CN1989426A - 含羟基和硅氧烷官能团的(甲基)丙烯酰胺单体和由其制备的聚合物 - Google Patents
含羟基和硅氧烷官能团的(甲基)丙烯酰胺单体和由其制备的聚合物 Download PDFInfo
- Publication number
- CN1989426A CN1989426A CNA2005800120962A CN200580012096A CN1989426A CN 1989426 A CN1989426 A CN 1989426A CN A2005800120962 A CNA2005800120962 A CN A2005800120962A CN 200580012096 A CN200580012096 A CN 200580012096A CN 1989426 A CN1989426 A CN 1989426A
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- Prior art keywords
- polymkeric substance
- group
- poly
- vinyl
- monomer
- Prior art date
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- Granted
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- 239000000178 monomer Substances 0.000 title claims abstract description 79
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920001296 polysiloxane Chemical group 0.000 title claims description 8
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 12
- -1 polyoxyethylene Polymers 0.000 claims description 85
- 239000000126 substance Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 25
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 21
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 14
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 150000001555 benzenes Chemical class 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000005401 siloxanyl group Chemical group 0.000 claims description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000012749 thinning agent Substances 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- RKOOOVKGLHCLTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.OCC(O)CO RKOOOVKGLHCLTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- SJHPCNCNNSSLPL-CSKARUKUSA-N (4e)-4-(ethoxymethylidene)-2-phenyl-1,3-oxazol-5-one Chemical compound O1C(=O)C(=C/OCC)\N=C1C1=CC=CC=C1 SJHPCNCNNSSLPL-CSKARUKUSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 2
- GAVHQOUUSHBDAA-UHFFFAOYSA-N 3-butyl-1-ethenylaziridin-2-one Chemical compound CCCCC1N(C=C)C1=O GAVHQOUUSHBDAA-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
- FJMKECANSIPFJO-UHFFFAOYSA-N carbamic acid ethenyl acetate Chemical compound C(=C)OC(C)=O.NC(=O)O FJMKECANSIPFJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920000669 heparin Polymers 0.000 claims description 2
- 229960002897 heparin Drugs 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000009736 wetting Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 150000002118 epoxides Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229960002668 sodium chloride Drugs 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 230000003139 buffering effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CBTJEAMLAOXIEA-UHFFFAOYSA-N 1-amino-3-prop-2-enoxypropan-2-ol Chemical compound NCC(O)COCC=C CBTJEAMLAOXIEA-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001348 alkyl chlorides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 235000011121 sodium hydroxide Nutrition 0.000 description 3
