Water-processable silicone-containing prepolymers and uses thereof

Patent metadata

Field	Value
Publication number	US-9187601-B2
Application number	US-201113253186-A
Country	US
Kind code	B2
Filing date	Oct 5, 2011
Priority date	Oct 6, 2010
Publication date	Nov 17, 2015
Grant date	Nov 17, 2015

Abstract

The invention provide a class of water-processable polymerizable prepolymers which comprises (1) siloxane-containing monomeric units derived at least one siloxane containing monomer having one hydrophilic group or chain and/or polysiloxane-containing crosslinking units derived from at least one hydrophilized polysiloxane or chain-extended polysiloxane crosslinker; (2) hydrophilic monomeric units derived from one or more hydrophilic vinylic monomers; and (3) from about 0.05% to about 5% by weight of polymerizable units each having a pendant or terminal, ethylenically-unsaturated group and free of any polysiloxane segment. The prepolymer comprises from about 20% to about 50% by weight of silicone relative to the total weight of the prepolymer and has a high water solubility or dispersibility of at least about 5% by weight in water and suitable for making silicone hydrogel contact lenses.

First claim

What is claimed is:

1. A water-processable prepolymer, comprising:
(1) siloxane-containing monomeric units and/or polysiloxane-containing crosslinking units, wherein the siloxane-containing monomeric units are derived from one or more siloxane-containing vinylic monomers each having at least one hydrophilic polymeric chain with a molecular weight of up to about 10000 Daltons, wherein the polysiloxane-containing crosslinking units are derived from at least one hydrophilized polysiloxane crosslinker and/or chain-extended hydrophilized polysiloxane crosslinker each having one or more pendant hydrophilic polymeric chains;
(2) hydrophilic monomeric units derived from one or more hydrophilic vinylic monomers;
(3) from about 0.05% to about 5% by weight of polymerizable units each having a pendant or terminal, ethylenically-unsaturated group and free of any polysiloxane segment; and
(4) optionally hydrophobic units derived from at least one hydrophobic vinylic monomer free of silicone,
wherein the prepolymer comprises the polysiloxane-containing crosslinking units derived from a hydrophilized polysiloxane or chain-extended polysiloxane crosslinker of formula (7) or (8)

In which
d2, d3, d4, ω1, ω2, and ω3 independent of one another are an integer from 0 to 20;

e3, e4, e5, e6, e7, ν1, ν2, ν3, ν4, and ν5 independent of one other are 0, 1, 2 or 3 and (e3+e4+e5+e6+e7)≧1 and (ν1+ν2+ν3+ν4+ν5)≧1;
X 1 is hydrogen or methyl;
D 3 , D 4 , D 5 , D 6 , D 7 , D 8 , D 9 and D 10 independently of one other are a divalent group of formula (9)

