MXPA97004920A - Networks containing silox - Google Patents

Abstract

The present invention describes a crosslinked polymer that is structured from a polymerization product of a highly unsaturated polymer (a), and a polysiloxane (b) with terminal or pendant hydrosilane groups, in which numerous carbon-carbon bonds are still retained, unsaturated, on which at least one vinyl monomer is optionally bonded, a process for the preparation of the cross-linked polymers, molded articles, especially contact lenses, biomedical articles or artificial corneas which consist totally or fundamentally of such cross-linked polymers, and furthermore describes the use of crosslinked polymers for the coating of surfaces of molded bodies

Description

OUE NETWORKS CONTAIN SILOXANE The present invention describes a cross-linked polymer, which is structured from a polymerization product of a highly saturated polymer (a) and a polysiloxane (b), which has terminal or pendant hydrosilane groups, still retaining numerous carbon bonds -carbon, unsaturated, in which at least one vinyl monomer is grafted, as well as the process for the production of entangled polymers; molded bodies, in particular contact lenses, biomedical articles, or synthetic cornea that consists of total, or for the most part, of such cross-linked polymers; and at the same time refers to the use of the crosslinked polymers to coat surfaces of shaped bodies. The polysiloxane- (meth) acrylate copolymers which are crosslinked, for example, by photopolymerization, often show a phase separation. Furthermore, it can be said that such materials in many cases do not possess sufficient stability because of their relatively high content of ester groups, so as to be autoclaved and treated in a physiological, buffered cooking salt solution. Neither do such materials (for example, in implants) show under physiological conditions, a sufficient stability for a long time, and especially in the enzymatic aspect can easily unfold. The task to be solved now lies in offering a material highly permeable to oxygen that has outstanding mechanical and optical properties, but which does not have readily dissociable bonds. In addition to the aforementioned properties, these materials should also show good storage stability, good biological compatibility, as well as good properties to be autoclaved in a physiological, buffered kitchen salt solution. The problem was solved by crosslinking an unsaturated polymer (a) with polysiloxane (b), in a second optional step, a graft copolymerization, according to the needs, applying a vinyl monomer. An object of the present invention therefore relates to a crosslinking product obtainable by reaction of an unsaturated polymer (a) with a polysiloxane (b) containing hydrosilane groups. The invention also relates to a graft copolymer obtainable by reacting a crosslinking product with a vinyl, hydrophilic or hydrophobic monomer, the crosslinking product being obtained by the reaction of an unsaturated polymer (a) with a polysiloxane (b) which contains hydrosilane groups.

An unsaturated polymer (a) within the context of the present invention, preferably denotes a compound containing iterative units, which are selected from the units of formulas (I) and (II): wherein: R x represents hydrogen, alkyl or trialkyl silyl; R2 represents alkyl, which is unsubstituted, or substituted by alkoxy, alkoxycarbonyl, hydroxy, hydroxycarbonyl, halogen or aryl; it also represents alkenyl, which is unsubstituted, or is substituted by alkoxy, alkoxycarbonyl, hydroxycarbonyl, halogen or aryl; either denotes alkynyl, which is unsubstituted, or is substituted by alkoxy, alkoxycarbonyl, hydroxycarbonyl, halogen or aryl; R3 and R4, independently of each other, denote hydrogen or alkyl; R2 and R3 together signify - (CH2) q-, where q is an integer from 3 to 5, or, R2 and R3 together represent a bivalent radical of Formula (III), wherein: r and s, independently of each other, mean an integer from 1 to 3; R3 and R4 together signify - (CH2) p-, where p is the integer from 3 to 5; n and m, independently of each other, mean an integer from 10 to 100,000; and the sum of n and m also reaches an integer from 10 to 100,000. An unsaturated polymer (a) containing repetitive, ie, iterative, units of Formula (I) and / or (II) typically ends in a radical Rlf R2, R3 or R4. The radicals Rx, R2, R3 and R4 in the units of the Formula (I) and / or (II) are preferably chosen with the indication that at least 20% of all segments have at least one unsaturated carbon-carbon bond. Ri preferably denotes hydrogen or lower alkyl with up to 8 carbon atoms, preferably hydrogen or lower alkyl, up to 4 carbon atoms, and more preferably hydrogen or lower alkyl up to 2 carbon atoms, and in particular hydrogen or methyl. Another preferred meaning of R? is trialkylsilyl lower, and especially triraethylsilyl, particularly when R? it is linked to a unit of Formula (II). R2 preferably means lower alkenyl with 8 carbon atoms, which is unsubstituted or substituted by lower alkoxy, lower alkoxycarbonyl, hydroxycarbonyl, halogen or phenyl; more preferably lower alkenyl with up to 4 carbon atoms, which is unsubstituted or substituted by lower alkoxy, lower alkoxycarbonyl, hydroxycarbonyl, halogen or phenyl; and in particular denotes lower alkenyl with up to 4 carbon atoms, which is unsubstituted or substituted by halogen or phenyl. R 2 preferably represents lower alkyl with 8 carbon atoms, which is unsubstituted or substituted by lower alkoxy, hydroxy, halogen or phenyl; more preferably lower alkyl with up to 4 carbon atoms, which is unsubstituted or substituted by lower alkoxy, halogen or phenyl; and in particular represents lower alkyl with up to 4 carbon atoms, which is unsubstituted, or is substituted by halogen or phenyl.

