USRE31422E - Hydrophilic polymers and contact lenses of high water content - Google Patents
Hydrophilic polymers and contact lenses of high water content Download PDFInfo
- Publication number
- USRE31422E USRE31422E US06/328,961 US32896181A USRE31422E US RE31422 E USRE31422 E US RE31422E US 32896181 A US32896181 A US 32896181A US RE31422 E USRE31422 E US RE31422E
- Authority
- US
- United States
- Prior art keywords
- monomer
- vinyl
- iadd
- cross
- iaddend
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 52
- 229920001477 hydrophilic polymer Polymers 0.000 title description 11
- 239000000178 monomer Substances 0.000 claims abstract description 134
- 238000004132 cross linking Methods 0.000 claims abstract description 49
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 27
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003440 styrenes Chemical class 0.000 claims abstract description 10
- 230000035699 permeability Effects 0.000 claims description 21
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- VVYDVQWJZWRVPE-UHFFFAOYSA-L dimethyltin(2+);diiodide Chemical group C[Sn](C)(I)I VVYDVQWJZWRVPE-UHFFFAOYSA-L 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 5
- XXVUSJBWYAWVQV-UHFFFAOYSA-N 1-ethenylpiperidine-2,6-dione Chemical compound C=CN1C(=O)CCCC1=O XXVUSJBWYAWVQV-UHFFFAOYSA-N 0.000 claims description 5
- VOCDJQSAMZARGX-UHFFFAOYSA-N 1-ethenylpyrrolidine-2,5-dione Chemical compound C=CN1C(=O)CCC1=O VOCDJQSAMZARGX-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 4
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 claims 3
- 239000002954 polymerization reaction product Substances 0.000 claims 3
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims 2
- 125000005399 allylmethacrylate group Chemical group 0.000 claims 1
- 238000012662 bulk polymerization Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 39
- 239000000499 gel Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 210000004087 cornea Anatomy 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical class 0.000 description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 4
- 230000004304 visual acuity Effects 0.000 description 4
- KAUVYPZCBVZESR-UHFFFAOYSA-N 2-methylidene-4-oxo-4-prop-2-enoxybutanoic acid Chemical compound OC(=O)C(=C)CC(=O)OCC=C KAUVYPZCBVZESR-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000002503 metabolic effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- FPODCVUTIPDRTE-UHFFFAOYSA-N bis(prop-2-enyl) hexanedioate Chemical compound C=CCOC(=O)CCCCC(=O)OCC=C FPODCVUTIPDRTE-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- -1 dimethallyl maleate Chemical compound 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 210000003813 thumb Anatomy 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- IZMZREOTRMMCCB-UHFFFAOYSA-N 1,4-dichloro-2-ethenylbenzene Chemical class ClC1=CC=C(Cl)C(C=C)=C1 IZMZREOTRMMCCB-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 1
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical class CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical class COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 208000028006 Corneal injury Diseases 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 206010047513 Vision blurred Diseases 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- HABAXTXIECRCKH-UHFFFAOYSA-N bis(prop-2-enyl) butanedioate Chemical compound C=CCOC(=O)CCC(=O)OCC=C HABAXTXIECRCKH-UHFFFAOYSA-N 0.000 description 1
- XZPPRVFUMUEKLN-UHFFFAOYSA-N bis(prop-2-enyl) nonanedioate Chemical compound C=CCOC(=O)CCCCCCCC(=O)OCC=C XZPPRVFUMUEKLN-UHFFFAOYSA-N 0.000 description 1
- 230000004397 blinking Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- USWYBRHUMHQHAG-UHFFFAOYSA-N dodecanoyl dodecaneperoxoate [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound C(CCCCCCCCCCC)(=O)OOC(CCCCCCCCCCC)=O.CC(C)(CCC(C)(OOC(C(CCCC)CC)=O)C)OOC(C(CCCC)CC)=O USWYBRHUMHQHAG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 210000005224 forefinger Anatomy 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004247 hand Anatomy 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Definitions
- gas permeability refers broadly to air, oxygen and carbon dioxide permeability. It has been found, that the gas permeability increases with increasing water content of the hydrophilic polymer from which the contact lens is formed. The increased gas permeability makes possible increased wearing time with increased comfort and absence of most of the undesirable physiological symptoms produced by conventional lens wear.
