MXPA97008910A - Macisters polisiloxano-poliol, its preparation and its - Google Patents

Abstract

The present invention discloses a polysiloxane-polio macromer, which is uninterrupted or interrupted by a bivalent structural element, and which further bears at least one polymerizable segment on a polyol segment, a polymer comprising a polymerization product of at least one macromer of according to the invention, and if appropriate, at least one vinyl comonomer, intermediates, processes for the preparation of a macromer and a polymerization product, moldings, contact lenses, corneal implants or biomedical articles of a polymerization product, or of a polymer prepared from it to cover a substratum

Description

MACISTERS OF POLYSYLXOXAN-POLYOL. Sü PREPARATION AND ITS USE The present invention describes a polysiloxane-polyol macromer, which is uninterrupted or interrupted by a bivalent structural element, and which furthermore carries at least one polymerizable segment on a polyol segment; a polymer comprising a polymerization product of at least one macromer according to the invention, and if appropriate, of at least one vinyl comonomer; intermediaries; processes for the preparation of a macromer and a polymerization product; mounts, contact lenses, corneal implants or bio-medical articles of a polymerization product; and further the use of a macromer according to the invention, or of a polymer prepared therefrom to coat a substrate. Japanese Patent Numbers JP 62/068820 and JP 63 / 139,106 (Kao Corporation) describe a polymer consisting of a polysiloxane carrying at least one primary amino group, and by which, the polysiloxane is modified with a sugar residue. These modified polysiloxanes are recommended as additives for hair care products. International Publication Number WO 83/01617 (Minnesota Mining) describes, among other things, a macromer which is a methacrylic or acrylamido-acyl derivative of a polysiloxane. It is said that these siloxane derivatives are useful as coatings for films. European Patent Number EP 362,145 (Ciba-Geigy) discloses a contact lens that is produced by the reaction of a polydialkylsiloxane prepolymer containing terminal isocyanate with a polydialkylsiloxane-di- or -polyalkanol. R. Stadler et al. (Macromolecules 28, 17-24 (1995)) describe polysiloxanes with pendant groups of glucone ina or altoheptaonamide, starting their synthesis, for example, from the corresponding peracylated N-allyldonamides, which are added to a group Si-H of a corresponding polysiloxane, by hydrosilylation, using a rhodium or platinum catalyst. Polymers containing biocompatible polysiloxane are still desired. Polysiloxanes having, for example, the following specific properties are particularly desirable; hardness, mechanical damping, slow mechanical relaxation, oxygen permeability, and resistance to deposits of proteins, lipids, and salts, and certain hydrophilicity. The problem described has been achieved with the preparation of polymerizable macromers containing free hydroxyl groups. Macromers are disclosed which are constructed, for example, from an aminoalkylated polysiloxane which is derived with at least one polyol component containing an unsaturated polymerizable side chain.

The polymers can be prepared, on the one hand, from the macromers according to the invention, by homopolymerization. The aforementioned macromers can be mixed and polymerized with one or more hydrophilic and / or hydrophobic comonomers. A special property of the macromers according to the invention is that they function as the element that controls the microphase separation between the selected hydrophilic and hydrophobic components in a cross-linked final product. The hydrophilic / hydrophobic microphase separation is in the region of less than 300 nanometers. The macromers are preferably crosslinked at the boundaries of the phases between, for example, an acrylate comonomer on the one hand, and an unsaturated polymerizable side chain of polyols linked with polysiloxane on the other, by covalent bonds, and additionally by reversible physical interactions. , for example hydrogen bridges. These are formed, for example, by numbers of amide or urethane groups. The continuous siloxane phase that exists in the phase compound has the product effect a surprisingly high oxygen permeability. The present invention relates to a macromer comprising at least one section of the formula (I): -a Z b- (I) I d where (a) is a polysiloxane segment, (b) is a polyol segment containing at least 4 carbon atoms, Z is segment (c) or a group X1 # in where: segment (c) is defined as X2-R-X2, wherein: R is a bivalent radical of an organic compound containing up to 20 carbon atoms, and each X2, independently of each other, is a bivalent radical that contains at least one carbonyl group, and wherein: Xx is defined as X2, and wherein: (d) is a radical of formula (II): X3-L- (Y) k-P1 (II) wherein P1 is a group that can be polymerized by free radicals; Y and X3, independently of one another, are a bivalent radical containing at least one carbonyl group; k is 0 or 1; and L is a bond or a bivalent radical having up to 20 carbon atoms of an organic compound.

A polysiloxane segment (a) is derived from a compound of the formula (III): R, where n is an integer from 5 to 500; from 99.8 to 25 percent of the radicals Rlf R2, R3, R4 / R5 / and R6 'independently of each other are alkyl, and from 0.2 to 75 percent of the radicals R1 # R2, R3, R4, R5, and R6 , independently of one another, are partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-alk-H2 or alk- (OCH2) m- (OCH2) p-OR7, wherein: R7 is hydrogen or lower alkyl , alk is alguylene, and m and p, independently of each other, are an integer from 0 to 10, one molecule containing at least one primary amino or hydroxyl group. The alkyleneoxy groups - (OCH2CH2) m and - (OCH2) p in the siloxane of the formula (III) are randomly distributed in a ligand of alk- (OCH2CH2) m- (0CH2) p-OR7, or are distributed as bloks in a chain. A polysiloxane segment (a) is bound a total of 1 to 50 times, preferably 2 to 30 times, and in particular 4 to 10 times, by means of a group Z, with a segment (b) or another segment (a), Z being always in a sequence aZa a segment (c). The binding site in a segment (a) with a group Z, is an amino or hydroxyl group reduced by a hydrogen. In a preferred meaning, a polysiloxane segment is derived from a compound of the formula (III), wherein: the radicals R1 # R2, R3, R4, R5, and R6 are a total of 1 to 50 times, more preferably from 2 to 30 times, and in particular from 4 to 10 times, in an independent manner, whether it is aminoalkyl or terminal or pendant hydroxyalkyl, the other variables being as defined above. In a preferred embodiment, a polysiloxane segment is derived from a compound of the formula (III), wherein: from 95 to 29 percent of the radicals Rl t R2, R3, R4, R5 # and R6 independently of others are alkyl, and from 5 to 71 percent of the radicals Rx, R2, R3, R4, R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH- alk-NH2 or alk- (OCH2CH2) m- (OCH2) p-OR7, and wherein the variables are as defined above. In another preferred embodiment, a polysiloxane segment (a) is derived from a compound of the formula (III), wherein: from 95 to 29 percent of the radicals R1 # R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, and from 5 to 71 percent of the radicals R1 f R2, R3, R4, R5, and R6, independently of each other, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl. In a preferred meaning, n is an integer from 5 to 400, more preferably from 10 to 250, and particularly preferably from 12 to 125. In a preferred meaning, the two terminal radicals Rx and R6 are aminoalkyl or hydroxyalkyl, the other variables being as previously defined. In another preferred meaning, the radicals R4 and R5 are from 1 to 50 times, more preferably from 2 to 30 times, and in particular from 4 to 10 times aminoalkyl or hydroxyalkyl pendants, and the other variables are as defined above. In another preferred meaning, the radicals R.sub.1 R.sub.2, R.sub.3, R.sub.4 / R.sub.5 'and R.sub.β are a total of 1 to 50 times, more preferably 2 to 30 times, and in particular 4 to 10 times, independently, both aminoalkyl or hydroxyalkyl terminals and pendants, and the other variables are as defined above. If Z is Xl f X? is a bivalent group that contains at least one carbonyl group. A mentioned carbonyl group is in any way flanked, if appropriate, by -O-, -CONH-, -NHCO-, or -NH-. Examples of the bivalent Z groups are typically carbonyls, esters, amides, urethanes, ureas or carbonates. X x is preferably an ester, amide, urethane, or urea group, in particular an ester or amide group.

X 2 is defined in the same manner as X 1 and t is preferably an ester, amide, urethane, carbonate, or urea group, more preferably an ester, amide, urethane, or reactant group, and in particular an amide, urethane, or urea group . If Z in formula (I) is X1 (a segment of polyol (b) is preferably understood to mean a polyol derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone, it is understood that a carbohydrate means a mono -, di-, tri-, tetra-, oligo-, or poly-saccharide It is understood that a carbohydrate lactone means the lactone of an aldonic or uronic acid An aldonic or uronic acid is, for example, a carboxylic acid formed by the oxidation of a mono-, tri-, tetra-, oligo-, or poly-saccharide Examples of the aldonic acid lactones are gluconolactone, galactonolactone, lactobionolactone, or maltoheptaonolactone, examples of the lactones of uronic acid are lactone of glucuronic acid, mannuronic acid lactone, or iduronic acid lactone An example of a carbohydrate dilactone is D-glucaro-1,4: 6,3-dilactone A carbohydrate lactone reacts with, for example, an amino group primary or a group hydroxyl of segment (a), to form a covalent bond of amide or ester of type X '. These bonds constitute a further preferred embodiment of the macromers according to the invention. These macromers have an alternating distribution of segments of type (a) and (b), which are interrupted by X? . A preferred embodiment is a macromer comprising at least one section of the formula (I): -a Z b- (I) wherein (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R1 # R2, R3, R, R5, and 6 # independently of each other, are alkyl lower, from 5 to 71 percent of the radicals R1 # R2, R3, R4, R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a segment of polyol (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or X1 # where X ^^ is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-R-X2, wherein R is alkylene, arylene, alkylenearylene, or arylenealkylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms, and X2 is an amide, urethane, or urea group; and (d) is a radical of the formula (II), wherein Px is alkenyl, X3 is an ester, amide, urethane, or urea group, Y is a carbonyl, ester or amide group, k is 0 or 1, and L is a bond or alkylene. The invention preferably relates to a macromer of the formula (IV): a Xx b (IV) where the variables are as defined above. The invention preferably also relates to a macromer according to formula (V), wherein the polysiloxane segment (a) contains q hanging ligands, and wherein: x is 0, 1, or 2, q has an average numerical value of 1 to 20, preferably 1 to 10, and in particular 1 to 5, and wherein: segments (b) in a macromer according to formula (V) are linked in total (per molecule) with up to 20, preferably up to 15, and in particular with up to 6 polymerizable segments ( d). The invention preferably also relates to a macromer according to formula (VI): wherein a linear sequence is present, wherein: x is 0, 1, or 2, q has an average numerical value from 1 to 20, preferably from 1 to 10, and in particular from 1 to 5, and wherein: segments (b) in a macromer according to formula (VI) are linked in total (per molecule) with up to 20, preferably with up to 15, and in particular with up to 6 polymerizable segments (d). The invention very preferably furthermore relates to a macromer according to formula (VII): wherein x is 0, 1, or 2, and the average number of segments (d) per molecule of formula (VII) is preferably in the range of 2 to 5, and most preferably in the range of 3 to 4. More preferred are the macromers of formula IV, V, VI, or VII, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of formula (III), wherein 95 to 29 percent of the radicals x, R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R? , R 2, R 3, R 4, R 5, and R 6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone; (d) is a radical of formula (II): X3-L- (Y) lc-P1, wherein Px is alkenyl, X3 is a urethane or urea group, and is a carbonyl, ester, or amide group, is 0 or 1, and L is bond or alkylene; and Xx is an ester, amide, urethane, or urea group.

Also preferred are the macromers of the formula IV, V, VI, or VII, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R 1 t R 2, R 3, R 4, R 5, and R 6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R x, R 2, R 3, R 4, R 5, and R6, independently of one another, are partially fluorinated lower alkyl, lower aminoalkyl, or lower hydroxyalkyl, and n is an integer from 10 to 250; a polyol segment (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone; (d) is a radical of the formula (II): X3-L- (Y)] t-Pif wherein P? is lower alkenyl, X3 is a urethane or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is lower alkylene or bond; Y ? it is an ester, amide, urethane, or urea group.