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- 230000003068 static effect Effects 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- PWNYZINJOHLMND-UHFFFAOYSA-N tert-butyl-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CC(C)(C)[Si](C)(C)CCCOCC1CO1 PWNYZINJOHLMND-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- 235000000126 Styrax benzoin Nutrition 0.000 description 2
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- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
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- 239000000539 dimer Substances 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 238000003760 magnetic stirring Methods 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
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- 125000002769 thiazolinyl group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- LVLANIHJQRZTPY-UHFFFAOYSA-N vinyl carbamate Chemical compound NC(=O)OC=C LVLANIHJQRZTPY-UHFFFAOYSA-N 0.000 description 2
- ZVGPPFGMUAUQFO-UHFFFAOYSA-N (3-amino-2-methyl-3-oxoprop-1-enyl) prop-2-enoate Chemical compound C(C=C)(=O)OC=C(C(=O)N)C ZVGPPFGMUAUQFO-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NWBTXZPDTSKZJU-UHFFFAOYSA-N 3-[dimethyl(trimethylsilyloxy)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)C NWBTXZPDTSKZJU-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BGFGZHGVQXGITL-UHFFFAOYSA-N C(=O)Cl.C=CC1=CC=CC=C1 Chemical compound C(=O)Cl.C=CC1=CC=CC=C1 BGFGZHGVQXGITL-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明涉及式(I，II)(甲基)丙烯酰胺单体，其中R为H或CH3，R1选自H、取代和未取代的具有1－8个碳原子的烷基、取代和未取代的苯和甲苯基团，R2、R3和R4独立选自具有1－8个碳原子的烷基、取代和未取代的苯和甲苯基团以及－OSiR5R6R7，其中R5、R6和R7独立选自具有1－4个碳原子的直链或支链烷基。还公开了由其制备的聚合物。
Description
发明领域
本发明涉及新的含羟基和硅氧烷官能团的(甲基)丙烯酰胺单体和由其制备的聚合物。
发明背景
已发现各种含硅氧烷的单体具有用作制备医疗装置，例如眼用装置，尤其是具有使氧渗透性改善的软接触镜片原料的实用性。一类适宜的单体包括三和二(三甲基甲硅烷氧基)甲硅烷基烷基甘油甲基丙烯酸酯(″SiAGMA″)。另一类硅氧烷单体包括含硅氧烷的氨基甲酸乙烯酯。但是，眼用装置领域仍需要可使含硅氧烷的单体和大分子单体与亲水性单体和聚合物相容，形成光学清洁和具有需要临床性质，例如氧渗透性和湿润性的聚合物和聚合物网络的其它单体。
发明概述
本发明涉及下式(甲基)丙烯酰胺单体：
其中R为H或CH3，R1选自H、取代和未取代的具有1-8个碳原子的烷基、取代和未取代的苯和甲苯基团以及
和R2、R3和R4独立选自具有1-8个碳原子的烷基、取代和未取代的苯和甲苯基团以及-OSiR5R6R7，其中R5、R6和R7独立选自具有1-4个碳原子的直链或支链烷基。
发明描述
本发明组合物具有下式：
式I
其中R为H或CH3，R1选自H、具有1-8个碳原子的取代和未取代的烷基、取代和未取代的苯和甲苯基团以及
和R2、R3和R4独立选自具有1-8个碳原子的烷基、取代和未取代的苯和甲苯基团以及-OSiR5R6R7，其中R5、R6和R7独立选自具有1-4个碳原子的直链或支链烷基。
在优选的实施方案中，R1为H或具有1-3个碳原子的烷基，R2、R3和R4中的至少两个相同，且选自具有1-4个碳原子的烷基和-OSiR5R6R7，其中R5、R6和R7独立选自具有1-4个碳原子的直链或支链烷基。更优选R2、R3和R4中的至少两个相同，且选自甲基、乙基、叔丁基和三甲基甲硅烷氧基。(甲基)丙烯酰胺单体的具体实例包括：
1)N-(2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅烷基)丙氧基)丙基)-2-甲基丙烯酰胺；
2)N-(2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅烷基)丙氧基)丙基)丙烯酰胺；
3)N，N-二[2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺；
4)N，N-二[2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅烷基)丙氧基)丙基]丙烯酰胺；
5)N-(2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基)-2-甲基丙烯酰胺；
6)N-(2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基)丙烯酰胺；
7)N，N-二[2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基]2-甲基丙烯酰胺；
8)N，N-二[2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基]丙烯酰胺；
9)N-[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺；
10)N-[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]丙烯酰胺；
11)N，N-二[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺；