- Polymers of the prior art which are of sufficiently high water content to give high gas permeabilities, e.g., about 60%-95% by weight of the combined weight of polymer plus water, and especially above about 70% water content, are very weak and are readily torn or otherwise physically damaged during handling.
- Such polymers are exemplified in British Pat. No. 1,391,438 and U.S. Pat. Nos. 3,639,524 and 3,943,045.
- the polymers are prepared from monomer compositions which contain a relatively high amount of cross-linking monomer, the latter being required to prevent the hydrophilic polymer from substantially dissolving in aqueous media. This excessive cross-linking frequently results in a weak polymer.
- hydrophilic polymers and contact lenses made therefrom which are of high water content, high strength, good durability, high gas permeability and which can be repeatedly disinfected or sterilized by thermal means without deterioration or destruction or impairment of their optical properties.
- Novel hydrophilic polymers and hydrophilic contact lenses made therefrom are provided, which lenses are suitable for extended wear times because they are sufficiently permeable to oxygen to provide for the metabolic needs of the cornea.
- the lenses can have up to 95% water content with excellent strength and optical properties and high gas permeability.
- hydrophilic polymers and contact lenses made therefrom although sufficiently flexible to provide patient comfort are stiffer than those of the prior art for the same water content, thereby providing improved visual acuity, strength, and durability while retaining the same high level of oxygen permeability.
- the present invention comprises cross-linked interpolymers, and contact lenses made therefrom, comprising hydrophilic units derived from .Iadd.vinyl pyridine or .Iaddend.N-vinyl heterocyclic monomers, units derived from hydrophobic monomers taken from the group consisting of styrene and ring substituted styrenes, and cross-linking units derived from monomers containing two or more polymerizable double bonds per monomer unit.
- the preferred .Iadd.hydrophilic .Iaddend.N-vinyl heterocyclic monomer is N-vinyl pyrrolidone and, optionally, other hydrophilic monomers can be used with the N-vinyl .[.heterocyclic monomer.]. .Iadd.pyrrolidone .Iaddend.as long as the N-vinyl pyrrolidone is present in major amount.
- Styrene is the preferred hydrophobic monomer and diallyl itaconate the preferred cross-linking monomer.
- Contact lenses such as corneal contact lenses, are made by shaping the hydrophilic polymer in the dry state using conventional and well-known procedures and apparatus and thereafter hydrating the dry lens to the final configuration.
- FIG. 1 is a graph showing the hardness of polymers of the present invention at various water contents as compared to polymers of the prior art.
- the hydrophilic interpolymer is made by polymerizing the monomeric ingredients in bulk (with no solvent), preferably in a container such that the resultant interpolymer will be in the form of a solid rod from which can be sliced cylindrical buttons or other convenient shape, the buttons or other shape shaped on a lathe, thereafter polished to form a contact lens, and then the contact lens hydrated in an aqueous medium such as a normal saline solution.
- the invention provides improved interpolymers and contact lenses made therefrom which in the water content range of 65%-95% are flexible and much stronger than prior art hydrophilic polymers of this high water content. Interpolymers of less than 65% water content can be made by increasing the hydrophobic monomer proportion and correspondingly decreasing the hydrophilic monomer proportion however, the gas permeability of such lenses becomes limiting.
- the interpolymers contain hydrophilic units, the major proportion of said units being derived from .Iadd.vinyl pyridine or .Iaddend. heterocyclic N-vinyl monomers, hydrophobic units derived from hydrophobic monomers from the group consisting of styrene and ring substituted styrenes and cross-linking monomers containing more than one polymerizable double bond therein.
- hydrophilic units present in major proportion are derived from the .Iadd.vinyl pyridine or .Iaddend.N-vinyl heterocyclic monomer, lesser amounts of hydrophilic units derived from other hydrophilic monomers may be added to modify the properties of the interpolymer.