A polyol segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c). Examples of these polyols are 1,2-polyol, for example the reduced monosaccharides, for example mannitol, glucitol, sorbitol, or iditol, a 1,3-polyol, for example polyvinyl alcohol (PVA), which is derived from of partially or completely hydrolyzed polyvinyl acetate, and also amino-terminal PVA telomers, aminopolyols, to inociclodextrins, aminomono-, -di-, -tri-, -oligo-, or -poly-saccharides or cyclodextrin derivatives, for example hydroxypropylcyclodextrin. A above-mentioned carbohydrate dilactone can be reacted, for example, preferably with two equivalents of an amino-terminal PVA telomer, to give a polyol macromer bearing, in the middle part, the carbohydrate compound derived from the dilactone. These polyols of this composition in the same way are understood as a suitable polyol. As illustrated in formula (I), a segment (b) carries at least one vinyl polymerizable segment (d), wherein the bond of a segment (d) with a segment (b), is intended by means of the bivalent radical X3 contained in a segment (d) with an amino and / or hydroxyl group minus a hydrogen atom preferably contained in the polyol segment (b). A vinyl polymerizable segment (d) is incorporated either terminally or pendently preferably 1 to 20 times, more preferably 2 to 15 times, and in particular 2 to 6 times, per macromer molecule according to the invention. A vinyl polymerizable segment (d) is incorporated terminally and also pendently as desired (as a terminal / pendant mixture) preferably 1 to 20 times, more preferably 2 to 15 times, and in particular 2 to 6 times, per macromer molecule according to the invention. A P- ^ group that can be polymerized by free radicals is, for example, alkenyl, alkenylaryl, or alkenylarylenealkyl having up to 20 carbon atoms. Examples of alkenyl are vinyl, allyl, l-propen-2-yl, 1-buten-2- or -3- or -4-yl, 2-buten-3-yl, and the isomers of pentenyl, hexenyl, octenyl , decenyl, or undecenyl. Examples of alkenylaryl are vinylphenyl, vinylnaphthyl, or allylphenyl. An example of alkenylarylenealkyl is vinylbenzyl. P? it is preferably alkenyl or alkenylaryl having up to 12 carbon atoms, more preferably alkenyl having up to 8 carbon atoms, and in particular alkenyl having up to 4 carbon atoms. L is preferably alkylene, arylene, a saturated bivalent cycloaliphatic group having 6 to 20 carbon atoms, 1 to 1 to 1 to not, alkylenearylene, alkylenealkylenealkylene, or arylenenalkylenearylene. In a preferred meaning, L is also preferably a bond. In a preferred meaning, L is a bivalent radical having up to 12 carbon atoms, and more preferably a bivalent radical having up to 8 carbon atoms. In a preferred meaning, L is also alkylene, or arylene having up to 12 carbon atoms. A most preferred meaning of L is lower alkylene, in particular lower alkylene having up to 4 carbon atoms. And it is preferably a carbonyl, ester, amide, or urethane group, in particular a carbonyl, ester, or amide group, and most preferably a carbonyl group. In another preferred meaning, Y is absent, i.e., k is 0. In a preferred meaning, X3 is a urethane, urea, ester, amide, or carbonate group, more preferably a urethane, urea, ester, or amide group, and in particular a urethane or urea group. A vinyl polymerizable segment (d) is derived, for example, from acrylic acid, methacrylic acid, methacryloyl chloride, 2-isocyanatoethyl methacrylate (IEM), allyl isocyanate, vinyl isocyanate, isomeric vinylbenzyl isocyanates or adducts of hydroxyethyl methacrylate (HEMA) and 2,4-tolylene ocyanate (TDI) or isophorone isocyanate (IPDI), in particular the 1: 1 adduct. The invention further preferably relates to a macromer wherein a segment (d) is incorporated either terminally or pendantly, or as a terminal / pendant mixture five times. The invention further preferably relates to a macromer wherein a segment (d) is terminally incorporated five times. The di-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 from 7 to 20 carbon atoms. In a preferred meaning, R is alkylene, arylene, alkylenearylene, arylenealkylene, or arylenenalkylenearylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms. In a preferred meaning, R is alkylene, arylene, alkylenearylene, or arylenealkylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms. In a preferred meaning, 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 meaning, R is alkylene or arylene having up to 10 carbon atoms, or is a saturated bivalent cycloaliphatic group having from 6 to 10 carbon atoms. In a highly preferred meaning, a segment (c) is derived from a ocyanate, for example from 1,6-hexane ocyanate, 1,6-ocyanate 2,2,4-trimethylhexane, tetramethylene ocyanate, Phenylene 1,4-ocyanate, toluene-2,4-ocyanate, toluene-2,6-ocyanate, m- or p-tetramethylxylene ocyanate, isophorone ocyanate, or 1,4-cyclohexane ocyanate. A preferred embodiment of segment (c) is further derived from a ocyanate wherein the isocyanate groups have different reactivities. The different reactivity is influenced, in particular, by the steric requirements and / or the density of electrons in the vicinity of an isocyanate group. The average molecular weight of a macromer according to the invention is preferably in the range of about 300 to about 30,000, most preferably in the range of about 500 to about 20,000, more preferably in the range of about 800 to about 12,000, and in a particularly preferable manner in the range of from about 1,000 to about 10,000. A preferred embodiment of the macromer has a sequence of the segment of the formula (VIII): b-Z-a-. { AC} r- (Z-b) t (VIII) wherein r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is 0 or 1, and preferably 1; wherein a linear chain (c-a) is present which may or may not be terminated by a segment (b) (t = l); and the previous preferences apply to the total number of segments (d), which are preferably linked to a segment (b).

A preferred embodiment of the macromer has a sequence of the segment of the formula (IX): b-Z-a-. { c-a- (Z-b) t} r (IX) where the sequence (c-a) - (Z-b) t hangs R times on segment (a), and may or may not be terminated by a segment (b); wherein r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is 0 or 1, and is preferably 1; Z is a segment (c) or a group X1 # * and the previous preferences apply to the total number of segments (d), which are preferably linked to a segment (b). Another preferred embodiment of the macromer has a sequence of the segment of the formula (X): b-c-. { a-c} s-B (X) wherein s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; B is a segment (a) or (b); and the above preferences are applied to the number of segments (d), which are linked to a segment (b).

Another preferred embodiment of the macromer has a sequence of the segment of the formula (XI): B- (c-b) s-Z-a- (Z-b) t (XI) the linear structures being, and wherein: s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; B is a segment (a) or (b); t is 0 or 1, and the previous preferences apply to the number of segments (d), which are linked to a segment (b).

A more preferred embodiment of a macromer is a sequence of the segment of formula (VIII), (IX), (X), or (XI), wherein the variables are defined as follows: a segment of polysiloxane (a) is derives from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R1; R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R1 # R2, R3, R4, R5, and R6, independently of each other, are partially alkyl fluorinated, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a segment of polyol (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or x1 # where X? is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-RX, wherein R is alkylene, arylene, alkylenearylene, or arylenealkylene having up to 14 carbon atoms, or a bivalent cycloaliphatic group saturated having 6 to 14 carbon atoms, and X2 is an amide, urethane, or urea group; (B) is a segment (a) or a segment (b), with the previously preferred definitions; and (d) is a radical of the formula (II): X3-L- (Y) k-P1, which is up to 15 times, still more preferably up to 6 times terminally and / or pendently attached to a segment (b), and wherein P1 is alkenyl, X3 is an ester, amide, urethane, or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is a bond or alkylene.

Another more preferred embodiment of a macromer is a sequence of the segment of formula (VIII), (IX), (X), or (XI), wherein the variables are defined as follows: a segment of polysiloxane (a) is derives from a compound of the formula (III), wherein from 95 to 29 percent of the radicals Rlf R2, R3, R4, R5, and R6, independently of each other, are lower alkyl, from 5 to 71 by one hundred of the radicals R1 # R2, R3, R4, R5, and R6, independently of one another, are partially fluorinated lower alkyl, lower aminoalkyl, or lower hydroxyalkyl, and n is an integer from 10 to 250; a polyol segment (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or Xl r wherein Xx is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-R-X2, wherein R is alkylene or arylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms, and X 2 is an amide, urethane, or urea group; (B) is a segment (a) or a segment (b), with the previously preferred definitions; and (d) is a radical of the formula (II): X3-L- (Y) k-P1, which is up to 6 times terminally and / or pendantly attached to a segment (b), and wherein P? is lower alkenyl, X3 is an ester, amide, urethane, or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is a lower alkylene or bond.

The proportion of the number of segments (a) and (b) in a macromer according to the invention is preferably on a scale of (a): (b) = 3: 4, 2: 3, 1: 2, 1 : 1, 1: 3, or 1: 4. The total sum of segments (a) and (b), or where appropriate, (a) and (b) and (c), is on a scale of 2 to 50, preferably 3 to 30, and in particular on the scale of 3 to 12. Alkyl has up to 20 carbon atoms, and can be straight or branched chain. Suitable examples include dodecyl, octyl, hexyl, pentyl, butyl, propyl, ethyl, methyl, 2-propyl, 2-butyl, or 3-pentyl. 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, or methyl-1,4-phenylene; or 1,5-naphthylene, or 1,8-naphthylene. Aryl is a carbocyclic aromatic radical, which is unsubstituted or preferably substituted by lower alkyl or lower alkoxy. Examples are phenyl, toluyl, xylyl, methoxyphenyl, tertiary butoxy-phenyl, naphthyl or phenanthryl. 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 radical of bivalent isophorone.

