US4379864A
Expired / Lapsed
US
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Polymeric compositions and hydrogels formed therefrom
Assignee: Syntex USA LLC
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Filing: 1981-03-05
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Granted: 1983-04-12
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Expires: 2001-03-05
Abstract
Abstract The invention provides new hydrogel forming materials comprising synthetic, hydrophilic, aqueous-insoluble polymer networks formed by copolymerization of a hydrophilic dihydroxyalkyl acrylate or methacrylate, a substantially water insoluble alkyl acrylate or methacrylate, one or more additional hydrophilic comonomers selected from the group of vinylic monomers, acrylates, and methacrylates, and a cross-linking agent. The hydrogels are preferably used for the formation of contact lenses, but may also be used for drug and pesticides delivery devices; dialysis, ultrafiltration and reverse osmosis membranes; implants in surgery and dentistry; and the like.
Inventors
- 👤 Paul M. Gallop
- 👤 Donald R. Korb
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 15:25
CPC Classifications
A; A01; A01N; A01N25/00; A01N25/08; A01N25/10; A61; A61K; A61K6/00; A61K6/80; A61K6/884; A61K6/887; A61K9/00; A61K9/20; A61K9/2004; A61K9/2022; A61K9/2027; A61L; A61L27/00; A61L27/14; A61L27/16; A61L27/50; A61L27/52; A61L33/00; A61L33/0005; A61L33/0064; A61L33/06; A61L33/064; B; B01; B01D; B01D71/00; B01D71/06; B01D71/40; B01D71/401; B01D71/4011; B29; B29D; B29D11/00; B29D11/02; C; C08; C08F; C08F220/00; C08F220/02; C08F220/10; C08F220/20; G; G02; G02B; G02B1/00; G02B1/04; G02B1/041; G02B1/043
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
245 words
A hydrogel comprising of hydrophilic polymer comprising the polymerization product of: a first monomer comprising a dihydroxyalkyl acrylate or dihydroxyalkyl methacrylate, a second monomer comprising a substantially water insoluble alkyl acrylate or alkyl methacrylate, the mole ratio of said first monomer to said second monomer varying within the range from about 1:3 to about 20:1; a third monomer comprising a compound selected from the group consisting of: ##STR10## where R 3 is hydroxyl, alkoxy having 1 to 6 carbon atoms, a sulfonic acid moiety, ##STR11## wherein R 4 and R 5 are independently selected from the group consisting of hydrogen and an unsubstituted or substituted alkyl group having from 1 to about 3 carbon atoms, or R 4 and R 5 may be combined to form a cyclic group, and n is an integer from 0 to about 4, except that n must be at least 1 when R 3 is hydroxyl; ##STR12## where R 6 is hydroxyalkoxy having 1 to 6 carbon atoms or --NR 7 R 8 where R 7 and R 8 are independently selected from hydrogen and lower alkyl groups having 1 to 4 carbon atoms; ##STR13## where R 9 is hydroxyalkoxy having from 1 to about 6 carbon atoms or vinyl acetate; and (d) mixtures thereof: the total of the molar quantities of said first and second monomers to the molar quantity of said third monomer being in the range of 1:1 to 1:0.2, which is substantially hydrated with water.
Claim 2
Dependent Claim
245 words
A hydrogel comprising of hydrophilic polymer comprising the polymerization product of: a first monomer comprising a dihydroxyalkyl acrylate or dihydroxyalkyl methacrylate, a second monomer comprising a substantially water insoluble alkyl acrylate or alkyl methacrylate, the mole ratio of said first monomer to said second monomer varying within the range from about 1:3 to about 20:1; a third monomer comprising a compound selected from the group consisting of: ##STR10## where R 3 is hydroxyl, alkoxy having 1 to 6 carbon atoms, a sulfonic acid moiety, ##STR11## wherein R 4 and R 5 are independently selected from the group consisting of hydrogen and an unsubstituted or substituted alkyl group having from 1 to about 3 carbon atoms, or R 4 and R 5 may be combined to form a cyclic group, and n is an integer from 0 to about 4, except that n must be at least 1 when R 3 is hydroxyl; ##STR12## where R 6 is hydroxyalkoxy having 1 to 6 carbon atoms or --NR 7 R 8 where R 7 and R 8 are independently selected from hydrogen and lower alkyl groups having 1 to 4 carbon atoms; ##STR13## where R 9 is hydroxyalkoxy having from 1 to about 6 carbon atoms or vinyl acetate; and (d) mixtures thereof: the total of the molar quantities of said first and second monomers to the molar quantity of said third monomer being in the range of 1:1 to 1:0.2, which is substantially hydrated with water.
