Organic compounds
View Patent ↗The invention relates to novel crosslinkable copolymers of formula wherein the variables are as defined in the claims. The copolymers of the invention are especially useful for the manufacture of biomedical molding, for example ophthalmic moldings such as in particular contact lenses.
1. An amphiphilic block copolymer of formula
wherein A is a hydrophobic polysiloxane or perfluoroalkyl polyether segment;
B is a surface-modifying hydrophilic segment having a weight average molecular weight of ≧100 that is devoid of a crosslinkable group;
Q is a moiety comprising at least one crosslinkable ethylenically unsaturated group;
(alk) is C 2 -C 20 -alkylene which is unsubstituted or substituted by hydroxy;
L 1 , L 2 and L 3 are each independently of the other a linking group;
p1 and q1 are each independently of the other an integer from 1 to 12; and either t is 0 and p and q are each independently of the other an integer from 2 to 20; or
t is an integer from 1 to 8 and p and q are each 0.
2. An amphiphilic block copolymer according to claim 1 of formula
wherein A, B, L 1 , L 2 , L 3 , Q, (alk), p1 and q1 are each as defined in claim 1 .
3. An amphiphilic block copolymer according to claim 1 of formula
(B−L 2 ) q —A—(L 1 −Q) p (1b),
wherein A, B, L 1 , L 2 and Q are each as defined in claim 1 , and p and q are each independently of the other an integer from 2 to 20.
4. An amphiphilic block copolymer according to claim 1 , wherein A is a polysiloxane segment of formula
wherein (alk′) is alkylene having 1 to 20 carbon atoms which may be interrupted by —O—;
x is 0 or 1;
80 to 100% of the radicals R 1 , R 1 ′, R 1 ″, R 2 , R 2 ′, R 2 ″, R 3 and R 4 , independently of one another, are C 1 -C 8 -alkyl, and 0-20% of the radicals R 1 , R 1 ′, R 1 ″, R 2 , R 2 ′, R 2 ″, R 3 and R 4 , independently of one another, are unsubstituted or C 1 -C 4 alkyl- or C 1 -C 4 -alkoxy-substituted phenyl, fluoro(C 1 -C 18 -alkyl) or cyano(C 1 -C 12 -alkyl),
s 1 is an integer from 5 to 700;
s 2 is the sum of (p+q+t−2) if x is 0, and is the sum of (p+q+t) if x is 1; wherein p, q and t are as defined in claim 1 , and
the sum (s 1 +s 2 ) is from 5 to 700.
5. An amphiphilic block copolymer according to claim 1 , wherein L 1 , L 2 and L 3 are each independently of the other a bivalent linking group of formula
—X 1 —C(O)—NH—R 10 —NH—C(O)—X 2 — (4a),
—X 1 —C(O)—R 10 —C(O)—X 2 — (4b),
—X 1 —C(O)— (4c),
—C(O)—X 2 — (4d), or
—X 1 —C(O)—X 2 — (4e),
wherein X 1 and X 2 are each independently of the other a group —O—, —S— or —NR 0 —, R 0 is hydrogen or C 1 -C 4 -alkyl, and R 10 is linear or branched C 1 -C 18 -alkylene or unsubstituted or C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted C 6 -C 10 -arylene, C 7 -C 18 -aralkylene, C 6 -C 10 -arylene-C 1 -C 2 -alkylene-C 6 -C 10 -arylene, C 3 -C 8 -cycloalkylene, C 3 -C 8 -cycloalkylene-C 1 -C 6 -alkylene, C 3 -C 8 -cycloalkylene-C 1 -C 2 -alkylene-C 3 -C 8 -cycloalkylene or C 1 -C 6 -alkylene-C 3 -C 8 -cycloalkylene-C 1 -C 6 -alkylene.
6. An amphiphilic block copolymer according to claim 5 , wherein L 1 is a linking group of formula (4a), (4c) or (4e), L 2 is a linking group of formula (4a), and L 3 is a linking group of formula (4b) or (4c).
