.

6. A macromonomer according to any of claims 1 to 5, wherein at least one B is hydrophobic.

7. A macromonomer according to any of claims 1 to 6, wherein at least one B is a block hydrophobic derivative from the group consisting of perfluorinated polysiloxanes and polyethers.

8. A macromonomer according to any of claims 1 to 5, wherein at least one B is hydrophilic.

9. A macromonomer according to any of claims 1 to 6, wherein at least one B is a hydrophilic block derived from the group consisting of polyalkylene oxides, such as polyethylene glycols and poly (cyclic) ethers.

10. A macromonomer according to any of claims 1 to 9, wherein the macromonomer comprises at least two B blocks that are polysiloxanes.

11. A macromonomer according to any of claims 1 to 10, wherein L is a bivalent residue (-C (0) -NH-R-NH-C (O) -) of a diisocyanate.

12. A macromonomer according to claim 11, wherein the bivalent residue is derived from a diisocyanate derived from the group consisting of trimethylhexamethylene diisocyanate (TMHMDI), isophorone diisocyanate (IPDI), methylenediphenyl diisocyanate (MDI) ), and 1,6-hexamethylene diisocyanate (HMDI).

13. A macromonomer according to any of claims 1 to 12, wherein T is a univalent terminal group that can not be polymerized by free radicals.

14. A macromonomer according to any of claims 1 to 13, wherein T is selected from the group consisting of hydrogen, optionally substituted alkyl, and optionally substituted aryl. 15. A macromonomer according to the claim 1, which is of formula III:

CH2 = C (C) COOC2H4NHCO-PDMS-CONH-R-NHCO-PDMS-H (III) wherein PDMS is the residue of a bis-hydroxyalkoxyalkylpolydimethylsiloxane of a molecular weight in the range of 800 to 3,000, and R is the trimethylhexamethylene component of TMHMDI.

16. A process for the production of a macromonomer according to any of claims 1 to 15, wherein this process comprises the steps of mixing a polydimethylsiloxane terminated by bis-hydroxyalkyl or alkoxyalkyl, with a precursor for the polymerizable group, and optionally with a precursor for the link group.

17. A process for the production of a polymer, which comprises the step of polymerizing a macromonomer of any of claims 1 to 15.

18. A process for the production of a polymer, which comprises the step of copolymerizing a macromonomer of any of claims 1 to 15.

19. A process for the production of a polymer, which comprises the step of homopolymerizing a macromonomer of any of claims 1 to 15.

20. A process according to claim 19, wherein the macromonomer is polymerized in the presence of at least a solvent

21. A process according to claim 20, wherein the solvent is selected from the group consisting of esters, alcohols, ethers, and halogenated solvents.

22. A process according to any of claims 20 or 21, wherein the solvent is selected from the group consisting of isopropyl acetate, tertiary butyl acetate, 2- (trifluoromethyl) -2-propanol, trichlorotrifluoroethane, and perfluoro-1,3-dimethylcyclohexane.

23. A process according to claim 18, wherein the macromonomer is copolymerized with at least one comonomer comprising one or more ethylenically unsaturated groups selected from the group consisting of acryloyl, methacryloyl, styryl, acrylamido, acrylamidoalkyl, methacrylate, urethane, or any substituted derivatives thereof, other macromonomers according to claims 1 to 15, and mixtures thereof.

24. A process according to claim 23, wherein the comonomer is selected from the group consisting of dihydroperfluorooctyl acrylate, 1,1- acrylate, and dihydroperfluorobutyl, methacrylate or tris (trimethylsilyloxy) propyl acrylate, and amine-containing comonomers, such as N, N-dimethylaminoethyl methacrylate and N, N-dimethylaminoethylacrylamide, and mixtures thereof.

25. A process according to any of claims 18, 23, or 24, wherein the macromonomer is copolymerized with at least one comonomer, wherein each comonomer is present in the polymerization formulation in the range of 0 to 60 parts.

26. A process according to any of claims 18, 23, 24, or 25, wherein the macromonomer is polymerized with at least one comonomer, wherein each comonomer is present in the polymerization formulation in the 0 to 40 scale. parts.

27. A polymer produced by a process according to any of claims 17 to 26.

28. A polymer comprising a macromonomer according to claim 1.

29. An ophthalmic device manufactured from a polymer produced by a process of according to any of claims 17 to 26.

30. An ophthalmic device comprising a macromonomer according to any of claims 1 to 15.

31. An ophthalmic device according to claim 30, which is a contact lens.

32. The use of a macromonomer of the formula I according to claim 1, for the manufacture of an ophthalmic device.

33. A process for the production of an ophthalmic device according to any of claims 29 or 30, wherein this process comprises the steps of: (a) mixing at least one macromonomer according to any of claims 1 to 15, with an optional solvent, a photoinitiator, an optional comonomer, to form a polymerization mixture; (b) flooding the polymerization mixture with nitrogen; (c) loading the polymerization mixture into the concave half of a mold; (d) close and hold the loaded mold; (e) irradiating the mold loaded with ultraviolet irradiation; and (f) separating the mold halves and extracting the ophthalmic device.

34. A contact lens made from a polymer produced by a process according to any of claims 17 to 26.

35. A soft contact lens comprising a polymerized macromonomer according to any of claims 1 to 15.

36. The use of a macromonomer of the formula I according to claim 1, for the manufacture of a soft contact lens.

37. Artificial cornea made from a polymer produced by a process according to any of claims 17 to 26.

38. Artificial cornea comprising a polymerized macromonomer according to any of claims 1 to 15.

39. The use of a macromonomer of the formula I according to claim 1, for the manufacture of artificial cornea.

40. A macromonomer substantially as previously described herein with reference to any of the above examples.

41. A process for the production of a macromonomer substantially as described hereinabove with reference to any of the above examples.

42. A process for the production of a polymer substantially as described hereinabove with reference to any of the above examples.

43. A polymer substantially as described hereinabove with reference to any of the above examples.

44. A soft contact lens substantially as it was described hereinabove with reference to any of the above examples.

45. A process for the production of a soft contact lens substantially as described hereinabove with reference to any of the above examples.