The term "lower" in the context of this invention in relation to radicals and compounds, unless defined otherwise, means, in particular, radicals or compounds having up to 8 carbon atoms, preferably having up to 4 atoms of carbon. 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 include decylene, octylene, hexylene, pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene, or 3-pentylene. Lower alkylene is alkylene having up to 8, and in a particularly preferable manner having up to 4 carbon atoms. A particularly preferred meaning of lower alkylene is propylene, ethylene, or methylene. The alkylenearylene or arylene-alkylene arylene unit is preferably phenylene, which is unsubstituted or substituted by lower alkyl or lower alkoxy, and the alkylene unit thereof 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. It is understood that partially fluorinated alkyl means alkyl wherein up to 90 percent, preferably up to 70 percent, and in particular up to 50 percent of the hydrogens are replaced by fluorine. Arylenenalkylene is preferably phenylene-lower alkylene-phenylene having up to 8, and in particular having up to 4 carbon atoms in the alkylene unit, for example phenylene-ethylene-phenylene or phenylene-methylene-phenylene. A monosaccharide in the context of the present invention is understood to mean an aldopentose, aldohexose, aldotetrose, ketopentose, or ketohexose. Examples of an aldopentose are D-ribose, D-arabinose, D-xylose, or D-liosa; examples of an aldohexose are D-alose, D-altrose, D-glucose, D-mannose, D-gulose, D-idosa, D-galactose, D-talose, L-fucose, or L-rhamnose; examples of a ketopentose are D-ribulose, or D-xylulose; the examples of a tetrosa are D-eritrosa or threose; and examples of a ketohexose are D-psychosa, D-fructose, D-sorbose, or D-tagatose. Examples of a disaccharide are trehalose, maltose, isomaltose, cellobiose, gentiobiose, sucrose, lactose, chitobiose, N, N-diacetyl chitosan, palatinose, or sucrose. Raffinose, panose, or maltotriose may be mentioned as an example of a trisaccharide. Examples of an oligosaccharide are maltotetraose, maltohexaose, quitoheptaose, and also cyclic oligosaccharides, such as cyclodextrins. The cyclodextrins contain from 6 to 8 identical units of an α-1,4-glucose. Some examples are α-, β-, and β-cyclodextrin, derivatives of these cyclodextrins, for example hydroxypropylcyclodextrins, and branched cyclodextrins. The macromers according to the invention can be prepared by processes known per se, for example, as follows. In a first step, a polysiloxane containing, for example, at least one primary amino- or hydroxy-alkyl group, is reacted with a carbohydrate lactone, forming an amide or ester bond, and forming a compound of the formula (Xlla) or (Xllb): (a-Z-b) ((Xlla) a- (Z-b) q (Xllb) wherein the variables are as defined above, and Z is a group Xl r after which, the compound (XII) is reacted with an unsaturated polymerizable compound of the formula (XIII): X ^ L-Wn-Pi (XIII) wherein X4 is a group that is coreactive with a hydroxyl or amino group of segment (b), forming a group X3 of a segment (d) according to formula (II) from this reaction, and wherein: X4 is preferably -COOH, -COOR10, -COCÍ or -NCO, wherein: R10 is alkyl, or is aryl that is unsubstituted or substituted by lower alkyl or lower alkoxy, and the other variables are as defined above, after which, a macromer is formed according to formula (IV) or (V): a-Xj- b A (IV) wherein the segments (d) are incorporated terminally and / or pendently. Another process starts from a polysiloxane (a) containing terminal primary- or hydroxy-alkyl amino groups, and is reacted with a carbohydrate dilactone to form structures of the formula: _ / a-XT- b - (XIV) \ 'q wherein the variables are as previously defined and preferred, after which, a compound of the formula (XIV) is reacted with a compound of the formula (XIII) in a manner analogous to the previous process, to give a macromer of the formula (VI): where the variables are as defined and preferred above. Another process starts from a polysiloxane (a) containing terminal primary- or hydroxy-alkyl amino groups, and is initially reacted with a bifunctional compound of the formula (XV): X4-R-X4 (XV) wherein X4 is a group that is coreactive with a hydroxyl or amino group of segment (a), forming a group X2 of a segment (c) from this reaction, and wherein: X4 is preferably -COOH, -COOR10, -COCY or -NCO, wherein R10 is alkyl, or aryl that is unsubstituted or substituted by lower alkyl or lower alkoxy, and R is as defined above, after which, this intermediate it is reacted with a polyol that does not carry lactone group, to give a compound of the formula (XVI): b-c-. { a-c} g-b (XVI) wherein the variables are as defined and preferred above, after which, the compound of the formula (XVI) is reacted with a compound of the formula (III), to give a macromer of the formula (X), (segments (d) in formula (X) are not shown), b-c-. { a-c} s-B (X) wherein s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; B is a segment (a) or (b); and the previous preferences apply to the number of segments (d) that are linked to a segment (b). Another process starts from a bifunctional compound of the formula (XV): X4-R-X4 (XV) which is reacted with an excess of polysiloxane (a) to give a sequence -a- (ca) r-, where the above meanings are applied, after which, in a second step, the intermediate is reacted with a polyol lactone-free, to give a compound of the formula (XVII): b-Z-a-. { AC} r-Z-b (XVII) after which, the compound (XVII) is reacted with the compound (XIII), to give a macromer of the formula (VIII), (the segments (d) in the formula (VIII) are not shown, b-Z-a-. { AC} r- (Z-b) t (VIII) wherein r is integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is 0 or 1, and is preferably 1; wherein a linear chain (c-a) is present, which may or may not be terminated by a segment (b) (t = l); and the previous preferences apply to the total number of segments (d), which are preferably linked to a segment (b). Another process starts from a carbohydrate lactone that is reacted in a first step with a compound of the formula (XIII), retaining the lactone function, after which, the intermediate is reacted with a polysiloxane which contains when minus an amino or hydroxyl group, to give a compound of the formula (IV) or (V): a Xi b (IV) a- (Xt-b) i 'q (V) (u). wherein q is typically 1 or 2, and wherein the foregoing meanings and preferences are applied differently, and segments (d) are incorporated terminally and / or pendently. The present invention also relates to intermediates which are novel, and which occur during the synthesis of the macromers according to the invention. Accordingly, the invention further relates to a compound of the formula (Xlla): (a-Z-b) q (Xlla) wherein q is greater than 1, (a) is derived from a polysiloxane as defined in the main claim, and (b) is derived from a carbohydrate dilactone. The invention also relates to a compound of the formula (Xllb): a- (Z-b) q (Xllb) wherein Z, (b), and q are as defined and preferred above, but with the proviso that a segment (a) is derived from a compound of the formula (III): R, where n is an integer from 5 to 500; from 99.8 to 25 percent of the radicals Rx, R2, R3, R4 »R5 / and R6 'independently of each other, are alkyl, and from 0.2 to 75 percent of the radicals Rx, R2, R3, R, R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-Alk-NH2 or alk- (OCH2CH2) m- (OCH2) p-OR7, wherein: R7 is hydrogen or lower alkyl, alk is alkylene, and m and p, independently of each other, are an integer from 0 to 10, one molecule containing at least one primary amino or hydroxyl group, and at least one partially fluorinated alkyl group. The invention also relates to a compound of the formula (XVI): b-c-. { a-c} s-b (XVI) wherein a segment (b) is derived from a polyol lactone-free, and the other variables are as defined and are preferred above. The invention also relates to a compound of the formula (XVII): b-Z-a-. { AC} r-Z-b (XVII) wherein a segment (b) is derived from a polyol lactone-free, and the other variables are as defined and preferred above. A siloxane (a) containing at least one primary amino or hydroxyl group, for example, can be obtained commercially. Examples are KF-6002, KF-8003, X-22-161C (Shin Etsu) or GP4 (Genesee). Other siloxanes can be synthesized with the help of published processes. A polyol (b) required for the synthesis, as a rule, can be obtained commercially. Examples are gluconolactone or lactobionolactone. Otherwise, they can be synthesized with the help of a published process. The processes according to the invention can be prepared in the presence or absence of a solvent. Conveniently a solvent is used which is largely inert, that is to say, that does not participate in the reaction. Suitable examples of these are ethers, such as tetrahydrofuran (THF), 1,2-dimethoxyethane, diethylene glycol dimethyl ether, or dioxane; halogenated hydrocarbons, such as chloroform or methylene chloride; bipolar aprotic solvents, such as acetonitrile, acetone, dimethyl formamide (DMF), or dimethyl sulfoxide (DMSO); hydrocarbons, such as toluene or xylene; and also pyridine or N-methylmorpholine. The reagents are conveniently used in stoichiometric amounts for the preparation of the compounds according to the invention. The reaction temperature can be, for example, from -30 ° C to 150 ° C. The scale from 0 ° C to 40 ° C is a preferred temperature scale. The reaction times here are on the scale of about 15 minutes to 7 days, preferably in the region of about 12 hours. If necessary, the reaction is carried out under argon or nitrogen as an inert gas. Conveniently a suitable catalyst is added for the urethane-forming reactions, for example dibutyl tin dilaurate (DBTDL). The present invention further relates to a polymer comprising a polymerization product of at least one macromer according to the invention as defined above, and if appropriate, at least one vinyl comonomer (a). The preferred composition of a polymer according to the invention comprises a content by weight, with respect to the total polymer, of a macromer according to the invention, on a scale of 100 to 0.5 percent, in particular on the scale of 80 to 10 percent, and preferably on the scale of 70 to 30 percent. In a preferred polymer comprising a polymerization product of at least one macromer according to the invention, comonomer (a) is absent, and the polymer is preferably a homopolymer. A comonomer (a) which is contained in a polymer according to the invention can be hydrophilic or hydrophobic or a mixture of both. Suitable comonomers include, in particular, those which are normally used for the preparation of contact lenses and biomedical materials. It is understood that a hydrophobic comonomer (a) means monomers that typically give, as a homopolymer, polymers that are insoluble in water, and that can absorb less than 10 weight percent water. Analogously, a hydrophilic comonomer (a) is understood to mean a monomer that typically gives, as a homopolymer, a polymer that is soluble in water, or that can absorb at least 10 percent by weight of water. Suitable hydrophobic comonomers (a) include, without this list being conclusive, alkyl acrylates and methacrylates of 1 to 18 carbon atoms and cycloalkyl of 3 to 18 carbon atoms, acrylamides and alkyl methacrylamides of 3 to 18 carbon atoms. carbon, acrylonitrile, methacrylonitrile, 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 ethers of lower alkyl, acrylates and perfluoroalkyl methacrylates of 2 to 10 carbon atoms or the correspondingly partially fluorinated acrylates and methacrylates, perfluoroalkyl acrylates and methacrylates of 3 to 12 carbon atoms-ethyl-thiocarbonylaminoethyl, acryloxy- and methacryloxy-alkylsiloxanes, N-vinylcarbazole and alkyl esters of 1 to 12 carbon atoms of maleic acid, fumaric acid, itaconic acid, mesaconic acid, and the like. Preferred comonomers are, for example, acrylonitrile, 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 (a) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, isobutyl acrylate (IBA), isooctyl acrylate (OA), isodecyl acrylate (DA), acrylate cyclohexyl, 2-ethylhexyl acrylate (EHA), methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride , vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinylethyl ether, perfluorohexylethylcarbonylaminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl (meth) acrylate (HFBMA and HFBA), methacrylate tris-trimethylsilyloxy-silyl-propyl (TRIS), 3-methacryloxypropylpentamethyldisiloxane, and bis (methacryloxypropyl) tetramethyldisiloxane.

Preferred examples of the hydrophobic comonomers (a) are methyl methacrylate, IBA, HFBA, HFBMA, OA, EHA, DA, TRIS, and acrylonitrile. Suitable hydrophilic comonomers (a) include, without this list being conclusive, lower alkyl acrylates and methacrylates substituted by hydroxyl, acrylamide, ratacrylamide, lower alkyl acrylamides and methacrylamides, ethoxylated acrylates and methacrylates, lower alkyl acrylamides and methacrylamides substituted by hydroxyl, hydroxy-substituted vinyl lower alkyl ethers, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyl oxazoline, 2-vinyl-4, 4'-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinyl unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, lower aminoalkyl acrylates and methacrylates (wherein the term "amino" also includes quaternary ammonium) ), lower monoalkyl-lower aminoalkyl, and lower dialkyl-lower aminoalkyl; allyl alcohol, and the like. Preferred comonomers are, for example, N-vinyl-2-pyrrolidone, acrylamide, methacrylamide, hydroxyl-substituted lower alkyl acrylates and methacrylates, hydroxyl-substituted lower alkyl acrylamides and methacrylamides, and vinyl unsaturated carboxylic acids having a total of 3 to 5 carbon atoms.

Examples of suitable hydrophilic comonomers (a) include hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylammonium-2-hydroxypropyl methacrylate hydrochloride (BlemerRQA, for example from Nippon Oil), dimethylaminoethyl methacrylate (DMAEMA ), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, N, N-dimethylacrylamide (DMA), allyl alcohol, vinylpyridine, glycerol methacrylate, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N-vinyl-2-pyrrolidone (NVP), acrylic acid, methacrylic acid, and the like. The preferred hydrophilic comonomers (a) are 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, trimethylammonium-2-hydroxypropyl methacrylate hydrochloride, N, N-dimethylacrylamide, and N-vinyl-2-pyrrolidone. The polymers according to the invention are constructed in a manner known per se from the corresponding monomers (here again including the term monomers to a macromer according to the invention), by means of a polymerization reaction with which the expert. Normally, a mixture of the aforementioned monomers is heated, with the addition of an agent that forms free radicals. This free radical forming agent is, for example, azoisobutyronitrile (AIBN), potassium peroxodisulfate, dibenzoyl peroxide, hydrogen peroxide, or sodium percarbonate. If the mentioned compounds are heated, then free radicals are formed, by homolysis, and then, for example, they can initiate a polymerization. A polymerization reaction can be carried out in a particularly preferable manner, using a photoinitiator. Light curing is the term used in this case. For photopolymerization, a photoinitiator is suitably added, which can initiate the photopolymerization of free radicals and / or cross-linking, by the use of light. Examples of this are familiar to the skilled person, and specifically, suitable photoinitiators are benzoin methyl ether, 1-hydroxycyclohexylphenyl ketone, and the Darocur and Irgacur types, preferably Darocur 1173R, and Darocur 2959R. Reactive photoinitiators that can be incorporated, for example, into a macromer, or that can be used as a special comonomer (a), are also suitable. Examples of these will be found in European Patent Number EP 632,329. The photopolymerization can then be triggered by actinic radiation, for example, in particular ultraviolet light of a suitable wavelength. According to the same, the spectral requirements can be controlled, if appropriate, by the addition of suitable photosensitizers. A polymerization can be carried out in the presence or absence of a solvent. Suitable solvents are in principle all solvents which dissolve the monomers used, for example, water, alcohols, such as lower alkanols, for example methanol or ethanol, and furthermore carboxylic acid amides, such as dimethyl formamide, dipolar aprotic solvents, such as dimethyl sulfoxide or methylethyl ketone, ketones, for example acetone or cyclohexanone, hydrocarbons, for example toluene, ethers, for example tetrahydrofuran, dimethoxyethane or dioxane, and halogenated hydrocarbons, for example trifluoroethane, and also mixtures of suitable solvents, for example mixtures of water with an alcohol, for example a mixture of water with an alcohol, for example a mixture of water / ethanol or water / methanol. A preferred embodiment also relates to a polymer comprising the polymerization product of the following components in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer according to the definition of the main claim, (2) from 25 to 75 percent of a hydrophobic monomer, and (3) from 15 to 40 percent of a hydrophilic monomer.