- the specific monomers and their ranges are more fully described below.
- Suitable hydrophilic .[.N-vinyl heterocyclic.]. monomers are N-vinyl pyrrolidones, N-vinyl succinimide, N-vinyl- ⁇ -caprolactam .[.N-.]. vinyl .[.pyrridine.]. .Iadd.pyridine .Iaddend.and N-vinyl glutarimide.
- the preferred hydrophilic N-vinyl heterocyclic monomer is N-vinyl-2 pyrrolidone. The foregoing may be used alone or in combination.
- the concentration (percent by weight based on the total monomer weight exclusive of cross-linking monomer) of N-vinyl heterocyclic monomers used in the hydrophilic interpolymer will depend on the water content desired in the swollen gel at equilibrium and the amounts of cross-linking monomers used.
- a hydrophobic monomer such as styrene
- the .Iadd.vinyl pyridine or .Iaddend.N-vinyl heterocyclic monomer will range from about 75% for about a 65% water content gel, to about 95% for about a 95% water content gel.
- a minor portion of the .Iadd.vinyl pyridine or .Iaddend.N-vinyl heterocyclic may be substituted with other hydrophilic monomers for specific property modifications of the interpolymer.
- Suitable auxiliary hydrophilic monomers include the hydroxy alkyl esters of acrylic and methacrylic acids, such as hydroxyethyl acrylate and methacrylate and hydroxypropyl methacrylate, acrylic, methacrylic, itaconic, fumaric, maleic, and crotonic acids and other olefinic acids which can be copolymerized by free radical mechanism with the other monomers in the interpolymer.
- the use of small amounts of copolymerizable acids, e.g., up to 5% has been found to sharply increase the water content of the interpolymer.
- the upper amount of such acids which may be used will be limited by their compatibility with the styrenic hydrophobic monomer. Incompatibility is evidenced as excessive haze in the final interpolymer.
- cross-linking monomers may be employed in preparing the interpolymers of the invention.
- One class of suitable cross-linking monomers are the methacrylates and acrylates with two or more polymerizable double bonds in the monomer molecule, such as ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylates, bisphenol A bismethacrylate, trimethylol propane trimethacrylate, glycerol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate and the corresponding acrylates.
- Suitable cross-linking monomers are the allyl monomers with two or more polymerizable allyl bonds in the monomer molecule, such as diallyl itaconate, diallyl maleate, diallyl fumarate, dimethallyl maleate, diallyl diglycollate, diethylene glycol bis (allyl carbonate), triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, N,N diallyl melamine, multifunctional allyl monomers formed by the esterification of polybasic acids with allyl alcohol, examples of the latter esters being dially oxalate, diallyl adipate, diallyl succinate, diallyl azelate, diallyl phthalate and diallyl isophthalate.
- cross-linking monomers are the mixed allyl-acrylic or allyl-methacrylic types, examples of which are, diallyl itaconate, monoallyl itaconate, allyl methacrylate and allyl acrylate.
- Other suitable cross-linking monomers are methylene bis-acrylamide, methylene bis-methacrylamide and divinyl benzene.
- the preferred cross-linking monomers are diallyl itaconate and allyl methacrylate. Mixtures of the foregoing cross-linking monomers may be used without departing from the scope of the invention.
- the concentration of cross-linking monomers used in the interpolymer will depend partly on its efficiency.
- the efficiency as used herein, is characterized by the amount of cross-linking monomer employed to produce a cross-linked structure which is not excessively dissolved away in its aqueous environment. The lower the amount of cross-linker required to provide this non-dissolving structure, the greater is considered to be its efficiency.
- a suitable measure of efficiency is provided by measuring the percentage by weight of material which is extracted from the cross-linked interpolymer in an aqueous extracting medium, under some standard conditions of temperature and time.
- An experimental procedure for evaluating such polymeric gels is set forth below and consists of carrying out successive extractions on the same sample and measuring the percentage of weight loss after each extraction.
