US4401797A
Expired / Lapsed
US
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Copolymers and hydrogels: process and articles made thereof
Assignee: Syntex USA LLC
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Filing: 1981-05-20
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Granted: 1983-08-30
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Expires: 2001-05-20
Abstract
Abstract Copolymers having improved machining and water resistant properties are produced using a monomer containing an adduct protecting group, particularly an alkyl boronic acid adduct, of glyceryl acrylate or glyceryl methacrylate, in combination with an alkyl acrylate or methacrylate, and optionally a glycidyl acrylate or methacrylate. After machining and shaping, the adduct is removed to provide a hydrogel useful as a contact lens material.
Inventors
- 👤 Paul M. Gallop
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 20:44
CPC Classifications
G; G02; G02B; G02B1/00; G02B1/04; G02B1/041; G02B1/043; C; C08; C08F; C08F220/00; C08F220/02; C08F220/10; C08F220/12; C08F220/20; C08F220/26; C08F230/00; C08F230/04; C08F230/06; C08F230/065
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
309 words
A polymer formed by a free radical bulk polymerization of: (a) a first monomer of the formula: ##STR29## wherein: R 1 is hydrogen or methyl; m is an integer from 1 to 4; and n is an integer from 0 to 1; X and Y are protecting groups and are independently selected from the group consisting of: (1) --C(O)OR 2 wherein R 2 is an alkyl group containing from 1 to 8 carbon atoms; (2) hexahydropyranyl; and (3) where X and Y together form one protecting group selected from the group consisting of: (i) >B--R 3 wherein: R 3 is a lower alkyl group containing 1 to 6 carbon atoms, cycloalkyl group containing 3 to 6 carbon atoms; and aryl selected from the group consisting of phenyl, tolyl and naphthyl; and (ii) >S═O (b) a second substantially water insoluble monomer of the formula: ##STR30## wherein: R 7 is hydrogen or methyl; and R 8 is lower alkyl having 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; the molar ratio of said first monomer to said second monomer being between about 1:30 and 20:1; and (c) optionally, a third substantially water insoluble monomer of the formula: ##STR31## wherein: R 9 is hydrogen or methyl; and p is an integer from 1 to 6; or ##STR32## wherein: R 10 and R 11 are independently hydrogen or methyl, and q is an integer from 1 to 6; the concentration of said third monomer when present being between about 0 and 30 percent by weight of the first monomer; said protection group(s) being subsequently removable by chemical means after said bulk polymerization; wherein said polymer can be handled, machined, and shaped over a wide humidity range as compared to a hydrogel polymer and can be polished and machined using water based and water-compatible oils, abrasives and polishes.
Claim 2
Dependent Claim
309 words
A polymer formed by a free radical bulk polymerization of: (a) a first monomer of the formula: ##STR29## wherein: R 1 is hydrogen or methyl; m is an integer from 1 to 4; and n is an integer from 0 to 1; X and Y are protecting groups and are independently selected from the group consisting of: (1) --C(O)OR 2 wherein R 2 is an alkyl group containing from 1 to 8 carbon atoms; (2) hexahydropyranyl; and (3) where X and Y together form one protecting group selected from the group consisting of: (i) >B--R 3 wherein: R 3 is a lower alkyl group containing 1 to 6 carbon atoms, cycloalkyl group containing 3 to 6 carbon atoms; and aryl selected from the group consisting of phenyl, tolyl and naphthyl; and (ii) >S═O (b) a second substantially water insoluble monomer of the formula: ##STR30## wherein: R 7 is hydrogen or methyl; and R 8 is lower alkyl having 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; the molar ratio of said first monomer to said second monomer being between about 1:30 and 20:1; and (c) optionally, a third substantially water insoluble monomer of the formula: ##STR31## wherein: R 9 is hydrogen or methyl; and p is an integer from 1 to 6; or ##STR32## wherein: R 10 and R 11 are independently hydrogen or methyl, and q is an integer from 1 to 6; the concentration of said third monomer when present being between about 0 and 30 percent by weight of the first monomer; said protection group(s) being subsequently removable by chemical means after said bulk polymerization; wherein said polymer can be handled, machined, and shaped over a wide humidity range as compared to a hydrogel polymer and can be polished and machined using water based and water-compatible oils, abrasives and polishes.
Claim 3
Dependent Claim
43 words
The polymer of claim 1 wherein: (a) said first and second monomers are present in a ratio of about 1:1 and 10:1; and (b) said third monomer is optionally present in about 1 to about 20 percent by weight of said first monomer.