Another preferred embodiment also relates to a polymer comprising the polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer of the formula IV, V, VI, or VII, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R1 # R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals Rlf R2, R3, R4, R5, and R6, independently of each other, are partially fluorinated alkyl , aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone; (d) is a radical of formula (II): X3-L- (Y) k-P1, wherein P1 is alkenyl, X3 is a urethane or urea group, and is a carbonyl, ester, or amide group, is 0 or 1, and L is bond or alkylene; and X is an ester, amide, urethane, or urea group, (2) from 25 to 75 percent of a hydrophobic monomer, and (3) from 15 to 40 percent of a hydrophilic monomer. Another preferred embodiment also relates to a polymer comprising the polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 30 to 40 percent of a macromer of formula IV, V, VI, or VII, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R1 # R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R1, R2, R3, R4, R5, and R6, independently of each other, are partially alkyl fluorinated, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone; (d) is a radical of the formula (II): X3-L- (Y) k-P1, wherein P? is alkenyl, X3 is a urethane or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is bond or alkylene; and X1 is an ester, amide, urethane, or urea group, (2) from 30 to 70 percent of a hydrophobic monomer, and (3) from 20 to 35 percent of a hydrophilic monomer.

Another preferred embodiment also relates to a polymer comprising the polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer having the sequence of the segment according to formula (VIII), (IX), (X), or (XI), wherein the variables are defined as follows: a polysiloxane segment is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R- ^ R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals Rx, R2, R3, R4 , R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a segment of polyol (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or Xl t where X? is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-R-X2, wherein R is alkylene, arylene, alkylene-arylene, or arylene-alkylene having up to 14 carbon atoms, or a group saturated bivalent cycloaliphatic having 6 to 14 carbon atoms, and X 2 is an amide, urethane, or urea group; (B) is a segment (a) or a segment (b), with the previously preferred definitions; and (d) is a radical of the formula (II): X3-L- (Y) k-P1, which is up to 15 times, still more preferably up to 6 times terminally and / or pendently attached to a segment (b), and wherein P 1 is alkenyl, X 3 is an ester, amide, urethane, or urea group, Y is a carbonyl, ester, or amide group, k is 0 6 1, and L is a bond or alkylene, (2) 75 percent of a hydrophobic monomer; and (3) 15 to 40 percent of a hydrophilic monomer.

If appropriate, a polymer network can be reinforced by the addition of a so-called crosslinking agent, for example a polyunsaturated comonomer (b). The invention further relates to a polymer comprising the polymerization product of a macromer according to the invention, if appropriate, with at least one vinyl comonomer (a), and with at least one comonomer (b). Examples of the typical comonomers (b) are, for example, allyl (meth) acrylate, lower alkylene glycol di (meth) acrylate, lower polyalkylene glycol di (meth) acrylate, alkylene di (meth) acrylate. lower, divinyl ether, divinyl sulfone, di- or tri-vinylbenzene, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, bisphenol A di (meth) acrylate, methylenebis (meth) acrylamide, triallyl phthalate, or diallyl phthalate. The amount of the comonomer (b) used is expressed in the weight content with respect to the total polymer, and is in the range of 20 to 0.05 percent, particularly in the range of 10 to 0.1 percent, and preferably in the the scale from 2 to 0.1 percent. The polymers according to the invention can be processed in a manner known per se to give castings, in particular contact lenses, for example by carrying out the photopolymerization or photocrosslinking of the polymers according to the invention, in a casting suitable contact lens. Accordingly, the invention further relates to slurries that essentially comprise the polymers according to the invention. Other examples of mounts according to the invention, in addition to contact lenses, are biomedical articles, or specifically ophthalmic blunts, for example artificial corneas, intraocular lenses, eye bandages, molars that can be used in surgery, such as valves. cardiac, artificial arteries or the like, and in addition coatings, films or membranes, for example membranes for diffusion control, films for storage of information that can be photo-structured, or photoresist materials, for example membranes or slides for recording resistances or resistances of screen printing, and in addition particles, in particular microparticles, capsules, in particular microcapsules, films and plasters for drug application systems. A special embodiment of the invention relates to contact lenses that include a polymer according to the invention, or that comprise in an essential or complete manner, a polymer according to the invention. These contact lenses have a range of unusual and extremely convenient properties. These properties are, for example, their excellent tolerability by the human cornea (if appropriate, after adequate surface treatment (coating)), and by the tear fluid, which is based on a balanced relationship between the water content, the oxygen permeability, and mechanical and adsorbent properties. This results in high comfort, no irritation, and no allergenic effect. 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 invention do not impair or only impair a insignificant way, to the natural metabolic processes of the cornea. In contrast to many other contact lenses containing siloxane, for example, hydrophilic lenses comprising a macromer according to the invention as an essential constituent, do not exhibit the effect of unwanted suction cup. The contact lenses according to the invention are specifically suitable for use over a relatively long period of time (prolonged use). In addition, the contact lenses according to the invention are of high dimensional stability and storage stability. The surface treatment as referred to above, refers in particular to a process for making a surface ophthalmically more compatible, where, by contact with a vapor or liquid, and / or by means of the application of an energy source (a) is applied a coating on the surface of an article (b) the chemical species are adsorbed on the surface of an article, (c) the chemical nature (eg, electrostatic charge) of the chemical groups on the surface of an article is altered, or (d) the surface properties of an article are modified differently. There are a variety of methods disclosed in the art to make a surface of a material hydrophilic. For example, the lens can be coated with a layer of a hydrophilic polymeric material. Alternatively, hydrophilic groups can be grafted onto the surface of the lens, thereby producing a monolayer of hydrophilic material. These coating or grafting processes can be effected by a number of processes, including without limitation, exposing the lens to plasma gas, or immersing the lens in a monomer solution under appropriate conditions. Another set of methods for altering the surface properties of a lens involves the treatment before polymerization to form the lens. For example, the molding can be treated with plasma (i.e., an ionized gas), with a static electric charge, with irradiation, or with another energy source, thereby causing the prepolymerization mixture immediately adjacent to the molding surface , differ in its composition from the core of the prepolymerization mixture. A preferred class of surface treatment processes are plasma processes, where an ionized gas is applied to the surface of an article. Plasma gases and processing conditions are more fully described in U.S. Patent Nos. 4,312,575 and 4,632,844, which are incorporated herein by reference. The plasma gas is preferably a mixture of lower alkanes and nitrogen, oxygen, or an inert gas. In a preferred embodiment, the lens is treated with plasma in the presence of a mixture of (a) an alkane of 6 carbon atoms, and (b) a gas selected from the group consisting of nitrogen, argon, oxygen, and mixtures thereof. An alkane of 1 to 6 carbon atoms (a) is preferably selected from an alkane of 1 to 4 carbon atoms, and may be, for example, methane, propane, or butane. A gas (b) is preferably selected from nitrogen, oxygen, and a mixture thereof, and in particular from air, wherein air within the meaning of the present invention denotes 79 percent nitrogen and 21 percent nitrogen. oxygen cent. In a more preferred embodiment, the lens is treated with plasma in the presence of a mixture of methane and air. The plasma treatment (apparatus and process) as referred to hereinbefore and hereinafter, is preferably performed in analogy to the description of H. Yasuda, "Plasma Polymerization", Academic Press, Orlando, Florida (1985) , pages 319 and following. The present invention also relates to a molding comprising one of the novel polymers, wherein the molding surface is treated with plasma in the presence of an alkane of 1 to 6 carbon atoms (a) and a gas (b), which is selected from the group consisting of nitrogen, argon, oxygen, and mixtures thereof. A preferred embodiment refers to the molding comprising the polymer of a polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer of formula IV , V, VI, or VII, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R ?, R2, R3, R4, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals Rlf R2, R3, R4 , R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone; (d) is a radical of the formula (II): X3-L- (Y) k-Plf wherein P? is alkenyl, X3 is a urethane or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is bond or alkylene; and X? is an ester, amide, urethane, or urea group, (2) from 25 to 75 percent of a hydrophobic monomer, and (3) from 15 to 40 percent of a hydrophilic monomer, where the surface of this molding is treated with plasma in the presence of an alkane of 1 to 4 carbon atoms and air. Another preferred embodiment also relates to a molding comprising the polymer of a polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 30 to 40 percent of a macromer of the formula IV, V, VI, or VII, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals R1 # R2, R3, R, R5, and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R1 # R2, R3, R4, R5, and R6, independently of each other, they are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone; (d) is a radical of the formula (II): X3-L- (Y) k-P1, wherein P? is alkenyl, X3 is a urethane or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is bond or alkylene; and X1 is an ester, amide, urethane, or urea group, (2) from 30 to 70 percent of a hydrophobic monomer, and (3) from 20 to 35 percent of a hydrophilic monomer, wherein the surface of this molding it is treated with plasma in the presence of an alkane of 1 to 4 carbon atoms and air. Another preferred embodiment also relates to a molding comprising the polymer of a polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer having the sequence of the segment according to formula (VIII), (IX), (X), or (XI), wherein the variables are defined as follows: a segment of polysiloxane (a) is derived from a compound of the formula (III), wherein from 95 to 29 percent of the radicals Rlf R2, R3, R4, R5, and R6, independently of each other, are lower alkyl, from 5 to 71 percent of the radicals R ^ R2 , R3, R4, R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or X1; wherein X- is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-R-X2, wherein R is alkylene, arylene, alkylenearylene, or arylenealkylene having up to 14 carbon atoms , or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms, and X2 is an amide, urethane, or urea group; (B) is a segment (a) or a segment (b), with the previously preferred definitions; and (d) is a radical of the formula (II): X3-L- (Y) k-P1, which is up to 15 times, still more preferably up to 6 times terminally and / or pendently attached to a segment (b), and wherein Px is alkenyl, X3 is an ester, amide, urethane, or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is a bond or alkylene, (2) to 75 percent of a hydrophobic monomer, and (3) 15 to 40 percent of a hydrophilic monomer, where the surface of this molding is treated with plasma in the presence of an alkane of 1 to 4 carbon atoms and air . Furthermore, the present invention relates to contact lenses comprising essentially one of the polymers according to the invention, the contact lenses being in particular soft contact lenses, which preferably comprise from 1 to 40 percent water .

