CA2001969C - Polysiloxane-polyurethanes and contact lenses thereof - Google Patents
Polysiloxane-polyurethanes and contact lenses thereof Download PDFInfo
- Publication number
- CA2001969C CA2001969C CA002001969A CA2001969A CA2001969C CA 2001969 C CA2001969 C CA 2001969C CA 002001969 A CA002001969 A CA 002001969A CA 2001969 A CA2001969 A CA 2001969A CA 2001969 C CA2001969 C CA 2001969C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- polysiloxane
- urethane
- prepolymer
- groups
- 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 - Fee Related
Links
- 239000004814 polyurethane Substances 0.000 title abstract description 13
- 229920002635 polyurethane Polymers 0.000 title abstract description 9
- -1 polysiloxane Polymers 0.000 claims abstract description 60
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 51
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 6
- 239000003937 drug carrier Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- SXHIHQWBQIQESC-UHFFFAOYSA-N ethyl N-silylcarbamate Chemical compound CCOC(=O)N[SiH3] SXHIHQWBQIQESC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- ODKSRULWLOLNJQ-UHFFFAOYSA-N 1,2-diisocyanatocyclohexane Chemical compound O=C=NC1CCCCC1N=C=O ODKSRULWLOLNJQ-UHFFFAOYSA-N 0.000 claims description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 claims description 2
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 claims description 2
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 claims description 2
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- UIXGIVWFAFVOFU-UHFFFAOYSA-N 2,3-diisocyanatonaphthalene Chemical compound C1=CC=C2C=C(N=C=O)C(N=C=O)=CC2=C1 UIXGIVWFAFVOFU-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- FVJRDQJIINHISA-UHFFFAOYSA-N 5,5-dichloro-4-isocyanato-1-(4-isocyanatophenyl)cyclohexa-1,3-diene Chemical group C1=C(N=C=O)C(Cl)(Cl)CC(C=2C=CC(=CC=2)N=C=O)=C1 FVJRDQJIINHISA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- GKOZKEKDBJADSV-UHFFFAOYSA-N disilanol Chemical compound O[SiH2][SiH3] GKOZKEKDBJADSV-UHFFFAOYSA-N 0.000 claims 4
- 229920001477 hydrophilic polymer Polymers 0.000 claims 3
- 229920001600 hydrophobic polymer Polymers 0.000 claims 3
- 229920000307 polymer substrate Polymers 0.000 claims 3
- 238000007334 copolymerization reaction Methods 0.000 claims 2
- 229920001228 polyisocyanate Polymers 0.000 claims 2
- RQBUVIFBALZGPC-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenyl)benzene Chemical group C1=CC(N=C=O)=CC=C1C1=CC=C(N=C=O)C=C1 RQBUVIFBALZGPC-UHFFFAOYSA-N 0.000 claims 1
- FIZISCYJKFWLRW-UHFFFAOYSA-N 2,7-diisocyanato-1-methylnaphthalene Chemical compound C1=C(N=C=O)C=C2C(C)=C(N=C=O)C=CC2=C1 FIZISCYJKFWLRW-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000013271 transdermal drug delivery Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 11
- 229920002379 silicone rubber Polymers 0.000 description 10
- 239000004945 silicone rubber Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WDRCWISGZGOZPY-UHFFFAOYSA-N [dihydroxy(methyl)silyl]oxy-[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(O)O WDRCWISGZGOZPY-UHFFFAOYSA-N 0.000 description 2
- QLTIQRMARFXIDD-UHFFFAOYSA-N [dihydroxy(methyl)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(O)O QLTIQRMARFXIDD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- DTLIXPLJFCRLJY-UHFFFAOYSA-N 1-(1-aminocyclooctyl)cyclooctan-1-amine Chemical compound C1CCCCCCC1(N)C1(N)CCCCCCC1 DTLIXPLJFCRLJY-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- PSABUFWDVWCFDP-UHFFFAOYSA-N 2,2-dimethylheptane Chemical compound CCCCCC(C)(C)C PSABUFWDVWCFDP-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- TWIWZGKZQLKCAE-UHFFFAOYSA-N chlorosilyl hypochlorite Chemical class [SiH2](OCl)Cl TWIWZGKZQLKCAE-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
- A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
- A61K9/7038—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer
- A61K9/7046—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds
- A61K9/7069—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. polysiloxane, polyesters, polyurethane, polyethylene oxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
Abstract
A novel polysiloxane polyurethane is described which is obtained by reaction of an isocyanate capped polysiloxane prepolymer with a polysiloxane-disilanol and which contains O-silyl-urethane linkages. The novel polysiloxane-poly-urethanes are useful as oxygen permeable membranes or films, as bandages and drug carriers, for example in transdermal drug delivery, and especially as highly oxygen permeable, soft contact lenses.
Description
,n 2~Q1969 6V-17294/+/CGC 1380 Novel Pol siloxane- of urethanes and Contact Lenses Thereof Silicones occupy an important place in the chemical industry in~a variety of applications ranging from lubricants to sealants. Silicone fluids composed of polydimethylsiloxane combine many useful properties such as excellent thermal stability, chemical inertness, small changes in viscosity with changes in temperature, high oxygen permeability, outstanding shear stability, and excellent lubricity. They have found extensive use as adhesives, sealants, coatings, softeners, lubricants, dispersants, and antifoam agents in non-aqueous systems in industries as diverse as construction, pharmaceuticals, rubber, plastics, textiles, cosmetics, printing and founding.
More recently silicone rubber materials have been used in biomedical products such as artificial organs and contact lenses. The great benefit of silicone to the latter stems from its high permeability to oxygen although this advantage is offset by its intrinsic hydrophobicity. For this reason all present commercial contact lens formulations which incorporate silicone are hard lens formulations which contain it only in limited amounts. It would be highly desirable to produce a contact lens composed entirely of silicone rubber since it offers the highest oxygen permeability of all presently available materials. The enhancement of eye comfort and wearing time would represent a significant improvement in contact lens technology. However, this goalcannot be achieved until the hydrophobic surface of the silicone is rendered hydrophilic by some kind of surface modification, since silicone rubber alone adheres very strongly to the cornea and also rapidly attracts particulate matter.
More recently silicone rubber materials have been used in biomedical products such as artificial organs and contact lenses. The great benefit of silicone to the latter stems from its high permeability to oxygen although this advantage is offset by its intrinsic hydrophobicity. For this reason all present commercial contact lens formulations which incorporate silicone are hard lens formulations which contain it only in limited amounts. It would be highly desirable to produce a contact lens composed entirely of silicone rubber since it offers the highest oxygen permeability of all presently available materials. The enhancement of eye comfort and wearing time would represent a significant improvement in contact lens technology. However, this goalcannot be achieved until the hydrophobic surface of the silicone is rendered hydrophilic by some kind of surface modification, since silicone rubber alone adheres very strongly to the cornea and also rapidly attracts particulate matter.
Silicone rubber is made by crosslinking liquid polysiloxanes.
These rubbers are thermoset polymers which can be made to varying degrees of hardness and elasticity by controlling the degree of crosslinking and the molecular weight of the silicone fluid. Silicone rubber is usually made by vul-canizing polydimethylsiloxane fluids with organic peroxidesat elevated temperatures. Another approach to crosslinking employs hydrosilation in which poly(vinylalkylsiloxanes) are cured with poly(hydridoalkylsiloxanes) in the presence of transition metal catalysts. Silicone rubber has also been formed by chemically reacting, a,W-difunctionalpoly(di-organosiloxanes) with polyfunctional silanes andsiloxanes.
Typically the crosslinking reaction is a condensation which forms a siloxane bond and a volatile by product. Common examples of this type of cure reaction are silanol-alkoxy-silane (French Pat. 1,042,019), silanol-acetoxysilane (L. F.Ceyzeriat and P.Dumonth, German Appl. 1,121,803), silanol-silane (Midland Silicones, Brit.Pat. 804,199), and silanol-silanol (via the corresponding acetone oxime) (E.
Sweet, Dow Corning, Belg.Pat. 614,394.Suitable catalysts for these reactions are amines and carboxylic acid salts of Sn, Pb, Zn, Sb, Fe, Cd, Ba, Ca and Mn .
Organosiloxane isocyanates have been prepared (U. S. Patent 3,179,622) which vulcanize when exposed to moisture. In these cases the isocyanate group is joined to the siloxane through an alkyl group, rendering it unhydrolyzable.
Relatively few reports exist for the curing of silicones via the reaction of a silanol with an isocyanate yielding an 0-silylurethane linkage. This is probably due to the well known hydrolytic instability of this bond. To our knowledge there are no existing reports of a silicone rubber cross-linked by 0-silylurethane bonds that is resistant to hydrolytic decomposition.
The use of silanol terminated polydimethylsiloxanes has been reported in the modification of polysiloxanes with poly-urethanes (Moretto, U.S. Pat. No. 4,202,807) to improve the mechanical properties of the former at elevated temperatures.
No mention was made of the hydrolytic stability of the O-silylurethane bond in these materials. The only other mention of this bond in a polymeric material was made by Kaufman, Muller, and Wegchaupt (U. S. Patent No. 4,292,423in the preparation of organopolysiloxanes for coating purposes.
However, when the claimed organopolysiloxane was prepared entirely through the reaction of siloxanol groups withiso-cyanate groups (Example 1 of this patent), the coating was decomposed by atmospheric moisture and addition of 75 ~ by weight of the polyurethane, Desmodur L, wasnecessary to produce a hydrolytically stable coating.
