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Patent US4536554 - Hydrophilic polymers and contact lenses made therefrom - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsAn interpenetrating network polymer is obtained by mixing hydrophilic monomer vinyl pyrrolidone and hydrophobic monomer (5-alkylene-m-dioxanyl) acrylic ester in the presence of at least two crosslinking agents and, optionally, hydroxyalkyl acrylic ester and catalysts and causing polymerization to occur....http://www.google.com/patents/US4536554?utm_source=gb-gplus-sharePatent US4536554 - Hydrophilic polymers and contact lenses made therefromAdvanced Patent SearchPublication numberUS4536554 APublication typeGrantApplication numberUS 06/582,362Publication dateAug 20, 1985Filing dateFeb 22, 1984Priority dateFeb 22, 1984Fee statusLapsedAlso published asCA1242299A1, DE3579014D1, EP0154270A2, EP0154270A3, EP0154270B1Publication number06582362, 582362, US 4536554 A, US 4536554A, US-A-4536554, US4536554 A, US4536554AInventorsChidambar L. Kulkarni, Drahoslav Lim, Dennis A. RepellaOriginal AssigneeBarnes-Hind, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (4), Referenced by (31), Classifications (16), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetHydrophilic polymers and contact lenses made therefromUS 4536554 AAbstract An interpenetrating network polymer is obtained by mixing hydrophilic monomer vinyl pyrrolidone and hydrophobic monomer (5-alkylene-m-dioxanyl) acrylic ester in the presence of at least two crosslinking agents and, optionally, hydroxyalkyl acrylic ester and catalysts and causing polymerization to occur. Contact lenses made from the polymer have high tensile strength and can absorb a high degree of water.
What is claimed is: 1. A contact lens comprised of an interpenetrating network polymer comprising(a) hydrophilic vinyl pyrrolidone, 50-80% by weight; (b) a first crosslinking agent having an affinity for hydrophilic vinyl pyrrolidone, 0.1-1.0% by weight; said first crosslinking agent being 3,3'-ethylidine-bis (N-vinyl-2-pyrrolidone), diallyl itaconate, diallyl maleate, diallyl fumarate, dimethallyl fumarate, dimethallyl maleate, diallyl diglycollate, diethylene glycol bis (allyl carbonate), diallyl oxalate, diallyl adipate, diallyl succinate, diallyl azelate, divinyl benzene, divinyl adipate, or divinylethers; (c) (5-alkylene-m-dioxanyl)acrylic ester, 10-45% by weight, having the formula ##STR2## wherein R and R.sub.1 are independently H or C.sub.1 -C.sub.4 alkyl,R.sub.2 and R.sub.3 are independently H, C.sub.1 -C.sub.4 alkyl, or phenyl, and n is an integer from 1-4; (d) hydroxyalkyl acrylic ester, 0-20% by weight; (e) a second crosslinking agent having an affinity for acrylic esters of (c) and (d), 0.1-2% by weight, said agent being neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,6-hexane diol dimethacrylate, glycerol trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, trimethylol propane trimethyacrylate, allylmethacrylate, or corresponding acrylates. 2. A contact lens of claim 1 wherein(a) is N-vinyl-2-pyrrolidone; (c) has the formula whereinR is methyl, n is 1, R.sub.1 is methyl, R.sub.2 and R.sub.3 are H, being (5-methyl-5-m-dioxanyl)methyl methacrylate; and (d) is 2-hydroxyethyl methacrylate. 3. A contact lens of claim 2 wherein (b) is 3,3'-ethylene-bis (N-vinyl-2-pyrrolidine) and (e) is neopentyl glycol dimethacrylate.
The most important component for overall mechanical properties of the polymer is the hydrophobic monomer of a (5-alkylene-m-dioxanyl) acrylic ester which is disclosed in U.S. Pat. No. 3,267,084. This class of monomer has the formula ##STR1## wherein R and R.sub.1 are independently H or C.sub.1 -C.sub.4 alkyl,
R.sub.2 and R.sub.3 are independently H, C.sub.1 -C.sub.4 alkyl, or phenyl, and
The polymerization is generally carried out at temperatures from about room temperature to about 145 the polymerization at relatively low temperatures such as from about 45 110 post-curing is done at about 140
EXAMPLE 1 A polymerization mixture was prepared by mixing 96 parts vinyl-2-pyrrolidone, 56 parts (5-methyl 5-m-dioxanyl) methylmethacrylate, 8 parts HEMA, 0.64 parts 3,3'-ethylidene bis (N-vinyl-2-pyrrolidone), 0.48 parts neopentyl glycol dimethacrylate and organic peroxide initiators, 0.048 parts t-butyl peroxy neodecanoate, 0.048 parts t-butylperoctoate and 0.128 parts t-butylperbenzoate and then poured into polypropylene stationary molds. These molds were placed in a vacuum oven and evacuated. Then it was backfilled with nitrogen. This process was repeated two more times.
The copolymerization was effected by initially heating the mixture to about 40 completed by heating for 6 hours at 80 C. and then heating for another hour at 130 polymerization was completed, lens blanks were removed from the molds and were post-cured at 140 atmosphere. The lens obtained was clear and had excellent mechanical and optical properties and had a water content of 65% at osmotic equilibrium.
The hydrogel had Young's modulus of 10.1.times.10.sup.6 dynes/cm.sup.2 and ultimate tensile strength of 10.1.times.10.sup.6 dynes/cm.sup.2.