The invention also relates to contact lenses essentially comprising one of the polymers according to the invention, the contact lenses being in particular flexible contact lenses which are gas permeable, and which are preferably of a low content of water (RGP), and that can also be hybrid lenses. Of course, all the aforementioned advantages apply not only to contact lenses, but also to other mounts according to the invention. The present invention further relates to the use of a macromer according to the invention, or of a polymer or a cross-linked polymer prepared therefrom, and described above for coating a base material, for example glass, ceramic, or metal , and preferably polymeric substrates, for example products that can be used ophthalmically, such as contact lenses, intraocular lenses, or eye bandages, as well as medically usable products, for example in surgical or pharmaceutical systems, with preferred hydrophilic coatings in the cases mentioned at the end (ophthalmic uses). The polymers according to the invention are also suitable for use as a corneal implant or as an artificial cornea; and also as cell growth substrates, as a material for binding and culturing animal cells in vitro and in vivo, such as medical implants, for example implantable semipermeable membrane materials, such as tissue implants for cosmetic surgery, as an implant comprising cells that secrete hormones, for example pancreatic islet cells, such as a breast implant, or as an artificial joint and the like. Accordingly, the present invention further relates to a corneal implant that is produced from a polymer described above. This corneal implant can be produced by the same process as described above for the production of contact lenses. The corneal implants can be implanted by conventional surgical procedures, for example under, in, or through the epithelial tissue of the cornea, or within the stroma of the cornea, or within other layers of corneal tissue. These implants can change the optical properties of the cornea, for example in the sense of correcting a visual defect, and / or changing the appearance of the eye, for example the coloration of the pupils. A corneal implant may include the region on the optic axis that covers the pupil on the implant, and imparts the ability to see, and also the region surrounding the periphery of the optic axis. The implant can have the same visual properties over the entire region. It has been discovered that the flow through of the high molecular weight components of tissue fluid, for example of proteins or glycoproteins, for example growth factors, peptides, hormones, or proteins that are responsible for the transport of the essential metal ions through a corneal implant, in particular between the epithelial cells and the stromal cells, and even behind the endothelial layer, it is important both for tissue survival and for tissue viability outside and inside a corneal implant. Accordingly, a corneal implant is preferably produced with a porosity that is sufficient to allow the fluid components of the tissue that it traverses to have a molecular weight greater than 10,000 Daltons, ensuring a flow through of the components of the tissue fluid, in addition to a cross-flow of the low molecular weight nutrient components or metabolites, for example glucose, fats, or amino acids, or the respiratory gases between the cells on both sides of an implant. The porosity of a corneal implant is determined either by the polymeric material itself from which it is produced, or on the other hand, pores can additionally be incorporated into a polymer according to the invention, in particular by one of the numerous known processes which are described, for example, in Patent Numbers WO 90/07575, WO 91/07687, US 5,244,799, US 5,238,613, US 4,799,931 or US 5,213,721. Regardless of the method by which the required porosity of an implant according to the invention is developed, an implant preferably has a porosity that is sufficient to allow traversing proteins and other biological macromolecules to have a molecular weight up to or greater than 10,000. Daltons, for example 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 region on the optical axis of the implant. Where the permeability of the implant is made possible by pores, the region on the optical axis comprises a large number of pores, the number of which should not be limited, but should be sufficient to allow a free flow through the tissue components between the region external and internal of an implant. The pores that remain above the optical axis region of preference do not cause scattering of visible light to a degree that can cause problems with respect to vision correction. The term "pore" above and below is understood to mean a pore that has no geometric restrictions, and that has a regular or irregular morphology. The declaration of a pore size does not mean that all pores have the same diameter. Rather, it is an average diameter. In the region outside the optic axis, the corneal implant may have the same porosity as in the region on the optic axis. This peripheral region of an implant that surrounds the region of the optic axis is also called a skirt, but in contrast to the region of the optic axis, it can allow the corneas to grow inwards, over which the implant is anchored to the eye . The porosity in the skirt can also be an independent feature of the material from which the skirt is produced. If the skirt is made of the same material as the material on the optical axis, pores of different diameter can be incorporated on the one hand on the skirt, and on the other hand on the optical axis. On the other hand, the skirt can be produced from a material other than the material on the optical axis, in which case, as mentioned above, the porosity of the skirt must be greater than that on the optical axis. A skirt preferably comprises an optically transparent polymer, such as one on the optic; however, the skirt may also comprise an optically non-transparent material, or it may be produced from a porous material that is optically non-transparent. A polymer according to the invention can aid colonization with tissue cells, such as, for example, vascular endothelial cells, fibroblasts or cells formed in bone, not being necessary for a specific nature of the surface that are present for the purpose. to stimulate cell adhesion and cell growth. This is convenient, since the costs of the process can be kept low. On the other hand, a polymer according to the invention can be modified on its surface by a known technique, for example the treatment with plasma of a surface by means of a radiofrequency corona discharge, for example as described in Patent Numbers US 4,919,659 or WO 89/00220, or by irradiation, or with a chemical treatment. A polymer according to the invention can be coated on the surface with one or more components, for example, to promote tissue growth. These materials are, for example, fibronectin, chondroitin sulfate, collagen, laminin, cell-binding proteins, globulin, chondronectin, epidermal growth factors, muscle fiber proteins and / or derivatives thereof, and active fragments and mixtures thereof. same. Fibronectin, epidermal growth factors, and / or derivatives thereof, and active fragments and mixtures thereof, are especially useful. If necessary, this surface coating can also be carried out after a surface modification described above. A polymer according to the invention can conveniently combine several of the properties mentioned by itself, for example to be fixed to the cells with a good biostability and resistance to deposits. The mechanical properties of a polymer according to the invention are suitable for use as a corneal implant, the material preferably having an E module of 0.5 to 10 MPa. The aforementioned module E imparts to a corneal implant adequate flexibility to allow its insertion into the eye, for example over the region of the Bowman's membrane. A polymer according to the invention can also be used as a cell growth substrate, for example as a cell culture apparatus, for example utensils, jars, plates, and the like, and also in biological reactors, for example in the preparation of valuable proteins and other cell culture components. The examples described below serve to further illustrate the present invention; however, they are not intended to limit your scope in any way. Temperatures are mentioned in degrees Celsius.

Example When preparing: PDMS = polydimethylsiloxane.

Reaction of o-.β- bis-aminopropyl-dimethylpolysiloxane with «S-lactone of Df + luclonic acid Before the reaction, the amino-functionalized polydimethylsiloxane used for the synthesis (X-22-161-C, Shin Etsu, JP) it was finely dispersed in acetonitrile, extracted, and then subjected to molecular distillation. The following reactions take place with the exclusion of H20. 200 grams of purified amino functionalised polydimethylsiloxane (0.375 milliequivalents of NH2 / gram; Mn (VPO) 3400-3900 (VPO, Vapor Pressure Osmometry)), dissolved in 200 milliliters of absolute tetrahydrofuran, are slowly added dropwise to a suspension of 13.35 grams (75 millimoles) of D (+) gluconic acid 5-lactone in 50 milliliters of absolute tetrahydrofuran, and the mixture is stirred at 40 ° C for about 24 hours, until the lactone completely reacts. (Supervision of the reaction by thin layer chromatography (TLC): silica gel, isopropanol / H20 / ethyl acetate, 6: 3: 1, stained with Ce (IV) sulfate / phosphoromolybdic acid solution (CPS reagent)) . After the reaction, the reaction solution is concentrated to dryness, and the residue is dried under 3 Pa (0.03 mbar) for 48 hours. 213.3 grams of α, β-bis (3-gluconamidopropyl) -polydimethylsiloxane are obtained. The titration of the amino groups with perchloric acid shows a conversion of the amino groups of more than 99.8 percent.

Reaction of a, β-bis-3-qluconamidopropyl-dimethylpolysiloxane with IEM The product obtained above (213.3 grams) is dissolved in 800 milliliters of absolute tetrahydrofuran, and the solution is heated to 40 ° C with the addition of catalytic amounts of dilaurate from dibutyl tin (DBTDL). 14 grams (90 millimoles) of IEM in 20 milliliters of absolute tetrahydrofuran are added dropwise to this solution over a period of about 4 hours. This corresponds to a concentration of 1.2 equivalents of IEM per gluconamide unit. The reaction is carried out within 48 hours (monitoring of the reaction by infrared spectroscopy detection of the NCO bands). The reaction solution is concentrated, and the product is dried in a brown glass flask under 3 Pa (0.03 mbar) for 24 hours, with cooling with ice. There remain 227.2 grams of an elastic product like rubber, colorless, with a high optical transparency.

Examples A2-A7 Other aminopropyldimethyl polysiloxanes (PDMS) are reacted with a different amount of gluconolactone, and concentrations of IEM, analogously to Example Al. The examples are summarized in Table 1.

TABLE 1 Caption: X-22-161-C and KG 8003 are products of Shin Etsu (Japan), PS 813 is a product of Petrarch-Hüls, GP4 and GP6 are products of Genesee. * Amino groups per macromer chain. GLA: D (+) gluconic acid d-lactone. term .: terminal. Cabbage: pendant.

Example A8 The reaction is carried out according to Example Al, but instead of D (+) gluconic acid d-lactone, 75 millimoles of lactobionic acid 1,5-lactone, suspended in 50 milliliters of tetrahydrofuran, are added dropwise. absolute, to a solution of amino functionalized polydimethylsiloxane (X-22-161-C) in 180 milliliters of absolute tetrahydrofuran and 20 milliliters of dimethyl sulfoxide (99 percent pure). The titration of the amino groups with perchloric acid indicates a conversion of the reaction of 99 percent (< 0.01 milliequivalents of NH2 / gram). Here also, an optically transparent colorless macromer is obtained.

Examples A9 v A10 The reactions are carried out in a manner analogous to Example Al. However, the catalyst necessary for the addition of the isocyanate to the hydroxyl groups varies. In place of DBTDL, catalytic amounts of 1,4-diazabicyclo [2.2.2] octane (DABCO) or 4-dimethylaminopyridine (DMAP) are added, and the reaction is continued as described in Example Al. In both cases, it results an elastic, colorless, optically clear, rubbery macromer, in a manner corresponding to Example 1.

EXAMPLE All The reaction is performed in a manner analogous to Example Al. In a manner corresponding to Example A8, 0.1 moles of 1,5-lactone lactobionic acid is suspended in 50 milliliters of absolute tetrahydrofuran, and the suspension is added dropwise. to a solution of amino functionalized polydimethylsiloxane (KF-8003) in 180 milliliters of absolute tetrahydrofuran and 20 milliliters of dimethyl sulfoxide (99 percent pure). The reaction time is increased to approximately 48 hours. A residual content of 0.07 milliequivalents of NH 2 / gram can be detected, and they are reacted completely by adding the corresponding molar amount of D (lactone) d-lactone to the solution of the reaction. The highly transparent colorless product has a residual content of amino groups of < 0.01 milliequivalents / gram.

Example A12 Preparation of: D-Glucaro, 1,4: 6,3-dilactone.

PDMS polydimethylsiloxane functionalized with amino. 52. 09 grams (9.78 mmol) of purified amino functionalised polydimethylsiloxane (X-22-161-C, Shin Etsu JP), dissolved in 110 milliliters of absolute tetrahydrofuran, are initially introduced into the reaction vessel under an inert gas atmosphere, and 1.14 grams (6.52 millimoles) of D-glucaro-l, 4: 6,3-dilactone, dissolved in 20 milliliters of absolute tetrahydrofuran, are added. The reaction solution is stirred at room temperature for 15 hours, and then worked in a manner corresponding to Example Al. The amine content is 0.134 milliequivalents / gram. The terminal amino groups of the resulting tentabloque macromer are reacted with gluconolactone in the next reaction step. 41.84 grams (5146 milliequivalents of NH2) of the above macromer, and 0.917 grams (5.15 millimoles) of D (+) gluconic acid--lactone, are suspended in 300 milliliters of absolute tetrahydrofuran, and the suspension is stirred under nitrogen at 40 °. C for 18 hours. Then the filtered solution is concentrated, and the residue is dried under 3 Pa (0.03 mbar) for 48 hours. It results in a highly viscous, optically transparent substance, which has a residual content of amino groups of 0.013 milliequivalents / gram.

Preparation of a polydimethylsiloxane functionalized with amino- and perfluoroalkyl: Example A13 3.0 milliliters of absolute toluene is added at 15 > grams of poly (dimethylsiloxane-co-methylhydrosiloxane) [Bayer Silopren U-230; 10,000 grams / mol; 2.3 millimoles of Si-H / gram], and then 1.72 grams (9.2 millimoles) of allylphthalimide are added [CAS Reg. No. 5428-09-1]. The mixture is frozen several times, and the flask is evacuated and then brought to room temperature again. Then the flask is left with argon. 0.7 milliliters of a 0.005 molar solution of Lamoreaux catalyst (prepared according to US Pat. No. 3,220,972, General Electric) is added in absolute toluene (100 ppm Pt / mol Si-H), and the mixture is heated to 80 ° C. After a half-hour reaction time, a colorless solution is obtained, from clear to slightly cloudy, whose 1 H-NMR spectrum no longer shows resonances of allylic hydrogen atoms. Subsequently, 6.2 grams (15.3 mmol) of deionized allyl ÍH, HH, 2H, 2H-perfluorooctyl ether are added slowly, and the mixture is stirred at 80 ° C for 2 hours. A spectrum of ^? - NMR now shows a severely weakened resonance of the Si-H function at 4.6 ppm, and an intense resonance at 0.5 ppm, which originates from the hydrogen atoms of Si-CH2. Then 3.0 milliliters of 1-hexene are added in order to react the remaining excess Si-H group, which could otherwise cause the polymer to cross-link when the air was subsequently accessed. The mixture is further stirred at 80 ° C for another half hour. Then the reaction mixture is allowed to stand overnight. The product is purified on a column of silica gel with hexane / ethyl acetate (3: 2), the solvent is removed, and the macromer is dried under a high vacuum. A clear colorless viscous product is obtained. The macromer purified in this way is recovered in 20 milliliters of hexane, 20 milliliters of methylamine [33 percent in ethanol] are added, and the mixture is heated to 40 ° C. After 10 to 15 minutes, a white bulky precipitate separates. After 30 minutes, the suspension is cooled and filtered, and the precipitate is washed with a little hexane. The filtrate is evaporated, and then the residue is dried under a high vacuum. Subsequently, the content of amino groups is determined by titrimetry (perchloric acid). The resulting macromer is transparent and viscous. The amino group content is 78.6 percent of the theory. The total yield of macromer after chromatographic purification is 75 percent.

