# US 10,246,543 B2 · Hydrophilized polydiorganosiloxane vinylic crosslinkers and uses thereof

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- Number: US 10,246,543 B2
- Document ID: US10246543B2
- Status: Granted
- Kind: B2
- Application number: 16/110,194
- Filed: 2018-08-23
- Published: 2018-12-20
- Granted: 2019-04-02
- Earliest claimed: 2015-12-15
- Assignees: Novartis AG
- Applicants: Novartis AG
- Inventors: Jinyu Huang; Frank Chang; Steve Yun Zhang; Feng Jing
- Web page: https://patentgrep.com/patent/US10246543B2

## CPC

- C08F 290/068: {Polysiloxanes}
- C08G 77/16: to hydroxy groups
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/392: containing sulfur
- G02B 1/043: {Contact lenses}
- C08G 77/12: containing silicon bound to hydrogen
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

The invention provides a hydrophilized polydiorganosiloxane vinylic crosslinker which comprises (1) a polydiorganosiloxane polymer chain comprising dimethylsiloxane units and hydrophilized siloxane units each having one methyl substituent and one monovalent C4-C40 organic radical substituent having two to six hydroxyl groups, wherein the molar ratio of the hydrophilized siloxane units to the dimethylsiloxane units is from about 0.035 to about 0.15, and (2) two terminal (meth)acryloyl groups. The hydrophilized polydiorganosiloxane vinylic crosslinker has a number average molecular weight of from about 3000 Daltons to about 80,000 Daltons. The present invention is also related to a silicone hydrogel contact lens, which comprises repeating units derived from a hydrophilized polydiorganosiloxane vinylic crosslinker of the invention.

## Claims

### Claim 1

A silicone hydrogel contact lens comprising a crosslinked polymeric material which comprises:
units of a hydrophilized polydiorganosiloxane vinylic crosslinker which comprises (1) a polydiorganosiloxane polymer chain comprising dimethylsiloxane units and siloxane unit having one methyl substituent and one monovalent C4-C40 organic radical substituent having two to six hydroxyl groups, wherein the molar ratio of the hydrophilized siloxane units to the dimethylsiloxane units is from about 0.035 to about 0.15 and (2) two terminal (meth)acryloyl groups, wherein the polydiorganosiloxane vinylic crosslinker has a number average molecular weight of from about 3000 Daltons to about 80,000 Daltons;
units of a siloxane-containing vinylic monomer; and
units of at least one hydrophilic vinylic monomer,
wherein the silicone hydrogel contact lens, when being fully hydrated, has an oxygen permeability (Dk) of at least about 70 barrers, a water content of from about 25% to about 70% by weight, and an elastic modulus of from about 0.2 MPa to about 1.2 MPa.

### Claim 2 (depends on 1)

The silicone hydrogel contact lens of claim 1, wherein the hydrophilic vinylic monomer is N-vinylpyrrolidone, N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol (meth)acrylate having a number average molecular weight of up to 1500, polyethylene glycol C1-C4-alkyl ether (meth)acrylate having a number average molecular weight of up to 1500, N-[tris(hydroxymethyl)methyl]-acrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, (meth)acrylic acid, ethylacrylic acid, or combinations thereof.

### Claim 3 (depends on 1)

The silicone hydrogel contact lens of claim 1, wherein the crosslinked polymeric material further comprises units of a hydrophobic vinylic monomer free of silicone, units of a non-silicone vinylic crosslinker, units of a UV-absorbing vinylic monomer, or a combination thereof.

### Claim 4 (depends on 1)

The silicone hydrogel contact lens of claim 1, wherein the silicone hydrogel contact lens comprises from about 30% to about 60% by weight of the units of said at least one hydrophilic vinylic monomer, wherein the weight percentage of the units of said at least one hydrophilic vinylic monomer is the weight percentage of said at least one hydrophilic vinylic monomer relative to the total weight of all polymerizable components in a polymerizable composition for making the crosslinked polymeric material.

### Claim 5

A method for producing silicone hydrogel contact lenses, comprising the steps of:
preparing a lens-forming composition which is clear at room temperature and optionally but preferably at a temperature of from about 0 to about 4° C., wherein the lens-forming composition comprises
(a) from about 5% to about 35% by weight of a hydrophilized polydiorganosiloxane vinylic crosslinker of which comprises (1) a polydiorganosiloxane polymer chain comprising dimethylsiloxane units and siloxane unit having one methyl substituent and one monovalent C4-C40 organic radical substituent having two to six hydroxyl groups, wherein the molar ratio of the hydrophilized siloxane units to the dimethylsiloxane units is from about 0.035 to about 0.15 and (2) two terminal (meth)acryloyl groups, wherein the polydiorganosiloxane vinylic crosslinker has a number average molecular weight of from about 3000 Daltons to about 80,000 Daltons,
(b) a siloxane-containing vinylic monomer,
(c) from about 30% to about 60% by weight of at least one hydrophilic vinylic monomer, and
(d) at least one free-radical initiator,
provided that the above-listed polymerizable components and any additional polymerizable components add up to 100% by weight;
introducing the lens-forming composition into a mold, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens and a second mold half with a second molding surface defining the posterior surface of the contact lens, wherein said first and second mold halves are configured to receive each other such that a cavity is formed between said first and second molding surfaces; and curing thermally or actinically the lens-forming composition in the lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 70 barrers, a water content of from about 25% to about 70% by weight, and an elastic modulus of from about 0.2 MPa to about 1.2 MPa.