in which Y 28 is as defined below, A 8 , A 8 ′, A 9 ′, and A 9 ′ independent of one other are a direct bond, a linear or branched C 1 -C 10 alkylene divalent radical, —(CH 2 CH 2 O) r1 —CH 2 CH 2 — in which r1 is an integer of 1 to 20, or a C 1 -C 7 alkyleneoxy-C 1 -C 7 alkylene divalent radical, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 1 ′, R 2 ′, R 3 ′, R 4 ′, R 5 ′, R 6 ′, R 7 ′, and R 8 ′ independently of one another, are C 1 -C 4 -alkyl, -alk-(OCH 2 CH 2 ) r2 —OR 9 in which alk is C 1 -C 6 -alkylene divalent radical, R 9 is C 1 -C 4 alkyl and r2 is an integer from 1 to 20, f1 is an integer of 0 to 8, m1, m2, p1 and p2 independently of each other are an integer of from 0 to 150, (m1+p1) and (m2+p2) independent of each other are from 2 to 150;
L 4 , L 5 , L 6 , L 7 , L 8 , L 9 , L 10 , L 11 , L 12 , L 13 , L 14 , L 15 , L 16 , L 17 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Y 13 , Y 14 , Y 15 , Y 16 , Y 17 , Y 18 , Y 19 , Y 20 , Y 21 , Y 22 , Y 23 , Y 24 , Y 25 , Y 26 , Y 27 , and Y 28 independent of one another are a direct bond or a divalent radical of
—Z 1 —X 2 —Z 2 —X 3 —Z 3 —X 4 —Z 4 — In which X 2 , X 3 and X 4 independent of one other are a linkage selected from the group consisting of a direct bond —O—, —NR′— in which R′ is H or C 1 -C 4 alkyl, —C(O)—NH—, —NH—C(O)—, —NH—C(O)—NH—, —O—C(O)—NH—, —S—, —NH—C(O)—O—, —C(O)—O—, —O—C(O)—, —NH—C(O)—NH—Z 0 —NH—C(O)—NH—, —O—C(O)—NH—Z 0 —NH—C(O)—O—, —O—C(O)—NH—Z 0 —NH—C(O)—NH—, and —NH—C(O)—NH—Z 0 —NH—C(O)—O—, Z 0 is a linear or branched C 2 -C 12 alkylene divalent radical or a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—, Z 1 , Z 2 , Z 3 and Z 4 independent of one other are is a direct bond, a linear or branched C 1 -C 12 alkylene divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—, a divalent radical of —CH 2 —CH(OH)—CH 2 — or —(CH 2 CH 2 O) r1 —CH 2 CH 2 — with r1 as defined above, or a C 5 -C 45 cycloaliphatic or aliphatic-cycloaliphatic divalent radical optionally containing therein one or more linkages of —O—, —NR′—, —S— and —C(O)—;
B 5 , B 6 , B 7 , B 8 , B 9 , B 10 , B 11 , B 12 , B 13 , and B 14 independent of one another are hydroxyl or a linear or 3-arm hydrophilic polymer chain having a molecular weight of about 10000 Daltons or less and comprising at least about 60% by weight of one or more hydrophilic monomeric units selected from the group consisting of ethyleneoxide units, (meth)acrylamide units, C 1 -C 3 alkyl (meth)acrylamide units, di-(C 1 -C 3 alkyl) (meth)acrylamide units, N-vinylpyrrole units, N-vinyl-2-pyrrolidone units, 2-vinyloxazoline units, 4-vinylpyridine units, mono-C 1 -C 4 alkoxy, mono-(meth)acryloyl terminated polyethyleneglycol units having a molecular weight of 600 Daltons or less, di(C 1 -C 3 alkyl amino)(C 2 -C 4 alkyl) (meth)acrylate units, N—C 1 -C 4 alkyl-3-methylene-2-pyrrolidone units, N—C 1 -C 4 alkyl-5-methylene-2-pyrrolidone units, N-vinyl C 1 -C 6 alkylamide units, N-vinyl-N—C 1 -C 6 alkyl amide units, and combinations thereof, provided that at least one of B 5 , B 6 , B 7 , B 8 , and B 9 and at least one of B 10 , B 11 , B 12 , B 13 , and B 14 are the linear or 3-arm hydrophilic polymer chain; and
T 1 , T 2 , T 3 , T 4 , T 5 , T 6 , T 7 , T 8 , T 9 , T 10 , T 11 , T 12 , T 13 , and T 14 independent of one another are an aliphatic or cycloaliphatic or aliphatic-cycloaliphatic trivalent radical which has up to 15 carbon atoms and can be interrupted by —O—, —NR′—, —C(O)— and/or —S—,
wherein the prepolymer comprises from about 20% to about 50% by weight of silicone relative to the total weight of the prepolymer and has a high water solubility or dispersibility of at least about 5% by weight in water, wherein the prepolymer is capable of being actinically crosslinked, in the absence of one or more vinylic monomers, to form a silicone hydrogel contact lens having a water content of from about 20% to about 75% by weight when fully hydrated, an oxygen permeability (Dk) of at least about 40 barrers, and optionally a hydrophilic surface characterized by an average water contact angle of about 90 degrees or less without post-molding surface treatment.

2. The prepolymer of claim 1 , wherein the prepolymer comprises the polysiloxane-containing crosslinking units derived from a hydrophilized polysiloxane or chain-extended polysiloxane crosslinker of formula (8).

3. The prepolymer of claim 1 , wherein the prepolymer comprises the polysiloxane-containing crosslinking units derived from a hydrophilized polysiloxane or chain-extended polysiloxane crosslinker of formula (7).

4. The prepolymer of claim 1 , wherein the prepolymer comprises the siloxane-containing monomeric units derived from a siloxane-containing vinylic monomer of formula (2) or (3)

in which
a1 is an integer from 1 to 5;
b1 is an integer from 1 to 10;
d1 is an integer from 0 to 4;
e1 and e2 independent of each other are 0, 1, 2 or 3;
A 4 , A 5 , A 6 , and A 7 independent of one another are methyl or ethyl;
X 1 is hydrogen or methyl;
D 1 and D 2 independently of each other are a divalent group of formula (4)

in which A 8 and A 9 independent of each other are a direct bond, a linear or branched C 1 -C 10 alkylene divalent radical, —(CH 2 CH 2 O) r1 —CH 2 CH 2 — in which r1 is an integer of 1 to 20, or a C 1 -C 7 alkyleneoxy-C 1 -C 7 alkylene divalent radical, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 , independently of one another, are C 1 -C 4 -alkyl, -alk-(OCH 2 CH 2 ) r2 —OR 9 in which alk is C 1 -C 6 -alkylene divalent radical, R 9 is C 1 -C 4 alkyl and r2 is an integer from 1 to 20, m and p independently of each other are an integer of from 0 to 150

Assignees

• Huang Jinyu
• Chang Frank
• Scott Robert
• Medina Arturo Norberto
• Shankernarayanan Manivakkam J
• Kuyu Selma
• Smith Dawn Alison
• Wu Daqing
• Novartis Ag

Inventors

• Huang Jinyu
• Chang Frank
• Scott Robert
• Medina Arturo Norberto
• Shankernarayanan Manivakkam J
• Kuyu Selma
• Smith Dawn Alison
• Wu Daqing

Classifications

• C08L83/04

  Polysiloxanes · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• G02B1/043 Primary

  Contact lenses · CPC title

• C08L83/10

  Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00) · CPC title

• C08G77/42 Primary

  Block-or graft-polymers containing polysiloxane sequences (polymerising aliphatic unsaturated monomers on to a polysiloxane C08F283/12) · CPC title