Preparation of a glueonamide: 17.3 grams (corresponding to an amine content of 5.4 milliequivalents) of this product substituted by aminoalkyl, are dissolved in 20 milliliters of dry tetrahydrofuran. The solution is repeatedly frozen, degassed, and left with argon. All the following operations are carried out in an argon atmosphere. Then 712 milligrams of D (+) gluconic acid d-lactone (4 millimoles) are added. Due to the low solubility of the lactone, a suspension is initially obtained. After stirring overnight at 50 ° C, the solution is clear, and the lactone has been used completely. Then the remaining stoichiometric amount of D (+) gluconic acid λ-lactone (260 milligrams, 1.46 millimoles) is added, and the mixture is again stirred at 50 ° C overnight. A trace of unreacted lactone is observed. The completion of the reaction is monitored by means of thin layer chromatography on silica gel plates, with the mobile phase of 1-propanol / ethyl acetate / water (6: 1: 3). The silica gel plates are developed by means of Ce (IV) sulphate / phosphoromolybdic acid solution. Subsequent titration on amino groups produces a residual amino content of < 0.1 percent. After filtration and removal of the solvent by distillation, a highly viscous transparent macromer is obtained with 0.295 milliequivalents of gluconamide per gram of macromer.

Example Bl Before polymerization, the acrylates used, isobutyl acrylate (IBA), N, N-dimethylacrylamide (DMA), and 3-methacryloyloxypropyltris (trimethylsilyloxy) silane (TRIS), each of the inhibitors is released by distillation . Weigh 0.32 grams (2.76 millimoles) of IBA, 0.80 grams (8.1 millimoles) of DMA, and 1.44 grams (3.4 millimoles) of TRIS, into a 50 milliliter round bottom flask, and the flask is flooded with N2 for half an hour , with cooling with ice. 1.44 grams of the macromer of Example Al are transferred to a round bottom flask with a nitrogen connection, degassed under 3 Pa (0.03 mbar) for 24 hours, and then dissolved in 2.7 grams of ethanol which has been flooded with N2 during half an hour in advance. The subsequent preparation of samples, and the polymerization, are carried out inside a glove box, with the exclusion of oxygen. The above monomeric mixture, and the macromer solution of Example Al, are mixed, with the addition of 0.012 grams (0.21 millimoles) of Darocure 1173R, and the mixture is subjected to microfiltration (0.45 millimeter filter). 180 microliters of this mixture are introduced into a polypropylene molding, which is then closed with a suitable polypropylene lid. The mixture is then irradiated with a UV-A high pressure mercury lamp in a nitrogen atmosphere, in an ultraviolet oven equipped for this for 5 minutes. The lamps (5, each of the brand TLK 40W / 10R, Philips) are above and below the inserted bra. The intensity of the irradiation is 14.5 mW / cm2. The polypropylene molding is opened, and the finished discs or lenses are removed by soaking by means of a solvent mixture of methylene chloride and ethanol (2: 3). The lenses and discs are extracted in ethanol at room temperature in special polypropylene cages for 48 hours, and then dried at 40 ° C under 10 Pa (0.1 mbar) for 24 hours (autoclave at 120 ° C, 30 minutes) . The discs show an E module of 1.1 MPa, oxygen permeability of 183 bars, and a hass (Shore A) of 53.

Examples B2-B12 Other polymers are prepared with different macromer starting compounds (Examples A1-A8), and of a different nature and composition of the comonomers, in a manner corresponding to Example Bl (composition in percentages by weight). Table 2 shows the examples B2-B12, and the properties of the resulting materials measured on disks.

TABLE 2 Ex. Container Macromer IBA DMA TRI8 HFBA DMEA do% by weight% by weight% by weight% by weight% by weight% by weight Water % B2 4.6 A2 36.0 8.0 20.0 36.0 - - B3 9.1 A2 35.0 5.0 20.0 35.0 5.0 - B4 12.1 A2 35.0 20.0 20.0 25.0 - - B5 13.7 A3 32.8 - 30.0 37.2 - - B6 - A3 32.8 - - 37.2 - 30.0 B7 19.9 A3 32.9 - 34.3 32.7 - - B8 25.1 A3 39.3 - 34.3 36.4 - - B9 17.5 A3 35.7 - 34.3 30.0 - - BIO 23.4 A3 33.3 - 33.3 33.4 - - Bll - A7 34.0 23.0 - 43.0 - - B12 13.8 A8 35.8 8.0 20.4 35.8 - - Legend IBA: isobutyl acrylate. DMA: N, N-dimethylacrylamide TRIS: 3-methacryloyloxypropyltris (trimethylsilyloxy) silane.

HFBA: 2,2, 3,4,4,4-hexafluorobutyl acrylate. DMEA: 2-dimethylaminoethyl acrylate.

Example B13 The synthesis of this polymer corresponds to Example Bl, with the following composition the comonomer: Example A3- / TRIS / DMA, 32.8 percent / 32.6 percent / 34.2 percent (in percentages by weight), and an addition of the 0.4 percent by weight of trimethylammonium-2-hydroxypropyl methacrylate hydrochloride (BlemerRQA, Nippon Oil Corp.). The polymer has a modulus of 0.9 MPa, and an oxygen permeability of + 2 barrer. The water content is 25.1 percent (after 30 minutes of autoclaving at 120 ° C). For a comparison, Example B7 has a water content of 20 percent, with a very similar comonomer composition (without addition of BlemerRQA).

Examples B14-B29 Polymers are prepared in a manner analogous to Example Bl, but the polymerization is carried out in bulk, which means without the addition of ethanol. Table 3 shows the composition of the comonomers and the properties of the materials of the synthesized polymers, measured in disks.

TABLE 3 Ex. IBA Macromer NVP AM EHA OA DA% by weight (% by weight) (% by weight) (% by weight) (% by weight) (% by weight) (% by weight) B14 Al (40) 60 B15 Al (63) 37 B16 Al (40) 60 B17 Al (54) 46 B18 Al (54) 46 B19 A4 (40) 60 B20 A4 (40) 60 B21 A5 (40) 60 B22 A5 (40) 60 B23 A6 (40) 60 B24 A6 (40) 60 B25 A6 (53.5) 8.6 37.9 B26 A7 (40) 60 B27 A7 (40) 60 B28 A7 (63) 37 B29 A7 (41) 23 24 12 Table 3 continued Example Module E (MPa) 02Dk (sweeping) Hardness (Shore A) B14 0.6 160 30 B15 - 290 52 B16 0.5 200 20 B17 0.7 224 47 B18 - 268 52 B19 0.6 150 40 B20 0.4 135 35 B21 1.5 90 55 B22 0.7 100 45 B23 - 120 55 B24 - 150 35 B25 0.9 260 51 B26 1 180 50 B27 0.6 170 40 B28 1.3 330 60 B29 - - 68 OA: Isooctyl acrylate. AN: Acrylonitrile. DA: isodecyl acrylate. NVP: l-vinyl-2-pyrrolidone. EHA: 2-ethylhexyl acrylate.

Example B30 The polymerization is carried out according to Example Bl, but with the following changed comonomer composition: macromer A7 / IBA / TRIS, 20 percent / 19 percent / 60 percent, and 1 percent (in percentages by weight ) of bis (3-methacryloyloxy-propyl) tetramethyldisiloxane. An optically clear polymer is obtained with an E modulus of 0.4 MPa, an oxygen permeability of 241 barrer, and a hardness (Shore A) of 42.

Example B31 The polymerization is carried out analogously to Example Bl, with the following comonomer composition: Al / IBA / TRIS macromer, 37 percent / 17 percent / 43 percent (in percentages by weight). The polymerization is carried out in 1,4-dimethoxyethane, instead of ethanol, and 3 percent of N- (m-isocyanato-p-toluyl) -acyloxy-oxyethyl carbamate (prepared according to literature) is added as an agent of additional crosslinking. The resulting polymer has a high optical transparency, a modulus of 0.7 MPa, an oxygen permeability of 330 bars, and a Shore A hardness of 41.

Example B32 5.0 grams of the macromer substituted by gluconamide of Example A13 are dissolved in 5.0 grams of absolute tetrahydrofuran. A mixture of 572 milligrams (3.69 millimoles) of freshly distilled IEM and 0.5 grams of absolute tetrahydrofuran is added. This mixture is stirred at 50 ° C for 24 hours. Subsequently, an infrared spectrum does not show isocyanate absorption bands at 2250 cm "1. The solvent is removed under a high vacuum, after which a transparent intermediate results., slightly yellowish, and highly viscous. 2.54 grams of this are mixed with 1.7 grams of absolute ethanol under an argon atmosphere. The mixture is repeatedly frozen, and the flask is evacuated and thawed again. Finally, the flask is left with argon. In a second flask, 2.54 grams of TRIS and 1.27 grams of DMA are added together, and the mixture is repeatedly frozen, evacuated, and thawed again. Then it is left with argon. 30 milligrams of DarocureR 1173 photoinitiator are added, and the mixture is frozen again, evacuated, and thawed again, and left with argon. The two flasks are transferred to a glove box with an inert gas atmosphere. In this, the macromer solution and the comonomer mixture are mixed. The homogenous solution is filtered and pipetted into polypropylene slides for lenses or discs. The lens slides and filled discs are irradiated with ultraviolet light (maximum emission at 360 nanometers) for 5 minutes. After the rocks are opened, the lenses and reticulated discs thus obtained are extracted in ethanol for 24 hours, and then dried and subsequently equilibrated in distilled water. For sterilization, the lenses and discs are autoclaved in a phosphate-buffered sodium chloride solution at 120 ° C. Transparent lenses and discs are obtained. The permeability of the discs to oxygen is 120 sweeping units, and the absorption is 3.8 percent by weight. Example B33 A contact lens is prepared in a manner corresponding to Example Bl, using the macromer of Example A3, with the following composition in weight percentages: A3 Macromer: 33.3 DMA: 33.3 TRIS: 33.4 The lens has a Dk of about 94, and a water content of about 20.0 weight percent. The results are summarized in Table 4 for a comparison.

Example B34 Dry lenses prepared according to the procedures described in Example B33, are transferred to a plasma coating apparatus, where the lenses are surface treated in a methane / air mixture. The apparatus and the plasma treatment process are both in accordance with Yasuda's previously identified disclosure. Dry plasma-treated contact lenses are equilibrated in autoclave-resistant flasks in physiological phosphate-buffered saline, and then autoclaved for 30 minutes at approximately 120 ° C. The lens autoclaved and treated with plasma, has a Dk of 90, and a water content of 21.5 percent. The results are summarized in Table 4 for a comparison. Table 4 Example B35 In analogy to Example Bl, the polymerization is carried out with the following comonomer composition, in percent by weight, based on the total weight of the polymer: Al Macromer: 33.3 DMA: 33.3 TRIS: 33.3 An optically clear polymer is obtained.

Claims (64)

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 macromer comprising at least one section of the formula (I): -a Z b- (I) where (a) is a polysiloxane segment, (b) is a polyol segment that contains at least 4 carbon atoms, Z is segment (c) or a group Xl r where: segment (c) is defined as X2-R-X2, where: R is a bivalent radical of an organic compound containing up to 20 atoms of carbon, and each X2, independently of each other, is a bivalent radical containing at least one carbonyl group, and wherein: X2 is defined as X2, and wherein: (d) is a radical of the formula (II) : X3-L- (Y) k-P- (II) wherein Px is a group that can be polymerized by free radicals; Y and XJ (independently of one another) are a bivalent radical containing at least one carbonyl group, k is 0 or 1, and L is a bond or a bivalent radical having up to 20 carbon atoms of an organic compound.