R3 preferably represents hydrogen or lower alkyl with up to 8 carbon atoms, more preferably hydrogen or lower alkyl with up to 4 carbon atoms, and with special preference means hydrogen or lower alkyl with up to 2 carbon atoms, and in particular represents hydrogen or methyl. R4 has, independently of R3, the same meaning and preference. R2 and R3 mean in a preferred meaning, together, - (CH2) q-, where q means the integer of 3 or 4 > and R2 and R3 represent in particular, and preferably trimethylene. R2 and R3 also preferably together mean a bivalent radical of Formula (III): wherein: r means an integer from 1 to 3, and s represents 2. R3 and R4 denote in a preferred definition as a whole - (CH2) -, where p represents an integer of 3 or 4, and R3 and R4 particularly they mean trimethylene. A preferred definition of n and m is independently between them an integer from 10 to 10,000, and more preferably from 20 to 10,000, and particularly between 25 and 1,000. The sum of the indices of m and n also preferably represents an integer from 10 to 100,000, more preferably from 20 to 10,000, and particularly from 25 to 1,000. A preferred unsaturated polymer (a) is a compound containing repeating units that are selected from the units of Formula (I) and (II), wherein Rlf R3 and R4 mean hydrogen, and R2 is lower alkenyl, or lower alkenyl. replaced by halogen. A preferred unsaturated polymer (a) is a compound containing repeating units that are selected from units of Formula (I) and (II), wherein Rlf R3 and R4 represent hydrogen, and R2 means lower alkenyl up to 4 carbon atoms . A preferred unsaturated polymer (a) is a compound containing repeating units of Formula (I), wherein R ?, R3 and R represent hydrogen, and R2 represents lower alkenyl to 4 carbon atoms. A preferred unsaturated polymer (a) is a compound containing repeating units of Formula (II), wherein R? means lower trialkylsilyl, and R2 represents lower alkyl.

A preferred unsaturated polymer (a) is a compound containing alternating repeating units of the Formula (I) and (II), wherein R 1, R 3 and R 4 represent hydrogen, and R 2 represents lower alkyl or lower alkenyl up to 4 carbon atoms. An unsaturated polymer (a) is, for example, a polymer of a conjugated, aliphatic or alicyclic diene, which is substituted, for example, by halogen or lower alkyl; a polymer of an alkyne or dialkine, which is unsubstituted or substituted by lower alkyl or trimethylsilyl; a copolymer of a conjugated diene with a vinyl monomer, hydrophilic or hydrophobic; and also the partially hydrogenated derivatives of the compounds mentioned. Examples of preferred polymeric conjugated dienes are: poly-1,2-butadiene, poly-1,4-butadiene or polyisoprene; of the trans-, iso- or non-diotactic type; the poly-pentenamere; polychloroprene; polypropylene; Examples of copolymers are butadiene or isoprene copolymers with vinyl monomers, hydrophilic or hydrophobic, such as for example acrylonitrile, styrene, acrylic acid, or hydroxyethyl methacrylate; an example of a polyalkine is poly-1-trimethylsilyl proprin. A strongly preferred unsaturated polymer (a) is selected from poly-l-2-butadiene, poly-1,4-butadiene and polyisoprene, of syndiotactic type. A highly preferred unsaturated polymer (a) is poly-1-trimethylsilyl proprin. By a polysiloxane (b) containing hydrosilane groups within the scope of the present invention, a polysiloxane of the formula (IV) is preferentially understood in which the index x represents from 1 to 1,000, especially from 1 to 500, first of all from 1 to 200, or from 1 to 100, and with particular preference from 2 to 85. The radicals R5, R6 and R7, independently between they denote hydrogen, alkyl, alkoxy, phenyl or fluorine-containing lower alkyl, with the indication that in a compound of Formula (IV) at least two of the radicals R5, R6 and R7 signify hydrogen. Preferably it means in a compound of the Formula (IV), at most about 20% of the radicals R5, R6 and R? ' hydrogen.

