US 4,605,712 AGranted

Unsaturated polysiloxanes and polymers thereof

AssigneeCiba-Geigy Corporation

InventorsKarl F. Mueller, Dieter Lohmann, Robert A. Falk

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Abstract

Polysiloxanes of uniform molecular weight (MW) distribution with 500-10,000 MW segments of polysiloxane and containing at least one vinyl group connected to said polysiloxane segments through intervening alkylene-urea or -urethane linkages are prepared from polysiloxane-polyols, -polyamines or -polythiols by reaction with an unsaturated compound containing an isocyanato moiety, for example 2-isocyanatoethyl methacrylate. The polysiloxanes containing the vinyl groups are useful as radiation- or thermally curable coatings for glass, textiles, plastics, wood, ceramics, metals, as films or bandages for medicinal purposes, or molded shapes, in form of contact lenses, catheters or implants, either by themselves or in combination with other vinyl monomers; and are particularly useful in preparing hard or soft contact lenses, including hydrogel contact lenses.

Claims40

Dependent claims

A linear or branched polysiloxane macromer having a molecular weight from about 400 to 100,000, as measured by end group analysis or gel permeation chromatography, said macromer containing at least one terminal or pendant, polymerizable olefinic group per each 5000 molecular weight unit of polysiloxane, said group being attached to the polysiloxane through one urethane, thiourethane or urea linkage, said macromer having the structure A.sub.1, A.sub.2, A.sub.3 or A.sub.4 ##STR22## wherein:

R.sub.1 is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structure G or G.sub.1 ##STR23## wherein R.sub.3 is hydrogen or methyl and p is an integer from 1-50, R.sub.2, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e, R.sub.f, R.sub.g, R.sub.h, R.sub.i, R.sub.j and R.sub.k are independently methyl or phenyl, x.sub.1, x.sub.2 are integers from 1 to 500 with the proviso that the sum of x.sub.1 +x.sub.2 is 7 to 1300, y.sub.1 is 0 to 14 and y.sub.2 is 1 to 13 with the proviso that the ratio of ##EQU3## is not greater than 70, X is --Z.sub.1 --CO--NH--
Z.sub.1 is oxygen, sulfur or NR.sub.5, wherein R.sub.5 is hydrogen or lower (C.sub.1 -C.sub.4) alkyl, Z.sub.1 is connected to R.sub.1 ;
Y.sub.1 is ##STR24## wherein:
R.sub.6 is:
hydrogen, methyl, --COOR.sub.5 or --COOR.sub.7 OH,
Z.sub.2 =oxygen or --NR.sub.5 --
Y is the same as Y.sub.1, or Y may also be H, alkyl of 1 to 8 carbon atoms, cyclohexyl, phenyl, o-tolyl, m-tolyl or p-tolyl, with the proviso that at least one of Y must have the same meaning as Y.sub.1,
R.sub.7 is a linear or branched alkylene of 2 to 10 carbon atoms, phenylene or phenylalkylene with 2 to 10 carbon atoms in the alkylene, or polyoxyalkylene of structure G or G.sub.1 ;
R.sub.8 is an alkylene group of from 2 to 6 carbon atoms,
R.sub.4 is a diradical obtained by removing the NCO-groups from an aliphatic, cycloaliphatic, araliphatic or aromatic diisocyanate;
T is the group ##STR25## T.sub.1 is the group ##STR26## n is 0 to 10.

8 more elements

A polymer, suitable for use in contact lenses, comprising the crosslinked copolymerization product of

(A) from 5 to 75% by weight of said polymer of a linear or branched polysiloxane macromer having a molecular weight from about 400 to about 100,000, as measured by end group analysis or gel permeation chromatography, said macromer containing at least two terminal or pendant, polymerizable olefinic groups per each 5000 molecular weight unit of polysiloxane, said groups being attached to the polysiloxane, said groups being attached to the polysiloxane through one urethane, thiourethane or urea linkage, said macromer having the structure A.sub.1 A.sub.2, A.sub.3 or A.sub.4, ##STR27## wherein:
R.sub.1 is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structure G or G.sub.1 ##STR28## wherein R.sub.3 is hydrogen or methyl and p is an integer from 1-50, R.sub.2, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e, R.sub.f, R.sub.g, R.sub.h, R.sub.i, R.sub.j and R.sub.k are independently methyl or phenyl, x.sub.1, x.sub.2 are integers from 1 to 500 with the proviso that the sum of x.sub.1 +x.sub.2 is 7 to 1300, y.sup.1 is 0 to 14 and y.sup.2 is 1 to 13 with the proviso that the ratio of ##EQU4## is not greater than 70, X is --Z.sub.1 --CO--NH--
Z.sub.1 is oxygen, sulfur or NR.sub.5, wherein R.sub.5 is hydrogen or lower (C.sub.1 -C.sub.4) alkyl, Z.sub.1 is connected to R.sub.1 ;
Y.sub.1 is ##STR29## wherein R.sub.6 is:
hydrogen, methyl, --COOR.sub.5 or --COOR.sub.7 OH,
Z.sub.2 =oxygen or --NR.sub.5 --
Y is the same as Y.sub.1, or Y may also be H, alkyl of 1 to 8 carbon atoms, cyclohexyl, phenyl, o-tolyl, m-tolyl or p-tolyl, with the proviso that at least one of Y must have the same meaning as Y.sub.1,
R.sub.7 is a linear or branched alkylene of 2 to 10 carbon atoms, phenylene or phenylalkylene with 2 to 10 carbon atoms in the alkylene, or polyoxyalkylene of structure G or G.sub.1 ;
R.sub.8 is an alkylene group of from 2 to 6 carbon atoms,
R.sub.4 is a diradical obtained by removing the NCO-groups from an aliphatic, cycloaliphatic, araliphatic or aromatic diisocyanate;
T is the group ##STR30## T.sub.1 is the group ##STR31## n is 0 to 10, and (B) 95 to 25% by weight of said polymer of one or more mono-, di- or trifunctional vinyl monomer polymerizable by free radical polymerization.

8 more elements

Dependencies are inferred from the claim text.