- the weight loss should approach zero after a few such extractions. If the extractibles from a given gel do not approach zero, then it can be expected that the contact lens made from such a material will gradually waste away since at all times in use it is being exposed to an aqueous medium whether in storage or in the eye.
- Polymers with extractibles as high as 50%-60% may be suitable provided that the state of zero extraction is reached.
- the amount of cross-linking monomer employed will also depend on the water content desired in the final interpolymer. The water content is decreased with increasing amounts of cross-linking monomer.
- cross-linking monomers of higher efficiency which can be used to give insoluble polymer networks at low concentrations are preferred over the cross-linking monomers of lower efficiency.
- the type and amount of cross-linking monomer is but one of the variables of composition which determine the properties of the final interpolymer so that selection of their type and amount is not exclusive of the other components of the interpolymer.
- concentrations (percent by weight based on the total weight of monomers exclusive of cross-linking monomer) of cross-linking monomers may range from about 0.01% to about 5% depending on the water content desired. However, a preferred range is 0.01% to 1%.
- the principal hydrophobic monomers employed in the interpolymer of the invention are selected from the group consisting of styrene and ring substituted styrenes. Suitable examples are styrene, vinyl toluene, p-methyl styrene, o-methyl styrene, other monoalkyl and dialkyl ring substituted styrenes, chlorostyrene, 2,5-dichlorostyrene, methoxy styrenes and ethoxy styrenes. Mixtures of the aforesaid may be used. Styrene is the preferred hydrophobic monomer.
- styrenic hydrophobic monomers may be substituted with other polymerizable hydrophobic monomers without departing from the scope of the invention.
- examples of such other monomers are the alkyl esters of methacrylic and acrylic acids. It is emphasized that the unusual strength of the high water content interpolymers of the present invention, are distinctive and are the result of the use of the styrene monomers as the major hydrophobic monomer component, which must be present in sufficient amount to provide the unique interpolymers.
- these interpolymers and contact lenses made therefrom while adequately flexible for patient comfort are less flexible than prior art polymers of the same water content.
- the lower flexibility at high water content provides for better visual acuity as well as strength and durability.
- the improved visual acuity may result from the fact that the lens on the cornea does not flex as easily during blinking thereby preventing blurred vision.
- the foregoing unexpected improvement in properties are obtained without sacrifice in oxygen permeability.
- FIG. 1 The differences between the polymers of the present invention and those of the prior art are clearly demonstrated in FIG. 1.
- the Type A-2 Durometer hardness measured in accordance with ASTM D-2240-68 on a Shore hardness tester is plotted against water content. It has been found that the Durometer hardness and the flexibility of the polymer correlate well, the lower the Durometer number, the greater the flexibility.
- Curve A was obtained from measurements on polymers of the present invention containing 0.15% cross-linking monomer while Curve B is obtained from measurements on polymers typical of the prior art with the same level of cross-linking.
- the prior art polymers are based on copolymers of vinyl pyrrolidone and methyl methacrylate. It is readily seen, that at the same water content Curve A is representative of polymers with lower flexibility. In spite of this, the oxygen permeability at the same water content does not differ.
- the interpolymer contains about the maximum amount of hydrophobic monomer consistent with the water content of the interpolymer, i.e., the cross-linking monomer is kept as low as is practical.
- the interpolymer contains about 25% for a water content of about 65% and about 5% for a water content of about 95% for cross-linking monomer contents in the range of about 0.01 to 0.5%.
- other ring substituted styrene monomers are used, adjustments are made in the amounts depending on the hydrophobicity of the particular substituted styrene.
- vinyl toluene is used in sightly smaller amounts to produce an interpolymer of like water content.
- the interpolymers of the invention are formed by the use of conventional free radical polymerization procedures.
- Typical free radical initiators can be used. Examples are benzoyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, (2,5-dimethyl-2,5-bis(2-ethyl hexoyl peroxy) hexane) lauroyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, diisopropyl peroxydicarbonate, t-buty-peroxypivalate, and the like.