In relation to the radicals R5, R6 and R7, the condition must be fulfilled that at least two of them and preferably not more than 20% of all the radicals R5, R6 and R7 mean hydrogen. It is particularly preferred that no more than 15% of all radicals R5, R6 and R7 mean hydrogen. It is particularly preferred that just two of the radicals R5, R6 and R7 mean hydrogen. They are preferably the two R7 radicals. A preferred combination of meanings in which two silicon-hydrogen bonds are terminally located, is as follows: The radicals R5 and R6 are preferably alkyl, lower alkyl containing fluorine, or phenyl, especially lower alkyl, such as methyl or ethyl, or phenyl. Particularly preferred for the radicals R5 and R6 is the meaning of lower alkyl with up to 8 carbon atoms, such as methyl. The R7 radicals mean hydrogen. The compounds of the formula (IV), in which the radicals R5, R6 and R7 have these meanings, are the α, β-dihydrogen-polysiloxanes. Another preferred combination of meanings in which the silicon-hydrogen bonds are not necessarily located in terminal positions, is the following: The radicals R5, Re and R7 mean hydrogen, lower alkyl containing fluorine, alkyl or phenyl, especially hydrogen, lower alkyl , as methyl or ethyl, or phenyl, with the indication that at least two of the radicals R5, R6 and R7, and preferably a maximum of 20% of the radicals R5, R6 and R7 mean hydrogen. An unsaturated polymer (a) and a polysiloxane mentioned above (b) containing hydrosilane groups, is reacted in the presence or absence of a solvent, and advantageously in the presence of a catalyst, which is identified in the following as reticulation. Preferably, a solvent is used which behaves in a high degree in an inert manner, that is to say, it does not participate in the reaction. Examples suitable for such are ethers, such as tetrahydrofuran (THF), dimethoxyethane, diethylene glycol dimethyl ether or dioxane, halogenated hydrocarbons, such as chloroform or chlorobenzene, hydrocarbons such as toluene, hexane, methylcyclohexane or mixtures of several of these solvents. The amount of solvent applied is preferably in such a range that solutions are obtained with a concentration of 1 to 60%, more preferably 20 to 60%, and particularly 5 to 50% by weight / volume, with the indication of the weight to the quantity of reagents used. As catalysts for the crosslinking reaction (or polyaddition reaction) between an unsaturated polymer (a), and a polysiloxane (b) containing hydrosilane groups, i.e., a hydrosilylation reaction, the platinum and rhodium complexes are especially suitable. , or the salts of such metals, such as for example H2PtCl6, PtCl4, or the divinyltetramethyldi-siloxane of platinum; also peroxides, such as, for example, dibenzoyl peroxide, or an energy-rich irradiation, such as, for example, ultraviolet light of a suitable wavelength. The amount of suitable catalyst is especially located in the case of liquid materials in a range of 0.0001 to 1% by volume, and advantageously in a range of 0.001% to 0.1% by volume. In the case of solid catalysts, these numerical ranges are referred to weight percent. The reagents, namely an unsaturated polymer (a) and a polysiloxane (b), they are typically used in a proportion of masses such that a crosslinking product thus obtained have a polysiloxane content of preferably 30 to 80% by weight, and particularly 40 to 70% by weight. The reaction temperature of the crosslinking can advantageously be from -30 ° C to 150 ° C. The range of 10 ° C to 100 ° C is a preferred temperature range. Another preferred temperature range is the ambient temperature (international abbreviation: RT). The reaction times are in the range of about 5 minutes to 48 hours, preferably in the range of about 0.5 to 12 hours. If necessary, work under argon or hydrogen as protective gas. The determination of the end point of the reaction is carried out effectively by means of an infrared absorption (IR) measurement of the Si-H oscillation. As soon as the Si-H band disappears in the infrared spectrum, cross-linking (polyadicide reaction) approaches its end. A vinyl monomer, which can be inserted on a crosslinking product obtainable by reacting an unsaturated polymer (a) with a polysiloxane (b), containing hydrosilane groups, can be of the hydrophilic or hydrophobic type. This reaction is called graft copolymerization. A graft copolymerization is typically heated with the addition of a radical former (or radical initiator). Such a radical former is, for example, azadiisobutyronitrile (AIBN), potassium peroxodisulfate, dibenzoyl peroxide, hydrogen peroxide or sodium percarbonate. If the mentioned components are heated, for example, radicals are formed under a homolysis, which then typically introduce a graft copolymerization. The amount by added radical former is typically in the range of about 0.001% to 5% by weight, based on the total amount of polymer, preferably in the range of about 0.01% to 2% by weight, and especially in the range of approximately 0.05% to 1% by weight. A graft copolymerization can also be initiated by energy-rich irradiation, such as ultraviolet light with a suitable wavelength, especially with the addition of suitable photoinitiators, for example Darocure * 2959, Darocure * 1171 or Irgacure "184. The aggregate photoinitiator is typically in the range of about 0.001% to 10% by weight, relative to the total amount of polymer, and preferably in the range of about 0.01 to 5% by weight, and particularly in the range of about 0.05. % to 2% by weight A graft copolymerization can be carried out in the presence or absence of a solvent As a solvent, basically all solvents dissolving the monomers used, such as, for example, bipolar aprotic solvents, such as dimethylsulfoxide, acetonitrile, are suitable. , N-methylpyrrolidone (NMP), or dimethylacetamide, ketones, such as, for example, methyl ethyl ketone or cyclohexanone, ethers, such as or, for example, THF, dimethoxyethane or dioxane, hydrocarbons, such as, for example, toluene or cyclohexane. as well as mixtures of suitable solvents, such as for example mixtures of THF and methyl ethyl ketone or NMP and cyclohexanone. Solutions containing a vinyl monomer for grafting are preferably adjusted in a range of 10% to 70%, and preferably in a range of 20% to 60% by weight / volume, the weight indication being related to the amount of monomer used. When no solvent is present, for example, a vinyl monomer can be used as solvent, which is used under ideal conditions, also graft copolymerization. A crosslinking product, in which a vinyl monomer must be grafted, swells, for example, in a solution containing a vinyl monomer, for example, for a time of 2 to 15 minutes, is removed from the solution and then copolymerized by grafting in thermal form or with an energy-rich irradiation according to the following methods. Graft polymerization, in its thermal variant, is preferably carried out in a temperature range of 0 ° C to 150 ° C, and more preferably in a range of 20 ° C to 100 ° C. Reaction times are typically in the range of about 5 minutes to about 12 hours, preferably in a range of 0.5 to 4 hours. If necessary, work under argon or nitrogen as protective gas. When the graft polymerization is carried out under the influence of an energy-rich irradiation, irradiation is typically done with ultraviolet light of a suitable wavelength, usually at room temperature and typically for a lapse of about 2 to 10 minutes. (for example, with a high-pressure lamp of ultraviolet type, 2,000 watts). If necessary, work under argon or nitrogen as protective gas.The extent to which a vinyl monomer is grafted typically depends on the condition of a crosslinking product on the one hand, and on the other, on the vinyl monomer. When more carbon-carbon saturated bonds generally contain a crosslinking product, more vinyl monomer can also be applied by grafting, in general terms. Another factor is, for example, the stereo impairment, both in the basic body and also in the case of a vinyl monomer, which decides, for example, on the amount of grafting monomer. A vinyl monomer grafted onto a crosslinking product (primary polymer) constitutes a secondary polymer that penetrates the crosslinking product, either partially or completely, or forms a layer applied by grafting. The layer thickness of a graft polymer, which can be controlled typically by the duration of a graft copolymerization, is generally in the range of 1 to 200 microns, preferably in the range of 1 to 150 microns, and particularly in the range of margin of 1 to 100 microns. The quantitative ratio of primary polymer to secondary polymer can vary widely, and is preferably in the range of 10:90 to 90: 10% by weight. When a secondary polymer is grafted with a hydrophilic vinyl monomer, the amount of hydrophilic vinyl monomer is preferably oriented with the aqueous content of the final product, of the graft copolymer, which will preferably be, for example, up to 50% by weight, and particularly it will be between 15% and 35% by weight. By a hydrophobic vinyl monomer is meant a monomer which, as a homopolymer, typically generates a polymer which will be insoluble in water, and which will be able to absorb less than 10% by weight of water. Analogously, a hydrophilic vinyl monomer means a monomer which, as a homopolymer, characteristically generates a polymer which is soluble in water, or which can absorb at least 10% by weight of water. Suitable hydrophobic vinyl monomers include, but are not limited to, the alkyl acrylates with 1 to 18 carbon atoms, and the cycloalkylacrylates with 3 to 18 carbon atoms, as well as the methacrylates of the above type, the alkyl acrylamides and alkyl methacrylamides with at 18 carbon atoms, acrylonitrile, ethacrylonitrile, vinyl C1-C18 alkanoates, alkenes with 2 to 18 carbon atoms, haloalkenes with 2 to 18 carbon atoms, styrene, lower alkyl styrene, lower alkylvinylether, perfluoroalkylacrylates and -methacrylates having 2 to 10 carbon atoms, or the corresponding partially fluorinated acrylates and methacrylates, perfluoroalkylethylthiocarbonylaminoethyl acrylates and methacrylates with 3 to 12 carbon atoms, the alkylsiloxanes of acryloxy and methacryloxy, N-vinylcarbazole, alkyl esters with 1 to 12 carbon atoms of maleic acid, fumaric acid, itaconic acid, esaconic acid co and similar. Preferred are, for example, acrylonitrile, the alkyl ester having 1 to 4 carbon atoms of the vinyl unsaturated carboxylic acids having 3 to 5 carbon atoms, or the vinyl ester of the carboxylic acids containing up to 5 carbon atoms. Examples of suitable hydrophobic vinyl monomers include methacrylate, ethylacrylate, propyl acrylate, isopropyl acrylate, cyclohexylacrylate, 2-ethylhexylacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butylacrylate, vinylacetate, vinylpropionate, vinyl butyrate, vinylvalerate, styrene, chloroprene, isoprene, vinyl chloride, vinylidene chloride. , acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinyl ethyl ether, perfluorhexiltiocarbonilaminoetilmetacrilato, isobornilmeta-crilato, trifluoretilmetacrilato, hexafluorisopropilmeta-crilato, hexafluorbutilmetacrilato, tris-trimethylsilyloxy-sililpropilmetacrilato, 3-methacryloxypropylpentamethyldisiloxane and bis (methacryloxypropyl) tetramethyldisiloxane. Preferred examples of hydrophobic vinyl monomers are: tris-tri-ethylsilyloxysilylpropylmethacrylate, methyl methacrylate, trifluoroethylmethacrylate and hexafluorisopropylmethacrylate. Suitable hydrophilic vinyl monomers include, but are not limited to, lower alkyl acrylates and lower alkyl methacrylates, substituted by hydroxy, acrylamide, methacrylamide, lower alkylacrylamides and lower alkyl ethacrylamides, ethoxylated acrylates and methacrylates, lower alkylacrylamides and lower alkylmethacrylamides substituted by hydroxy , lower alkyl vinyl ether substituted by hydroxy, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropansulphonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2- and 4-vinylpyridine, vinyl unsaturated carboxylic acids with a total of 3 to 5 carbon atoms, lower aminoalkyl- (in which the concept of "amino" also includes quaternary ammonium), -monoalkylamino lower-lower alkyl- and dialkylamino lower-lower alkyl-acrylates and -methacrylates, alcohol allylic and the like. Preferred are, for example, N-vinyl-2-pyrrolidone, acrylamide, methacrylamide, lower alkyl- (meth) acrylates substituted by hydroxy, lower alkyl acrylamides and -methacrylamides substituted by hydroxy, as well as vinyl unsaturated carboxylic acids with a total of 3. to 5 carbon atoms Examples of suitable hydrophilic vinyl monomers comprise hydroxyethylmethacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, ammonium methyl methacrylate hydrochloride, acrylamide, methacrylamide, N, N-dimethylacrylamide, N- (meth) acryloylmorpholine, allyl alcohol , vinylpyridine, glycerin methacrylate, N- (1, 1-dimethyl-3-oxobutyl) acylamide, N-vinyl-2-pyrrolidone, (meth) acrylic acid, methacrylic acid and the like. Preferred hydrophilic vinyl monomers are N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, glycerin methacrylate, (meth) acrylic acid and N- (meth) acryloylmorpholine. By a crosslinked polymer is meant in the above text as follows, both a crosslinking product, as well as a graft copolymer, as long as it is not expressly stated otherwise. In a preferred definition, a crosslinked polymer is understood as a graft copolymer. The alkyl contains up to 20 carbon atoms, and can be straight or branched chain. The alkyl preferably represents lower alkyl, which contains up to 8 carbon atoms and more preferably up to 4, and particularly up to 2 carbon atoms. Suitable examples include dodecyl, octyl, hexyl, pentyl, butyl, propyl, ethyl, methyl 2-propyl, 2-butyl or 3-pentyl. Aryl represents a carbocyclic aromatic compound with up to 20 carbon atoms, which is unsubstituted or which is preferably substituted by lower alkyl or lower alkoxy. Examples are phenyl, toluyl, xylyl, methoxyphenyl, t-butoxyphenyl, naphthyl or phenanthryl. The term "lower" means, within the scope of this invention, in relation to radicals and compounds, if not defined otherwise, in particular radicals or compounds with up to 8 carbon atoms, preferably up to 6, and especially up to 4 carbon atoms. The lower fluorine-containing alkyl represents a straight or branched chain lower alkyl of up to 8 carbon atoms, which is partially or wholly substituted by fluorine. Examples thereof are: trifluoromethyl, difluoromethyl, hexafluoropropyl or 1,11-trifluoropropyl. The alkenyl contains from 2 to 20 carbon atoms, and may have straight or branched chain. Alkenyl represents especially lower alkenyl with 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, and especially 2 to 4 carbon atoms. Examples of alkenyl are vinyl, allyl, 1-propen-2-yl, l-buten-2-6 -3- or -4-yl, 2-buten-3-yl, the isomers of pentenyl, hexenyl or octenyl. The alkynyl contains from 2 to 20 carbon atoms, and may have a straight or branched chain. Alkynyl represents especially lower alkynyl with 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, and particularly 2 to 4 carbon atoms. Examples of alkynyl are ethynyl, propargyl, 1-butynyl-, 3- or 4-yl, the pentinyl, hexynyl or octynyl isomers.