High hydrolytic susceptibility is a property characteristic of O-silylurethanes since they were first reported by Andrianov, Losev, and Astakhin (Proc. Akad. Sci., USSR, Sect.
Chem 113, 247, [1957]) from the reaction of triethylsilanol and m-toluene-diisocyanate. These authors subsequently described their alcoholysis and hydrolysis (J. General Chem., USSR, 29, 2655, [1959]). This behaviour of 0-silylurethanes has been summarized by Noll in "Chemistry and Technology of Silicones", Academic Press, 1968, pp 99-100.
It has now unexpectedly been discovered, that by reaction of essential equivalent amounts of diisocyanate-capped poly-dialkylsiloxane-polyalkanols and poly-dimethylsiloxane-disilanols, a clear, flexible and elastic siloxane poly-urethane rubber is obtained which is completely resistant to hydrolysis under physiological conditions, despite the fact that half of all urethane groups in the polymer contain the -Si-O-C- bond. This novel polysiloxane-polyurethane is uniquely suited as a biocompatible, oxygen-permeable membrane ,~,, 2oossss or film and especially, as a crosslinked rubber, as a soft contact lens.
It has further been discovered that this polyurethane is uniquely suited to be grafted to polyvinyl alcohol or hydroxy-alkyl cellulose and thereby allows production of a composite.
material not only with excellent optical clarity and the characteristically high permeability to oxygen, but also with high wettability as well.
The instant invention therefore pertains to said novel polysiloxane-polyurethane, to ophthalmic devices thereof, such as contact lenses, to a process for manufacture of said polysiloxane-polyurethane polymers and to the use thereof for making e.g. ophthalmic devices, such as contact lenses. The polymers can be used as oxygen permeable membranes or films, as bandages and drug carriers, for example in transderma.l drug delivery, and especially as highly oxygen permeable, soft contact lenses.
The instant invention pertains to a polymer, suitable for use as an oxygen permeable membrane or an ophthalmic device, having based on total urethane groups 50 to 75 ~k of alkyl-urethane -C-NH-C00-C- groups and 50 to 25 ~ of silyl-urethane -C-NH-COO-Si- groups, which comprises the polymerization product of (a) 80-95 ~ by weight (based on the total polymer) of a poly-isocyanate capped, linear or branched polysiloxane pre-polymer (A), having.a molecular weight of about 1000 to about 10,000 and containing at least one isocyanate group per 3000 molecular weight unit of polysiloxane, said isocyanate groupsbeing attached to the polysiloxane through urethane linkages, said polysiloxane prepolymer having the structure A1, A2 or A3 (which are described in detail below); and :2001969 (b) 20-5 ~ by weight (based on the total polymer) of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) Ra I
HO Si H (B) I
Rb n where n is 2-50, and Ra and Rb are alkyl of 1 to 4 carbon atoms or phenyl. The molecular weight of these terminal silanol groups containing compounds is from about 24Oto about 10000, preferably from about 240 to about 1000.
The linear or branched polysiloxane prepolymer A is of one of the following general structures, A1, A2, or A3:
X-R1 Si0 Si0 Si0 Si-R1-X1 (Al) R2 X1 R1 R2 x2 R2 x ~2)3Si0 Si0 Si0 Si0 Si(R2y3 (A2) R2 X1 i 1 R2 X2 x y2 X-CH2CHCH20(CH2)g Si0 Si- (CHZY3~H2CHCH2 X3 (A3 ) R2 m R2 wherein R1 is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structures 20019x9 -[CH2 ~ HO]pCH2 ~ H- o r -(CHZ)30CH2 ~ HCH2_ wherein R3 is hydrogen or methyl and p is an integer from -1-50; each R2 is independently methyl or phenyl; m is 2 to 50; x1 and x2 are integers from 1 to 500 with the proviso that the sum of xl + x2 is 12 to 1,000; y1 is 0 to 4 and y2 is 2to with the proviso that the respective ratios of xl+x2y1 ( for Al) and x1+x2y2 (for A2) are not greater than 70, yl + 2 y2 H
X 1 s -~-N-R4-NCO ~
O
H H
X1 is X or -~N-R4-NCO-Tl and O O
H H
X 3 i s X o r -~N-R4-N-CO-Tg O O
wherein T1 is A1 from which X1 has been abstracted, T3 is A3 from which X3 has been abstracted, and Rq is a diradical obtained by removing the NCO groups from an aliphatic, cycloaliphatic or aromatic di-isocyanate.
A preferred embodiment of the instant invention is a polymer where component A is a polysiloxane of structure A1 or A2, R1 is alkylene of 3 or 4 carbon atoms, each of R2 is methyl, xl+ x2 is 10 to 100, yl is 0 to 2, y2 is 2 to 3 and R4 is a 2p01.969 diradical of an aliphatic or cycloaliphatic diisocyanate with 6 to 10 carbon atoms.
A most preferred embodiment of the instant invention is a polymer where component A is polysiloxane of structure A1.
A further preferred embodiment is a polymer having based on total urethane groups 50 ~ of alkyl-urethane -C-NH-COO-C-groups and 50 ~ of silyl-urethane -C-NH-C00-Si- groups, which comprises the polymerization product of (a) 80-95 ~ by weight (based on the total polymer) of a poly-isocyanate capped, linear or branched polysiloxane pre-polymer A, having a molecular weight of about 1000 to about 10,000 and containing at least one isocyanate group per 3000 molecular weight unit of polysiloxane, said isocyanate groups being attached to the polysiloxane through urethane linkages, said polysiloxane prepolymer having the structure A1, A2 or A3, as disclosed hereinbefore, wherein Rl is alinear or branched alkylene group with 2-6carbon atoms or a polyoxy-alkylene group of structure -[CH21 HO]pCH21 H_ wherein R3 is hydrogen or methyl and p is an integer from 1-5; each R2 is methyl; m is 30 to 50; xl and x2 are integers from 10 to 50 with the proviso that the sum of xl + x2 is l2to 100: yl is 0 to 4 and y2is 2to 5 with the proviso that the respective ratios of "~ +"2y1 ( for A1 ) and xl +X2y2 ( for A2 ) are not greater than 40, yl+2 y2 -$_ H
each X, X1 and X3 iS OII N R4 NCO -~
O
and Rq is a diradical obtained by removing the NCO groupsfrom a cycloaliphatic di-isocyanate having up to 10 carbon atoms .
and (b) 20-5 $ by weight (based on the total polymer). of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) Ra I
HO Si H (B) I
Rb n where n is 2-10, and Ra and Rb are alkyl of l to 4 carbon atoms or phenyl.
Poly-functional polysiloxanes, useful as starting materials for the prepolymer (A), are of structures S1, S2 or S3:
I2 (2 ~2 I2 Hp-Rl Si0 Si0 Si0 Si-R1-OH
I I I I (sl) R2 xl I1 R2 x2 R2 (R2)3Si0 Si0 Si0 Si0 Si(R2y3 I I I (s2) R2 xl i 1 R2 x2 OH y2 ~oosss9 ~2 ~2 HO-CH2CHCH20(CH2)3 Si0 Si- (CH2)3~H2CHCH2 OH
(OH R R OH
2 m 2 wherein Rl, R2, xl, x2, Y1, Y2 and m are as described for formula A1, A2 and A3.
Diisocyanates useful to form the prepolymer.intermediate are aliphatic, cycloaliphatic or aromatic isocyanates. Said aliphatic diisocyanates are e.g. alkyl diisocyanates having up to 12 alkyl carbon atoms, preferably having 2 to 9alkyl carbon atoms, wherein alkyl is e.g. ethyl, propyl, hexyl or trimethylhexyl.
Said cycloaliphatic diisocyanates are e:g. cycloalkyl diisocyanates having up to three C5 or C6 cycloalkyl or .
cycloalkenyl groups which are unsubstituted or substituted by lower alkyl and/or carboxy, including cycloalkyl lower alkyl, unsubstutited or substituted by e.g. lower alkyl, diiso-cyanates. In case that more than one cycloalkyl group is present, these are connected to each other by a bond, lower alkylene, or a urethane group.
Said aromatic diisocyanates are e.g. diisocyanates having a naphthalene or up to three phenyl groups, which are unsub-stituted or substituted by lower alkyl, halogen, or lower alkoxy, e.g. methyl, chloro, or methoxy. In case that more than one phenyl group is present these are connected to each other by a bond, lower alkylene, or lower alkylidene or oxygen. "Lower" refers to groups having up to 7 carbon atoms.
Said diisocyanates are selected preferably from the group consisting of ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane, 1,6-diiso-cyanato-2,2,4-(2,4,4)-trimethylhexane, 2,2'-diisocyanato-2flfl19f 9 diethyl fumarate, 1,2- 1,3-, 1,5-, 1,6-, 1,7-, 1,8-, 2,7- and 2,3-diisocyanatonaphthalene: 2,4- and2,7-diisocyanato-1-methyl-naphthalene 4,4'-diisocyanatobiphenyl; 1,2-diiso--cyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diiso-cyanatobenzene, bis-(4-isocyanatocyclohexanyl)methane, bis(4-isocyanato-phenyl)methane, 1,2- and 1,4-toluene diiso-cyanate, 3,3-dichloro-4,4'-diisocyanatobiphenyl, hydrogenated toluene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane (isophorone diisocyanate).
The diisocyanates can be used alone or in combination with each other. They have preferably 6 to 10 carbon atoms except from the two NCO-groups.
Preferred are aliphatic diisocyanates, withisophorone-diiso-cyanate andl,6-diisocyanato-2,2,4-(-2,4,4)trimethylhexane being most preferred.