Claim 3
Dependent Claim
24 words
The hydrogel of claim 1 wherein said hydrated polymer has a Shore A durometer Type A-2 reading of from about 40 to about 50.
Claim 4
Dependent Claim
25 words
The hydrogel of claim 1 wherein said hydrated polymer is insoluble in a solvent selected from the group consisting of acetone, dioxane, and mixtures thereof.
Claim 5
Dependent Claim
31 words
The hydrogel of claim 1 wherein said first monomer comprising a compound having the formula: ##STR14## wherein R is hydrogen or methyl and n is an integer from 1 to 4.
Claim 6
Dependent Claim
35 words
The hydrogel of claim 4 wherein said first monomer comprises a compound selected from the group consisting of dihydroxypropyl methacrylates; dihydroxybutyl methacrylates; dihydroxypentyl methacrylates; dihydroxyhexyl methacrylates; dihydroxypropyl acrylates; dihydroxybutyl acrylates; dihydroxypentyl acrylates; and dihydroxyhexyl acrylates.
Claim 7
Dependent Claim
18 words
The hydrogel of claim 1 wherein said hydrogel comprises from about 35 to about 50 weight percent water.
Claim 8
Dependent Claim
37 words
The hydrogel of claim 1 wherein said second monomer comprises a compound having the formula: ##STR15## wherein R' is hydrogen or methyl and R 2 is an alkyl group having from 1 to about 6 carbon atoms.
Claim 9
Dependent Claim
36 words
The hydrogel of claim 7 wherein said second monomer comprises a compound selected from the group consisting of methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and butyl methacrylate.
Claim 10
Dependent Claim
40 words
The hydrogel of claim 1 wherein said third monomer is selected from the group consisting of vinyl acetate, 3-buten-1-ol, 2-propen-1-ol, 5-hexenol, methyl vinyl ether, propyl vinyl ether, butyl 3-buten-1-ol ether, N-methyl vinyl amide, N-propyl vinyl amide, N-ethyl-3-butenamide and vinyl pyrrolidone.
Claim 11
Dependent Claim
30 words
The hydrogel of claim 1 wherein said third monomer comprises a compound selected from the group consisting of 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, methacrylamide, N-methyl methacrylamide, N,N-dimethyl methacrylamide, and 2-hydroxyethyl acrylate.
Claim 12
Dependent Claim
20 words
A shaped article made from the hydrogel of any one of claims 1 through 5, 7, 8, 9 or 10.
Claim 13
Dependent Claim
14 words
The hydrated shaped article of claim 11 in the form of a contact lens.
Claim 14
Dependent Claim
21 words
The hydrogel of claim 1 wherein said molar ratio of said first monomer to said second monomer is at least 1:1.
Claim 15
Dependent Claim
17 words
The hydrogel of claim 1, wherein said polymer further includes a minor amount of a cross-linking agent.
Claim 16
Dependent Claim
13 words
The hydrogel of claim 14 wherein said cross-linking agent comprises a divinyl compound.
Claim 17
Dependent Claim
20 words
The hydrogel of claim 14 wherein said cross-linking agent is present in an amount less than about 5 mole percent.
Claim 18
Dependent Claim
40 words
The hydrogel of claim 14 wherein said cross-linking agent is selected from the group consisting of ethylene glycol dimethyacrylate, propylene glycol dimethacrylate, ethylene glycol diacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, tartaric acid dimethacrylate, triethylene glycol dimethacrylate, and the dimethacrylate of bishydroxyethylacetamide.
Claim 19
Dependent Claim
172 words
A hydrogel comprising a hydrophilic polymer comprising: a first monomer comprising a hydrophilic compound having the formula: ##STR16## wherein: R is hydrogen or methyl; and n is an integer from 1 to 4; a second monomer comprising a substantially insoluble acrylate or methacrylate selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, and butyl methacrylate, the mole ratio of said first monomer to said second monomer varying within the range from about 1:3 to about 20:1; and a third monomer selected from the group consisting of vinyl acetate, 3-buten-1-ol, 2-propen-1-ol, 5-hexenol, methyl vinyl ether, propyl vinyl ether, butyl 3-buten-1-ol ethyl, N-methyl vinyl amide, N-propyl vinyl amide, N-ethyl-3-butenamide, vinyl pyrrolidone, 3-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methacrylamide, N-methyl methacrylamide, N,N-dimethyl methacrylamide, and mixtures thereof: the total of the molar quantities of said first and second monomers to the molar quantity of said third monomer being in the range of 1:1 to 1:02, which is subsequently hydrated with water.