12)N，N-二[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]丙烯酰胺。
在醇的存在下，可通过使取代的环氧化物与氨反应形成含羟基的胺，然后使含羟基的胺与酰氯反应产生需要的(甲基)丙烯酰胺单体，从而制备本发明(甲基)丙烯酰胺单体。适宜的取代环氧化物包括下式那些环氧化物：
其中R2、R3和R4定义同上。第一步的反应条件包括高达约30℃温度，和约10小时至约5日反应时间。压力并不重要，可使用环境压力。优选的醇包括甲醇、乙醇和异丙醇，优选甲醇。可将溶液在真空下浓缩。
使得自第一步的胺与烷基氯，例如异丁烯酰氯或丙烯酰氯和任选阻聚剂反应。烷基氯的用量可从等摩尔至略微过量，例如胺：烷基氯约1∶1至约1∶约1.2。
可使用能降低聚合速度的任何阻聚剂。适宜的阻聚剂包括氢醌单甲醚、丁基化羟基甲苯及其混合物等。加入阻聚剂的量可最高达约10,000ppm，优选加入量为约1至约1,000ppm。
反应在非极性有机溶剂，例如己烷或二氯甲烷中，在约室温中进行，反应时间为约12至约24小时。
可通过已知的方法，例如但不限于真空，将得到的(甲基)丙烯酰胺单体浓缩。可通过包括酸性萃取或硅胶层析、用离子交换树脂处理、离子交换柱及其组合等的各种方法，纯化(甲基)丙烯酰胺单体。这些纯化方法的条件在本领域中已知。
本领域技术人员将认识到温度与反应时间成反比，较高的反应温度可使反应时间缩短，反之亦然。另外，例如降低试剂浓度的降低反应速度的其它反应条件也可用于本发明方法。
在通过自由基聚合形成聚合物的制备中，可用本发明(甲基)丙烯酰胺单体作为组分。本发明(甲基)丙烯酰胺单体可与含至少一个可聚合基团的其它单体、预聚物或大分子单体均聚或聚合。适宜的可聚合基团包括可进行自由基和/或阳离子聚合的单价基团。优选的可聚合基团包含自由基活性基团，例如丙烯酸酯、苯乙烯基、乙烯基、乙烯基醚、C1-6烷基丙烯酸酯、丙烯酰胺、C1-6烷基丙烯酰胺、N-乙烯基内酰胺、N-乙烯基酰胺、C2-12烯基、C2-12烯基苯基、C2-12烯基萘基或C2-6烯基苯基C1-6烷基，或阳离子活性基团，例如乙烯基醚或环氧化物基团及其混合物。尤其优选的可聚合基团包括甲基丙烯酸酯、丙烯酰氧基、甲基丙烯酰胺、丙烯酰胺及其混合物。除可聚合的基团外，单体、预聚体和大分子单体可含任何能够给聚合物提供需要的性质，例如弹性、刚度、含水量、防水性、亲水性、润滑性、抗老化和抗高温及其组合等的其它官能团。适宜的其它官能团包括羧酸、酸酐、酯、酰卤、酮、醛、醚、醇、胺、酰胺、腈、硝基、硫化物、硫醇、硅烷、硅氧烷、卤化物，直链、支链和环状烷和烯、炔及其组合等。
在一个实施方案中，聚合物是水凝胶聚合物，例如用于生物医学装置例如眼用装置的那些聚合物。
在一个实施方案中，本发明(甲基)丙烯酰胺单体用作形成硅氧烷水凝胶的活性混合物的组分。硅氧烷水凝胶含至少一种(甲基)丙烯酰胺单体、至少一种亲水性组分和任选至少一种含硅氧烷的组分。(甲基)丙烯酰胺单体尤其可用于制备含至少一种内湿润剂的硅氧烷水凝胶。(甲基)丙烯酰胺单体起相容性试剂的作用，使亲水性单体和含硅氧烷的单体聚合在一起，形成清洁的物品，例如眼用装置。
本发明(甲基)丙烯酰胺单体的“相容有效量”是用选择的稀释剂溶解水凝胶制剂中的高分子量亲水性聚合物和其它组分所需的量。因此，(甲基)丙烯酰胺单体的量将部分取决于使用内湿润剂的量，其使用需要更多的(甲基)丙烯酰胺单体，以便使更高浓度的内湿润剂增溶。制剂中的(甲基)丙烯酰胺单体的有效量包括约5％(％重量，以活性组分重量百分比计)至约90％，优选约10％至约80％，最优选约20％至约50％。
当与其余活性组分组合时，亲水性组分包括能够为得到的镜片提供至少约20％，优选至少约25％含水量的那些组分。适宜的亲水性组分可存在的量占所有活性组分重量约10％至约60％重量，约15％至约50％重量，更优选约20％至约40％重量。可用于制备本发明聚合物的亲水性单体具有至少一个可聚合的双键，和至少一种亲水性官能团。可聚合双键的实例包括丙烯酸、甲基丙烯酸、丙烯酰胺基、甲基丙烯酰胺基、富马酸、马来酸、苯乙烯基、异丙烯基苯基、O-乙烯基碳酸酯、O-乙烯基氨基甲酸酯、烯丙基、O-乙烯基乙酰基和N-乙烯基内酰胺和N-乙烯基酰胺基双键。此类亲水性单体本身可用作交联剂。
“丙烯酸型”或“含丙烯酸的”单体是含丙烯酸基(CR′H＝CRCOX)的那些单体，其中R是H或CH3，R′是H、烷基或羰基，且X是O或N，还已知它们容易聚合，例如N，N-二甲基丙烯酰胺(DMA)、丙烯酸2-羟基乙基酯、甘油甲基丙烯酸酯、N-2-羟基乙基(甲基丙烯酰胺)、聚乙二醇单甲基丙烯酸酯、甲基丙烯酸、丙烯酸及其混合物。
可结合至本发明水凝胶的含乙烯基的亲水性单体包括单体例如N-乙烯基内酰胺(例如N-乙烯基吡咯烷酮(NVP))、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基乙酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基甲酰胺、N-2-羟基乙基氨基甲酸乙烯酯、N-羧基-β-丙氨酸N-乙烯基酯，优选NVP。
可 用于本发明的其它亲水性单体包括具有一个或多个被含可聚合双键的官能团置换的末端羟基的聚氧乙烯多元醇。实例包括具有一个或多个被含可聚合双键的官能团置换的末端羟基的聚乙二醇。实例包括与一个或多个摩尔当量的封端基团，例如异氰酸乙酯基甲基丙烯酸酯(″IEM″)、甲基丙烯酸酐、异丁烯酰氯、乙烯基苯甲酰氯等反应的聚乙二醇，产生具有一个或多个末端可聚合烯基的聚乙烯多元醇，该烯基通过连接部分，例如氨基甲酸酯或酯基与聚乙烯多元醇结合。
还再一个实例是在美国专利号5,070,215中公开的亲水性碳酸乙烯酯或氨基甲酸乙烯酯单体，和在美国专利号4,190,277中公开的亲水性唑酮单体。其它适宜的亲水性单体对本领域技术人员而言是显而易见的。
更优选的可结合至本发明聚合物的亲水性单体包括亲水性单体，例如N，N-二甲基丙烯酰胺(DMA)、丙烯酸2-羟基乙基酯、甲基丙烯酸2-羟基乙基酯(HEMA)、甘油甲基丙烯酸酯、N-2-羟基乙基(甲基丙烯酰胺)、N-乙烯基吡咯烷酮(NVP)和聚乙二醇单甲基丙烯酸酯。
最优选的亲水性单体包括HEMA、DMA、NVP及其混合物。