### Claim 6 (depends on 5)

The method of claim 5, wherein the lens-forming composition is a solventless liquid mixture and comprises a blending vinylic monomer selected from the group consisting of a C1-C10 alkyl methacrylate, isobornylmethacrylate, isobornylacrylate, cyclopentylmethacrylate, cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate, styrene, 2,4,6-trimethylstyrene (TMS), and t-butyl styrene (TBS), and combinations thereof (preferably, the blending vinylic monomer is methylmethacrylate).

### Claim 7 (depends on 5)

The method of claim 5, wherein the lens-forming composition comprises an organic solvent.

### Claim 8 (depends on 5)

The method of claim 5, wherein the total amount of all silicone-containing polymerizable components present in the lens-forming composition is about 65% or less.

### Claim 9 (depends on 5)

The method of claim 5, wherein the hydrophilic vinylic monomer is a hydrophilic N-vinyl monomer, preferably is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, or combinations thereof, even more preferably is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or combinations thereof.

### Claim 10 (depends on 5)

The method of claim 5, wherein the lens-forming composition further comprises a non-silicone vinylic crosslinker.

### Claim 11 (depends on 10)

The method of claim 10, wherein the non-silicone vinylic crosslinker is selected from the group consisting of ethyleneglycol di-(meth)acrylate, diethyleneglycol di-(meth)acrylate, triethyleneglycol di-(meth)acrylate, tetraethyleneglycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate, bis[2-(meth)acryloxyethyl] phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuan, diacrylamide (i.e., N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e., N-(1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide), N,N-di(meth)acryloyl-N-methylamine, N, N-di(meth)acryloyl-N-ethylamine, N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide, N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-propylene bis(meth)acrylamide, N,N′-2-hydroxypropylene bis(meth)acrylamide, N,N′-2,3-dihydroxybutylene bis(meth)acrylamide, 1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate (i.e., N,N′-2-phosphonyloxypropylene bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth)acryloyl piperazine), vinyl methacrylate, allylmethacrylate, allylacrylate, N-allyl-methacrylamide, N-allyl-acrylamide, tetraethyleneglycol divinyl ether, triethyleneglycol divinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, combinations thereof (preferably selected from the group consisting of tetra(ethyleneglycol) di-(meth)acrylate, tri(ethyleneglycol) di-(meth)acrylate, ethyleneglycol di-(meth)acrylate, di(ethyleneglycol) di-(meth)acrylate, glycerol dimethacrylate, allyl (meth)acrylate, N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide, N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-2-hydroxypropylene bis(meth)acrylamide, N,N′-2,3-dihydroxybutylene bis(meth)acrylamide, 1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate (i.e., N,N′-2-phosphonyloxypropylene bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth)acryloyl piperazine), triallyl isocyanurate, tetraethyleneglycol divinyl ether, triethyleneglycol divinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinyl ether, and combinations thereof).

### Claim 12 (depends on 5)

The method of claim 5, wherein the siloxane-containing vinylic monomer is 3-(meth)acryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxyethoxypropyloxypropylbis(trimethylsiloxy)methylsilane, 3-(meth)acrylamidopropyl-bis(trimethylsiloxy)methylsilane, 3-N-methyl (meth)acrylamidopropylbis(trimethylsiloxy) methylsilane, mono-(meth)acryloxy-terminated polydimethylsiloxanes of various molecular weight, mono-(meth)acrylamido-terminated polydimethylsiloxanes of various molecular weight, or a combination thereof.

### Claim 13 (depends on 5)

The method of claim 5, wherein the step of curing is carried out thermally.

### Claim 14 (depends on 1)

The silicone hydrogel contact lens of claim 1, wherein the polydiorganosiloxane vinylic crosslinker is a polymer of formula (1)
in which:
υ1 is an integer of from 30 to 500 and ω1 is an integer of from 1 to 75, provided that ω1/υ1 is from about 0.035 to about 0.15;
X0 is O or NR′ in which R′ is hydrogen or C1-C10-alkyl;
R1 is hydrogen or methyl;
R2 and R3 independently of each other are a substituted or unsubstituted C1-C10 alkylene divalent radical or a divalent radical of —R5—O—R6— in which R5 and R6 independently of each other are a substituted or unsubstituted C1-C10 alkylene divalent radical;
R4 is a monovalent radical of any one of formula (2) to (6)
q1 is zero or 1;
n1 is an integer of 2 to 4;
n2 is an integer of 1 to 5;
n3 is an integer of 3 to 6;
n4 is an integer of 2 to 5
R7 is hydrogen or methyl;
R8 and R9 independent of each other are a C2-C6 hydrocarbon radical having (n2+1) valencies;
R10 is ethyl or hydroxymethyl;
R11 is methyl or hydromethyl;
R12 is hydroxyl or methoxy;
X1 is a sulfur linkage of —S— or a teriary amino linkage of —NR13— in which R13 is C1-C3 alkyl, hydroxylethyl, hydroxypropyl, or 2,3-dihydroxypropyl; and
X2 is an amide linkage of
in which R14 is hydrogen or C1-C10 alkyl.

### Claim 15 (depends on 14)

The silicone hydrogel contact lens of claim 14, wherein R4 is a monovalent radical of formula (2).

### Claim 16 (depends on 14)

The silicone hydrogel contact lens of claim 14, wherein R4 is a monovalent radical of formula (3).

### Claim 17 (depends on 14)

The silicone hydrogel contact lens of claim 14, wherein R4 is a monovalent radical of formula (4).

### Claim 18 (depends on 14)

The silicone hydrogel contact lens of claim 14, wherein R4 is a monovalent radical of formula (5).

### Claim 19 (depends on 14)

The silicone hydrogel contact lens of claim 14, wherein R4 is a monovalent radical of formula (6).

### Claim 20 (depends on 19)

The silicone hydrogel contact lens of claim 19, wherein in formula (6) n1 is 3 and q1 is 1.