7. An amphiphilic block copolymer according to claim 1 , wherein B is a non-ionic segment selected from the group consisting of a polyoxyalkylene, polysaccharide, polypeptide, poly(vinylpyrrolidone), polyalkylacrylate, polymethacrylate, polyhydroxyalkylacrylate, polyhydroxymethacrylate, polyacryl alkylene imine, polyacryl amide, polyvinyl alcohol, polyvinyl ether and a polyol, or B is a polyionic segment selected from the group consisting of a polyallylammonium, polyethyleneimine, polyvinylbenzyltrimethylammonium, polyaniline, sulfonated polyaniline, polypyrrole, polypyridinium segment, polyacrylic acid, polymethacrylic acid, a polythiophene-acetic acid, a polystyrenesulfonic acid and a zwitterionic segment, or a salt thereof.
8. An amphiphilic block copolymer according to claim 1 , wherein Q is a radical Q 1 of formula
wherein (Alk) is linear or branched C 1 -C 12 -alkylene, X is —O— or —NH—, R 11 is an olefinically unsaturated copolymerisable radical having from 2 to 24 carbon atoms which is unsubstituted or further substituted by C 1 -C 4 alkoxy, halogen, phenyl or carboxy, and w is the number 0 or 1.
9. An amphiphilic block copolymer according to claim 1 , wherein Q is a polyoxyalkylene, poly(vinylpyrrolidone), poly(hydroxyethylacrylate), poly(hydroxyethylmeth-acrylate), polyacrylamide, poly(N,N-dimethylacrylamide), polyacrylic acid, polymethacrylic acid, polyacyl alkylene imine or a copolymeric mixture of two or more of the above-mentioned polymers which in each case comprises one or more ethylenically unsaturated bond and has a weight average molecular weight of ≧100.
10. An amphiphilic block copolymer according to claim 9 , wherein Q is a hydrophilic segment of formula
—((alk″)—O) c —[(CH 2 —CH 2 —O) a —(CHR 6 —CHR 7 —O) b ]—(alk″)—L 1 ′—Q 2 (5a)
wherein L 1 ′ is a bivalent linking group of formula
—X 1 —C(O)—NH—R 10 —NH—C(O)—X 2 — (4a),
—X 1 —C(O)—R 10 —C(O)—X 2 — (4b),
—X 1 —C(O)— (4c),
—C(O)—X 2 — (4d), or
—X 1 —C(O)—X 2 — (4e),
wherein X 1 and X 2 are each independently of the other a group —O—, —S— or —NR 0 —, R 0 is hydrogen or C 1 -C 4 -alkyl, and R 10 is linear or branched C 1 -C 18 -alkylene or unsubstituted or C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted C 6 -C 10 -arylene, C 7 -C 18 -aralkylene, C 6 -C 10 -arylene-C 1 -C 2 -alkylene-C 6 -C 10 -arylene, C 3 -C 8 -cycloalkylene, C 3 -C 8 -cycloalkylene-C 1 -C 6 -alkylene, C 3 -C 8 -cycloalkylene-C 1 -C 2 -alkylene-C 3 -C 8 -cycloalkylene or C 1 -C 6 -alkylene-C 3 -C 8 -cycloalkylene-C 1 -C 6 -alkylene, Q 2 is a radical of formula
wherein (Alk) is linear or branched C 1 -C 12 -alkylene, X is —O— or —NH—, R 11 is an olefinically unsaturated copolymerisable radical having from 2 to 24 carbon atoms which is unsubstituted or further substituted by C 1 -C 4 alkoxy, halogen, phenyl or carboxy, and w is the number 0 or 1, Q 3 is C 3 -C 12 -alkenyl or a radical —(CH 2 ) 1-4 —O—R 16 wherein R 16 is acryloyl, methacryloyl or a group —C(O)—NH—(CH 2 ) 2-4 —O—C(O)—C(R 17 )═CH 2 and R 17 is hydrogen or methyl, Q 4 is a radical of formula
wherein X 3 is —O— or —NR—, R is hydrogen or C 1 -C 4 -alkyl, X 4 is a group —C(O)—O—, —O—C(O)—NH— or —NH—C(O)—O—, (Alk′) is C 1 -C 8 -alkylene, e is an integer of 0 or 1, and R 18 is C 1 -C 12 -alkylene, phenylene or C 7 -C 12 -phenylenealkylene,
one of the radicals R 6 and R 7 is hydrogen and the other is methyl,
(alk″) is C 1 -C 6 -alkylene, c is the number 0 or 1, and each of a and b independently of the other is a number from 0 to 100, the sum of (a+b) being from 2 to 100,
R 8 is hydrogen; C 1 -C 12 -alkyl unsubstituted or substituted by hydroxy or fluoro and/or uninterrupted or interrupted by oxygen; C 5 -C 8 -cycloalkyl; phenyl; or benzyl,
R 9 is C 1 -C 12 -alkyl, benzyl, C 2 -C 4 -alkanoyl, benzoyl or phenyl, and
z is an integer from 2 to 150.