The linear polydialkyl- or polyphenyl-siloxane disilanol is of structure tB) disclosed hereinbefore where n is 2-50, and Ra and Rb are alkyl of 1 to 4 carbon atoms, or phenyl preferably methyl.
Preferred are polydialkylsiloxane-disilanols wherein n is 3-6 and Ra and Rb are methyl.
Preferably the polymers of the instant invention are useful as ophthalmic devices such as contact lenses or intraocular lenses. Most preferably the polymers are useful as contact lenses.
The isocyanato functional polysiloxane prepolymers A1-A3 are obtained conveniently from the corresponding poly-hydroxy-alkylene functional polysiloxanes S1-S3 by the known techniques of polyurethane prepolymer synthesis.Polysiloxane di-, tri- and tetraalkanols can be used alone or as mixtures, r 2oossss as long as the functionality of the mixture isgreater than2.
As a first step, the polysiloxane is reacted, either in bulk - or in solution, with a given amount of diisocyanate, prefer-ably in the presence of a catalyst. This catalyst may be a tertiary amino group containing compound such astriethyl- _ amine, pyridine or diaminobicyclooctane, or a metalbased catalyst like dibutyltin dilaurate or stannous octoate.The reaction is carried out at either ambient or elevated tem-peratures under a dry nitrogen blanket and can be followed conveniently by NCO-titration or IR analysis. The molar ratio of OH to NCO groups can be 1:1.5 to 1:3 and is preferably in the range of 1:2.05-1:2.1.
Although it is preferable to react one equivalent reactive polysiloxane with close to two equivalents diisocyanate and thereby obtain an isocyanate-endcapped polysiloxane, due to the laws of polycondensation kinetics a certain amount o.f chain extended product, in which the endcapped polymer contains two polysiloxane chains connected by a diisocyanate unit, is always obtained and can be analyzed, for instance by gel permeation chromatography.
It is therefore within the scope of the present invention to use as polysiloxanes prepolymer obtained from polysiloxanes of structures A1 and A3 by chain-extension reactions commonly used by those skilled in the art of polycondensation, especially polyurethane chemistry. Such chain extension can be achieved by instance by polycondensation of the afore-mentioned polysiloxane diols, with diacid chlorides or anhydrides or dianhydrides, such as terephthaloyl chloride, adipic acid dichloride, malefic anhydride, phthalic anhydride or benzophenone-tetracarboxylic acid and dianhydride~ but preferably with diisocyanates of the structures mentioned above, in which case the synthesis step for preparing the NCO-capped prepolymer as described is simply carried out with less than a 2:1 excess of NCO over -OH-groups likewise, the 2~~~gG9 NCO-terminated prepolymers obtained can be chain extended with diols or diamines according to the known techniques of poly-urethane technology, with, for example, ethylene glycol, propylene glycol, butanediol, hexanediol or polyetherdiols containing ethyleneoxide, propyleneoxide or n-butylene oxide repeating units or fluorinated polyether groups; polyester diols;
ethylenediamine, hexanediamine and diprimary or di-secondary amines in general, including diamines derived from polyalkylene oxides. To the extent that through these chain extension additional amide, urethane or urea groups are introduced into the structure, they contribute by hydrogen-bonding to the rigidity and clarity of the polymer. Chain extensions of the sort just described, however, dilute the overall polysiloxane extent of the polymer and therefore lower the oxygen permeability in the final polymer.
For producing contact lenses, the thoroughly mixed components - isocyanate capped polysiloxane prepolymer, polysiloxane-di-silanol and catalyst - are preferably filled into one part of a contact lens mold, the mold is closed and the assembly is kept at the reaction temperature (50-80°C) for the required length of time, after which the mold is opened up and the lens is taken out.
Since polysiloxane-rubbers, including the one described in this invention, are very hydrophobic and therefore by them-selves unsuited as contact lens materials, the surfaces of the prepared lenses need to be made hydrophilic. This can be achieved by surface treatments or preferably by transfer grafting ,A
polyvinyl alcohol (PVA), ethoxylated polyvinyl alcohol (EPVA) or hydroxy-ethyl cellulose (HEC) as described in European Patent No.
362,137. For transfer-grafting, the contact lens molds are coated with a thin (0.5-100 or preferably 0.5-10 micron) film of PVA or HEC prior to casting the lens. During polymerization, the PVA or HEC film is transferred from the mold to the forming polymer by covalent bonding via urethane linkages. After the lens is removed, en extremely wettable surface is obtained, which is not dissolved away in hot water or in a solvent and resists abrasion. It has been discovered that the polysiloxane-polyurethanes of this invention are uniquely suited for carrying out the transfer-grafting process described in European Patent No. 362,137 by using polyvinyl alcohol as surface coating. Thus, contact lenses prepared according to this invention in a mold coated with PVA or hydroxyalkyl cellulose are a preferred embodiment of this invention.
The following examples are presented for the purpose of illustration only and are not to be construed to limit the nature and scope of the invention in any manner whatsoever.
In the following examples, specific oxygen permeability (o2~DK) is determined by measuring dissolved oxygen permeability at 25°C with a polarographic electrode in an air-saturated aqueous environment and is expressed in units 02 ~DK - cm3 ( STP ) x~ cm X1010 ( barrers ) cm2x sec x cmAg p,."...
13a 2 O O 1 9 6 9 Wettability is determined by measuring the contact angle of an n-octane droplet which has risen to the lower surface of a 1 mm thick sample sheet immersed in octane saturated distilled water at 36°C.
Tensile strength, Young's modulus and elongation are measured on 1 mm thick sheets using an INSTRON model 1123 testing apparatus.
Hardness is determined using a Shore-A durometer on center cut buttons of 10 mm diameter and 8 mm height.
2001.969 - _ Example 1 a) Svnthesis of Tri-isocyanate Macromer: Polydimethylsiloxane trialkanol of structure S2 wherein R1 is 1,3-butylene (MW 6690) (159.86 g, 0:0277 mole) are mechanically stirred with two equivalents of isophorone diisocyanate (IPDI), (18.56g, 0.0832 mole) under a nitrogen atmosphere. After ten minutes, dibutyltin dilaurate (DBTL) (32 mg, 0.02 ~) catalyst is added. The reaction mixture becomes homogeneous 90-120mi-nutes after addition of the catalyst and the NCO concen-tration reaches the theoretical level after six hoursand does not change with further stirring. The triisocyanate macromer is stored at 5°C under nitrogen in plastic containers. It has an intrinsic viscosity [~] of 0.13 and a MW, based on ~ NCO, of 7400. Its dispersity, by GPC, is 5.9.
b) Preparation of oligomeric siloxane diols from a,w-siloxane dichloride: The siloxane diols are prepared by hydrolysis of the corresponding siloxane dichlorides in a cooled mixture of pH 7 buffered water and diethyl ether.After extraction, the polysiloxane diols are purified by distillation. The following disilanols of formula B, wherein Ra and Rb are methyl, are prepared:
_n _MW YIELD
3 240 87 72-74C/0.3 mm 4 314 85 86-88C/0.4 mm 6 463 86 113C/1.2 mm 8 611 82 135C/0.4 mm These oligomers are stable with respect to self-condensation when stored in plastic containers under nitrogen.
c) Preparation of 0- --Silylurethane Crosslinked Silicone Rubber: The polydimethylsiloxane tri-isocyanate macromer (MW7400) (24.25 g, 3.286 mmole) is stirred in vacuo (15 torr) 2oo19s9 with hexamethyltrisiloxane -diol (1.14 g, 4.765 mmole) for 30 minutes. The formulation is stable for over 30 days when stored under nitrogen at 5°C; at room temperature the formulation is stable for one week. Five square inch sheet molds are filled with the siloxane formulations in thickness of 1.O mm, 0.5 mm, 0.3 mm and 0.1 mm. The molds are made against MYLAR, which has previously been coated with a thin layer (1.0 ~) of PVA (Mn 41,000, Mw 114,000) which becomes grafted to the silicone during cure, leaving it with a clear, wettable surface. Polypropylene button molds (diam. =15 mm, height = 10 mm) are also filled. Curing is done at 60 °C under a nitrogen atmosphere for 24 hours. A clear, resilient rubber is obtained which is completely resistant to hydrolysis in distilled water at 80°C for one month. Hardness measurements, as well as degree of swelling and percent extractibles after two weeks in absolute ethanol are made on buttons weighing approximately 2.3 g.
Example 2: The polydimethylsiloxane tri-isocyanate macromer of example 1 (MW 7400) (22.47 g, 3.047 mmoles) is mixed with octamethyltetrasiloxane diol (1.38 g, 4.419 mmole) on a rotaevaporator in vacuo (15 torr) for 30 minutes. Polymers are cast in form of sheets and buttons, as described in example lc), with curing carried out at 60°C in a nitrogen atmosphere for 24 hours. The properties of the 0-silyl-urethane linked polysiloxane of this example are as follows:
Property Initial After 4 weeks at 80°C
in distilled water Tensile strength [kg/cm2] 7.27 7.32-Young's modulus [kg/cm2] 10.67 10.73 Elongation to break (~) 150 180 Shore A hardness 34 -Contact Angles Advancing 32 35 Receding 27 24 Ethanol swelling (~) 39.2 -Extractibles (~) 1.2 -02DK (barrers) 376 Example 3 a) Synthesis of Tri-isocyanate Macromer: Polydimethylsiloxane trialkanol of Structure S1 wherein R1 is 3,.6-dioxaocta-methylene (MW 6280), (270.14 g, 43.00 mmole) is mechanically stirred with three equivalents of isophorone diisocyanate (IPDI) (29.65 g, 133.90 mmole) under a nitrogen atmosphere.