除所述(甲基)丙烯酰胺单体外，活性组分还可任选包含至少一种含硅氧烷的组分。适宜的含硅氧烷的组分在单体、大分子单体或预聚物中包括至少一个[-Si-O-Si]基团。优选，按含硅氧烷的组分的总分子量计，存在于含硅氧烷的组分中Si与所连接的O的量大于20％重量，更优选大于30％重量。优选，有用的含硅氧烷的组分含可聚合官能团，例如丙烯酸酯、甲基丙烯酸酯、丙烯酰胺、甲基丙烯酰胺、N-乙烯基内酰胺、N-乙烯基酰胺和苯乙烯基官能团。可包括在硅氧烷水凝胶制剂中的硅氧烷组分的实例包括但不限于硅氧烷大分子单体、预聚物和单体。硅氧烷大分子单体的实例包括但不限于在美国专利号4,259,467；4,260,725和4,261,875中描述的用亲水性侧基甲基丙烯酸酯化的聚二甲基硅氧烷；在美国专利号4,136,250；4,153,641；4,189,546；4,182,822；4,343,927；4,254,248；4,355,147；4,276,402；4,327,203；4,341,889；4,486,577；4,605,712；4,543,398；4,661,575；4,703,097；4,837,289；4,954,586；4,954,587；5,346,946；5,358,995；5,387,632；5,451,617；5,486,579；5,962,548；5,981,615；5,981,675；和6,039,913中描述的具有可聚合官能团的聚二甲基硅氧烷大分子单体；结合亲水性单体的聚硅氧烷大分子单体，例如在美国专利号5,010,141；5,057,578；5,314,960；5,371,147和5,336,797中描述的那些大分子单体；含聚二甲基硅氧烷嵌段和聚醚嵌段的大分子单体，例如在美国专利号4,871,785和5,034,461中描述的那些大分子单体，及其组合等。本文中引用的所有专利均通过引用结合到本文中。
也可使用在美国专利号5,760,100；5,776,999；5,789,461；5,807,944；5,965,631和5,958,440中描述的含硅氧烷和/或氟的大分子单体。适宜的硅氧烷单体包括甲基丙烯酸三(三甲基甲硅烷氧基)甲硅烷基丙基酯；含具有羟基官能团的硅氧烷的单体，例如3-甲基丙烯酰氧基-2-羟基丙氧基)丙基二(三甲基甲硅烷氧基)甲基硅烷和在WO03/22321中描述的那些单体，和在美国专利号4,120,570；4,139,692；4,463,149；4,450,264；4,525,563；5,998,498；3,808,178；4,139,513；5,070,215；5,710,302；5,714,557和5,908,906中描述的含mPDMS或硅氧烷单体。
其它适宜的含硅氧烷的单体包括在美国专利4,711,943中描述的TRIS的酰胺类似物，在美国专利5,070,215中描述的乙烯基氨基甲酸酯或碳酸酯类似物，和包括在美国专利6,020,445中的单体、单甲基丙烯酰氧基丙基封端的聚二甲基硅氧烷、聚二甲基硅氧烷、3-甲基丙烯酰氧基丙基二(三甲基甲硅烷氧基)甲基硅烷、甲基丙烯酰氧基丙基五甲基二硅氧烷及其组合。
本发明硅氧烷水凝胶还可包括内湿润剂，例如但不限于“高分子量亲水性聚合物”，它是指重均分子量不小于约100,000道尔顿的物质，当所述物质加入到硅氧烷水凝胶制剂时，可增加固化的硅氧烷水凝胶的湿润性。适宜的高分子量亲水性聚合物在WO03/022321中描述，其通过引用整体结合到本文中。
高分子量亲水性聚合物的适宜量包括约1％至约15％重量，更优选约3％至约15％，最优选约3％至约12％，它们均按所有活性组分的总量计。
高分子量亲水性聚合物的实例包括但不限于聚酰胺、聚内酯、聚酰亚胺、聚内酰胺和官能化的聚酰胺、聚内酯、聚酰亚胺、聚内酰胺，例如通过DMA与较小摩尔量含羟基官能团的单体例如HEMA共聚，然后使得到的共聚物的羟基与含可聚合自由基的物质，例如异氰酸乙酯基甲基丙烯酸酯或甲基丙烯酰氯反应，从而官能化的DMA。也可使用由DMA或正-乙烯基吡咯烷酮与甲基丙烯酸缩水甘油酯制备的亲水性预聚物。可使甲基丙烯酸缩水甘油酯环开环，得到二醇，该二醇可与在混合系统中的其它亲水性预聚物联合使用，以增加高分子量亲水性聚合物、含羟基官能化硅氧烷的单体和赋予相容性的任何其它基团的相容性。优选的高分子量亲水性聚合物是在它们骨架中含环部分的那些聚合物，更优选环酰胺或环状亚胺。高分子量亲水性聚合物包括但不限于聚-N-乙烯基吡咯烷酮、聚-N-乙烯基-2-哌啶酮、聚-N-乙烯基-2-己内酰胺、聚-N-乙烯基-3-甲基-2-己内酰胺、聚-N-乙烯基-3-甲基-2-哌啶酮、聚-N-乙烯基-4-甲基-2-哌啶酮、聚-N-乙烯基-4-甲基-2-己内酰胺、聚-N-乙烯基-3-乙基-2-吡咯烷酮和聚-N-乙烯基-4，5-二甲基-2-吡咯烷酮、聚乙烯基咪唑、聚-N-N-二甲基丙烯酰胺、聚乙烯醇、聚丙烯酸、聚环氧乙烷、聚2-乙基唑啉、肝素多糖、多糖、其混合物和共聚物(包括嵌段或无规、支化、多链、梳形或星形)，其中尤其优选聚-N-乙烯基吡咯烷酮(PVP)。也可使用共聚物，例如PVP的接枝共聚物。
用于制备本发明硅氧烷水凝胶的反应混合物还可包括一种或多种交联剂，又称为交联单体，例如乙二醇二甲基丙烯酸酯(″EGDMA″)、三羟甲基丙烷三甲基丙烯酸酯(″TMPTMA″)、甘油三甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯(其中，优选聚乙二醇的分子量最高达如约5000)和其它聚丙烯酸酯及聚甲基丙烯酸酯，例如上述含两个或多个末端甲基丙烯酸酯部分的封端聚氧乙烯多元醇。反应混合物中，交联剂的常用量为例如约0.000415至约0.0156摩尔/100克活性组分。(活性组分是反应混合物中除不会成为聚合物结构部分的稀释剂和任何其它处理助剂以外的所有物质)，或者，如果亲水性单体和/或含硅氧烷的单体起交联剂的作用，向反应混合物中加入交联剂是任选的。可用作交联剂和存在时不需要向反应混合物中加入另外交联剂的亲水性单体的实例，包括上述含两个或多个末端甲基丙烯酸酯部分的聚氧乙烯多元醇。
可用作交联剂和存在时不需要向反应混合物中加入交联单体的含硅氧烷单体的实例包括α，ω-双甲基丙烯酰基丙基聚二甲基硅氧烷。
反应混合物可含其它组分，例如但不限于UV吸收剂、药物、抗微生物化合物、活性调色剂、颜料、共聚和非聚合染料、脱模剂及其组合。
优选聚合催化剂包括在反应混合物内。聚合引发剂包括例如月桂酰过氧化物、过氧化苯甲酰、过碳酸异丙酯、偶氮二异丁腈等化合物，它们在中等提高温度下产生自由基；和光敏引发剂系统，例如芳族α-羟基酮、烷氧基氧基苯偶姻、苯乙酮、酰基膦氧化物、二酰基膦氧化物和叔胺+二酮及其混合物等。光敏引发剂的示例性实例是1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基-丙-1-酮、二(2，6-二甲氧基苯甲酰基)-2，4-4-三甲基戊基膦氧化物(DMBAPO)、二(2，4，6-三甲基苯甲酰基)-苯基膦氧化物(Irgacure 819)、2，4，6-三甲基苄基二苯基膦氧化物和2，4，6-三甲基苯甲酰基二苯基膦氧化物、苯偶姻甲酯以及莰醌和4-(N，N-二甲基氨基)苯甲酸乙酯的组合。市售可见光引发剂系统包括Irgacure 819、Irgacure 1700、Irgacure 1800、Irgacure 819、Irgacure 1850(均来自CibaSpecialty Chemicals)和Lucirin TPO引发剂(BASF有售)。市售UV光敏引发剂包括Darocur 1173和Darocur 2959(Ciba Specialty Chemicals)。可使用的这些和其它光敏引发剂在J.V.Crivello&K.Dietliker的Photoinitiators for Free Radical Cationic&Anionic Photopolymerization，第III卷，第2版；G.Bradley编辑；John Wiley and Sons；New York；1998中公开，该文献通过引用结合到本文中。以引发反应混合物光聚合反应的有效量，例如约0.1至约2份/100份活性单体(重量)，在反应混合物中使用引发剂。
