US5010141A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
Assignee: Ciba Vision Corp
•
Filing: 1990-04-18
•
Granted: 1991-04-23
•
Expires: 2010-04-18
Abstract
Abstract Vinyl unsaturated copolymers are described which are obtained in a two-step process and which consist of monomeric units A, B, C, D and E, copolymerized in a first step, and in a second step reacted with a reactive vinyl monomer Mv, and in which A is a silicon or fluorine containing vinyl monomer, 20-79.5% by weight; B is N,N-dimethylacrylamide, N-vinylpyrrolidone, or N-vinylacetamide, 20-79.5% by weight; C is an active hydrogen containing vinyl monomer, 0.5-25% by weight; D are other copolymerizable comonomers, 0-30% by weight, and E is a chain transfer agent, 0-10 mol percent. Mv is a vinyl unsaturated isocyanate. These vinyl unsaturated polymers are useful, either by themselves or in combination with other copolymerizable vinyl monomers, as heat or UV-curable coatings or glass, plastic, wood, paper, textiles, metal or ceramics, said coatings possessing low surface energies and low refractive indices. They are especially useful as UV-curable hydrophilic coatings and water-swelling biocompatible polymers, especially fully molded highly oxygen-permeable contact lenses.
Inventors
- 👤 Karl F. Mueller
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 09:15
CPC Classifications
C; C08; C08F; C08F14/00; G; G02; G02B; G02B1/00; G02B1/04; G02B1/041; G02B1/043; C08F8/00; C08F8/30
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
176 words
A hydrophilic prepolymer containing silicon or fluorine or both silicon and fluorine as well as ethylenically unsaturated groups, which is the reaction product of the random copolymer of, the weight percent amounts of components (A), (B), (C), (D) and (E) being based on the total amount of said components, (A) 20 to 79.5% by weight of a silicon or fluorine containing vinyl monomer or mixtures thereof, (B) 79.5 to 20% by weight of N N-dimethyl acrylamide N-vinyl pyrrolidone or N-vinylacetamide or mixtures thereof, (C) 0.5 to 25% by weight of a vinyl monomer containing an active hydrogen atom or mixtures thereof, (D) 0 to 30% by weight of an ethylenically unsaturated monomer or mixtures thereof other than a monomer of component (A), (B) or (C), (E) 0 to 10 mol %, based on the total moles of components (A), (B), (C), (D) and (E) of a chain transfer agent, with (M v ) 0.2 to 10 mol %, based o the total moles of components (A), (B), (C), (D) and (E), of an ethylenically unsaturated isocyanate.
Claim 2
Dependent Claim
176 words
A hydrophilic prepolymer containing silicon or fluorine or both silicon and fluorine as well as ethylenically unsaturated groups, which is the reaction product of the random copolymer of, the weight percent amounts of components (A), (B), (C), (D) and (E) being based on the total amount of said components, (A) 20 to 79.5% by weight of a silicon or fluorine containing vinyl monomer or mixtures thereof, (B) 79.5 to 20% by weight of N N-dimethyl acrylamide N-vinyl pyrrolidone or N-vinylacetamide or mixtures thereof, (C) 0.5 to 25% by weight of a vinyl monomer containing an active hydrogen atom or mixtures thereof, (D) 0 to 30% by weight of an ethylenically unsaturated monomer or mixtures thereof other than a monomer of component (A), (B) or (C), (E) 0 to 10 mol %, based on the total moles of components (A), (B), (C), (D) and (E) of a chain transfer agent, with (M v ) 0.2 to 10 mol %, based o the total moles of components (A), (B), (C), (D) and (E), of an ethylenically unsaturated isocyanate.
Claim 3
Dependent Claim
140 words
A prepolymer according to claim 1 wherein the fluorine containing monomer of component (A) contains at least three fluorine atoms and consists of hexafluoroisopropyl acrylate or methacrylate, perfluorocyclohexyl acrylate or methacrylate, 2,3,4,5,6-pentafluorostryene or the acrylate or methacrylate esters or amides of the formula ##STR5## wherein R f is --(CF 2 ) t CF 2 L or --(CF 2 CF 2 ) q OCF(CF 3 ) 2 R 1 is hydrogen or methyl, X is oxygen or --NR 7 -- wherein R 7 is hydrogen or an alkyl group with 1-5 carbon atoms. r is an integer from 1-4, t is an integer from 0-14, q is an integer from 1-3, L is hydrogen or fluorine, with the proviso that, when t is 0, L is fluorine, and W is a direct bond or a divalent group of the structure ##STR6##
Claim 4
Dependent Claim
38 words
A prepolymer according to claim 2 where the fluorine containing monomer is of formula A-1 where X is oxygen, r is 1 or 2, W is a direct bond, t is 1 to 10 and L is fluorine.
Claim 5
Dependent Claim
22 words
A prepolymer according to claim 2 wherein the fluorine containing monomer is hexafluoroisopropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 1,1,2,2-tetrahydroperfluorooctyl- or 1,1,2,2-tetrahydroperfluorodecyl acrylate or methacrylate.
Claim 6
Dependent Claim
23 words
A prepolymer according to claim 1 wherein the silicon containing monomer A-2 of component (A) contains at least 2 to 10 silicon atoms.