- the amounts employed are conventional and are such as to give a controlled polymerization at conventional polymerization temperatures.
- the polymerization method and conditions, as well as the apparatus are conventionally employed and detailed discussion is not deemed necessary. Moreover, these conditions are not intended to limit the scope of the present novel polymers and contact lenses.
- the contact lenses can be formed from the unhydrated hydrophilic polymer by any of the conventional lens lathing and polishing processes, followed by any of the conventional hydration procedures used in this art.
- Cylindrical discs of 0.4 inch ⁇ 0.05 inch thickness were cut from each rod and sanded smooth.
- the weighed discs (dry weight) were placed in an aqueous hydration medium at 95° C. for four hours, then cooled to room temperature.
- the discs were then placed in an aqueous medium for seven days, whereupon the wet weight of the discs was determined. After drying at 110° C. overnight the discs were weighed again to give the redry weight.
- the water content in percent is calculated from 100X (wet wt.--redry wt.)/(wet wt.) and the extractible in percent is given by 100X (dry wt.--redry wt.)/(dry wt.).
- the hydration-extractions were repeated until no further substantial weight loss occurred, usually two or three extractions.
- Hand pull tests were performed on hydrated contact lenses of 0.2 mm center thickness and 14 mms diameter.
- the lens was grasped by both hands between thumb and forefinger so that there was about a 7 mm distance between the thumbs.
- the lens was pulled over a scale graduated in mms and the elongation at break noted.
- the percent elongation is the ratio of the final length over the original length multiplied by 100.
- the control lens was a commercial gel lens of the polyhydroxyethyl methacrylate type (tradename DuraSoft) of 0.2 mm center thickness and 30% water content. Its strength rating is 10 on a scale of 0 to 10 which corresponds to about 10 kg/cm 2 tensile strength and its elongation at break is about 400%. Lenses with strength ratings of at least about 2-3 are desirable for practical use.
- the lenses made from the polymers of the invention are strong but have relatively low extensibilities. The lower extensibility is not a disadvantage with lenses of such high strength.
- ASTM method No. D-2240-68 was used. Measurements were made on a shore hardness tester and the instantaneous value utilized.
- composition of polymers is given in percent by weight of the monomers in the interpolymers exclusive of the cross-linking monomer.
- amount of cross-linking monomer is in percent by weight based on 100 parts of the polymer exclusive of the cross-linking monomer.
- a polymer consisting of 90 parts vinyl pyrrolidone, 10 parts of vinyl toluene and 0.5 parts of divinyl benzene was made and tested according to the procedures set forth above.
- the hydrated polymer gave an 80% water content and 18% extractibles.
- the polymer was used to make hydrophilic contact lenses which were of good quality.
- Example 20 The experiment of Example 20 was repeated except that the vinyl toluene was replaced with an equal weight of styrene.
- the hydrated polymer gave a water content of 81% and 16% extractibles.
- the hydrated lens made from it was of good quality and slightly greater clarity than that of Example 20.
- a polymer consisting of 82 parts of vinyl pyrrolidone, 18 parts of styrene and one part of divinyl benzene was made according to the procedure set forth above.
- the hydrated polymer gave a water content of 60% and 16% extractibles and a satisfactory hydrated contact lens was made therefrom.
- Example 22 was repeated except that two parts of the styrene were replaced with two parts of methyl methacrylate.
- the hydrated polymer gave a water content of 66% and 22% extractibles. This demonstrates that the small amount of methyl methacrylate reduced the hydrophobic effect of the styrene.
- the hydrophilic contact lens made from the polymer of this example was of slightly lower strength than that of Example 22, but was satisfactory.
- Example 16 was repeated in preparing a series of polymers except that the methacrylic acid was replaced, separately and in turn, with an equal weight of acrylic acid, itaconic acid, maleic anhydride, crotonic acid, and fumaric acid. In each case, hydrated polymer of similar properties was obtained.
- Example 4 was repeated except that 10 parts of the vinyl pyrrolidone was replaced with an equal weight of hydroxyethyl methacrylate. A suitable polymer of slightly higher water content and slightly lower strength was obtained.