可通过本领域技术人员已知的任何方法形成硅氧烷水凝胶。例如，可通过将活性组分与任何稀释剂和聚合引发剂混合，形成活性混合物，和通过适宜的条件固化形成产物，可随后通过车床加工、切割等使其成型具有适宜的形状，从而制备本发明眼用装置。或者，可将反应混合物置于模具中，随后固化成适当的物品。
已知在制备接触镜片时处理镜片配料的各种方法，包括旋模成型(spincasting)和静模铸造(static casting)。旋模成型方法在美国专利3,408,429和3,660,545中公开，静模铸造方法在美国专利4,113,224和4,197,266中公开。制备本发明接触镜片的优选方法是模制。按该方法，将镜片配料置于具有最后需要的镜片形状的模具中，使镜片配料经历使各组分聚合以形成镜片的条件。可将镜片用溶剂处理，除去稀释剂，最后用水取代稀释剂。该方法在美国专利号4,495,313；4,680,336；4,889,664；和5,039,459中进一步描述，这些专利通过引用结合到本文中。优选的固化方法是用照射，优选UV或可见光，最优选用可见光。
为说明本发明，引入以下实施例。这些实施例不限制本发明。它们仅用于介绍本发明的实施方法。用接触镜片的那些知识和其它专业知识可发现实施本发明的其它方法。但认为那些方法在本发明的范围中。
在23℃下，在硼酸盐缓冲盐水中，用Wilhelmy天平测量动态接触角或DCA。在按100微米/秒的速度，将从镜片中心部分切下的样品条浸入盐水中，同时用Wilhelmy微量天平测量镜片表面与硼酸盐缓冲盐水之间的润湿力。
用以下方程
F＝2γpcosθ或θ＝cos-1(F/2γp)
其中F是润湿力，γ是探测液体的表面张力，p是样品在弯液面的周长，θ是接触角。通常，由动态润湿实验得到两个接触角-前进接触角和后退接触角。前进接触角由其中将样品浸入探测液体的润湿实验部分得到，这些是本文中报道的值。测量每种组合物的至少4个镜片，报道平均值。
含水量测量如下：将待测镜片置于润湿溶液(packing solution)，保持24小时。用顶端装海棉的药签将3个测试镜片中的每个镜片从润湿溶液中取出，将镜片放置在已用润湿溶液润湿的吸湿擦拭物上。使镜片两面与擦拭物接触。用镊子将测试镜片置于称量盘，称重。再制备两组样品，如上称重。将盘称重3次，平均值为湿重。
通过将样品盘置于已经预热至60℃并保持30分钟的真空干燥箱中，来测量干重。抽真空，直至达到至少0.4英寸Hg。关闭真空阀和泵，将镜片干燥4小时。开启放气阀，使干燥箱达到常压。取出盘，称重。含水量计算如下：
湿重＝盘加镜片的湿重-称得的盘重量
干重＝盘加镜片的干重-称得的盘重量
含水量％＝[(湿重-干重)/湿重]×100
计算样品中含水量的平均值和标准差，并报道。
用配备降至初始计量高度的载样室的恒速移动型拉伸试验机十字头测量模量。适宜的试验机包括Instron型1122。将长0.522英寸，“耳”宽0.276英寸和“颈”宽0.213英寸的狗骨(dog-bone)形样品置于夹子内，以2英寸/分钟恒速拉伸，直至断裂。测量样品的初始计量长度(Lo)和样品断裂时的长度(Lf)。测量每种组合物的12份样品，报道平均值。在应力/应变曲线的初始线性部分测量拉伸模量。
以下实施例中使用以下缩写：
SiNAA N-(2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅
烷基)丙氧基)丙基)-2-甲基丙烯酰胺
SiNAA二聚体 N，N-二[2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基
甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺
MEHQ 氢醌单甲醚
环氧化物 (3-环氧丙氧基丙基)二(三甲基甲硅烷氧基)甲基
硅烷
用GC测定百分转化率如下。将10μL样品浸入1mL IPA。用GC-FID分析分散样品，条件如下：
载气：氦气
载气压：70 PSI
总流速：75mL/min
隔膜吹扫：3-5mL/min
氢气压：60 PSI
空气压：30 PSI
检测器：火焰离子化检测器@280℃
入口温度：280℃
自动进样器洗涤溶剂：异丙醇
柱：Restek RTX-5 30m×0.25mm×1.0μm(5％二苯基(diphenyl)，95％二甲基的聚硅氧烷)
进样体积：2μl(100∶1)分流
升温程序：
初始温度：60℃
升温速度(Ramp)：10℃/min
最终温度：325℃
最终时间：5min
平衡：7min
实施例1
在0℃下，将环氧化物(50g)加入带磁力搅拌棒的厚壁玻璃圆底烧瓶中。向该瓶中加入327mL 2.0M氨的甲醇溶液。将烧瓶用隔膜塞住，在室温(约25℃)下搅拌。约12小时后，取出少量等分试样(约200μL)反应混合物，用GC分析。GC表明反应物仍含一些环氧化物。另用薄层层析(TLC)分析反应混合物，再次证实有少量环氧化物存在(TLC展开剂：己烷/乙酸乙酯10/1，Rf0.65，用香草醛溶液显色)。将氨的甲醇溶液(2M，73mL)加入该溶液，在25℃下，再搅拌溶液。约20小时后，GC表明仅有少量环氧化物。TLC未检测出任何环氧化物，但的确表明胺出现(在基线上有新斑点，对茚三酮显阳性，TLC展开剂：己烷/乙酸乙酯10/1)。在55℃下，将溶液在真空下浓缩，得到49.00g粘性浅黄色液体。
实施例2
向装有冷凝器和加料漏斗的250mL三颈圆底烧瓶中加入32.53g得自实施例1的胺混合物、9.4g三乙胺和65mL己烷。将溶液用磁力搅拌棒搅拌。将甲基丙烯酰氯(10.61g)滴加到溶液中，将反应物搅拌过夜。约18小时后，将溶液用约200mL己烷稀释，依次用约250mL去离子水洗涤；用250mL 0.5M NaOH水溶液洗涤两次，用约250mL2.5％重量NaCl水溶液洗涤两次，和用约250mL饱和氯化钠水溶液洗涤一次。浅黄色有机相经硫酸钠干燥，过滤。将滤液真空浓缩，得到36.2g淡黄色液体。使该黄色液体通过硅胶柱层析纯化，用1∶4→1∶2的乙酸乙酯：己烷作洗脱液。将SiNAA和SiNAA二聚体分离。
实施例3
按表1所示量，加入100份以下表1所示组分和40份27.5∶72.5的PVP2500：叔-戊醇，形成反应混合物。将反应混合物在高真空下脱气，持续约15分钟。将反应混合物定量加入到热塑性接触镜片模具中，在氮气氛下，照射30-150秒，然后在45-65℃下固化，按1.5-3mW/cm2照射，持续约13分钟。将得到的镜片手工脱模，使其经历表2中列举的水化过程。在硼酸盐缓冲润湿溶液中检查镜片，将镜片置于含有硼酸盐缓冲润湿溶液的小瓶中，盖住，灭菌。按上述测量物理性质，包括45.2(10.6)psi模量，动态前进接触角64°(5)和含水量约50.1％(0.6)。圆括号中的值是标准差。因此，可用实施例2中制备的单体制备具有需要物理性质的接触镜片。
表1
| 组分 | 重量％ |
| SiNAA | 30.00 |
| mPDMS 1000 | 22.00 |
| DMA | 31.00 |
| HEMA | 8.50 |
| EGDMA | 0.75 |
| Norbloc | 1.50 |