The temperature is raised to 50°C for 3 hours after which time the NCO level drops to the theoretical level. The triisocyanate macromer is stored at 5°C under nitrogen in plastic containers. It has a molecular weight, based on NCO, of 6980, and a polydispersity, by GPC of 20.6.
b) Pre aration of Sil 1-Urethane Crosslinked Silicone Rubber:
The polydimethyl siloxane tri-isocyanate macromer (MW 6980) (20.91 g,. 3.00 mmole) is stirred in vacuo (15 torr) with hexamethyltrisiloxane diol (1.08 g, 4.50 mmole) for 30mi-nutes. The formulation is stable for over 30 days when stored under nitrogen at 5°C; at room temperature the formulation is stable for 48 hours. Five inch square sheet molds are filled with the siloxane formulations in thickness of 1.00 mm, 2pp1~69 0.5 mm, 0.3 mm and ~.1 mm. The molds are made against MYLAR, which has previously been coated with polyvinyl alcohol, as described in example 1. Polypropylene button molds (diam: -15 mm, height = 10 mm) are also filled and curing is done at 60°C unter a nitrogen atmosphere for 24 hours. A clear, resilient rubber is obtained which is completely resistant to hydrolysis in distilled water at 80°C for one month.
Example 4: Example Usina Structure A3 (Mercor Tetraol) a) Synthesis of Tetra-isocyanate Macromer:Polydimethyl-siloxane tetra-alkanol of structure S3 (MW 3400) (167.18 g, 49.17 mmole) is mechanically stirred with two equivalents of isophorone diisocyanate (IPDI) (43.72 g, 196.7 mmole) for ten minutes under a nitrogen atmosphere. Then dibutyltin-dilaurate (33 mg, 0.02 ~) catalyst is added. The theoretical endpoint is reached after 21 hours of stirring. The tetra-~isocyanate macromer is stored at 5°C under nitrogen in plastic containers and has a Mw of 4265 (by NCO titration).
b) Pre aration of a Sil 1 Urethane Crosslinked Silicone Rubber: The polydimethylsiloxane tetra-isocyanate macromer (MW 4265) (16.79 g, 3.94 mmole) is stirred on a roto-evaporator in vacuo (25 torr) with octamethyltetrasiloxane diol (2.47 g, 7.88 mmole) for 30 minutes. The mixture is filled into molds and cured at 60°C under a nitrogen atmosphere for 24 hours as described in example 1. A clear, resilient rubber is obtained which is completely resistant to hydrolysis in distilled water for 80°C for one month.
Example 5: Preparation of a Contact Lens The silicone composition described in example 1c is prepared.
Zero expansion polypropylene) lens molds are dip coated with a 2 ~ solution of EPVA in water-isopropanol (4:1) containing 0.1 ~ LODYNE S-100 surfactant (CIBA-GEIGY). After drying in a 60°C oven for one hour, each mold is filled with four drops of the silicone composition and subsequently clamped shut.
. 2oo~.9s9 Curing is carried out as previously described at 60°C for 24 hours. Lenses are removed by opening the molds and dropping them in boiling water. Clear, resilient, highly wettable lenses are obtained.
These rubbers are thermoset polymers which can be made to varying degrees of hardness and elasticity by controlling the degree of crosslinking and the molecular weight of the silicone fluid. Silicone rubber is usually made by vul-canizing polydimethylsiloxane fluids with organic peroxidesat elevated temperatures. Another approach to crosslinking employs hydrosilation in which poly(vinylalkylsiloxanes) are cured with poly(hydridoalkylsiloxanes) in the presence of transition metal catalysts. Silicone rubber has also been formed by chemically reacting, a,W-difunctionalpoly(di-organosiloxanes) with polyfunctional silanes andsiloxanes.
Typically the crosslinking reaction is a condensation which forms a siloxane bond and a volatile by product. Common examples of this type of cure reaction are silanol-alkoxy-silane (French Pat. 1,042,019), silanol-acetoxysilane (L. F.Ceyzeriat and P.Dumonth, German Appl. 1,121,803), silanol-silane (Midland Silicones, Brit.Pat. 804,199), and silanol-silanol (via the corresponding acetone oxime) (E.
Sweet, Dow Corning, Belg.Pat. 614,394.Suitable catalysts for these reactions are amines and carboxylic acid salts of Sn, Pb, Zn, Sb, Fe, Cd, Ba, Ca and Mn .
Organosiloxane isocyanates have been prepared (U. S. Patent 3,179,622) which vulcanize when exposed to moisture. In these cases the isocyanate group is joined to the siloxane through an alkyl group, rendering it unhydrolyzable.
Relatively few reports exist for the curing of silicones via the reaction of a silanol with an isocyanate yielding an 0-silylurethane linkage. This is probably due to the well known hydrolytic instability of this bond. To our knowledge there are no existing reports of a silicone rubber cross-linked by 0-silylurethane bonds that is resistant to hydrolytic decomposition.
The use of silanol terminated polydimethylsiloxanes has been reported in the modification of polysiloxanes with poly-urethanes (Moretto, U.S. Pat. No. 4,202,807) to improve the mechanical properties of the former at elevated temperatures.
No mention was made of the hydrolytic stability of the O-silylurethane bond in these materials. The only other mention of this bond in a polymeric material was made by Kaufman, Muller, and Wegchaupt (U. S. Patent No. 4,292,423in the preparation of organopolysiloxanes for coating purposes.
However, when the claimed organopolysiloxane was prepared entirely through the reaction of siloxanol groups withiso-cyanate groups (Example 1 of this patent), the coating was decomposed by atmospheric moisture and addition of 75 ~ by weight of the polyurethane, Desmodur L, wasnecessary to produce a hydrolytically stable coating.
High hydrolytic susceptibility is a property characteristic of O-silylurethanes since they were first reported by Andrianov, Losev, and Astakhin (Proc. Akad. Sci., USSR, Sect.
Chem 113, 247, [1957]) from the reaction of triethylsilanol and m-toluene-diisocyanate. These authors subsequently described their alcoholysis and hydrolysis (J. General Chem., USSR, 29, 2655, [1959]). This behaviour of 0-silylurethanes has been summarized by Noll in "Chemistry and Technology of Silicones", Academic Press, 1968, pp 99-100.
It has now unexpectedly been discovered, that by reaction of essential equivalent amounts of diisocyanate-capped poly-dialkylsiloxane-polyalkanols and poly-dimethylsiloxane-disilanols, a clear, flexible and elastic siloxane poly-urethane rubber is obtained which is completely resistant to hydrolysis under physiological conditions, despite the fact that half of all urethane groups in the polymer contain the -Si-O-C- bond. This novel polysiloxane-polyurethane is uniquely suited as a biocompatible, oxygen-permeable membrane ,~,, 2oossss or film and especially, as a crosslinked rubber, as a soft contact lens.
It has further been discovered that this polyurethane is uniquely suited to be grafted to polyvinyl alcohol or hydroxy-alkyl cellulose and thereby allows production of a composite.
material not only with excellent optical clarity and the characteristically high permeability to oxygen, but also with high wettability as well.
The instant invention therefore pertains to said novel polysiloxane-polyurethane, to ophthalmic devices thereof, such as contact lenses, to a process for manufacture of said polysiloxane-polyurethane polymers and to the use thereof for making e.g. ophthalmic devices, such as contact lenses. The polymers can be used as oxygen permeable membranes or films, as bandages and drug carriers, for example in transderma.l drug delivery, and especially as highly oxygen permeable, soft contact lenses.
The instant invention pertains to a polymer, suitable for use as an oxygen permeable membrane or an ophthalmic device, having based on total urethane groups 50 to 75 ~k of alkyl-urethane -C-NH-C00-C- groups and 50 to 25 ~ of silyl-urethane -C-NH-COO-Si- groups, which comprises the polymerization product of (a) 80-95 ~ by weight (based on the total polymer) of a poly-isocyanate capped, linear or branched polysiloxane pre-polymer (A), having.a molecular weight of about 1000 to about 10,000 and containing at least one isocyanate group per 3000 molecular weight unit of polysiloxane, said isocyanate groupsbeing attached to the polysiloxane through urethane linkages, said polysiloxane prepolymer having the structure A1, A2 or A3 (which are described in detail below); and :2001969 (b) 20-5 ~ by weight (based on the total polymer) of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) Ra I
HO Si H (B) I
Rb n where n is 2-50, and Ra and Rb are alkyl of 1 to 4 carbon atoms or phenyl. The molecular weight of these terminal silanol groups containing compounds is from about 24Oto about 10000, preferably from about 240 to about 1000.