- Example 4 was repeated in preparing two polymers except that the diallyl itaconate was successively replaced with an equal weight of monoallyl itaconate and a mixture of 80% diallyl itaconate and 20% monoallyl itaconate. Suitable hydrated polymers were obtained in each instance.
- Example 4 was repeated in preparing a series of polymers with the exception that the vinyl pyrrolidone was replaced, separately and in turn, with an equivalent weight of N-vinyl succinimide, N-vinyl- ⁇ -caprolactam, .[.N-.]. vinyl pyridine, and N-vinyl glutarimide. Suitable hydrophilic polymers were obtained in each case.
- Example 12 was repeated with the exception that 0.5 parts of diallyl itaconate was replaced, separately and in turn, with an equal weight of ethylene glycol dimethacrylate, 1,6 hexanediol diacrylate, diallyl maleate, dially diglycollate, triallyl cyanurate, N,N diallyl melamine, methylene bis acrylamide, diallyl adipate, and diallyl phthalate. In all instances, similar suitable polymers were obtained.
- a pair of contact lenses of appropriate base curve radius, diameter and optometric specifications was prepared from the composition of Example 4 by lathing.
- the lenses were hydrated according to the procedure described above.
- the resulting lenses when placed on a patient's eyes provided excellent comfort and vision, and after proper adaptation, the lenses could be worn continuously for up to several weeks without removing them.
- Example 7 is repeated with the exception that the vinyl pyrrolidone content used is 75% by weight and the styrene content is 25% by weight.
- a hydrated lens is made from this copolymer.
- the lens has a water content of 65% and an oxygen permeability of about ##EQU2##
- the lens is fairly rigid and strong and cannot be pulled apart by application of the hand test.
Abstract
Description
TABLE I __________________________________________________________________________ Water Composition % Content (% by Wt.) % Strength Extensi- Examples % VP STY DAI MAA AMA Permeability Extr..sup.1 Rating bility __________________________________________________________________________ 1 95 95 5 0.15 0 0 52 12 3 80 2 90 90 10 0.05 0 0 47 17 3 40 3 60 95 5 3.00 0 0 14 7 5 <40 4 85 90 10 0.20 0 0 39 18 5 40 5 85 87.5 12.5 0.10 0 0 39 11 5 40 6 83 85 15 0.10 0 0 35 13 6-7 40 7 81 85 15 0.15 0 0 33 8 7 <40 8 80 90 10 0.50 0 0 31 15 7 <40 9 77 80 20 0.10 0 0 28 8 9 <40 10 74 90 10 1.00 0 0 24 15 6 <40 11 68 85 15 1.00 0 0 19 20 7 <40 12 82 90 10 0 0 0.50 34 9 6 40 13 80 84 16 0 0 0.20 31 11 7 <40 14 74 90 10 0 0 1.00 24 10 6 <40 15 70 85 15 0 0 1.00 20 12 7 <40 16 81 77 20 0.10 3 0 33 10 7 <40 17 88 83 15 0.10 2 0 44 10 3-4 40 18 79 78 20 0.10 1 0 30 12 7 <40 19 78 79 20 0.10 1 0 31 11 8 <40 __________________________________________________________________________ .sup.1 Percent by weight extracted from the polymer usually after three extractions; no substantial increase in extractibles was noted between th last and nextto-last extraction.
Claims (13)
Priority Applications (1)
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US06/328,961 USRE31422E (en) | 1977-12-27 | 1981-12-09 | Hydrophilic polymers and contact lenses of high water content |
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US05/864,275 US4182802A (en) | 1977-12-27 | 1977-12-27 | Hydrophilic polymers and contact lenses of high water content |
US06/328,961 USRE31422E (en) | 1977-12-27 | 1981-12-09 | Hydrophilic polymers and contact lenses of high water content |
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US05/864,275 Reissue US4182802A (en) | 1977-12-27 | 1977-12-27 | Hydrophilic polymers and contact lenses of high water content |
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