| Blue HEMA | 0.02 |
| PVP 360,000 | 6.00 |
| CGI 819 | 0.23 |
表2
| 水化溶液 | 水化时间 |
| 70℃(±5℃)去离子水 | 180分钟(最小) |
| 45℃(±5℃)去离子水 | 30分钟(最小) |
| 室温，润湿溶液 | 30分钟(最小) |
实施例4
按表3所示量，加入100份表3所示组分和40份27.5∶72.5的PVP2500：叔-戊醇，形成反应混合物。将反应混合物在高真空下脱气约15分钟。将反应混合物定量加入到热塑性接触镜片模具中，在氮气氛下，照射30-150秒，然后在45-65℃下固化，按1.5-3mW/cm2照射，持续约13分钟。将得到的镜片手工脱模，使其经历表4中列举的水化过程。在硼酸盐缓冲润湿溶液中检查镜片，将镜片放入含有硼酸盐缓冲润湿溶液的小瓶中，盖住，灭菌。按上述测量物理性质，包括52.6(5.7)psi模量，动态前进接触角61°(6)和含水量约45.6％(0.1)。
表3
| 组分 | 重量％ |
| SiNAA | 30.00 |
| DMA | 20.00 |
| HEMA | 40.48 |
| EGDMA | 0.75 |
| PVP 360,000 | 7.00 |
| CGI 819 | 0.25 |
| Norbloc | 1.50 |
| Blue HEMA | 0.02 |
表4
| 水化溶液 | 水化时间 |
| 95℃(±5℃)去离子水 | 30分钟(±5分钟) |
| 70℃(±5℃)去离子水 | 180分钟(最小) |
| 70℃(±5℃)去离子水 | 30分钟(最小) |
| 室温，润湿溶液 | 30分钟(最小) |
实施例5
合成3-叔丁基二甲基甲硅烷基丙基缩水甘油醚
将烯丙氧基缩水甘油醚(50.6g，0.44mol)、氯化铂(36mg，200ppm)和甲苯(300mL)加入配备具有氮气出、入口的冷凝器和与温度控制器连接的热电偶的1升三颈烧瓶中。将混合物加热至86℃。在86℃下，搅拌下，将叔丁基二甲基硅烷(50.0g，0.43mol)滴加到以上混合物中。叔丁基二甲基硅烷加入结束后，在86℃下，将整个混合物搅拌。通过气相色谱监测反应。搅拌40小时后，将反应溶液用饱和碳酸氢钠水溶液、5％氯化钠水溶液洗涤，然后用饱和氯化钠水溶液最后洗涤。有机相经硫酸钠干燥，过滤。在45℃下，将滤液减压浓缩，得到褐色液体(～38g)。通过真空蒸馏，得到纯3-叔丁基二甲基甲硅烷基丙基缩水甘油醚，为透明、无色油状物。
实施例6
合成3-(3-(叔丁基二甲基甲硅烷基)丙氧基)-2-羟基丙胺
将氨的甲醇溶液(7mol氨的甲醇溶液，100mL，0.7mol)加入置于冰浴中的500mL单颈圆底烧瓶中。在0℃下，向以上溶液中滴加3-叔丁基二甲基甲硅烷基丙基缩水甘油醚(23.04g，0.1mol)。让混合物升温至室温，搅拌3天。然后将反应溶液升温至40-50℃，除去过量的氨。将甲醇减压除去。得到粗3-(叔丁基二甲基甲硅烷基丙氧基)-2-羟基丙胺，为透明、无色油状物(24g，98％收率)。
实施例7
合成N-[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺
将3-(3-(叔丁基二甲基甲硅烷基)丙氧基)-2-羟基丙胺(19.0g，0.077mol)、三乙胺(7.8g，10.8mL，0.08mol)和二氯甲烷(57mL)在置于冰浴中的250mL单颈烧瓶中混合。在0℃下，通过加料漏斗，向以上混合物中滴加甲基丙烯酰氯(8.3g，7.73mL，077mol)。甲基丙烯酰氯加入结束后，让全部混合物升温至室温，在室温下搅拌2天。将反应悬浮液用100mL二氯甲烷稀释，依次用去离子水、0.5N氢氧化钠水溶液、5％氯化钠水溶液两次、饱和氯化钠水溶液洗涤。有机相经硫酸钠干燥。将硫酸钠过滤除去后，用旋转蒸发仪将溶剂真空蒸发。通过硅胶柱层析纯化后，得到N-[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺，为白色固体。
实施例8
合成3-烯丙氧基-2-羟基-丙胺
将氢氧化铵(28％-30％(约14.82mol)氨水，202mL，3mol)加入在冰浴中冷却的1升单颈圆底烧瓶中。在0℃下，向以上溶液中滴加烯丙基缩水甘油醚(57.07g，0.5mol)。烯丙基缩水甘油醚加入结束后，让混合物升温至室温，搅拌2天。通过在0-1mbar下，在76℃-82℃下蒸馏，将3-烯丙氧基-2-羟基-丙胺分离，为透明液体(～33g)。
实施例9
合成N-(3-烯丙氧基-2-羟基丙基)-2-甲基丙烯酰胺
将实施例8中制备的3-烯丙氧基-2-羟基-丙胺(110g，0.84mol)、三乙胺(85.6g，0.84mol)和二氯甲烷(300mL)在置于冰浴中的2升两颈烧瓶中混合。在0℃下，通过加料漏斗，向以上混合物中滴加甲基丙烯酰氯(90.36g，84mol)。甲基丙烯酰氯加入结束后，让整个混合物升温至室温，在环境温度下搅拌过夜(～15小时)。将反应悬浮液用250mL二氯甲烷稀释，用5％氯化钠水溶液、饱和碳酸氢钠水溶液、5％氯化钠水溶液洗涤，然后用饱和氯化钠水溶液洗涤。有机相经硫酸钠(100g)干燥。将硫酸钠过滤除去后，将4-甲氧基苯酚(0.5g)加入滤液中。用旋转蒸发仪将溶液真空浓缩，得到约122g粗N-(3-烯丙氧基-2-羟基-丙基)-2-甲基丙烯酰胺。用Kugelrohr蒸馏仪器，通过在真空(7-8mbar下，在168℃-170℃，将用1％4-甲氧基苯酚阻聚的粗物质蒸馏，纯化N-(3-烯丙氧基-2-羟基-丙基)-2-甲基丙烯酰胺。
实施例10
合成N-(2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基)-2-甲基丙烯酰胺
将按实施例9制备的N-(3-烯丙氧基-2-羟基-丙基)-2-甲基丙烯酰胺(18g，0.09mol)、氯化铂(4mg，100ppm)、BHT(36mg，2000ppm)和甲苯(90mL)加入配备具有氮气出、入口的冷凝器和与温度控制器连接的热电偶的500mL三颈烧瓶中。在96-97℃下，将三(三甲基甲硅烷氧基)硅烷(26.8g，0.09mol)滴加到以上混合物中。在约96℃下搅拌16小时后，向反应溶液中再加入氯化铂(4mg，100ppm)。通过气相色谱监测反应。搅拌47小时后，将反应溶液用0.5N氢氧化钠水溶液洗涤，用2.5％氯化钠水溶液洗涤两次。随后用饱和氯化钠水溶液洗涤。有机相经硫酸钠干燥，过滤。在30℃-40℃下，将用4-甲氧基苯酚(0.02g)阻聚的滤液减压浓缩，得到油状物(～36g)。N-(2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基)-2-甲基丙烯酰胺通过柱层析纯化。
Claims (28)
1.一种下式组合物：
其中R为H或CH3，R1选自H、具有1-8个碳原子的取代和未取代的烷基、取代和未取代的苯和甲苯基团以及
和R2、R3和R4独立选自具有1-8个碳原子的烷基、取代和未取代的苯和甲苯基团以及-OSiR5R6R7，其中R5、R6和R7独立选自具有1-4个碳原子的直链或支链烷基。
2.权利要求1的组合物，其中R3为CH3，R2和R4为-OSiR5R6R7。