Claim 20
Dependent Claim
172 words
A hydrogel comprising a hydrophilic polymer comprising: a first monomer comprising a hydrophilic compound having the formula: ##STR16## wherein: R is hydrogen or methyl; and n is an integer from 1 to 4; a second monomer comprising a substantially insoluble acrylate or methacrylate selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, and butyl methacrylate, the mole ratio of said first monomer to said second monomer varying within the range from about 1:3 to about 20:1; and a third monomer selected from the group consisting of vinyl acetate, 3-buten-1-ol, 2-propen-1-ol, 5-hexenol, methyl vinyl ether, propyl vinyl ether, butyl 3-buten-1-ol ethyl, N-methyl vinyl amide, N-propyl vinyl amide, N-ethyl-3-butenamide, vinyl pyrrolidone, 3-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methacrylamide, N-methyl methacrylamide, N,N-dimethyl methacrylamide, and mixtures thereof: the total of the molar quantities of said first and second monomers to the molar quantity of said third monomer being in the range of 1:1 to 1:02, which is subsequently hydrated with water.
Claim 21
Dependent Claim
12 words
The hydrogel of claim 18 wherein said first monomer comprises 2,3-dihydroxypropyl methacrylate.
Claim 22
Dependent Claim
12 words
The hydrogel of claim 18 wherein said second monomer comprises methyl methacrylate.
Claim 23
Dependent Claim
20 words
The hydrogel of claim 18 wherein said third monomer comprises a compound selected from vinyl pyrrolidone, 2-hydroxyethyl acrylate or methacrylamide.
Claim 24
Dependent Claim
42 words
The hydrogel of claim 18, wherein said polymer further includes cross-linking agent selected from the group consisting of, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, ethylene glycol diacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, tartaric acid dimethacrylate, triethylene glycol dimethacrylate, and the dimethacrylate of bis-hydroxyethylacetamide.
Claim 25
Dependent Claim
37 words
The hydrogel of claim 18 wherein said first monomer comprises 2,3-dihydroxypropyl methacrylate, said second monomer comprises methyl methacrylate and said third monomer comprises a compound selected from the group consisting of vinyl pyrrolidone, 2-hydroxyethyl acrylate, and methacrylamide.
Claim 26
Dependent Claim
16 words
The hydrogel of claim 18 wherein said polymer further includes a cross-linking agent comprising glycidyl methacrylate.
Claim 27
Dependent Claim
28 words
The hydrogel of claim 23 wherein said molar ratio of said first monomer to said second monomer is in the range of from about 1:1 to about 10:1.
Claim 28
Dependent Claim
35 words
The hydrogel of claim 23 wherein said third monomer comprises vinyl pyrrolidone that is present in a molar ratio of 1:1 to 1.0:0.2 when compared to the total moles of said first and second monomers.
Claim 29
Dependent Claim
33 words
The hydrogel of claim 23 wherein said third monomer comprises methacrylamide that is present in a molar ratio of 1:1 1.0:0.2 when compared to the total moles of said first and second monomers.
Claim 30
Dependent Claim
34 words
The hydrogel of claim 23 wherein said third monomer comprises 2-hydroxyethyl acrylate that is present in a molar ratio of 1:1 1.0:0.2 when compared to the total moles of said first and second monomers.
Claim 31
Dependent Claim
31 words
The hydrogel of any one of claims 18 through 27 or 28 wherein said polymer comprises water of hydration in an amount of from about 35 to about 50 weight percent.
Claim 32
Dependent Claim
30 words
The hydrogel of any one of claims 18 through 27 or 28 wherein said polymer has a Shore A duromater type A-2 reading of from about 40 to about 50.
Claim 33
Dependent Claim
27 words
The hydrogel of any one of claims 18 through 28 wherein said polymer when hydrated exhibits a linear expansion of from about 15 to about 25 percent.
Claim 34
Dependent Claim
17 words
A shaped article made from the hydrated hydrophilic polymer of any one of claims 18 through 28.
Claim 35
Dependent Claim
15 words
A contact lens formed from the hydrogel of any one of claims 18 through 28.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-04-11 | 1986-10-11 | 1987-04-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-04-11 | 1990-10-11 | 1991-04-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-04-11 | 1994-10-11 | 1995-04-12 | $7700.00 | Window Closed / Lapsed |