Polysiloxane-polyol macromers, their preparation and their use
First Claim
1. 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 R1, R2, R3, R4, R5 and R6 independently of one another are alkyl and 0.2-75% of the radicals R1, R2, R3, R4, R5 and R6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk--NH--alk--NH2 or alk--(OCH2)m --(OCH2)p --OR7, in whichR7 is hydrogen or lower alkyl,alk is alkylene, andm 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 R4 and R5 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 X1, in which segment (c) is defined as X2 --R--X2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X1 is defined as X2, and in which(d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals;
Y and X3 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.
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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.
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Citations
64 Claims
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1. 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 R1, R2, R3, R4, R5 and R6 independently of one another are alkyl and 0.2-75% of the radicals R1, R2, R3, R4, R5 and R6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk--NH--alk--NH2 or alk--(OCH2)m --(OCH2)p --OR7, in which
R7 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 R4 and R5 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 X1, in which segment (c) is defined as X2 --R--X2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X1 is defined as X2, and in which (d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals; Y and X3 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. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 17, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 37, 38, 39, 40, 48, 49, 50, 51, 52, 53, 54, 55, 58, 59, 60, 61, 62, 63, 64)
- 38. A macromer according to claim 1, which is a compound of the formula (XI)
- space="preserve" listing-type="equation">B-(c-b).sub.s -Z-a-(Z-b).sub.t (XI)
wherein the macromer has a linear structure, and in which s is an integer from 1 to 10; B is a segment (a) or (b);
wherein a segment (d) is bonded to at least one segment (b);and t is 0 or 1.
- 99.8-25% of the radicals R1, R2, R3, R4, R5 and R6 independently of one another are alkyl and 0.2-75% of the radicals R1, R2, R3, R4, R5 and R6 independently of one another are partly fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, alk--NH--alk--NH2 or alk--(OCH2)m --(OCH2)p --OR7, in which
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39. A macromer according to claim 1, in which the ratio of the number of segments (a) and (b) is in a range of (a):
- (b)=3;
4, 2;
3, 1;
2, 1;
1, 1;
3 or 1;
4.
- (b)=3;
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40. A macromer according to claim 1, in which the total sum of segments (a) and (b) or, where appropriate, (a) and (b) and (c) is in a range from 2 to 50.
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48. A polymer comprising a polymerization product of at least one macromer as defined in claim 1 and, if appropriate, of at least one vinylic comonomer (a).
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49. A polymer according to claim 48, in which the weight content of the macromer is in the range from 100 to 0.5%, based on the total weight of the polymer.
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50. A polymer according to claim 48, in which comonomer (a) is absent.
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51. A polymer according to claim 48, in which comonomer (a) is hydrophilic or hydrophobic or a mixture of both.
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52. A polymer according to claim 48, in which comonomer (a) is chosen from C1 -C18 alkyl and C3 -C18 cycloalkyl acrylate and methacrylate, C3 -C18 alkylacrylamide and -methacrylamide, acrylonitrile, methacrylonitrile, vinyl C1 -C18 alkanoate, C2 -C18 alkene, C2 -C18 haloalkene, styrene, lower alkyl styrene, lower alkyl vinyl ether, C2 -C10 perfluoroalkyl acrylate and methacrylate or correspondingly partly fluorinated acrylate and methacrylate, C3 -C12 perfluoroalkyl-ethyl-thio carbonylaminoethyl acrylate and methacrylate, acryloxy- and methacryloxy-alkylsiloxane, N-vinylcarbazole and C1 -C12 alkyl ester of maleic acid, fumaric acid, itaconic acid, and mesaconic acid.
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53. A polymer according to claim 48, in which comonomer (a) is chosen from hydroxyl-substituted lower alkyl acrylate and methacrylate, acrylamide, methacrylamide, lower alkylacrylamide and -methacrylamide, ethoxylated acrylate and methacrylate, hydroxyl-substituted lower alkylacrylamide and -methacrylamide, hydroxyl-substituted lower alkyl vinyl ether, sodium vinylsulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyloxazoline, 2-vinyl-4,4'"'"'-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinylically unsaturated carboxylic acid having a total of 3 to 5 carbon atoms, amino-lower alkyl (where the term "amino" also includes quaternary ammonium), mono-lower alkylamino-lower alkyl and di-lower alkylamino-lower alkyl acrylate and methacrylate, and allyl alcohol.
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54. A polymer according to claim 48, furthermore comprising at least one comonomer (b).
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55. A polymer according to claim 54, in which comonomer (b) is chosen from allyl (meth)acrylate, lower alkylene glycol di(meth)acrylate, poly lower alkylene glycol di(meth)acrylate, lower alkylene di(meth)acrylate, divinyl ether, divinyl sulfone, di- or trivinylbenzene, tetramethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylenebis(meth)acrylamide, triallyl phthalate or diallyl phthalate.