3.权利要求1的组合物，其中R2、R3和R4中的至少两个为-OSiR5R6R7。
4.权利要求1的组合物，其中R2、R3和R4选自具有1-4个碳原子的烷基。
5.权利要求1的组合物，所述组合物具有式
6.权利要求1的组合物，所述组合物具有式
7.一种由反应混合物形成的聚合物，其中所述反应混合物包含至少一种亲水性单体、至少一种含硅氧烷的组分和至少一种下式(甲基)丙烯酰胺单体：
其中R为H或CH3，R1选自H、具有1-8个碳原子的取代和未取代的烷基、取代和未取代的苯和甲苯基团以及
和R2、R3和R4独立选自具有1-8个碳原子的烷基、取代和未取代的苯和甲苯基团以及-OSiR5R6R7，其中R5、R6和R7独立选自具有1-4个碳原子的直链或支链烷基。
8.权利要求7的聚合物，其中所述至少一种亲水性单体包含至少一个可聚合双键和至少一种亲水性官能团。
9.权利要求7的聚合物，其中所述至少一种亲水性单体选自亲水性含乙烯基的单体、聚氧化乙烯多元醇、碳酸乙烯酯单体、氨基甲酸乙烯酯单体、唑酮单体及其混合物。
10.权利要求7的聚合物，其中所述至少一种亲水性单体选自N，N-二甲基丙烯酰胺、丙烯酸2-羟基乙基酯、甲基丙烯酸2-羟基乙基酯、甘油甲基丙烯酸酯、N-2-羟基乙基(甲基丙烯酰胺)、N-乙烯基吡咯烷酮和聚乙二醇单甲基丙烯酸酯。
11.权利要求7的聚合物，其中所述至少一种亲水性单体选自甲基丙烯酸2-羟基乙基酯、N，N-二甲基丙烯酰胺、N-乙烯基吡咯烷酮及其混合物。
12.权利要求7的聚合物，其中所述至少一种亲水性单体存在的量占所有活性组分重量约10％至约60％重量。
13.权利要求7的聚合物，其中所述至少一种亲水性单体存在的量占所有活性组分重量约15％至约50％重量。
14.权利要求7的聚合物，其中所述至少一种亲水性单体存在的量占所有活性组分重量约20％至约40％重量。
15.权利要求7的聚合物，其中所述含硅氧烷的组分选自硅氧烷大分子单体、预聚物和单体。
16.权利要求15的聚合物，其中所述含硅氧烷的组分为选自以下的硅氧烷大分子单体：被侧链亲水性基团甲基丙烯酸酯化的聚二甲基硅氧烷、具有可聚合官能团的聚二甲基硅氧烷大分子单体、结合亲水性单体的聚硅氧烷大分子单体、包含聚二甲基硅氧烷嵌段和聚醚嵌段的大分子单体、含硅氧烷和氟的大分子单体及其组合。
17.权利要求15的聚合物，其中所述含硅氧烷的组分为选自以下的硅氧烷单体：甲基丙烯酸三(三甲基甲硅烷氧基)甲硅烷基丙基酯、含羟基官能团的硅氧烷单体、TRIS的酰胺类似物、氨基甲酸乙烯酯类似物、碳酸乙烯酯类似物、单甲基丙烯酰氧基丙基封端的聚二甲基硅氧烷、聚二甲基硅氧烷及其混合物。
18.权利要求15的聚合物，其中所述含硅氧烷的组分为选自以下的硅氧烷单体：甲基丙烯酸三(三甲基甲硅烷氧基)甲硅烷基丙基酯、mPDMS及其组合。
19.权利要求7的聚合物，所述聚合物还包含至少一种内湿润剂。
20.权利要求19的聚合物，其中所述内湿润剂包含至少一种高分子量亲水性聚合物。
21.权利要求20的聚合物，其中所述高分子量亲水性聚合物选自聚酰胺、聚内酯、聚酰亚胺、聚内酰胺和官能化的聚酰胺、聚内酯、聚酰亚胺、官能化聚内酰胺、亲水性预聚物及其组合。
22.权利要求20的聚合物，其中所述高分子量亲水性聚合物选自：
1)聚-N-乙烯基吡咯烷酮，
2)聚-N-乙烯基-2-哌啶酮，
3)聚-N-乙烯基-2-己内酰胺，
4)聚-N-乙烯基-3-甲基-2-己内酰胺，
5)聚-N-乙烯基-3-甲基-2-哌啶酮，
6)聚-N-乙烯基-4-甲基-2-哌啶酮，
7)聚-N-乙烯基-4-甲基-2-己内酰胺，
8)聚-N-乙烯基-3-乙基-2-吡咯烷酮，和
9)聚-N-乙烯基-4，5-二甲基-2-吡咯烷酮，
10)聚乙烯基咪唑，
11)聚-N-N-二甲基丙烯酰胺，
12)聚乙烯醇，
13)聚丙烯酸，
14)聚氧化乙烯，
15)聚2-乙基唑啉，
16)肝素多糖，
17)多糖，
其混合物和共聚物。
23.权利要求20的聚合物，其中所述高分子量亲水性聚合物包含聚-N-乙烯基吡咯烷酮。
24.权利要求20的聚合物，其中所述高分子量亲水性聚合物存在的量占所有活性组分总量约1％至约15％重量。
25.权利要求20的聚合物，其中所述高分子量亲水性聚合物存在的量占所有活性组分总量约3％至约15％。
26.权利要求7的聚合物，其中所述反应混合物还包含选自以下的其它组分：交联剂、光敏引发剂、稀释剂、UV吸收剂、药物、抗微生物化合物、活性调色剂、颜料、共聚和非共聚染料、脱模剂及其组合。
27.一种组合物，所述组合物选自
1)N-(2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅烷基)丙氧基)丙基)丙烯酰胺；
2)N，N-二[2-羟基-3-(3-(双(三甲基甲硅烷氧基)甲基甲硅烷基)丙氧基)丙基]丙烯酰胺；
3)N-(2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基)-2-甲基丙烯酰胺；
4)N-(2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基)丙烯酰胺；
5)N，N-二[2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基]2-甲基丙烯酰胺；
6)N，N-二[2-羟基-3-(3-(三(三甲基甲硅烷氧基)甲硅烷基)丙氧基)丙基]丙烯酰胺；
7)N-[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺；
8)N-[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]丙烯酰胺；
9)N，N-二[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]-2-甲基丙烯酰胺；
10)N，N-二[2-羟基-3-(3-(叔丁基二甲基甲硅烷基)丙氧基)丙基]丙烯酰胺。
28.一种聚合物，所述聚合物包含至少一种下式基团：
其中R为H或CH3，R1选自H、具有1-8个碳原子的取代和未取代的烷基、取代和未取代的苯和甲苯基团以及
和R2、R3和R4独立选自具有1-8个碳原子的烷基、取代和未取代的苯和甲苯基团以及-OSiR5R6R7，其中R5、R6和R7独立选自具有1-4个碳原子的直链或支链烷基。
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| US10/776,739 US7214809B2 (en) | 2004-02-11 | 2004-02-11 | (Meth)acrylamide monomers containing hydroxy and silicone functionalities |
| US10/776,739 | 2004-02-11 | ||
| PCT/US2005/004192 WO2005078482A1 (en) | 2004-02-11 | 2005-02-09 | (meth)acrylamide monomers containing hydroxy and silicone functionalities and polymers made therefrom |