11. An amphiphilic block copolymer according to claim 2 of formula (1a), wherein A is a polysiloxane segment of formula
wherein x and s 2 are each 0, and R 1 , R 1 ″, R 2 , R 2 ′, R 2 ″, R 3 and R 4 are each independently of one another C 1 -C 4 -alkyl, B is a polyoxyalkylene, poly(vinylpyrrolidone), poly(hydroxy-ethylacrylate), poly(hydroxyethylmethacrylate), polyacrylamide, poly(N,N-dimethylacrylamide), polyacrylic acid, polymethacrylic acid, polyacyl alkylene imine or a copolymeric mixture of two or more of the above-mentioned polymers,
L 1 is a linking group of formula
—X 1 —C(O)—NH—R 10 —NH—C(O)—X 2 — (4a),
—X 1 —C(O)— (4c), or
—X 1 —C(O)—X 2 — (4e),
L 2 is a linking group of the above formula (4a), and L 3 is a linking group of the above formula (4c) or of the formula
—X 1 —C(O)—R 10 —C(O)—X 2 — (4b),
wherein X 1 and X 2 are each independently of the other a group —O—, —S— or —NR 0 —, R 0 is hydrogen or C 1 -C 4 -alkyl, and R 10 is linear or branched C 1 -C 18 -alkylene or unsubstituted or C 1 -C 4 -alkyl- or C 1 -C 4 -alkoxy-substituted C 6 -C 10 -arylene, C 7 -C 18 -aralkylene, C 6 -C 10 -arylene-C 1 -C 2 -alkylene-C 6 -C 10 -arylene, C 3 -C 8 -cycloalkylene, C 3 -C 8 -cycloalkylene-C 1 -C 6 -alkylene, C 3 -C 8 -cycloalkylene-C 1 -C 2 -alkylene-C 3 -C 8 -cycloalkylene or C 1 -C 6 -alkylene-C 3 -C 8 -cycloalkylene-C 1 -C 6 -alkylene, Q is a radical Q 1 of formula
wherein (Alk) is linear or branched C 1 -C 12 -alkylene, X is —O— or —NH—, R 11 is an olefinically unsaturated copolymerisable radical having from 2 to 24 carbon atoms which is unsubstituted or further substituted by C 1 -C 4 alkoxy, halogen, phenyl or carboxy, and w is the number 0 or 1, or Q is a polyoxyalkylene, poly(vinylpyrrolidone), poly(hydroxyethylacrylate), poly(hydroxyethylmeth-acrylate), polyacrylamide, poly(N,N-dimethylacrylamide), polyacrylic acid, polymethacrylic acid, polyacyl alkylene imine or a copolymeric mixture of two or more of the above-mentioned polymers which in each case comprises one or more ethylenically unsaturated bond and has a weight average molecular weight of ≧100, and p1 is an integer from 1 to 6, and q1 is an integer from 1 to 8.
12. An amphiphillic block copolymer according to claim 3 of formula (1b), wehrein A,B, L 1 , L 2 and Q are defined in claim 11 , and p and q are each independently of the other an integer of 2 to 15.