Polysiloxane-polyol macromers, their preparation and their use
AssigneeNovartis AG
InventorsAngelika Domschke, Dieter Lohmann, Jens Hopken
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Abstract
The present invention describes a polysiloxane-polyol macromer which is uninterrupted or interrupted by a bivalent structural element and 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 vinylic 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; and furthermore the use of a macromer according to the invention or of a polymer prepared therefrom for coating a substrate.
Claims64
A macromonomer comprising at least one section of the formula (I) ##STR15## in which (a) is a polysiloxane segment derived from a compound of the formula (III) ##STR16## in which n is an integer from 5 to 500;
- 99.8-25% of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of one another are alkyl and 0.2-75% of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk--NH--alk--NH.sub.2 or alk--(OCH.sub.2).sub.m --(OCH.sub.2).sub.p --OR.sub.7, in which
- R.sub.7 is hydrogen or lower alkyl,
- alk is alkylene, and
- m and p independently of one another are an integer from 0 to 10, one molecule of the formula (III) containing at least one primary amino or hydroxyl group;
- wherein the radicals R.sub.4 and R.sub.5 are 1-50 times pendently aminoalkyl or hydroxyalkyl;
- (b) is a polyol segment derived from a carbohydrate, carbohydrate monolactone, carbohydrate dilactone, a 1,3-polyol, or a polyvinyl alcohol,
- Z is a segment formed by a condensation reaction and is
- (c) or a group X.sub.1, in which segment (c) is defined as X.sub.2 --R--X.sub.2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X.sub.2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X.sub.1 is defined as X.sub.2, and in which
- (d) is a radical of the formula (II)
- X.sub.3 --L--(Y).sub.k --P.sub.1 (II)
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y and X.sub.3 independently of one another are a bivalent radical which contains at least one carbonyl group;
- k is 0 or 1;
- and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound.
A macromer comprising at least one section of the formula (I) ##STR17## in which (a) is a polysiloxane segment;
- (b) is a polyol segment derived from a mono-, di-, tri-, tetra-, oligo- or polysaccharide;
- from a lactone of an aldonic or uronic;
- or from glucuronic acid lactone, mannuronic acid lactone or iduronic acid lactone,
- Z is a segment formed by a condensation reaction and is (c) or a group X.sub.1, in which segment (c) is defined as X.sub.2 --R--X.sub.2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X.sub.2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X.sub.1 is defined as X.sub.2, and in which
- (d) is a radical of the formula (II)
- X.sub.3 --L--(Y).sub.k --P.sub.1 (II)
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y and X.sub.3 independently of one another are a bivalent radical which contains at least one carbonyl group;
- k is 0 or 1;
- and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound.
A macromer of the formula (V) ##STR19## in which (a) is a polysiloxane segment containing q pendent ligands and in which
- x is 1 or 2,
- q has an average numerical value of 1-20, and in which the segments (b) in a macromer according to the formula (V) are linked in total (per molecule) with up to 20 polymerizable segments (d);
- (b) is a polyol segment derived from a carbohydrate, carbohydrate monolactone, carbohydrate dilactone or a 1,3-polyol.
- X.sub.1 is a bivalent radical which contains at least one carbonyl group, and in which
- (d) is a radical of the formula (II)
- X.sub.3 --L--(Y).sub.k --P.sub.1 (II)
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y and X.sub.3 independently of one another are a bivalent radical which contains at least one carbonyl group;
- k is 0 or 1;
- and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound.
A macromer of the formula (VII) ##STR21## in which (a) is a polysiloxane segment, x is 0, 1 or 2, and
- the average number of segments (d) per molecule of the formula (VII) is in the range from 2 to 5;
- (b) is a polyol segment derived from a carbohydrate, carbohydrate monolactone, carbohydrate dilactone or a 1,3-polyol,
- X.sub.1 is a bivalent radical which contains at least one carbonyl group, and in which
- (d) is a radical of the formula (II)
- X.sub.3 --L--(Y).sub.k --P.sub.1 (II)
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y and X.sub.3 independently of one another are a bivalent radical which contains at least one carbonyl group;
- k is 0 or 1;
- and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound.