2. A macromer according to claim 1, wherein a polysiloxane segment (a) is derived from a compound of the formula (III): where n is an integer from 5 to 500; from 99.8 to 25 percent of the radicals R1 t R2, R3, Rr Rs / Y R6 > independently of one another are alkyl, and from 0.2 to 75 percent of the radicals Rx, R2, R3, R4, Rs, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alkaline, NH-alk-NH2 or alk- (OCH2) m- (OCH2) p-OR7, wherein: R7 is hydrogen or lower alkyl, alk is alkylene, and m and p, independently of each other, are an integer from 0 to 10, containing a molecule of the formula (III) at least one primary amino or hydroxyl group.

3. A macromer according to claim 1, wherein a polysiloxane segment (a) is bound a total of 1 to 50 times, preferably 2 to 30 times, and in particular 4 to 10 times, by means of a group Z, with a segment (b) or another segment (a), Z being always in a sequence aZa a segment (c).

4. A macromer according to claim 2, wherein a polysiloxane segment is derived from a compound of the formula (III), wherein: the radicals R1 # R2, R3, R4, R5, and R6 are a total from 1 to 50 times, more preferably from 2 to 30 times, and in particular from 4 to 10 times, in an independent manner, either aminoalkyl or terminal or terminal hydroxyalkyl.

5. A macromer according to claim 2, wherein a polysiloxane segment is derived from a compound of the formula (III), wherein: from 95 to 29 percent of the radicals Rl R2, R3, R4, Rs 'and R6' independently of one another are alkyl, and from 5 to 71 percent of the radicals R1 t R2, R3, R4, R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-alk-H2 or alk- (OCH2CH2) m- (OCH2) p-OR7.

6. A macromer according to claim 2, wherein n is an integer from 5 to 400, more preferably from 10 to 250, and particularly preferably from 12 to 125.

7. A macromer according to claim 2 , wherein the two terminal radicals Rx and R6 are aminoalkyl or hydroxyalkyl.

8. A macromer according to claim 2, wherein the radicals R4 and R5 are from 1 to 50 times, more preferably from 2 to 30 times, and in particular from 4 to 10 times aminoalkyl or hydroxyalkyl pendants.

9. A macromer according to claim 2, wherein the radicals R1 t R2, R3, R4, R5, and R6 are a total of 1 to 50 times, more preferably 2 to 30 times, and in particular of 4 to 10 times, independently both terminal and pendant aminoalkyl or hydroxyalkyl.

10. A macromer according to claim 1, wherein Z is Xx.

11. A macromer according to claim 10, wherein X1 is a bivalent group containing at least one carbonyl group.

12. A macromer according to claim 11, wherein X? is a carbonyl group that is flanked no more than 2 times by -0-, -CONH-, -NHCO- or -NH-.

13. A macromer according to claim 12, wherein X? it is a carbonyl, ester, amide, urethane, or urea or carbonate group.

14. A macromer according to claim 1, wherein X2 has the same meaning as Xx.

15. A macromer according to claim 14, wherein X2 is an ester, amide, urethane group. carbonate, or urea.

16. A macromer according to claim 1, wherein a polyol b segment is derived from a carbohydrate, a carbohydrate monolactone, or a carbohydrate dilactone.

17. A macromer according to claim 16, wherein a polyol b segment is derived from a mono-, di-, tri-, tetra-, oligo-, or poly-saccharide; or from a lactone of an aldonic or uronic acid, for example gluconolactone, galactonolactone, lactobionolactone, or maltoheptaonolactone; from glucuronic acid lactone, mannuronic acid lactone, or iduronic acid lactone; and further, for example, from D-glucaro-l, 4: 6,3-dilactone.

18. A macromer according to claim 1, which is a compound of the formula (IV): (IV) where the variables are as defined above.

19. A macromer according to claim 1, which is a compound of the formula (V): wherein the polysiloxane segment (a) contains q pending ligands, and wherein: x is 0, 1, or 2, q has an average numerical value of 1 to 20, preferably 1 to 10, and in particular 1 to 5, and wherein: segments (b) in a macromer according to formula (V) are linked in total (per molecule) with up to 20, preferably up to 15, and in particular with up to 6 polymerizable segments ( d).

20. A macromer according to claim 1, which contains a section of the formula (VI): I '(VI) where a linear sequence is present, wherein: x is 0, 1, or 2, q has an average numerical value of 1 to 20, preferably 1 to 10, and in particular 5; , and wherein: the segments (b) in a macromer according to the formula (VI) are linked in total (per molecule) with up to 20, preferably with up to 15, and in particular with up to 6 polymerizable segments (d) .

21. A macromer according to claim 1, which is a compound of the formula (VII): (d) x (d) x b-x ^ a-X ^ b (VII) wherein x is 0, 1, or 2, and the average number of segments (d) per molecule of formula (VII) is preferably in the range of 2 to 5, and most preferably in the range of 3 to 4.

22. A macromer according to claim 1, wherein a polyol segment (b) is derived from a polyol bearing no lactone group, and the group Z is a segment (c).

23. A macromer according to claim 1, wherein a polyol segment (b) is derived from a 1,2-polyol, for example, the reduced monosaccharides, for example mannitol, glucitol, sorbitol, or iditol, from 1,3-polyol, for example polyvinyl alcohol (PVA), which is derived from partially or completely hydrolyzed polyvinyl acetate; and further it is of amino-terminal PVA telomers, aminopolyols, aminocyclodextrins, aminomono-, -di-, -tri-, -oligo-, or -poly-saccharides or cyclodextrin derivatives, for example hydroxypropylcyclodextrin.

24. A macromer according to claim 1, wherein a segment (b), as illustrated in formula (I), carries at least one vinyl polymerizable segment (d), a segment (d) being linked by means of the bivalent radical X3 thereof with an amino or hydroxyl group, of a segment (b), reduced by a hydrogen atom.

25. A macromer according to claim 1, wherein, per macromer molecule according to the invention, a vinyl polymerizable segment (d) is incorporated either terminally or pendently preferably 1 to 20 times, more preferably 2 to 15 times, and in particular from 2 to 6 times.

26. A macromer according to claim 1, wherein, per molecule of the macromer according to the invention, a vinyl polymerizable segment (d) is incorporated terminally, and also pendently as desired (as a terminal / pendant mixture), preferably from 1 to 20 times, more preferably from 2 to 15 times, and in particular from 2 to 6 times.

27. A macromer according to claim 1, wherein P1 is alkenyl, alkenylaryl, or alkenylarylenealkyl having up to 20 carbon atoms.

28. A macromer according to claim 1, wherein L is alkylene, arylene, a saturated bivalent cycloaliphatic group having from 6 to 20 carbon atoms, arylenenalkylene, alkylenearylene, alkylenenarylenealkylene, or arylenenalkylenearylene.

29. A macromer according to claim 1, wherein L is a bond.

30. A macromer according to claim 1, wherein Y is a carbonyl, ester, amide or urethane group.

31. A macromer according to claim 1, wherein k is 0.

32. A macromer according to claim 1, wherein X3 is a urethane, urea, ester, amide, or carbonate group.

33. A macromer according to claim 1, wherein a segment (d) is derived from acrylic acid, methacrylic acid, methacryloyl chloride, 2-isocyanatoethyl methacrylate (IEM), allyl isocyanate, vinyl isocyanate, isomeric vinylbenzyl isocyanates or adducts of hydroxyethyl methacrylate (HEMA) and 2,4-tolylene diisocyanate (TDI) or isophorone diisocyanate (IPDI), in particular the 1: 1 adduct.

34. A macromer according to claim 1, wherein a segment (d) is incorporated either terminally or pendantly, or as a terminal / pendant mixture, five times per molecule.

35. A macromer according to claim 1, wherein R is alkylene, arylene, alkylenearylene, arylenenalkylene, or arylenenalkylenearylene having up to 20 carbon atoms, a saturated bivalent cycloaliphatic group having from 6 to 20 carbon atoms, or cycloalkylenealkylene -cycloalkylene having from 7 to 20 carbon atoms.

36. A macromer according to claim 1, wherein a segment (c) is derived from hexane-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, tetramethylene diisocyanate, , Phenylene 4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, m- or p-tetramethylxylene diisocyanate, isophorone diisocyanate, or 1,4-cyclohexane diisocyanate.

37. A macromer according to claim 1, wherein the average molecular weight is in the range of about 300 to 30,000, most preferably in the range of about 500 to about 20,000, more preferably in the range of about 800 to about 12,000 , and in a particularly preferable manner in the range of from about 1,000 to about 10,000.

38. A macromer according to claim 1, which is a compound of the formula (VIII): b-Z-a-. { AC} r- (Z-b) t (VIII) wherein r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is 0 or 1, and preferably 1; wherein a linear chain (c-a) is present which may or may not be terminated by a segment (b) (t = l); wherein a segment (d) is linked with at least one segment (b); and the previous preferences apply to the total number of segments (d), which are preferably linked to a segment (b).

39. A macromer according to claim 1, which is a compound of the formula (IX): b-Z-a-. { c-a- (Z-b) t} r (IX) wherein the sequence (c-a) - (Z-b) t hangs R times on segment (a), and may or may not be terminated by a segment (b); wherein r is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is 0 or 1, and is preferably 1; Z is a segment (c) or a group X1; wherein a segment (d) is linked with at least one segment (b); and the previous preferences apply to the total number of segments (d), which are preferably linked to a segment (b).

40. A macromer according to claim 1, which is a compound of the formula (X): b-c-. { a-c} s-B (X) wherein s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; B is a segment (a) or (b); wherein a segment (d) is linked with at least one segment (b); and the above preferences are applied to the number of segments (d), which are linked to a segment (b).

41. A macromer according to claim 1, which is a compound of the formula (XI): B- (c-b) s-Z-a- (Z-b) t (XI) the linear structures being, and wherein: s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; B is a segment (a) or (b); wherein a segment (d) is linked with at least one segment (b); t is 0 or 1, and the previous preferences apply to the number of segments (d), which are linked to a segment (b).

42. A macromer according to claim 1, wherein the ratio of the number of segments (a) and (b) is on the scale of (a): (b) = 3: 4, 2: 3, 1: 2 , 1: 1, 1: 3, or 1: 4.

43. A macromer according to claim 1, wherein the total sum of the segments (a) and (b) or, where appropriate (a) and (b) and (c), is on the scale of 2. at 50, preferably from 3 to 30, and in particular in the scale from 3 to 12.

44. A macromer according to claims 18 to 21, wherein the variables are defined as follows: a segment of polysiloxane (a) is derived from a compound of the formula (III): R where 95 to 29 percent of the radicals R? , R2, R3, R4, R5, and R &, independently of each other, are lower alkyl, from 5 to 71 percent of the radicals R? , R 2, R 3, R 4, R 5, and R 6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone; (d) is a radical of formula (II): X3-L- (Y) k-P? , wherein Px is alkenyl, X3 is a urethane or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is bond or alkylene; and X1 is an ester, amide, urethane, or urea group.

45. The macromer according to claims 38 to 41, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III): wherein from 95 to 29 percent of the Rlf radicals R2, R3, R, R5 and R6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R ?, R2, R3, R4, R5 , and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a segment of polyol (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or Xl t where X? is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-R-X2, wherein R is alkylene, arylene, alkylene-arylene, or arylene-alkylene having up to 14 carbon atoms, or a group saturated bivalent cycloaliphatic having 6 to 14 carbon atoms, and X 2 is an amide, urethane, or urea group; (B) is a segment (a) or a segment (b), with the previously preferred definitions; and (d) is a radical of the formula (II): X3-L- (Y) k-Plf which is up to 15 times, still more preferably up to 6 times terminally and / or pendantly attached to a segment (b), and where P? is alkenyl, X3 is an ester, amide, urethane, or urea group, Y is a carbonyl, ester, or amide group, k is 0 or 1, and L is a bond or alkylene. 46. A process for the preparation of a macromer as defined in claim 1, which comprises first reacting a polysiloxane containing at least one primary amino or hydroxyalkyl group with a carbohydrate lactone, forming an amide or ester bond, and forming a compound of the formula (Xlla) or (Xllb): (aZb) q (Xlla) a- (Zb) q (Xllb) wherein the variables are as defined above, and Z is a group Xl t after which a compound (Xlla) or (Xllb) is reacted with an unsaturated polymerizable compound of the formula (XIII):

X4-L- (Y) k-P! (XIII) wherein X is a group that is coreactive with a hydroxyl or amino group of segment (b), forming a group X3 of a segment (d) according to formula (II) from this reaction, and wherein: X4 is preferably -COOH, -COOR10, -COCÍ or -NCO, wherein: R10 is alkyl, or is aryl that is unsubstituted or substituted by lower alkyl or lower alkoxy, and the other variables are as defined above, after which, a macromer is formed according to formula (IV) or (V): (IV) wherein the segments (d) are incorporated terminally and / or pendently.