Halogen represents especially fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine and bromine, and especially fluorine and chlorine. The alkoxy contains up to 20 carbon atoms and preferably represents lower alkoxy. Lower alkoxy contains up to 8 carbon atoms, preferably up to 6 carbon atoms, and is, for example, methoxy, ethoxy, propoxy, butoxy, tertiary butoxy or hexyloxy. Trialkylsilyl represents silyl which, independently of one another, supports three alkyl bonds. Trialkylsilyl represents preferably lower trialkylsilyl. Examples of the lower trialkylsilyl are: t-butyl-dimethylsilyl, t-exyl-dimethylsilyl or trimethylsilyl. The invention also relates to a process for obtaining the crosslinked polymers according to the present invention. An unsaturated polymer (a), for example, polybutadiene, is mixed, for example, with a polysiloxane dihydride, for example, in a ratio of 1: 1 or 2: 1, wherein a suitable solvent is usually used here; the resulting mixture is preferably degassed at once, it is usually mixed with a suitable catalyst and preferably filled under some protective gas, for example, in some mold, for example, a contact lens mold; the molds are closed and typically heated for half an hour to 12 hours at 20 to 100 ° C until all the Hi-Si groups have been reacted, which can be effectively determined with an infrared spectroscopy measurement; finally the molded bodies removed from the mold are removed. These molded bodies containing the crosslinking product (primary, as described above) can be copolymerized by grafting, typically in a second step, for example, as follows: The molded bodies are immersed, for example, in a solution that it contains vinyl monomer, as well as possibly a catalyst for graft copolymerization, and the material is swollen, for example, for 10 minutes. The swollen molded bodies are generally removed from the solution and finally heated as a typical process under protective gas, and alternatively or additionally thereto, it is irradiated, for example, with ultraviolet light with suitable wavelength. Alternatively, the two process steps can also be performed in a reverse sequence, namely, for example, as follows: A vinyl monomer can first be grafted onto an unsaturated polymer (a), typically under the aforementioned conditions of a copolymerization. by grafting, and then, in a second step, it can be crosslinked with a polysiloxane (b), which contains hydrosilane groups, usually under the crosslinking conditions of a hydrosilylation reaction, mentioned above. The polymers according to the invention can be processed in a manner known per se to create molded bodies, especially contact lenses, for example, crosslinking of the polymers in a mold suitable for contact lenses. Another object of the invention is therefore aimed at the molded bodies, and especially at contact lenses that consist mainly or in a total form of a crosslinking product according to the invention, and particularly of a graft copolymer. Further examples of molded bodies according to the invention, in addition to contact lenses, are biomedical articles in specially ophthalmic molded bodies, for example, artificial cornea, intraocular lenses, eye bandages, molded bodies that can be used in surgery, such as heart valves, synthetic arteries or the like, and then also coatings, films or membranes, for example, membranes for the control of diffusion, photorestructible films for the storage of data, or else photoresist materials, for example, membranes or bodies moldings for cauterization resistances or screen resistances, and also particles, especially icroparticles, capsules, especially microcapsules, films, and dressings for drug delivery systems. Contact lenses, especially soft lenses, which contain a crosslinked polymer according to the present invention, have a blade, that is, a range of rare and highly advantageous properties. Among these properties are mentioned, for example, their outstanding tolerance to the human cornea (possibly after a suitable surface treatment (eg, plasma hydrophilization)), as well as with the liquid of tears, which are based on a weighted proportion of content Acuse, oxygen permeability and mechanical properties, as well as adsorbents. Due to their favorable permeability properties with respect to different salts, nutrients, water and various other components of the tear fluid and gases (C02, 02), the contact lenses, according to the present invention, influence the natural metabolic processes in the cornea, in an unimportant way or in no way. In contrast to many contact lenses containing siloxane from the state of the art, lenses containing a crosslinked polymer, according to the invention, as a fundamental component, a high molding resistance and an excellent stability during storage. Another object of the present invention aims at molded bodies, especially contact lenses, which consist fundamentally or entirely of a crosslinking product according to the invention, or of a graft copolymer according to the invention. Another object aims at contact lenses that consist fundamentally or totally of a graft copolymer according to the invention, the aqueous content being particularly in a range of 15 to 30% by weight. The contact lenses according to the invention, with a preferred aqueous content in a range of 15 to 30% by weight, also show a high water permeability and in addition, an advantageous mobility on the eye. Another object of the present invention is oriented towards contact lenses consisting essentially of a cross-linked polymer according to the invention, in the case of contact lenses that contain water in a minor degree, which are flexible and gas-permeable (abbreviation: RGP). All the advantages mentioned above are applied by their nature not only to contact lenses, but also to other shaped bodies according to the invention. Another object of the present invention aims at the use of a crosslinked polymer according to the present invention intended for the coating of some basic material, such as glass, ceramic or metal, as well as preferably polymeric substrates, such as for example ophthalmically products Applicable, such as contact lenses, intraocular lenses or bandages for the eyes, as well as products applicable in medicine, such as surgical or pharmaceutical systems, in the latter cases (ophthalmic applications) preferring the hydrophilic coatings ("Coatings") ). A cross-linked polymer according to the present invention is also suitable for use as a cornea implant, or artificial cornea ("corneal implant", "artificial cornea"); then also as substrates for cell growth, as a material for the fixation and breeding of animal cells, both in vitro and in vivo, as medicinal implants, as for example implantable semipermeable membrane materials, as tissue implants for cosmetic surgery, as an implant containing hormone secreting cells, such as pancreatic island cells, as a breast implant, or also as a synthetic joint and the like. Another object of the present invention is thus oriented to a corneal implant, which is manufactured from a crosslinked polymer, described above. A corneal implant as mentioned herein can be made with the same procedure as described above in the manufacture of contact lenses. Corneal implants can be introduced with conventional surgical procedures, for example, below, in or through the epithelial tissue of the cornea, or in the stroma of the cornea, or also in other tissue layers of the cornea. Such implants can modify the optical properties of the cornea, for example, in the sense of a correction of a visual deficiency and / or by building the appearance image of the eye, such as the color of the pupil. A corneal implant may comprise the field that covers the optical axis, which in the case of the implant covers the pupil, and which produces visual acuity and, in addition, the area surrounding the periphery of the optical axis. The implant can have the same visual properties over the entire area. It was found that the flow of components of high molecular level, within the tissue fluid, for example, proteins or glycoproteins, such as growth factors, peptides, hormones or proteins, which are responsible for the transport of essential metal ions, Through a corneal implant, especially between epithelial cells and stromal cells, and even behind the endothelial layer, it is important both for tissue survival as well as for the vital capacity of the tissue outside and inside a corneal implant. Therefore, a cornea implant is preferably made with a porosity that will be sufficient to allow liquid components of the tissue with a molecular weight of more than 100,000 daltons to pass through, guaranteeing a flow or passage of tissue fluid components in addition to a component passage. low molecular weight nutrients, such as glucose, fat or amino acids, or also breathing gases between the cells on both sides of an implant.