Claim 4
Dependent Claim
57 words
The polymer of claims 1 or 2 wherein (a) with regard to said first monomer, R 1 is methyl, R 3 is butyl, and m is 1; (b) with regard to said second monomer, R 7 and R 8 are methyl; and (c) with regard to said third monomer, R 9 is methyl and p is 1.
Claim 5
Dependent Claim
215 words
A polymer formed by a free radical bulk polymerization of: (a) a first monomer of the formula: ##STR33## wherein: R 1 is hydrogen or methyl; R 3 is lower alkyl containing 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms and aryl selected from the group consisting of phenyl, tolyl and naphthyl; and m is an integer from 1 to 4; n is an integer from 0 to 1; (b) a second substantially water insoluble monomer of the formula: ##STR34## wherein: R 7 is hydrogen or methyl; and R 8 is lower alkyl having 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; the molar ratio of said first monomer to said second monomer being between about 1:30 and 20:1; and (c) optionally a third substantially water insoluble monomer of the formula: ##STR35## wherein: R 9 is hydrogen or methyl; and p is an integer from 1 to 6; the concentration of said third monomer when present being between about 0.1 and 30 percent by weight of the first monomer; wherein said polymer can be handled, machined, and shaped over a wide humidity range as compared to a hydrogel polymer and can be polished and machined using water-based and water compatible oils, abrasives and polishes.
Claim 6
Dependent Claim
215 words
A polymer formed by a free radical bulk polymerization of: (a) a first monomer of the formula: ##STR33## wherein: R 1 is hydrogen or methyl; R 3 is lower alkyl containing 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms and aryl selected from the group consisting of phenyl, tolyl and naphthyl; and m is an integer from 1 to 4; n is an integer from 0 to 1; (b) a second substantially water insoluble monomer of the formula: ##STR34## wherein: R 7 is hydrogen or methyl; and R 8 is lower alkyl having 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; the molar ratio of said first monomer to said second monomer being between about 1:30 and 20:1; and (c) optionally a third substantially water insoluble monomer of the formula: ##STR35## wherein: R 9 is hydrogen or methyl; and p is an integer from 1 to 6; the concentration of said third monomer when present being between about 0.1 and 30 percent by weight of the first monomer; wherein said polymer can be handled, machined, and shaped over a wide humidity range as compared to a hydrogel polymer and can be polished and machined using water-based and water compatible oils, abrasives and polishes.
Claim 7
Dependent Claim
42 words
The polymer of claim 4 wherein: (a) said first and second monomers are present in a ratio between about 1:1 and 10:1; and (b) said third monomer is optionally present between about 1 to 20 percent by weight of said first monomer.
Claim 8
Dependent Claim
57 words
The polymer of claims 4 or 5 wherein (a) with regard to said first monomer, R 1 is methyl, R 3 is butyl and m is 1; (b) with regard to said second monomer, R 7 and R 8 are methyl; and (c) with regard to said third monomer, R 9 is methyl, and n is 1.
Claim 9
Dependent Claim
170 words
A polymer formed by a free radical bulk polymerization of: (a) a first monomer of the formula: ##STR36## wherein: R 1 is hydrogen or methyl; R 2 is lower alkyl containing 1 to 6 carbon atoms; and m is an integer from 1 to 4; n is an integer from 0 to 1; (b) a second substantially water insoluble monomer of the formula: ##STR37## wherein: R 7 is hydrogen or methyl; and R 8 is lower alkyl having 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; the molar ratio of said first monomer to said second monomer being between about 1:30 and 20:1; and (c) a third substantially water insoluble monomer of the formula: ##STR38## wherein: R 9 is hydrogen or methyl; and p is an integer from 1 to 6; the concentration of said third monomer being between about 0.001 and 30 percent by weight of the first monomer; said boron protecting group being subsequently removable by chemical means after said bulk polymerization.
Claim 10
Dependent Claim
170 words
A polymer formed by a free radical bulk polymerization of: (a) a first monomer of the formula: ##STR36## wherein: R 1 is hydrogen or methyl; R 2 is lower alkyl containing 1 to 6 carbon atoms; and m is an integer from 1 to 4; n is an integer from 0 to 1; (b) a second substantially water insoluble monomer of the formula: ##STR37## wherein: R 7 is hydrogen or methyl; and R 8 is lower alkyl having 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; the molar ratio of said first monomer to said second monomer being between about 1:30 and 20:1; and (c) a third substantially water insoluble monomer of the formula: ##STR38## wherein: R 9 is hydrogen or methyl; and p is an integer from 1 to 6; the concentration of said third monomer being between about 0.001 and 30 percent by weight of the first monomer; said boron protecting group being subsequently removable by chemical means after said bulk polymerization.