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| CN1989426B CN1989426B (zh) | 2013-05-08 |
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- 2005-02-09 KR KR1020067018517A patent/KR101195779B1/ko not_active IP Right Cessation
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- 2005-02-09 JP JP2006553221A patent/JP5575358B2/ja not_active Expired - Fee Related
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- 2005-02-09 CN CN2005800120962A patent/CN1989426B/zh not_active Expired - Fee Related
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- 2005-02-10 AR ARP050100479A patent/AR047607A1/es unknown
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2007
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| CN102170940A (zh) * | 2008-10-03 | 2011-08-31 | 迈图高新材料公司 | 亲水性硅酮单体、其制备方法及包含其的薄膜 |
| CN102170940B (zh) * | 2008-10-03 | 2015-10-07 | 迈图高新材料公司 | 亲水性硅酮单体、其制备方法及包含其的薄膜 |
| CN102803273A (zh) * | 2010-03-18 | 2012-11-28 | 庄臣及庄臣视力保护公司 | 有机硅水凝胶眼用透镜和接触镜片 |
| CN105566371A (zh) * | 2010-03-18 | 2016-05-11 | 庄臣及庄臣视力保护公司 | 有机硅(甲基)丙烯酰胺单体、聚合物、眼用透镜以及接触镜片 |
| CN102803273B (zh) * | 2010-03-18 | 2016-05-18 | 庄臣及庄臣视力保护公司 | 有机硅水凝胶眼用透镜和接触镜片 |
| CN104220448A (zh) * | 2012-04-20 | 2014-12-17 | 赢创工业集团股份有限公司 | 通过氨基烷基-烷氧基硅烷与丙烯酸酐的反应制备（甲基）丙烯酰氨基-官能的硅烷的方法 |
| CN104220448B (zh) * | 2012-04-20 | 2017-03-01 | 赢创德固赛有限公司 | 通过氨基烷基‑烷氧基硅烷与丙烯酸酐的反应制备(甲基)丙烯酰氨基‑官能的硅烷的方法 |
| CN106800626A (zh) * | 2012-11-30 | 2017-06-06 | 晶硕光学股份有限公司 | 硅水胶组合物及以该组合物制造的硅水胶镜片 |
| CN104447843A (zh) * | 2013-09-25 | 2015-03-25 | 信越化学工业株式会社 | 含有自由基聚合性基团的硅酮化合物及其制造方法 |
| CN106456830B (zh) * | 2014-04-18 | 2020-11-03 | 宾视研发公司 | 用于隐形眼镜和人工晶状体的(甲基)丙烯酰胺聚合物 |
| CN106456830A (zh) * | 2014-04-18 | 2017-02-22 | 宾视研发公司 | 用于隐形眼镜和人工晶状体的(甲基)丙烯酰胺聚合物 |
| CN104945570A (zh) * | 2015-07-03 | 2015-09-30 | 东南大学 | 一种硅凝胶接触透镜及其表面反转处理方法 |
| CN104945570B (zh) * | 2015-07-03 | 2017-06-09 | 东南大学 | 一种硅凝胶接触透镜及其表面反转处理方法 |
| CN109790353A (zh) * | 2016-07-06 | 2019-05-21 | 庄臣及庄臣视力保护公司 | 包含聚酰胺的有机硅水凝胶 |
| CN109790353B (zh) * | 2016-07-06 | 2021-12-03 | 庄臣及庄臣视力保护公司 | 包含聚酰胺的有机硅水凝胶 |
| CN113164642A (zh) * | 2018-12-12 | 2021-07-23 | 东丽株式会社 | 医疗设备 |
| CN113248719A (zh) * | 2021-04-19 | 2021-08-13 | 江苏海伦隐形眼镜有限公司 | 单封端有机硅氧烷齐聚物、硅水凝胶、角膜接触镜及制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005078482A1 (en) | 2005-08-25 |
| KR20070007798A (ko) | 2007-01-16 |
| HK1098536A1 (en) | 2007-07-20 |
| JP5575358B2 (ja) | 2014-08-20 |
| AU2005213698B2 (en) | 2011-10-20 |
| US7214809B2 (en) | 2007-05-08 |
| DE602005027319D1 (de) | 2011-05-19 |
| KR101195779B1 (ko) | 2012-11-06 |
| US7396890B2 (en) | 2008-07-08 |
| TW200604558A (en) | 2006-02-01 |
| AU2005213698A1 (en) | 2005-08-25 |
| JP2007526364A (ja) | 2007-09-13 |
| AR047607A1 (es) | 2006-01-25 |
| BRPI0507620A (pt) | 2007-07-03 |
| US20070167592A1 (en) | 2007-07-19 |
| CN1989426B (zh) | 2013-05-08 |
| US20050176911A1 (en) | 2005-08-11 |
| EP1716436A1 (en) | 2006-11-02 |
| CA2556167A1 (en) | 2005-08-25 |
| TWI370262B (en) | 2012-08-11 |
| EP1716436B1 (en) | 2011-04-06 |
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