The porosity of a corneal implant is generated, either by the polymeric material from which it is made or, on the other hand, pores can be incorporated in a supplementary form in a cross-linked polymer, according to the invention, ie, through any of the numerous known processes that are described, for example, in the patents WO 90/07575, WO91 / 07687, US 5,244,799, US 5,238,613, US 4,799,931 or US 5,213,721. No matter which method the necessary porosity of an implant according to the invention is formed, an implant preferably has a porosity sufficient to pass proteins and other biological macromolecules with a molecular weight up to 10,000 daltons, or even more, as for example with a molecular weight of 10,000 to 1,000,000 daltons, but not so large that whole cells can pass through and can penetrate the area below the optical axis of the implant. Where it makes possible the porosity of the implant through pores, the area above the optical axis contains a plurality of pores, the number of which should not be restricted, which, on the other hand, should be sufficient to allow free passage of the tissue components between the external and internal area of an implant. The pores that are located above the area of the optical axis do not preferably cause any diffusion of visible light to a degree that would cause problems in terms of establishing a correction in visual acuity. With the concept of a pore, it is understood both in the previous text and the one that follows, a pore that has no geometric restrictions, and that possesses a regular morphology, while irregular. The indication of a pore size does not mean that all pores have the same diameter. Rather, it is an average diameter. In the area outside the optical axis, the corneal implant can have the same porosity as in the field located above the optical axis. This peripheral zone of an implant that surrounds the area of the optic axis is also defined as a skirt, and in contrast to the area of the optical axis, it can allow an introduction with growth of the cornea cells, so which is an anchorage of the implant in the eye. The porosity in the skirt can also be an independent feature of the material, from which the skirt is made. If the skirt is made of the same material as that material that is located above the optical axis, pores with different diameter can be incorporated, on one side in the skirt, and on the other hand above the optical axis. On the other hand, the skirt of another material can be made than that material that is above the optical axis, in which case, as already pointed out above, the porosity in the skirt must be greater than that above the optical axis. A skirt preferably consists of an optically clear polymer, such as that which is above the optical axis; however, the skirt can also be made of some optically non-transparent material, or it is made of a porous material that will not optically be transparent. A crosslinked polymer according to the present invention can support settlement with tissue cells, such as vascular endothelial cells, fibroplasts, or cells formed in the bones, and in that case, it is not necessary for a specific surface condition to be present. , in order to stimulate cell adhesion and growth. This is advantageous, since the costs of the procedure can be kept low. On the other hand, a crosslinked polymer according to the present invention can be modified with a known technique, on its surface, such as for example the plasma treatment of a surface by applying a radiofrequency with luminescent discharge as described, for example, in the Patents US 4,919,659, or WO 89/00220, or also by irradiation or by applying a chemical treatment. A crosslinked polymer according to the invention can be coated with one or more components on its surface, in order to stimulate, for example, tissue growth. Such materials are, for example, fibronectin, chondroitin sulfate, collagen, laminin, cell adhesion proteins, globulin, chondronectin, epidermal growth factors, muscle fiber proteins and / or their derivatives, active fragments and mixtures thereof. Fibronectin, the epidermal growth factors and / or their derivatives, the active fragments, as well as their mixtures, turn out to be especially useful. Such a surface coating, if necessary, can also be carried out in accordance with a surface modification, described above. A crosslinked polymer according to the invention can combine within it, and advantageously, several of the indicated properties, for example, adhesion to cells with a good biostability, as well as a resistance to deposits. The mechanical properties of a cross-linked polymer according to the present invention are suitable for use as a corneal implant, the material preferably having a modulus of elasticity of 0.5 to 10 MPa. The modulus of elasticity mentioned imparts a suitable flexibility to a corneal implant to make it possible to insert it into the eye, such as, for example, above the area of Bowman's membrane. A crosslinked polymer according to the present invention can also be used as a cell growth base, for example, as an apparatus for cell culture, such as for example crockery, bottles, plates and the like, as well as in biological reactors, such as for example in the development of valuable proteins and other components of cell cultures.