EXAMPLE 2 26 parts N-vinyl-2-pyrrolidone, 12 parts (5-methyl-5-m-dioxanyl) methyl methacrylate, 2 parts HEMA, 0.24 parts 3,3'-ethyledine-bis (N-vinyl-2-pyrrolidone), 0.12 parts neopentyl glycol dimethacrylate, 0.012 parts t-butyl peroxy neodecanoate, 0.012 parts t-butylperoctoate and 0.08 parts t-butyl-perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 1.
EXAMPLE 3 28 parts of N-vinyl-2-pyrrolidone, 4 parts (5-methyl-5-m-dioxanyl) methyl methacrylate, 8 parts HEMA, 0.26 parts 3,3'-ethylidene-bis (N-vinyl-2-pyrrolidone), 0.1 parts neopentyl glycol dimethacrylate, 0.012 parts t-butyl-peroxy neodecanoate, 0.012 parts t-butyl peroctoate and 0.08 t-butyl perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 1, except that the heating cycle was as follows. Initially, the mixture was heated at 40 heating for 2 hours at 80 hours at 130
EXAMPLE 4 22 parts N-vinyl-2-pyrrolidone, 16 parts (5-methyl-5-m-dioxanyl) methyl methacrylate, 2 parts HEMA, 0.2 parts 3,3'-ethylidene-bis (N-vinyl-2-pyrrolidone), 0.15 parts neopentyl glycol dimethacrylate, 0.016 parts t-butyl peroxy neodecanoate, 0.016 parts t-butyl peroctoate, and 0.032 parts t-butyl perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 1.
The hydrogel had Young's molulus of 42.9.times.10.sup.6 dynes/cm.sup.2 and ultimate tensile strength of 18
EXAMPLE 5 12 parts N-vinyl-2-pyrrolidone, 5 parts (5-methyl-5-m-dioxanyl) methylmethacrylate, 3 parts HEMA, 0.08 parts 3,3'-ethylidene-bis(N-vinyl-2-pyrrolidone), 0.08 parts neopentyl glycol dimethacrylate, 0.016 par t-butyl peroxy neodeconoate, and 0.016 parts t-butyl peroctoate were mixed and then poured into the polypropylene circular molds and polymerized.
The copolymerization was effected by initially heating the mixture to about 50 heating was carried out at 87 107
EXAMPLE 6 24 parts N-vinyl-2-pyrrolidone, 12 parts (5-methyl-5-m-dioxanyl) methyl methacrylate, 4 parts HEMA, 0.16 parts 3,3'-ethylidene-bis(N-vinyl-2-pyrrolidone), 0.12 parts neopentyl glycol dimethacrylate, 0.012 parts t-butyl peroxy neodecanote, 0.012 parts t-butyl peroctoate and 0.032 parts t-butyl perbenzoate were mixed and then poured into polypropylene circular molds and polymerized under nitrogen atmosphere. The polymerization was effected by initially heating the mixture to about 45 heating for 6 hours at 83 C. and 1 hour at 130 completed, lens blanks were removed from the molds and were post cured at 140
The hydrogel had Young's molulus of 7.64.times.10.sup.6 dynes/cm.sup.2 and ultimate tensile strength of 10.21.times.10.sup.6 dynes/cm.sup.2.
EXAMPLE 7 24.8 parts N-vinyl-2-pyrrolidone, 13.2 parts (5-methyl-5-m-dioxanyl)methyl methacrylate, 2 parts HEMA, 0.16 parts 3,3'ethylidene bis (N-vinyl-2-pyrrolidone), 0.12 parts neopentyl glycol dimethacrylate, 0.012 parts t-butyl peroxy neodecanoate, 0.012 parts t-butyl peroctoate, and 0.032 parts t-butyl perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 6.
The hydrogel had Young's modulus of 6.16.times.10.sup.6 dynes/cm.sup.2 and ultimate tensile strength of 9.07.times.10.sup.6 dynes/cm.sup.2.
EXAMPLE 8 25.2 parts N-vinyl-2-pyrrolidone, 12.8 parts (5-methyl-5-m-dioxanyl)methyl methacrylate, 2 parts HEMA, 0.16 parts 3,3'-ethylidene bis(N-vinyl-2-pyrrolidone), 0.12 parts neopentyl glycol dimethacrylate, 0.012 parts t-butyl peroxy neodecanoate, 0.012 parts t-butyl peroctoate and 0.032 parts t-butyl perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 6.
The hydrogel had Young's modulus of 6.25.times.10.sup.6 dynes/cm.sup.2 and ultimate tensile strength of 7.27.times.10.sup.6 dynes/cm.sup.2.
EXAMPLE 9 24 parts N-vinyl-2-pyrrolidone, 12.8 parts (5-methyl-5-m-dioxanyl)methyl methacrylate, 3.2 parts HEMA, 0.16 parts 3,3'-ethylidene bis(N-vinyl-2-pyrrolidone), 0.12 parts neopentyl glycol dimethacrylate, 0.012 parts t-butyl peroxyneodecanoate, 0.012 parts t-butyl peroctoate and 0.032 parts t-butyl perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 6.
The hydrogel had Young's modulus of 11.80.times.10.sup.6 dynes/cm.sup.2 and ultimate tensile strength of 9.74.times.10.sup.6 dynes/cm.sup.2.
EXAMPLE 10 18 parts N-vinyl-2-pyrrolidone, 12 parts (5-methyl-5-m-dioxanyl) methyl methacrylate, 0.12 parts, 3,3-ethylidene bis (N-vinyl-2-pyrrolidone), 0.12 parts neopentyl glycol dimethacrylate, 0.009 parts t-butyl peroxyneodecanoate, 0.009 parts t-butyl peroctoate and 0.024 parts t-butyl perbenzoate were mixed and then poured into the polypropylene circular molds and polymerized as described in Example 6.
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