A macromer of the formula (VIII)
- b-Z-a-{c-a}.sub.r -(Z-b).sub.t (VIII)
- in which r is an integer from 1 to 10;
- in which a linear (c-a) chain which may or may not be terminated by a segment (b) is present (t=1);
- wherein a segment (d) is bonded to at least one segment (b);
- in which (a) is a polysiloxane segment;
- (b) is a polyol segment derived from a carbohydrate, carbohydrate monolactone, carbohydrate dilactone, or a 1,3-polyol;
- Z is a segment formed by a condensation reaction and is (c) or a group X.sub.1, in which segment (c) is defined as X.sub.2 --R--X.sub.2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X.sub.2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X, is defined as X.sub.2, and in which
- (d) is a radical of the formula (II)
- X.sub.3 --L--(Y).sub.k --P.sub.1 (II)
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y and X.sub.3 independently of one another are a bivalent radical which contains at least one carbonyl group;
- k is 0 or 1;
- and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound.
A macromer of the formula (IX)
- b-Z-a-{c-a-(Z-b).sub.t }.sub.r (IX)
- in which the sequence (c-a)-(Z-b).sub.t hangs pendently r times on the segment (a) and may or may not be terminated by a segment (b);
- in which t is an integer from 1 to 10;
- t is 0 or 1;
- wherein a segment (d) is bonded to at least one segment (b);
- in which (a) is a polysiloxane segment;
- (b) is a polyol segment derived from a carbohydrate, carbohydrate monolactone, carbohydrate dilactone or a 1,3-polyol;
- Z is a segment formed by a condensation reaction and is (c) or a group X.sub.1, in which segment (c) is defined as X.sub.2 --R--X.sub.2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X.sub.2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X.sub.1 is defined as X.sub.2, and in which
- (d) is a radical of the formula (II)
- X.sub.3 --L--(Y).sub.k --P.sub.1 (II)
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y and X.sub.3 independently of one another are a bivalent radical which contains at least one carbonyl group;
- k is 0 or 1;
- and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound.
Macromer of the formula (IV) ##STR22## in which (a) is a polysiloxane segment is derived from a compound of the formula ##STR23## in which 95-29% of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of one another are lower alkyl, 5-71% of the radicals R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of one another are partly fluorinated alkyl, aminoalkyl or hydroxyalkyl, and n is an integer from 5 to 400;
- the polyol segment (b) is derived from a carbohydrate, carbohydrate monolactone or carbohydrate dilactone;
- (d) is a radical of the formula (II):
- X.sub.3 --L--(Y).sub.k --P.sub.1, in which P.sub.1 is alkenyl, X.sub.3 is a urethane or urea group, Y is a carbonyl, ester or amide group, k is 0 or 1, and L is a bond or alkylene;
- and
- X.sub.1 is an ester, amide, urethane or urea group.
A process for the preparation of a macromer, which comprises first reacting a polysiloxane containing at least one primary amino- or hydroxyalkyl group with a carbohydrate lactone, an amide or ester bond being formed and a compound of the formula (XIIa) or (XIIb) being formed
- (a-Z-b).sub.q (XIIa)
- a-(Z-b).sub.q (XIIb)
- in which
- (a) is a polysiloxane segment;
- (b) is a polyol segment derived from a carbohydrate, carbohydrate monolactone, carbohydrate dilactone or a 1,3-polyol;
- Z is a group X.sub.1, wherein X.sub.1 is a bivalent radical which contains at least one carbonyl group, and q is an average numerical value of 1-20;
- after which a compound (XIIa) or (XIIb) is reacted with precursors of (d), an unsaturated polymerizable compound of the formula (XIII)
- X.sub.4 --L--(Y).sub.k --P.sub.1 (XII)
- in which X.sub.4 is a group which is coreactive with a hydroxyl or amino group of segment (b),
- in which P.sub.1 is a group which can be polymerized by free radicals;
- Y is a bivalent radical which contains at least one carbonyl group,
- k is 0 or 1, and
- L is a bond or a divalent radical having up to 20 C atoms of an organic compound;
- after which a macromer according to the formula (IV) or (V) is formed ##STR25## in which the segments (d) are incorporated terminally or pendently, and x is 0, 1 or 2.
Dependencies are inferred from the claim text.