The following examples illustrate the object of the invention, but without limiting its scope in any way by the examples. The percents in terms of quantitative indions are in weight, unless otherwise expressly indid. The temperatures indi in degrees centigrade. Example 1 2.2 grams of polybutadiene (1,2-syndiotactic) (Polysciences Inc.) with an average molecular weight of 100,000 grams / mole are charged in a three-necked flask. Under nitrogen and stirring, 50 milliliters of absolute dimethoxyethane (DME) are added and heated for a short time at 60 ° C. It is then cooled to room temperature (RT), and a solution of 1.1 gram of H-siloxane (product 1085 from Goldschmidt AG) is added slowly in 5 milliliters of absolute DME. It is heated to 40 ° C, so that a homogeneous solution is created (for approximately 10 minutes). Again it is cooled to room temperature, and then nitrogen is driven through this mixture for one hour. It is then heated to 40 ° C and under stirring 2 drops of the platinum divinyltetramethyl disiloxane lyst (PC 072, ABCR) are added. After 5 minutes of stirring, this reaction mixture is emptied to form a film with a thickness of 1.0 mm, between two glass plates. This film is left between these glass plates under nitrogen at 60 ° C, for 16 hours. It is then cooled to room temperature, the glass plates are removed, the optically clear film left behind is removed, which has a highly elastic character, with ethanol, and then dried to a constant weight.