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58. A molding comprising a polymer according to claim 48.
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59. A molding comprising a polymer according to claim 48, wherein the surface of the molding is plasma treated in the presence of a C1 -C6 alkane and a gas which is selected from the group consisting of nitrogen, argon, oxygen, and mixtures thereof.
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60. A molding according to claim 58, which is a contact lens.
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61. A molding according to claim 58, which is a soft contact lens having a water content of 1-40%, based on the total weight of the molding.
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62. A molding according to claim 58, which is a flexible contact lens which is permeable to gas and has a low water content (RGP).
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63. A method comprising polymerizing and shaping a macromer as defined in claim 1 for the production of a molding.
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64. A method comprising polymerizing and shaping a macromer as defined in claim 1 for the production of a contact lens.
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14. 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 X1, in which segment (c) is defined as X2 --R--X2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X1 is defined as X2, and in which (d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals; Y and X3 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.
- (b) is a polyol segment derived from a mono-, di-, tri-, tetra-, oligo- or polysaccharide;
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16. 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. X1 is a bivalent radical which contains at least one carbonyl group, and in which (d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals; Y and X3 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.
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18. 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, X1 is a bivalent radical which contains at least one carbonyl group, and in which (d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals; Y and X3 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. - View Dependent Claims (56)
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- 35. A macromer of the formula (VIII)
- space="preserve" listing-type="equation">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 X1, in which segment (c) is defined as X2 --R--X2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X, is defined as X2, and in which (d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals; Y and X3 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. - View Dependent Claims (42, 57)
- 36. A macromer of the formula (IX)
- space="preserve" listing-type="equation">b-Z-a-{c-a-(Z-b).sub.t }.sub.r (IX)
in which the sequence (c-a)-(Z-b)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 X1, in which segment (c) is defined as X2 --R--X2, in which R is a bivalent radical of an organic compound having up to 20 C atoms and each X2 independently of the other is a bivalent radical which contains at least one carbonyl group, and in which X1 is defined as X2, and in which (d) is a radical of the formula (II)
space="preserve" listing-type="equation">X.sub.3 --L--(Y).sub.k --P.sub.1 (II)in which P1 is a group which can be polymerized by free radicals; Y and X3 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.
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41. 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 R1, R2, R3, R4, R5 and R6 independently of one another are lower alkyl, 5-71% of the radicals R1, R2, R3, R4, R5 and R6 independently of one another are partly fluorinated alkyl, aminoalkyl or hydroxyalkyl, and n is an integer from 5 to 400;
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the 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, in which P1 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 a bond or alkylene; andX1 is an ester, amide, urethane or urea group.
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- 43. 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
- space="preserve" listing-type="equation">(a-Z-b).sub.q (XIIa)
space="preserve" listing-type="equation">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 X1, wherein X1 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)
space="preserve" listing-type="equation">X.sub.4 --L--(Y).sub.k --P.sub.1 (XII)in which X4 is a group which is coreactive with a hydroxyl or amino group of segment (b), in which P1 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. - View Dependent Claims (44, 45, 46, 47)
- 45. A process for the preparation of a macromer as defined in claim 43, which comprises first reacting a polysiloxane (a) which contains terminal primary amino- or hydroxyalkyl groups with a bifunctional compound of the formula (XV)
- space="preserve" listing-type="equation">X.sub.4 --R--X.sub.4 (XV)
in which X4 is a group which is coreactive with a hydroxyl or amino group of segment (a), and an X2 group of a segment (c) being formed from such a reaction, in which R10 is alkyl, or aryl which is unsubstituted or substituted by lower alkyl or lower alkoxy, after which this intermediate is reacted with a polyol which carries no lactone group to give a compound of the formula (XVI)
space="preserve" listing-type="equation">b-c-{a-c}.sub.s -b (XVI)in which s is an integer from 1 to 10, after which the compound of the formula (XVI) is reacted with a compound of the formula (XIII) to give a macromer of the formula (X)
space="preserve" listing-type="equation">b-c-{a-c}.sub.s -B (X)in which s is an integer from 1 to 10, preferably from 1 to 7, and in particular from 1 to 3; and
B is a segment (a) or (b).
- space="preserve" listing-type="equation">X.sub.4 --R--X.sub.4 (XV)
space="preserve" listing-type="equation">b-Z-a-{c-a}.sub.r -Z-b (XVII)
space="preserve" listing-type="equation">b-Z-a-{c-a}.sub.r (Z-b).sub.t (VIII)
Specification