The linear or branched polysiloxane prepolymer A is of one of the following general structures, A1, A2, or A3:
X-R1 Si0 Si0 Si0 Si-R1-X1 (Al) R2 X1 R1 R2 x2 R2 x ~2)3Si0 Si0 Si0 Si0 Si(R2y3 (A2) R2 X1 i 1 R2 X2 x y2 X-CH2CHCH20(CH2)g Si0 Si- (CHZY3~H2CHCH2 X3 (A3 ) R2 m R2 wherein R1 is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structures 20019x9 -[CH2 ~ HO]pCH2 ~ H- o r -(CHZ)30CH2 ~ HCH2_ wherein R3 is hydrogen or methyl and p is an integer from -1-50; each R2 is independently methyl or phenyl; m is 2 to 50; x1 and x2 are integers from 1 to 500 with the proviso that the sum of xl + x2 is 12 to 1,000; y1 is 0 to 4 and y2 is 2to with the proviso that the respective ratios of xl+x2y1 ( for Al) and x1+x2y2 (for A2) are not greater than 70, yl + 2 y2 H
X 1 s -~-N-R4-NCO ~
O
H H
X1 is X or -~N-R4-NCO-Tl and O O
H H
X 3 i s X o r -~N-R4-N-CO-Tg O O
wherein T1 is A1 from which X1 has been abstracted, T3 is A3 from which X3 has been abstracted, and Rq is a diradical obtained by removing the NCO groups from an aliphatic, cycloaliphatic or aromatic di-isocyanate.
A preferred embodiment of the instant invention is a polymer where component A is a polysiloxane of structure A1 or A2, R1 is alkylene of 3 or 4 carbon atoms, each of R2 is methyl, xl+ x2 is 10 to 100, yl is 0 to 2, y2 is 2 to 3 and R4 is a 2p01.969 diradical of an aliphatic or cycloaliphatic diisocyanate with 6 to 10 carbon atoms.
A most preferred embodiment of the instant invention is a polymer where component A is polysiloxane of structure A1.
A further preferred embodiment is a polymer having based on total urethane groups 50 ~ of alkyl-urethane -C-NH-COO-C-groups and 50 ~ of silyl-urethane -C-NH-C00-Si- groups, which comprises the polymerization product of (a) 80-95 ~ by weight (based on the total polymer) of a poly-isocyanate capped, linear or branched polysiloxane pre-polymer A, having a molecular weight of about 1000 to about 10,000 and containing at least one isocyanate group per 3000 molecular weight unit of polysiloxane, said isocyanate groups being attached to the polysiloxane through urethane linkages, said polysiloxane prepolymer having the structure A1, A2 or A3, as disclosed hereinbefore, wherein Rl is alinear or branched alkylene group with 2-6carbon atoms or a polyoxy-alkylene group of structure -[CH21 HO]pCH21 H_ wherein R3 is hydrogen or methyl and p is an integer from 1-5; each R2 is methyl; m is 30 to 50; xl and x2 are integers from 10 to 50 with the proviso that the sum of xl + x2 is l2to 100: yl is 0 to 4 and y2is 2to 5 with the proviso that the respective ratios of "~ +"2y1 ( for A1 ) and xl +X2y2 ( for A2 ) are not greater than 40, yl+2 y2 -$_ H
each X, X1 and X3 iS OII N R4 NCO -~
O
and Rq is a diradical obtained by removing the NCO groupsfrom a cycloaliphatic di-isocyanate having up to 10 carbon atoms .
and (b) 20-5 $ by weight (based on the total polymer). of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) Ra I
HO Si H (B) I
Rb n where n is 2-10, and Ra and Rb are alkyl of l to 4 carbon atoms or phenyl.
Poly-functional polysiloxanes, useful as starting materials for the prepolymer (A), are of structures S1, S2 or S3:
I2 (2 ~2 I2 Hp-Rl Si0 Si0 Si0 Si-R1-OH
I I I I (sl) R2 xl I1 R2 x2 R2 (R2)3Si0 Si0 Si0 Si0 Si(R2y3 I I I (s2) R2 xl i 1 R2 x2 OH y2 ~oosss9 ~2 ~2 HO-CH2CHCH20(CH2)3 Si0 Si- (CH2)3~H2CHCH2 OH
(OH R R OH
2 m 2 wherein Rl, R2, xl, x2, Y1, Y2 and m are as described for formula A1, A2 and A3.
Diisocyanates useful to form the prepolymer.intermediate are aliphatic, cycloaliphatic or aromatic isocyanates. Said aliphatic diisocyanates are e.g. alkyl diisocyanates having up to 12 alkyl carbon atoms, preferably having 2 to 9alkyl carbon atoms, wherein alkyl is e.g. ethyl, propyl, hexyl or trimethylhexyl.
Said cycloaliphatic diisocyanates are e:g. cycloalkyl diisocyanates having up to three C5 or C6 cycloalkyl or .
cycloalkenyl groups which are unsubstituted or substituted by lower alkyl and/or carboxy, including cycloalkyl lower alkyl, unsubstutited or substituted by e.g. lower alkyl, diiso-cyanates. In case that more than one cycloalkyl group is present, these are connected to each other by a bond, lower alkylene, or a urethane group.
Said aromatic diisocyanates are e.g. diisocyanates having a naphthalene or up to three phenyl groups, which are unsub-stituted or substituted by lower alkyl, halogen, or lower alkoxy, e.g. methyl, chloro, or methoxy. In case that more than one phenyl group is present these are connected to each other by a bond, lower alkylene, or lower alkylidene or oxygen. "Lower" refers to groups having up to 7 carbon atoms.
Said diisocyanates are selected preferably from the group consisting of ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane, 1,6-diiso-cyanato-2,2,4-(2,4,4)-trimethylhexane, 2,2'-diisocyanato-2flfl19f 9 diethyl fumarate, 1,2- 1,3-, 1,5-, 1,6-, 1,7-, 1,8-, 2,7- and 2,3-diisocyanatonaphthalene: 2,4- and2,7-diisocyanato-1-methyl-naphthalene 4,4'-diisocyanatobiphenyl; 1,2-diiso--cyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diiso-cyanatobenzene, bis-(4-isocyanatocyclohexanyl)methane, bis(4-isocyanato-phenyl)methane, 1,2- and 1,4-toluene diiso-cyanate, 3,3-dichloro-4,4'-diisocyanatobiphenyl, hydrogenated toluene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane (isophorone diisocyanate).
The diisocyanates can be used alone or in combination with each other. They have preferably 6 to 10 carbon atoms except from the two NCO-groups.
Preferred are aliphatic diisocyanates, withisophorone-diiso-cyanate andl,6-diisocyanato-2,2,4-(-2,4,4)trimethylhexane being most preferred.
The linear polydialkyl- or polyphenyl-siloxane disilanol is of structure tB) disclosed hereinbefore where n is 2-50, and Ra and Rb are alkyl of 1 to 4 carbon atoms, or phenyl preferably methyl.
Preferred are polydialkylsiloxane-disilanols wherein n is 3-6 and Ra and Rb are methyl.
Preferably the polymers of the instant invention are useful as ophthalmic devices such as contact lenses or intraocular lenses. Most preferably the polymers are useful as contact lenses.
The isocyanato functional polysiloxane prepolymers A1-A3 are obtained conveniently from the corresponding poly-hydroxy-alkylene functional polysiloxanes S1-S3 by the known techniques of polyurethane prepolymer synthesis.Polysiloxane di-, tri- and tetraalkanols can be used alone or as mixtures, r 2oossss as long as the functionality of the mixture isgreater than2.
As a first step, the polysiloxane is reacted, either in bulk - or in solution, with a given amount of diisocyanate, prefer-ably in the presence of a catalyst. This catalyst may be a tertiary amino group containing compound such astriethyl- _ amine, pyridine or diaminobicyclooctane, or a metalbased catalyst like dibutyltin dilaurate or stannous octoate.The reaction is carried out at either ambient or elevated tem-peratures under a dry nitrogen blanket and can be followed conveniently by NCO-titration or IR analysis. The molar ratio of OH to NCO groups can be 1:1.5 to 1:3 and is preferably in the range of 1:2.05-1:2.1.
Although it is preferable to react one equivalent reactive polysiloxane with close to two equivalents diisocyanate and thereby obtain an isocyanate-endcapped polysiloxane, due to the laws of polycondensation kinetics a certain amount o.f chain extended product, in which the endcapped polymer contains two polysiloxane chains connected by a diisocyanate unit, is always obtained and can be analyzed, for instance by gel permeation chromatography.
It is therefore within the scope of the present invention to use as polysiloxanes prepolymer obtained from polysiloxanes of structures A1 and A3 by chain-extension reactions commonly used by those skilled in the art of polycondensation, especially polyurethane chemistry. Such chain extension can be achieved by instance by polycondensation of the afore-mentioned polysiloxane diols, with diacid chlorides or anhydrides or dianhydrides, such as terephthaloyl chloride, adipic acid dichloride, malefic anhydride, phthalic anhydride or benzophenone-tetracarboxylic acid and dianhydride~ but preferably with diisocyanates of the structures mentioned above, in which case the synthesis step for preparing the NCO-capped prepolymer as described is simply carried out with less than a 2:1 excess of NCO over -OH-groups likewise, the 2~~~gG9 NCO-terminated prepolymers obtained can be chain extended with diols or diamines according to the known techniques of poly-urethane technology, with, for example, ethylene glycol, propylene glycol, butanediol, hexanediol or polyetherdiols containing ethyleneoxide, propyleneoxide or n-butylene oxide repeating units or fluorinated polyether groups; polyester diols;
ethylenediamine, hexanediamine and diprimary or di-secondary amines in general, including diamines derived from polyalkylene oxides. To the extent that through these chain extension additional amide, urethane or urea groups are introduced into the structure, they contribute by hydrogen-bonding to the rigidity and clarity of the polymer. Chain extensions of the sort just described, however, dilute the overall polysiloxane extent of the polymer and therefore lower the oxygen permeability in the final polymer.