Example 2 In analogy to Example 1, 2.2 grams of polybutadiene (1,2-syndiotactic) and 4.4 grams of H-siloxane (test product K-3272, Goldschmidt AG) in DME were converted by reaction. The film in this example is relatively fragile. Example 3 An amount of 1.1 gram of polybutadiene (1,2-syndiotactic) is dissolved in 20 milliliters of absolute THF, and under heating at 40 ° C, under nitrogen. For this material 1.1 gram of H-siloxane (test product 1085 of Goldschmidt AG) is added, and it is stirred at this temperature for 10 minutes. It is then cooled to room temperature, and degassed, still conducting for one hour nitrogen through the solution. Then two drops of the platinum divinyltetramethyl disiloxane lyst (PC 072, ABCR) are added and stirred for 5 minutes. Then a film with a thickness of 1.0 mm between two glass plates is emptied. The film is left to stand between the glass plates under nitrogen at 60 ° C for 16 hours. Then it is cooled to room temperature, the glass plates are removed, the film that is left behind once with THF is removed, and twice with isopropanol, and then it is dried until a constant weight is obtained. Example 4 2.2 grams of polybutadiene (1,2-syndiotactic) are dissolved in 30 milliliters of methylcyclohexane (MCH) at 40 ° C under nitrogen. A solution of 2 grams of H-siloxane (test product K-3272, Goldschmidt AG) in 5 milliliters of MCH is slowly added and stirred for 5 minutes. The mixture is then stirred at room temperature and the mixture is passed through nitrogen for 30 minutes under nitrogen. Then 3 drops of the platinum divinyltetramethyl disiloxane lyst (PC 072, ABCR) are added in 1 milliliter of MCH, and heated at 50 ° C under stirring for 3 minutes. Then a film with a thickness of 1.5 mm is emptied between two glass plates. The film is left between the glass plates under nitrogen at 60 ° C for 16 hours. Then it is cooled to room temperature, the glass plates are removed, the film left behind is extracted with THF, and then dried to a constant weight. Example 5 Analogously to Example 4, a polymer film with the following components is produced: 3.3 grams of polybutadiene (1,2-syndiotactic) and 2.0 grams of H-siloxane (test product K-3272, from Goldschmidt AG). EXAMPLE 6 Analogously to Example 4 a polymeric film is made with the following components: 3.0 grams of polybutadiene (1), 2-syndiotactic) and 2.0 grams of H-siloxane (test product 1085, from Goldschmidt AG). Example 7 7.0 grams of polybutadiene with terminal hydroxyl (Polysciences Inc., Catalog No. 06508, average molecular weight of the order of 2800) are dissolved under nitrogen and with stirring of 9 milliliters of MCH. 3.5 grams of H-siloxane (test product 1085 from Goldschmidt AG) are introduced into this solution with stirring. Then, for 30 minutes, nitrogen is passed through the solution. For this purpose, 3 drops of divinyltetramethyl disiloxane of platinum are added as catalyst (PC 072, ABCR), and stirring is continued for 10 minutes. With one part of this solution the polypropylene is filled into small contact lens molds with a diameter of 21 mm and with an average height of 0.5 mm, and then the molds are closed with a polypropylene cap of loose settling. These small molds are heated for 12 hours under nitrogen (60 ° C). Then the small molds are opened, the lenses are removed, the material is extracted with THF / acetone (1: 1), and dried to constant weight. Example 8 Analogously to Example 7, lenses are made starting from 6 grams of polybutadiene with terminal hydroxyl (Polysciences Inc., Catalog No. 06508), and 4.0 grams of H-siloxane (test product 1085 of Goldschmidt AG). Properties of the polymers of the Examples.

Properties of the polymers of the Examples.

Example 9 Analogously to Example 4 a polymer film is made and a fragment with a size of 2 x 1 cm thereof is immersed for 10 minutes in a solution containing 2.6 grams of N-vinylpyrrolidone (NVP), 6.4 grams of methyl ethyl ketone and 0.2 grams of Irgacure * 184 (Photoinitiator of Ciba-Geigy). The swollen film is removed, rinsed with methyl ethyl ketone and dried with blotting paper. The film thus prepared is irradiated on both sides for two minutes with ultraviolet light (2000 W). Then the film is extracted for 12 hours with methyl ethyl ketone and then dried to a constant weight.

Example 10 Analogously to Example 9, the polymeric film of Example 4 was treated with a solution containing 2.6 grams of dimethylacrylamide (DMA), 4 grams of methyl ethyl ketone and 0.2 grams of Irgacure * 184 (Ciba-Geigy photoinitiator). As in Example 9, it is immersed for 10 minutes, rinsed and irradiated with ultraviolet light.

Claims (24)