47. A process for the preparation of a macromer as defined in claim 1, which comprises reacting a polysiloxane (a) containing terminal primary or hydroxyalkyl amino groups, with a carbohydrate dilactone, to give the linear structurals of the Formula (XIV): _a-Xj- b - (?? v) wherein the variables are as previously defined and preferred, after which, a compound of the formula (XIV) is reacted with a compound of the formula (XIII) in a manner analogous to the previous process, to give a macromer of the formula (VI): where the variables are as defined and preferred above.

48. A process for the preparation of a macromer as defined in claim 1, which comprises first reacting a polysiloxane (a) containing terminal primary or hydroxyalkyl amino groups, with a bifunctional compound of the formula (XV): X4-R-X4 (XV) wherein X4 is a group that is coreactive with a hydroxyl or amino group of segment (a), forming a group X2 of a segment (c) from this reaction, and wherein X4 is preferably -COOH, -COORj ^ , -COCY or -NCO, wherein R10 is alkyl, or aryl that is unsubstituted or substituted by lower alkyl or lower alkoxy, and R is as defined above, after which, this intermediate is reacted with a polyol which does not carries lactone group, to give a compound of the formula (XVI): b-c-. { a-c} s-b (XVI) wherein the variables are as previously defined and preferred, after which, the compound of the formula (XVI) is reacted with a compound of the formula (X), to give a macromer of the formula (X): b-c-. { a-c} s-B (X) wherein s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; B is a segment (a) or (b); and the previous preferences apply to the number of segments (d) that are linked to a segment (b).

49. A process for the preparation of a macromer as defined in claim 1, which comprises reacting a bifunctional compound of the formula (XV): X4-R-X4 (XV) with an excess of polysiloxane (a) to give a sequence -a- (ca) r-, where the above meanings are applied, after which, in a second step, the intermediate is reacted with a polyol that does not carry lactone, to give a compound of the formula (XVII): b-Z-a-. { AC} r-Z-b (XVII) after which, the compound (XVII) is reacted with the compound (XIII), to give a macromer of the formula (VIII), b-Z-a-. { AC} r- (Z-b) t (VIII) wherein r is integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; t is 0 or 1, and is preferably 1; wherein a linear chain (c-a) is present, which may or may not be terminated by a segment (b) (t = l); and the previous preferences apply to the total number of segments (d), which are preferably linked to a segment (b).

50. A process for the preparation of a macromer as defined in claim 1, which comprises reacting, in a first step, a carbohydrate lactone, with a compound of the formula (XIII), retaining the lactone function, after which, the intermediate is reacted with a polysiloxane containing at least one amino or hydroxyl group, to give a compound of the formula (IV) or (V): a X b (IV) wherein q is typically 1 6 2, and wherein the foregoing meanings and preferences are applied differently, and segments (d) are incorporated terminally and / or pendently.

51. A compound of the formula (Xlla): (a-Z-b) q (Xlla) wherein q is greater than 1, (a) is derived from a polysiloxane as defined in the main claim, and (b) is derived from a carbohydrate dilactone.

52. A compound of the formula (Xllb): a- (Z-b) q (Xllb) wherein Z, (b), and q are as defined and preferred above, but with the proviso that a segment (a) is derived from a compound of the formula (III): R where n is an integer from 5 to 500; from 99.8 to 25 percent of the radicals R1 # R2, R3, 4f R5 'and R6' independently of each other, are alkyl, and from 0.2 to 75 percent of the radicals R-_, R2, R3, R4, R5 , and R6, independently of each other, are partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk-NH-Alk-NH2 or alk- (OCH2CH2) m- (OCH2) p-OR7, wherein: R7 is hydrogen or lower alkyl, alk is alkylene, and m and p, independently of each other, are an integer from 0 to 10, one molecule containing at least one primary amino or hydroxyl group, and at least one partially fluorinated alkyl group.

53. A compound of the formula (XVI): b-c-. { a-c} 8-b (XVI) wherein a segment (b) is derived from a polyol lactone-free, and the other variables are as defined and are preferred above.

54. A compound of the formula (XVII): b-Z-a-. { AC} r-Z-b (XVII) wherein a segment (b) is derived from a polyol lactone-free, and the other variables are as defined and are preferred above.

55. A polymer comprising a polymerization product of at least one macromer as defined in claim 1, and if appropriate, at least one vinyl comonomer (a).

56. A polymer according to claim 55, wherein the content by weight, with respect to the total polymer, of a macromer according to claim 1, is in the range of 100 to 0.5 percent, particularly in the scale from 80 to 10 percent, and preferably in the range of 70 to 30 percent.

57. A polymer according to claim 55, wherein the comonomer (a) is absent.

58. A polymer according to claim 55, wherein the comonomer (a) is hydrophilic or hydrophobic, or a mixture of both.

59. A polymer according to claim 55, wherein the comonomer (a) is selected from alkyl acrylate and methacrylate of 1 to 18 carbon atoms and of cycloalkyl of 3 to 18 carbon atoms, acrylamide and methacrylamide of alkyl of 3 to 18 carbon atoms, acrylonitrile, methacrylonitrile, vinyl alkanoate of 1 to 18 carbon atoms, alkene of 2 to 18 carbon atoms, haloalkene of 2 to 18 carbon atoms, styrene, lower alkyl-styrene, ether vinyl of lower alkyl, acrylate and perfluoroalkyl methacrylate of 2 to 10 carbon atoms or the correspondingly partially fluorinated acrylate and methacrylate, perfluoroalkyl acrylate and methacrylate of 3 to 12 carbon atoms-ethyl-thiocarbonylaminoethyl, acryloxy- and methacryloxy-alkylsiloxane, N-vinylcarbazole and alkyl ester of 1 to 12 carbon atoms of maleic acid, fumaric acid, itaconic acid, mesaconic acid, and the like.

60. A polymer according to claim 55, wherein the comonomer (a) is selected from lower alkyl acrylate and methacrylate substituted by hydroxyl, acrylamide, methacrylamide, acrylamide and methacrylamide of lower alkyl, acrylate and methoxylate methacrylate, acrylamide and hydroxy-substituted lower alkyl methacrylamide, hydroxyl-substituted lower alkyl vinyl ether, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyloxazoline , 2-vinyl-4,4 '-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinyl unsaturated carboxylic acid having a total of 3 to 5 carbon atoms, acrylate and lower aminoalkyl methacrylate (wherein the term "amino" also includes quaternary ammonium), lower monoalkyl-lower aminoalkyl, and lower dialkyl-lower aminoalkyl; allyl alcohol, and the like.

61. A polymer according to claim 55, which further comprises at least one comonomer (b).

62. A polymer according to claim 61, wherein the comonomer (b) is selected from allyl (meth) acrylate, lower alkylene glycol di (meth) acrylate, lower polyalkylene glycol di (meth) acrylate, lower alkylene di (meth) acrylate, divinyl ether, divinyl sulfone, di- or tri-vinylbenzene, tetramethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Bisphenol A di (meth) acrylate, methylenebis (meth) acrylamide, triallyl phthalate, or diallyl phthalate.

63. A polymer comprising the polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer of formula IV, V, VI, or VII, according to claims 18 to 21, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III): R wherein from 95 to 29 percent of the radicals R 1 R 2, R 3, R 4, R 5, and R 6, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R x, R 2, R 3, R 4, R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone, or carbohydrate dilactone; (d) is a radical of the formula (II): X3-L- (Y) k-P1, wherein Px is alkenyl, X3 is a urethane or urea group, and is a carbonyl, ester, or amide group, is 0 or 1, and L is bond or alkylene; and Xx is an ester, amide, urethane, or urea group, (2) from 25 to 75 percent of a hydrophobic monomer, and (3) from 15 to 40 percent of a hydrophilic monomer. 64. A polymer comprising the polymerization product of the following components, in percent by weight, based on the total weight of the polymer: (1) from 25 to 45 percent of a macromer of the formula (VIII), (IX) , (X), or (XI), according to the definitions of claims 38 to 41, wherein the variables are defined as follows: a polysiloxane segment (a) is derived from a compound of the formula (III) ), wherein from 95 to 29 percent of the Rlf radicals R2, R3, R, R5, and Rg, independently of one another, are lower alkyl, from 5 to 71 percent of the radicals R1 # R2, R3, R , R5, and R6, independently of one another, are partially fluorinated alkyl, aminoalkyl, or hydroxyalkyl, and n is an integer from 5 to 400; a segment of polyol (b) is derived from a carbohydrate polyol, carbohydrate, carbohydrate monolactone, or dilactone, with the proviso that segment (b) is derived from a polyol that does not carry a lactone group if the group Z is a segment (c); Z is a segment (c) or X1 (wherein Xx is an ester, amide, urethane, or urea group, and wherein segment (c) represents X2-R-X2, wherein R is alkylene, arylene, alkylenearylene, or arylenealkylene having up to 14 carbon atoms, or a saturated bivalent cycloaliphatic group having from 6 to 14 carbon atoms, and X2 is an amide, urethane, or urea group; (B) is a segment (a) or a segment (b), with the above-preferred definitions, and (d) is a radical of the formula (II): X3-L- (Y) k-P1, which is up to 15 times, still more preferably up to 6 times terminally and / or pendently attached to a segment (b), and wherein P is alkenyl, X3 is an ester, amide, urethane, or urea group, and is a carbonyl, ester, or amide group, k is 0 or 1, and L is a bond or alkylene, (2) from 25 to 75 percent of a hydrophobic monomer, and (3) from 15 to 40 percent of a hydrophilic monomer 65. A molding essentially comprising a polymer according to any of claims 55 to 64. 66. A molding comprising a polymer according to any of claims 55 to 64, wherein the molding surface is treated with plasma in the presence of an alkane of 1 to 6 carbon atoms, and a gas that is selected from the group consisting of nitrogen, argon, oxygen, and mixtures thereof. 67. A molding according to claim 65 or 66, which is a contact lens. 68. A molding according to claim 65 or 66, which is a soft contact lens having a water content of 1 to 40 percent. 69. A molding according to claim 65 or 66, which is a flexible contact lens which is gas permeable, and which has a low water content (RGP). 70. A molding according to claim 65 or 66, which is an intraocular lens. 71. A biomedical article essentially comprising a polymer according to any of claims 55 to 64. 72. The use of a macromer as defined in claim 1 for coating a surface of an article. 73. The use of a polymer as defined in any of claims 55 to 64, for coating a surface of an article. 74. The use of a macromer as defined in claim 1, for the production of a molding. 75. The use of a macromer as defined in claim 1, for the production of a contact lens. 76. A corneal implant essentially comprising a polymer according to any one of claims 55 to

64. 77. A corneal implant according to claim 76, which can be used to surgically implant on or into the cornea of a warm-blooded animal, this implant having an optical property in the region on the optic axis, which can impart visual acuity, and which also has a porosity that is sufficient to allow the components of the tissue fluid passing through to have a molecular weight greater than 10,000 Daltons, ensuring a flow through the tissue fluid from the cells outside the implant to the cells inside the implant, and the porosity being in the region on the optic axis such that a flow through of the components of the tissue fluid is possible, but the inward growth of the ocular tissue is excluded. 78. A corneal implant according to claim 76 or 77, wherein the implant is coated with one or more components that promote tissue growth in the vicinity of the implant, and / or promote adhesion of the cells to the implant. 79. A corneal implant according to any of claims 76 to 78, wherein the porosity of the implant is imparted by a large number of pores, the size of which is sufficient to ensure a flow of protein components from the tissue fluid, which have a molecular weight greater than 10,000 Daltons, through the implant, but whose pore size excludes inward tissue growth. 80. A corneal implant according to claim 79, wherein the majority of the pores have a diameter of 15 nanometers at 0.5 microns, preferably 150 nanometers at 0.5 microns. 81. A cell growth substrate comprising a polymer according to any of claims 55 to 64. 82. A medical implant comprising a polymer according to any of claims 55 to 64. 83. The use of a macromer as is defined in claim 1, in the production of a corneal implant, a cell growth substrate, or a medical implant.