For producing contact lenses, the thoroughly mixed components - isocyanate capped polysiloxane prepolymer, polysiloxane-di-silanol and catalyst - are preferably filled into one part of a contact lens mold, the mold is closed and the assembly is kept at the reaction temperature (50-80°C) for the required length of time, after which the mold is opened up and the lens is taken out.
Since polysiloxane-rubbers, including the one described in this invention, are very hydrophobic and therefore by them-selves unsuited as contact lens materials, the surfaces of the prepared lenses need to be made hydrophilic. This can be achieved by surface treatments or preferably by transfer grafting ,A
polyvinyl alcohol (PVA), ethoxylated polyvinyl alcohol (EPVA) or hydroxy-ethyl cellulose (HEC) as described in European Patent No.
362,137. For transfer-grafting, the contact lens molds are coated with a thin (0.5-100 or preferably 0.5-10 micron) film of PVA or HEC prior to casting the lens. During polymerization, the PVA or HEC film is transferred from the mold to the forming polymer by covalent bonding via urethane linkages. After the lens is removed, en extremely wettable surface is obtained, which is not dissolved away in hot water or in a solvent and resists abrasion. It has been discovered that the polysiloxane-polyurethanes of this invention are uniquely suited for carrying out the transfer-grafting process described in European Patent No. 362,137 by using polyvinyl alcohol as surface coating. Thus, contact lenses prepared according to this invention in a mold coated with PVA or hydroxyalkyl cellulose are a preferred embodiment of this invention.
The following examples are presented for the purpose of illustration only and are not to be construed to limit the nature and scope of the invention in any manner whatsoever.
In the following examples, specific oxygen permeability (o2~DK) is determined by measuring dissolved oxygen permeability at 25°C with a polarographic electrode in an air-saturated aqueous environment and is expressed in units 02 ~DK - cm3 ( STP ) x~ cm X1010 ( barrers ) cm2x sec x cmAg p,."...
13a 2 O O 1 9 6 9 Wettability is determined by measuring the contact angle of an n-octane droplet which has risen to the lower surface of a 1 mm thick sample sheet immersed in octane saturated distilled water at 36°C.
Tensile strength, Young's modulus and elongation are measured on 1 mm thick sheets using an INSTRON model 1123 testing apparatus.
Hardness is determined using a Shore-A durometer on center cut buttons of 10 mm diameter and 8 mm height.
2001.969 - _ Example 1 a) Svnthesis of Tri-isocyanate Macromer: Polydimethylsiloxane trialkanol of structure S2 wherein R1 is 1,3-butylene (MW 6690) (159.86 g, 0:0277 mole) are mechanically stirred with two equivalents of isophorone diisocyanate (IPDI), (18.56g, 0.0832 mole) under a nitrogen atmosphere. After ten minutes, dibutyltin dilaurate (DBTL) (32 mg, 0.02 ~) catalyst is added. The reaction mixture becomes homogeneous 90-120mi-nutes after addition of the catalyst and the NCO concen-tration reaches the theoretical level after six hoursand does not change with further stirring. The triisocyanate macromer is stored at 5°C under nitrogen in plastic containers. It has an intrinsic viscosity [~] of 0.13 and a MW, based on ~ NCO, of 7400. Its dispersity, by GPC, is 5.9.
b) Preparation of oligomeric siloxane diols from a,w-siloxane dichloride: The siloxane diols are prepared by hydrolysis of the corresponding siloxane dichlorides in a cooled mixture of pH 7 buffered water and diethyl ether.After extraction, the polysiloxane diols are purified by distillation. The following disilanols of formula B, wherein Ra and Rb are methyl, are prepared:
_n _MW YIELD
3 240 87 72-74C/0.3 mm 4 314 85 86-88C/0.4 mm 6 463 86 113C/1.2 mm 8 611 82 135C/0.4 mm These oligomers are stable with respect to self-condensation when stored in plastic containers under nitrogen.
c) Preparation of 0- --Silylurethane Crosslinked Silicone Rubber: The polydimethylsiloxane tri-isocyanate macromer (MW7400) (24.25 g, 3.286 mmole) is stirred in vacuo (15 torr) 2oo19s9 with hexamethyltrisiloxane -diol (1.14 g, 4.765 mmole) for 30 minutes. The formulation is stable for over 30 days when stored under nitrogen at 5°C; at room temperature the formulation is stable for one week. Five square inch sheet molds are filled with the siloxane formulations in thickness of 1.O mm, 0.5 mm, 0.3 mm and 0.1 mm. The molds are made against MYLAR, which has previously been coated with a thin layer (1.0 ~) of PVA (Mn 41,000, Mw 114,000) which becomes grafted to the silicone during cure, leaving it with a clear, wettable surface. Polypropylene button molds (diam. =15 mm, height = 10 mm) are also filled. Curing is done at 60 °C under a nitrogen atmosphere for 24 hours. A clear, resilient rubber is obtained which is completely resistant to hydrolysis in distilled water at 80°C for one month. Hardness measurements, as well as degree of swelling and percent extractibles after two weeks in absolute ethanol are made on buttons weighing approximately 2.3 g.
Example 2: The polydimethylsiloxane tri-isocyanate macromer of example 1 (MW 7400) (22.47 g, 3.047 mmoles) is mixed with octamethyltetrasiloxane diol (1.38 g, 4.419 mmole) on a rotaevaporator in vacuo (15 torr) for 30 minutes. Polymers are cast in form of sheets and buttons, as described in example lc), with curing carried out at 60°C in a nitrogen atmosphere for 24 hours. The properties of the 0-silyl-urethane linked polysiloxane of this example are as follows:
Property Initial After 4 weeks at 80°C
in distilled water Tensile strength [kg/cm2] 7.27 7.32-Young's modulus [kg/cm2] 10.67 10.73 Elongation to break (~) 150 180 Shore A hardness 34 -Contact Angles Advancing 32 35 Receding 27 24 Ethanol swelling (~) 39.2 -Extractibles (~) 1.2 -02DK (barrers) 376 Example 3 a) Synthesis of Tri-isocyanate Macromer: Polydimethylsiloxane trialkanol of Structure S1 wherein R1 is 3,.6-dioxaocta-methylene (MW 6280), (270.14 g, 43.00 mmole) is mechanically stirred with three equivalents of isophorone diisocyanate (IPDI) (29.65 g, 133.90 mmole) under a nitrogen atmosphere.
The temperature is raised to 50°C for 3 hours after which time the NCO level drops to the theoretical level. The triisocyanate macromer is stored at 5°C under nitrogen in plastic containers. It has a molecular weight, based on NCO, of 6980, and a polydispersity, by GPC of 20.6.
b) Pre aration of Sil 1-Urethane Crosslinked Silicone Rubber:
The polydimethyl siloxane tri-isocyanate macromer (MW 6980) (20.91 g,. 3.00 mmole) is stirred in vacuo (15 torr) with hexamethyltrisiloxane diol (1.08 g, 4.50 mmole) for 30mi-nutes. The formulation is stable for over 30 days when stored under nitrogen at 5°C; at room temperature the formulation is stable for 48 hours. Five inch square sheet molds are filled with the siloxane formulations in thickness of 1.00 mm, 2pp1~69 0.5 mm, 0.3 mm and ~.1 mm. The molds are made against MYLAR, which has previously been coated with polyvinyl alcohol, as described in example 1. Polypropylene button molds (diam: -15 mm, height = 10 mm) are also filled and curing is done at 60°C unter a nitrogen atmosphere for 24 hours. A clear, resilient rubber is obtained which is completely resistant to hydrolysis in distilled water at 80°C for one month.
Example 4: Example Usina Structure A3 (Mercor Tetraol) a) Synthesis of Tetra-isocyanate Macromer:Polydimethyl-siloxane tetra-alkanol of structure S3 (MW 3400) (167.18 g, 49.17 mmole) is mechanically stirred with two equivalents of isophorone diisocyanate (IPDI) (43.72 g, 196.7 mmole) for ten minutes under a nitrogen atmosphere. Then dibutyltin-dilaurate (33 mg, 0.02 ~) catalyst is added. The theoretical endpoint is reached after 21 hours of stirring. The tetra-~isocyanate macromer is stored at 5°C under nitrogen in plastic containers and has a Mw of 4265 (by NCO titration).
b) Pre aration of a Sil 1 Urethane Crosslinked Silicone Rubber: The polydimethylsiloxane tetra-isocyanate macromer (MW 4265) (16.79 g, 3.94 mmole) is stirred on a roto-evaporator in vacuo (25 torr) with octamethyltetrasiloxane diol (2.47 g, 7.88 mmole) for 30 minutes. The mixture is filled into molds and cured at 60°C under a nitrogen atmosphere for 24 hours as described in example 1. A clear, resilient rubber is obtained which is completely resistant to hydrolysis in distilled water for 80°C for one month.
Example 5: Preparation of a Contact Lens The silicone composition described in example 1c is prepared.
Zero expansion polypropylene) lens molds are dip coated with a 2 ~ solution of EPVA in water-isopropanol (4:1) containing 0.1 ~ LODYNE S-100 surfactant (CIBA-GEIGY). After drying in a 60°C oven for one hour, each mold is filled with four drops of the silicone composition and subsequently clamped shut.
. 2oo~.9s9 Curing is carried out as previously described at 60°C for 24 hours. Lenses are removed by opening the molds and dropping them in boiling water. Clear, resilient, highly wettable lenses are obtained.