1. CLAIMS 1. A crosslinking product that can be obtained by reacting an unsaturated polymer (a) with a polysiloxane (b) containing hydrosilane groups.
2. 2. A graft copolymer obtainable by reacting a crosslinking product with a hydrophilic or hydrophobic monomer, whereby the crosslinking product can be obtained by reacting an unsaturated polymer (a) with a polysiloxane (b) containing hydrosilane groups. The crosslinked polymer according to claim 1 or 2, wherein the unsaturated polymer (a) represents a compound containing repeating units, selected from the units of the Formula (I) and (II): wherein: Rx represents hydrogen, alkyl or trialkyl silyl; R2 represents alkyl, which is unsubstituted, or substituted by alkoxy, alkoxycarbonyl, hydroxy, hydroxycarbonyl, halogen or aryl; it also represents alkenyl, which is unsubstituted, or is substituted by alkoxy, alkoxycarbonyl, hydroxycarbonyl, halogen or aryl; either denotes alkynyl, which is unsubstituted, or is substituted by alkoxy, alkoxycarbonyl, hydroxycarbonyl, halogen or aryl; R3 and R4, independently of each other, denote hydrogen or alkyl; R2 and Rj together signify - (CH2) q-, where q is an integer from 3 to 5, or R2 and R3 together represent a bivalent radical of Formula (III), wherein: r and m, independently of each other, mean an integer from 1 to 3; R3 and R4 together signify - (CH2) -, where p is the integer from 3 to 5; n and m, independently of each other, mean an integer from 10 to 100,000; and the sum of n and m also reaches an integer from 10 to 100,000. The polymer according to claim 1 or 2, wherein the polysiloxane (b) containing hydrosilane groups represents a compound of the formula (IV): wherein the index x represents from 1 to 1,000, and the radicals R5, R6 and R7, independently of each other, denote hydrogen, alkyl, alkoxy, phenyl or lower alkyl containing fluorine, with the indication that in a compound of the Formula (IV) at least two of the radicals R5, R6 and R7 signify hydrogen. The polymer according to claim 3, wherein the unsaturated polymer (a) contains repeating units selected from the units of Formulas (I) and (II), wherein Rx, R3 and R represent hydrogen, and R2 means alkyl lower or lower alkenyl substituted by halogen. 6. The polymer according to claim 3, wherein the unsaturated polymer (a) contains repeating units that are selected from the units of Formulas (I) and (II), wherein R1 R3 and R4 represent hydrogen, and R2 means lower alkenyl up to 4 carbon atoms. The polymer according to claim 3, wherein the unsaturated polymer (a) contains repeating units of the formula (I), in which Rlf R3 and R4 represent hydrogen, and R2 means lower alkenyl up to 4 carbon atoms. 8. The polymer according to claim 3, wherein the unsaturated polymer (a) contains repeating units of the Formula (II), wherein R? represents lower trialkylsilyl, and R2 denotes lower alkyloxy. 9. The polymer according to claim 3, wherein the unsaturated polymer (a) contains alternately repeating units of the formulas (I) and (II), wherein R ?, R3 and R4 represents hydrogen, and R2 denotes lower alkyl or lower alkenyl up to 4 carbon atoms. 10. The polymer according to claim 3, wherein the unsaturated polymer (a) is selected from syndiotactic poly-1,2-butadiene, poly-l, 4-butadiene and polyisoprene. The polymer according to claim 4, wherein the polysiloxane ((b) denotes a compound of the Formula (IV), and the radicals R5, R6 and R7, independently of each other, mean hydrogen, alkyl, alkoxy, phenyl or alkyl lower fluorine-containing, and that at most 20% of the radicals of R5, R6 and R7 mean hydrogen., according to claim 4, in which the polysiloxane (b) represents a compound of the formula (IV), and the radicals R5, R6 and R7, independently of each other, mean hydrogen, alkyl, alkoxy, phenyl or lower alkyl containing fluorine , and in which just two of the radicals R5, R6 and R7 mean hydrogen. 13. The polymer according to claim 12, wherein the two R7s mean hydrogen. The polymer according to claim 4, wherein the polysiloxane (b) means a compound of the formula (IV), two silicon-hydrogen bonds are arranged at terminal points, and the radicals R5 and R6 represent alkyl, lower alkyl which contains fluorine, or phenyl, especially lower alkyl, such as methyl or ethyl, or also phenyl. 15. The polymer according to claim 14, wherein the radicals R5 and R6 mean lower alkyl with 8 carbon atoms, and especially methyl. 16. The polymer according to claim 4, wherein the polysiloxane (b) represents a compound of the Formula (IV), and the radicals R5, R6 and R7 mean hydrogen, lower alkyl containing fluorine, alkyl or phenyl, especially hydrogen lower alkyl, such as methyl or ethyl, or phenyl, with the indication that at least two of the radicals R5, R6 and R7, and preferably a maximum of 20% of the radicals R5 R3 and R7 mean hydrogen. 17. The polymer according to claim 4, wherein x means 1 to 500, first of all 1 to 200, wave 100, and particularly preferably 2 to 85. 18. The polymer according to claim 3, wherein the polymer unsaturated (a) is selected from the group of a polymeric conjugated aliphatic diene, or alicyclic conjugate which is substituted, for example, by halogen or lower alkyl; of a polymer of an alkene or dialkine, which is unsubstituted or substituted by lower alkyl or trimethylsilyl; of a copolymer of a conjugated diene with a vinyl, hydrophilic or hydrophobic monomer; and in addition to partially hydrogenated derivatives of the mentioned compounds. 19. The polymer according to claim 2, wherein the hydrophobic vinyl monomer is selected from alkylacrylate with 1 to 18 carbon atoms, and cycloalkylacrylate with 3 to 18 carbon atoms, and methacrylate of the same class, alkylacrylamide and methacrylamide with to 18 carbon atoms, acrylonitrile, methacrylonitrile, vinyl-alkanoic acid with 1 to 18 carbon atoms, alkene with 2 to 18 carbon atoms, haloalkene with 2 to 18 carbon atoms, styrene, lower alkyl styrene, lower alkyl vinyl ether, perfluoroalkyl-acrylate with 2 to 10 carbon atoms, and its methacrylate, or the partially fluorinated acrylate and methacrylate correspondingly, the perfluoroalkyl with 3 to 12 carbon atoms-ethyl-thiocarbonylamino-ethyl-acrylate and methacrylate, acryloxy and methacryloxy-alkylsiloxane, N- vinylcarbazole, alkyl ester with 1 to 12 carbon atoms of maleic acid, fumaric acid, itaconic acid, mesaconic acid and the like. The polymer according to claim 2, wherein the hydrophilic vinyl monomer is selected from the lower alkyl acrylate and methacrylate, substituted by lower hydroxy, acrylamide, methacrylamide, lower alkyl acrylamide and alkyl methacrylamide, ethoxylated acrylate and methacrylate, alkyl acrylamide and substituted lower methacrylamide. by hydroxy, lower alkylvinylether substituted by hydroxy, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2- and 4-vinylpyridine, vinyl unsaturated carboxylic acids with a total of 3 to 5 carbon atoms, lower aminoalkyl (the term "amino" also includes quaternary ammonium), lower monoalkylamino-lower alkyl- and lower dialkylamino-lower alkylacrylate and its methacrylate, allyl alcohol and the like. 21. Molded bodies, especially contact lenses that consist fundamentally or totally of a crosslinking product according to the invention, according to claim 1, or a graft polymer according to the invention according to claim 2. 22. The use of a polymer , according to any of claims 1 or 2, for the production of moldings, especially contact lenses. 23. The use of a polymer according to any of claims 1 or 2, for the coating of a basic material, such as glass, ceramic, metal or polymeric substrates, such as, for example, ophthalmically applicable products. 24. The use of a polymer according to any of claims 1 or 2, as an implant of cornea or artificial cornea ("corneal implant", "artificial cornea").