Claim 7
Dependent Claim
66 words
A prepolymer according to claim 4 wherein the silicon containing monomer is of formula A-2: ##STR7## wherein Z and Y are methyl, phenyl or Q where Q is ##STR8## wherein M is methyl or phenyl, n is 2 to 4, x is 0 to 6, with the proviso, that if x=0, at least one of Z or Y is Q, and R is hydrogen or methyl.
Claim 8
Dependent Claim
15 words
A prepolymer according to claim 6 wherein the silicon containing monomer A-2 is tris(trimethylsiloxysilyl)propyl methacrylate.
Claim 9
Dependent Claim
11 words
A prepolymer according to claim 1 wherein component (B) is N,N-dimethylacrylamide.
Claim 10
Dependent Claim
72 words
A prepolymer according to claim 1 wherein the vinyl monomer (C) containing an active hydrogen atom is a hydroxy or amino substituted vinyl monomer selected from the group consisting of 2-hydroxyethyl- 2 or 3-hydroxypropyl-, 4-hydroxybutyl acrylate and methacrylate; glycerol methacrylate; N-2-hydroxyethyl- and N-3-hydroxypropyl methacrylamide; 2-hydroxyethyl and 4-hydroxybutyl vinyl ether; bis-hydroxyethyl maleate and fumarate, N-tert-butyl-aminoethyl methacrylate, and aminostyrene; also acrylic and methacrylic acid and di, tri-, tetra- and polyethylene glycol acrylates and methacrylates.
Claim 11
Dependent Claim
21 words
A prepolymer according to claim 9 wherein the monomer (C) containing an active hydrogen atom is 2-hydroxyethyl methacrylate or N-tert-butylaminoethyl methacrylate.
Claim 12
Dependent Claim
112 words
A prepolymer according to claim 1 wherein the ethylenically unsaturated vinyl monomer of component (D) is selected from the group consisting of an alkyl ester or amide of acrylic or methacrylic acid with from 1-20 carbon atoms in a linear or branched aliphatic, cycloaliphatic or aromatic group containing ester or amide group and which may be interrupted by hetero atoms like sulfur or oxygen; analogous mono- or di-esters of maleic and itaconic acid; alkyl vinyl ethers with 1 to 10 carbon atoms in the alkyl group, vinyl esters of C 1 to C 12 -carboxylic acids, styrene and alkyl substituted styrene and α-methylstyrene; N-alkyl-acrylamides and methacrylamides, N-alkyl and N,N-dialkylamino-alkyl methacrylates and methacrylamides.
Claim 13
Dependent Claim
42 words
A prepolymer according to claim 1 wherein the chain transfer agent of component (E) is an alkyl mercaptan having 3 to 21 carbon atoms, thioglycerol, mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, mercaptomaleic acid, cysteine, mercapto-N,N-dimethylaminoethylene or a C 3-14 F 7-29 -ethyl mercaptan.
Claim 14
Dependent Claim
24 words
A prepolymer according to claim 12 wherein component (E) is C 5 -C 14 -alkyl mercaptan or a C 4 -C 12 -perfluoroalkylethyl mercaptan.
Claim 15
Dependent Claim
46 words
A prepolymer according to claim 1 wherein component (M v ) is 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl methacrylate, 1-methyl-2-isocyanatoethyl methacrylate, 1,1-dimethyl-2-isocyanatoethyl acrylate, 2-isocyanatobutyl vinyl ether, styrene isocyanate or m-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate or the reaction product of 2-hydroxyethyl methacrylate with toluene diisocyanate or isophorone diisocyanate in equimolar amounts.
Claim 16
Dependent Claim
59 words
A prepolymer according to claim 1 wherein the amounts of (A) to (M v ) are (A) is 30-69.5% by weight; (B) is 69.9 to 30% by weight; (C) is 0.5 to 25% by weight; (D) is 0 to 30 % by weight; (E) is 0 to 10 mol % (M v ) is 0.2 to 10 mol %.
Claim 17
Dependent Claim
61 words
A prepolymer according to claim 15 wherein the amounts of (A) to (M v ) are (A) is 30 to 69% by weight, (B) is 69 to 30% by weight, (C) is 1 to 20% by weight, (D) is 0 to 25% by weight, (E) is 0 to 5 mol %, and (M v ) is 0.5 to 6 mol %.
Claim 18
Dependent Claim
52 words
A prepolymer according to claim 16 wherein the amounts of (A) to (M v ) are (B) is 55 to 40% by weight, (C) is 5 to 15% by weight, (D) is 0 to 15% by weight, (E) is 0 to 2%, and (M v ) is 1 to 5 mol %.
References Cited (Backward Citations)
US3220960A
Cited
US3928299A
Cited
US4182822A
Cited
US4343927A
Cited
US4136250A
Cited
US4139692A
Cited
US4139513A
Cited
US4343919A
Cited
US4383091A
Cited
US4493910A
Cited
US4433111A
Cited
US4650843A
Cited
US4638040A
Cited
US4548983A
Cited
JPS6090855A
Cited
US4605712A
Cited
JPS6225104A
Cited
US4640965A
Cited
JPS63159820A
Cited
JPS6411116A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1994-04-22 | 1994-10-22 | 1995-04-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1998-04-22 | 1998-10-22 | 1999-04-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2002-04-22 | 2002-10-22 | 2003-04-23 | $7700.00 | Window Closed / Lapsed |