Claims (21)
1. A siloxane urethane polymer, suitable for use as an oxygen permeable membrane or an ophthalmic device, having based on total urethane groups 50 to 75 % of alkyl-urethane -C-NH-COO-C- groups and 50 to 25 % of silyl-urethane -C-NH-COO-Si- groups, which comprises the polymerization product of (a) 80-95 % by weight (based on the total polymer) of a polyisocyanate capped, linear or branched polysiloxane prepolymer A, having a molecular weight of about 1000 to about 10,000 and containing at least one isocyanate group per 3000 molecular weight unit of polysiloxane, said isocyanate groups being attached to the polysiloxane through urethane linkages, said polysiloxane prepolymer having the structure A1, A2 or A3:
wherein R1 is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structures wherein R3 is hydrogen or methyl and p is an integer from 1-50; each R2 is independently methyl or phenyl; m is 2 to 50; x1 and x2 are integers from 1 to 500 with the proviso that the sum of x1 + x2 is 12 to 1,000; yl is 0 to 4 arid y2 is 2 to with the proviso that the respective ratios of (for A1) and (for A2) are not greater than 70, wherein T1 is A1 from which X1 has been abstracted, T3 is A3 from which X3 has been abstracted, and R4 is a diradical obtained by removing the NCO groups from an aliphatic, cycloaliphatic or aromatic di-isocyanate: and (b) 20-5 % by weight (based on the total polymer) of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) where n is 2-50, and R a and R b are alkyl of 1 to 4 carbon atoms or phenyl.
wherein R1 is a linear or branched alkylene group with 2-6 carbon atoms or a polyoxyalkylene group of structures wherein R3 is hydrogen or methyl and p is an integer from 1-50; each R2 is independently methyl or phenyl; m is 2 to 50; x1 and x2 are integers from 1 to 500 with the proviso that the sum of x1 + x2 is 12 to 1,000; yl is 0 to 4 arid y2 is 2 to with the proviso that the respective ratios of (for A1) and (for A2) are not greater than 70, wherein T1 is A1 from which X1 has been abstracted, T3 is A3 from which X3 has been abstracted, and R4 is a diradical obtained by removing the NCO groups from an aliphatic, cycloaliphatic or aromatic di-isocyanate: and (b) 20-5 % by weight (based on the total polymer) of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) where n is 2-50, and R a and R b are alkyl of 1 to 4 carbon atoms or phenyl.
2. A siloxane urethane polymer, according to claim 1, having based on total urethane groups 50 % of alkyl-urethane -C-NH-COO-C- groups and 50 % of silyl-urethane -C-NH-COO-Si-groups, which comprises the polymerization product of (a) 80-95 % by weight (based on the total polymer) of a polyisocyanate capped, linear or branched polysiloxane prepolymer A, having a molecular weight of about 1000 to about 10,000 and containing at least one isocyanate group per 3000 molecular weight unit of polysiloxane, said isocyanate groups being attached to the polysiloxane through urethane linkages, said polysiloxane prepolymer having the structure A1, A2 or A3, as disclosed in claim 1, wherein R1 is a linear or branched alkylene group with 2-6carbon atoms or a polyoxyalkylene group of structure wherein R3 is hydrogen or methyl and p is an integer from 1-5; each R2 is methyl; m is 30 to 50: x1 and x2 are integers from 10 to 50 with the proviso that the sum of x1 + x2 is 12 to 100; y1 is 0 to 4 and y2 is 2 to 5 with the proviso that the respective ratios of (for A1) and (for A2) are not greater than 40, each X, X1 and X3 is and R4 is a diradical obtained by removing the NCO groups from a cycloaliphatic di-isocyanate having up to 10 carbon atoms:
and (b) 20-5 % by weight (based on the total polymer) of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) where n is 2-10, and R a and R b are alkyl of 1 to 4 carbon atoms or phenyl.
and (b) 20-5 % by weight (based on the total polymer) of a linear polydialkyl- or polydiphenyl-siloxane disilanol (B) where n is 2-10, and R a and R b are alkyl of 1 to 4 carbon atoms or phenyl.
3. A polymer according to claim 1 wherein the prepolymer of component (a) has structure A1 or A2.
4. A polymer according to claim 3 wherein the prepolymer of component (a) has structure A1.
5. A polymer according to claim 1 wherein the prepolymer of component (a) has structure A1 or A2, R1 is alkylene of 3 or 4 carbon atoms, each of R2 is methyl, x1 + x2 is 10 to 100, y1 is 0 to 2, y2 is 2 to 3, and R4 is a diradical of an aliphatic or cycloaliphatic diisocyanate with 6 to 10 carbon atoms.
6. A polymer according to claim 1 wherein the prepolymer of component (a) has structure A1, A2 or A3 and is capped with a diisocyanate or mixture of isocyanates selected from the group consisting of ethylene diisocyanate, 1,2-diisocyanato-propane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane, 1,6-diisocyanato-2,2,4-(2,9,4)-trimethylhexane, 2,2'-diiso-cyanatodiethylfumarate, 1,2- 1,3-, 1,5-, 1,6-, 1,7-, 1,8-, 2,7- and 2,3-diisocyanatonaphthalene; 2,4- and 2,7-diiso-cyanato-1-methyl-naphthalene; 4,4'-diisocyanatobiphenyl:
1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatobenzene, bis-(4-isocyanatocyclohexanyl)-methane, bis(4-isocyanato-phenyl)methane, 1,2-and 1,4-toluene diisocyanate, 3,3-dichloro-4,4'-diisocyanatobiphenyl, hydrogenated toluene diisocyanate, 1-isocyanatomethyl-5-iso-cyanato-1,3,3-trimethylcyclohexane (isophorone diisocyanate).
1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatobenzene, bis-(4-isocyanatocyclohexanyl)-methane, bis(4-isocyanato-phenyl)methane, 1,2-and 1,4-toluene diisocyanate, 3,3-dichloro-4,4'-diisocyanatobiphenyl, hydrogenated toluene diisocyanate, 1-isocyanatomethyl-5-iso-cyanato-1,3,3-trimethylcyclohexane (isophorone diisocyanate).
7. A polymer according to claim 6 wherein the isocyanate is isophorone diisocyanate or 1,6-diisocyanato-2,2,4-(2,4,4-)-trimethylhexane.
8. A polymer according to claim 1 where in the siloxane disilanol of component (b) R a and R b are methyl.
9. A polymer according to claim 8 where in the siloxane disilanol of component (b) n is 3-6.
10. A polymer according to claim 1 which is in the form of an ophthalmic device.
11. A polymer according to claim 10 which is in the form of a contact lens.
12. An ophthalmic device consisting essentially of a polymer as defined in claim 1.
13. An ophthalmic device comprising a preformed, thin, hydrophilic polymeric surface of a hydrophilic polymer being intimately bonded, through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface, to a polymer substrate of a polymer as defined in claim 1.
14. An ophthalmic device according to claim 13 wherein the hydrophilic polymer is polyvinyl alcohol, ethoxylated polyvinylalcohol or hydroxyethylcellulose.
15. An ophthalmic device according to claim 12 which is a contact lens.
16. An ophthalmic device according to claim 13 which is a contact lens.
17. An ophthalmic device according to claim l4 which is a contact lens.
18. A process for the manufacture of a polymer as defined in claim 1 by conventionally reacting components (A) and (B) which are as defined in claim 1.
19. A process for the manufacture of a contact lens as defined in claim 16, having a preformed, optically true, thin, conforming, continuous, integral, wettable hydrophilic polymeric surface on an essentially hydrophobic polymer form, said surface being intimately bonded and copolymerized through a multiplicity of covalent bonds distributed essentially uniformly across the entire polymeric surface/polymer substrate interface, which process comprises (a) coating a mold with a film-forming first hydrophilic polymer, said polymer containing sites capable of undergoing subsequent copolymerization with a prepolymer/disilanol mixture required to form a hydrophobic polymer as defined in claim 1, (b) polymerizing the prepolymer/disilanol mixture required to form the hydrophobic polymer as. defined in claim 1 in contact with the coated mold whereby effecting copolymerization with the reactive sites present in the mold coating to achieve intimate bonding therewith by way of a multiplicity of covalent bonds, and (c) releasing the product from the mold.