Claim 11
Dependent Claim
41 words
The polymer of claim 7 wherein (a) said first and monomers are present in a ratio between about 1:1 and 10:1; and (b) said third monomer is optionally present between about 1 and 20 percent by weight of said first monomer.
Claim 12
Dependent Claim
59 words
The polymer of claims 7 or 8 wherein (a) with regard to said first monomer, R 1 is methyl, R 3 is butyl, m is 1, n is 0; (b) with regard to said second monomer, R 7 and R 8 are methyl; and (c) with regard to said third monomer, R 9 is methyl, and p is 1.
Claim 13
Dependent Claim
213 words
A process for preparing a polymer which comprises: (a) treating a monomer of the formula: ##STR39## wherein: R 1 is hydrogen or methyl; and m is an integer from 0 to 6 or cycloalkyl containing from 3 to 6 carbon atoms; n is an integer from 0 to 1; with a boronic acid of the formula: R.sub.3 B(OH).sub.2 wherein: R 3 is lower alkyl containing 1 to 6 carbon atoms or aryl selected from the group consisting of phenyl tolyl and naphthyl to form an adduct of the formula: ##STR40## wherein B, R 1 , R 2 , m and n are defined above and ##STR41## corresponds to a boron-containing protecting group; (b) purifying said adduct using non-aqueous, non-hydroxylic organic solvents; (c) mixing said purified adduct with a second monomer of the formula: ##STR42## (d) optionally mixing said purified adduct and second monomer with a third monomer of the formula: ##STR43## wherein: R 9 is hydrogen or methyl; and r is an integer from 1 to 6; or a third monomer of the formula: ##STR44## wherein: R 10 and R 11 are independently hydrogen or methyl; and q is an integer from 1 to 6; (e) polymerizing by a free radical bulk polymerization process said mixture of said purified adduct and said monomer(s).
Claim 14
Dependent Claim
213 words
A process for preparing a polymer which comprises: (a) treating a monomer of the formula: ##STR39## wherein: R 1 is hydrogen or methyl; and m is an integer from 0 to 6 or cycloalkyl containing from 3 to 6 carbon atoms; n is an integer from 0 to 1; with a boronic acid of the formula: R.sub.3 B(OH).sub.2 wherein: R 3 is lower alkyl containing 1 to 6 carbon atoms or aryl selected from the group consisting of phenyl tolyl and naphthyl to form an adduct of the formula: ##STR40## wherein B, R 1 , R 2 , m and n are defined above and ##STR41## corresponds to a boron-containing protecting group; (b) purifying said adduct using non-aqueous, non-hydroxylic organic solvents; (c) mixing said purified adduct with a second monomer of the formula: ##STR42## (d) optionally mixing said purified adduct and second monomer with a third monomer of the formula: ##STR43## wherein: R 9 is hydrogen or methyl; and r is an integer from 1 to 6; or a third monomer of the formula: ##STR44## wherein: R 10 and R 11 are independently hydrogen or methyl; and q is an integer from 1 to 6; (e) polymerizing by a free radical bulk polymerization process said mixture of said purified adduct and said monomer(s).
Claim 15
Dependent Claim
19 words
The process of claim 10 further including removing the boron-containing protecting groups and the regeneration of the hydroxyl groups.
Claim 16
Dependent Claim
21 words
The process of claim 11 wherein said removal includes treating said polymer with boiling water to remove the boron-containing protecting groups.
Claim 17
Dependent Claim
23 words
The process of claim 11 wherein said removal includes treating said polymer with water and polyhydroxyl alcohol to remove the boron-containing protecting group.
Claim 18
Dependent Claim
28 words
The process of claim 11 wherein said removal includes treating said polymer at room temperature with hydrogen peroxide in a buffer solution to remove the boron-containing protecting groups.
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) | 1986-08-29 | 1987-02-28 | 1987-08-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-29 | 1991-02-28 | 1991-08-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-29 | 1995-02-28 | 1995-08-30 | $7700.00 | Window Closed / Lapsed |