20. Use of a polymer as defined in claim 1 for the manufacture of a contact lens.
21. Use of a polymer as defined in claim 1 as oxygen permeable membrane or film or as bandage or drug carrier.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US266,555 | 1981-05-22 | ||
US07/266,555 US4962178A (en) | 1988-11-03 | 1988-11-03 | Novel polysiloxane-polyurethanes and contact lens thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2001969A1 CA2001969A1 (en) | 1990-05-03 |
CA2001969C true CA2001969C (en) | 2000-05-30 |
Family
ID=23015064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002001969A Expired - Fee Related CA2001969C (en) | 1988-11-03 | 1989-11-01 | Polysiloxane-polyurethanes and contact lenses thereof |
Country Status (13)
Country | Link |
---|---|
US (1) | US4962178A (en) |
EP (1) | EP0367720B1 (en) |
JP (1) | JP2845998B2 (en) |
AT (1) | ATE108809T1 (en) |
AU (1) | AU629252B2 (en) |
CA (1) | CA2001969C (en) |
DE (1) | DE68916907T2 (en) |
DK (1) | DK547189A (en) |
ES (1) | ES2057173T3 (en) |
HK (1) | HK9297A (en) |
IE (1) | IE63682B1 (en) |
PT (1) | PT92162B (en) |
TW (1) | TW205557B (en) |
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DE4008259A1 (en) * | 1990-03-15 | 1991-09-19 | Bayer Ag | SILOXANE MODIFIED THERMOPLASTIC POLYURETHANE |
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DE4213217C2 (en) * | 1992-04-22 | 1999-11-25 | Geesthacht Gkss Forschung | Membrane based on graft copolymers, graft copolymene and process for their production |
GB9210653D0 (en) * | 1992-05-19 | 1992-07-01 | Ici Plc | Silane functional oligomer |
FR2708199B1 (en) * | 1993-07-28 | 1995-09-01 | Oreal | New cosmetic compositions and uses. |
US7468398B2 (en) | 1994-09-06 | 2008-12-23 | Ciba Vision Corporation | Extended wear ophthalmic lens |
US5760100B1 (en) | 1994-09-06 | 2000-11-14 | Ciba Vision Corp | Extended wear ophthalmic lens |
SI0819258T1 (en) * | 1995-04-04 | 2002-04-30 | Novartis Ag | Extended wear ophthalmic lens |
US5574122A (en) * | 1995-09-29 | 1996-11-12 | Bayer Corporation | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
EP0868457B1 (en) | 1995-12-22 | 2002-09-11 | Novartis AG | Polyurethanes made from polysiloxane/polyol macromers |
FR2743297B1 (en) * | 1996-01-05 | 1998-03-13 | Oreal | COSMETIC COMPOSITION BASED ON MULTISEQUENCE IONIZABLE POLYCONDENSATES POLYSILOXANE / POLYURETHANE AND / OR POLYUREE IN SOLUTION AND USE |
US5919441A (en) * | 1996-04-01 | 1999-07-06 | Colgate-Palmolive Company | Cosmetic composition containing thickening agent of siloxane polymer with hydrogen-bonding groups |
IL138889A0 (en) * | 1998-04-17 | 2001-11-25 | Bertek Pharm Inc | Topical formulations for the treatment of nail fungal diseases |
US6218503B1 (en) | 1998-05-15 | 2001-04-17 | Bausch & Lomb Incorporated | Silicone-containing prepolymers |
US5969076A (en) * | 1998-05-15 | 1999-10-19 | Bausch & Lomb Incorporated | Thermoplastic silicone-containing hydrogels |
US6008317A (en) | 1998-05-15 | 1999-12-28 | Bausch & Lomb Incorporated | Hydroxy or amino terminated hydrophilic polymers |
US6277364B1 (en) | 1998-10-09 | 2001-08-21 | Bertek Pharmaceuticals, Inc. | Polyurethanes as topical skin protectants |
DE60113066T2 (en) | 2000-02-07 | 2006-06-14 | Biocompatibles Uk Ltd | SILICON-CONTAINING COMPOUNDS MADE BY MICHAEL-LIKE ADDITIONAL REACTIONS AS MONOMERS AND MACROMERS |
US6451438B1 (en) | 2000-11-30 | 2002-09-17 | Mearthane Products Corporation | Copolymerization of reactive silicone and urethane precursors for use in conductive, soft urethane rollers |
US7976936B2 (en) * | 2002-10-11 | 2011-07-12 | University Of Connecticut | Endoprostheses |
US7084188B2 (en) * | 2003-12-05 | 2006-08-01 | Bausch & Lomb Incorporated | Surface modification of contact lenses |
US7176268B2 (en) * | 2003-12-05 | 2007-02-13 | Bausch & Lomb Incorporated | Prepolymers for improved surface modification of contact lenses |
WO2006014138A1 (en) * | 2004-08-03 | 2006-02-09 | Agency For Science, Technology And Research | Polymer having interconnected pores for drug delivery and method |
EP2087020A4 (en) * | 2006-11-17 | 2010-11-24 | Agency Science Tech & Res | Porous polymeric material with cross-linkable wetting agent |
US8101702B2 (en) * | 2007-01-12 | 2012-01-24 | Dow Corning Corporation | Silicone-containing composition |
US8222341B2 (en) | 2009-03-17 | 2012-07-17 | Mearthane Products Corporation | Semi-conductive silicone polymers |
US8513353B2 (en) | 2009-03-19 | 2013-08-20 | Agency For Science, Technology And Research | Forming copolymer from bicontinuous microemulsion comprising monomers of different hydrophilicity |
US9464159B2 (en) | 2009-11-02 | 2016-10-11 | Ocutec Limited | Polymers for contact lenses |
GB0919459D0 (en) | 2009-11-06 | 2009-12-23 | Ocutec Ltd | Polymer for contact lenses |
US20120316256A1 (en) * | 2009-11-02 | 2012-12-13 | Abdul Rashid | Polymers for Contact Lenses |
US20110136985A1 (en) * | 2009-12-09 | 2011-06-09 | Moon Douglas E | Molded article having a mold imparted release layer coating |
JP2014032273A (en) * | 2012-08-02 | 2014-02-20 | Talex Optical Co Ltd | Photochromic lens |
CN104781704B (en) | 2012-09-14 | 2021-01-01 | 奥库泰克有限公司 | Polymers for contact lenses |
JP2015011305A (en) * | 2013-07-02 | 2015-01-19 | スタンレー電気株式会社 | Device and method for attaching soft contact lens |
CN113773794A (en) * | 2021-08-27 | 2021-12-10 | 金冠电气股份有限公司 | High-barrier PBT-polysiloxane copolymer-based composite material for packaging lightning arrester |
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US3179622A (en) * | 1962-03-26 | 1965-04-20 | Dow Corning | Polysiloxane isocyanates |
US3562352A (en) * | 1968-09-06 | 1971-02-09 | Avco Corp | Polysiloxane-polyurethane block copolymers |
FR2168221A1 (en) * | 1972-01-21 | 1973-08-31 | Pechiney Ugine Kuhlmann | Polyurethane copolymers - used for coatings esp on textiles |
DE2730744A1 (en) * | 1977-07-07 | 1979-05-03 | Bayer Ag | ORGANOPOLYSILOXANE COMPOSITIONS MODIFIED WITH POLYURETHANE |
US4292423A (en) * | 1979-04-19 | 1981-09-29 | Wacker-Chemie Gmbh | Process for the preparation of organopolysiloxanes |
JPS57156005A (en) * | 1981-03-20 | 1982-09-27 | Nitto Electric Ind Co Ltd | Selective permeable membrane |
US4692476A (en) * | 1983-12-09 | 1987-09-08 | Rogers Corporation | Complex block multipolymer surfactants |
US4644046A (en) * | 1984-06-20 | 1987-02-17 | Teijin Limited | Ultrathin film, process for production thereof, and use thereof for concentrating a specific gas from a gas mixture |
US4590224A (en) * | 1984-08-20 | 1986-05-20 | The Dow Chemical Company | Siloxane-containing polyisocyanurate |
DE3517612A1 (en) * | 1985-05-15 | 1987-01-02 | Titmus Eurocon Kontaktlinsen | MODIFIED SILICONE RUBBER AND ITS USE AS A MATERIAL FOR AN OPTICAL LENS AND OPTICAL LENS OF THIS MATERIAL |
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US4740533A (en) * | 1987-07-28 | 1988-04-26 | Ciba-Geigy Corporation | Wettable, flexible, oxygen permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof |
EP0362137A3 (en) * | 1988-09-28 | 1991-09-04 | Ciba-Geigy Ag | Molded polymers with hydrophilic surfaces, and process for making them |
-
1988
- 1988-11-03 US US07/266,555 patent/US4962178A/en not_active Expired - Fee Related
-
1989
- 1989-10-24 AT AT89810801T patent/ATE108809T1/en not_active IP Right Cessation
- 1989-10-24 DE DE68916907T patent/DE68916907T2/en not_active Expired - Fee Related
- 1989-10-24 ES ES89810801T patent/ES2057173T3/en not_active Expired - Lifetime
- 1989-10-24 EP EP89810801A patent/EP0367720B1/en not_active Expired - Lifetime
- 1989-10-27 AU AU43852/89A patent/AU629252B2/en not_active Ceased
- 1989-10-31 PT PT92162A patent/PT92162B/en not_active IP Right Cessation
- 1989-11-01 CA CA002001969A patent/CA2001969C/en not_active Expired - Fee Related
- 1989-11-02 IE IE353189A patent/IE63682B1/en not_active IP Right Cessation
- 1989-11-02 JP JP1285146A patent/JP2845998B2/en not_active Expired - Lifetime
- 1989-11-02 DK DK547189A patent/DK547189A/en not_active Application Discontinuation
- 1989-12-11 TW TW078109554A patent/TW205557B/zh active
-
1997
- 1997-01-23 HK HK9297A patent/HK9297A/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
PT92162B (en) | 1996-04-30 |
AU4385289A (en) | 1990-05-10 |
IE893531L (en) | 1990-05-03 |
EP0367720A2 (en) | 1990-05-09 |
ES2057173T3 (en) | 1994-10-16 |
TW205557B (en) | 1993-05-11 |
EP0367720A3 (en) | 1991-07-03 |
JP2845998B2 (en) | 1999-01-13 |
PT92162A (en) | 1990-05-31 |
DE68916907T2 (en) | 1994-11-24 |
ATE108809T1 (en) | 1994-08-15 |
DK547189A (en) | 1990-05-04 |
DK547189D0 (en) | 1989-11-02 |
DE68916907D1 (en) | 1994-08-25 |
HK9297A (en) | 1997-01-31 |
EP0367720B1 (en) | 1994-07-20 |
IE63682B1 (en) | 1995-05-31 |
US4962178A (en) | 1990-10-09 |
AU629252B2 (en) | 1992-10-01 |
CA2001969A1 (en) | 1990-05-03 |
JPH02180920A (en) | 1990-07-13 |
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