JP4645016B2 - Method for producing silicone compound - Google Patents
Method for producing silicone compound Download PDFInfo
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- JP4645016B2 JP4645016B2 JP2003368529A JP2003368529A JP4645016B2 JP 4645016 B2 JP4645016 B2 JP 4645016B2 JP 2003368529 A JP2003368529 A JP 2003368529A JP 2003368529 A JP2003368529 A JP 2003368529A JP 4645016 B2 JP4645016 B2 JP 4645016B2
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- silicone compound
- formula
- compound represented
- following general
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 43
- 229920001296 polysiloxane Polymers 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 trimethylsiloxy Chemical group 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 210000004087 cornea Anatomy 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 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 1
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 1
- LBRXIILHIHJEAW-UHFFFAOYSA-N 2-ethyl-3-oxopent-4-enoic acid Chemical compound CCC(C(O)=O)C(=O)C=C LBRXIILHIHJEAW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 1
- AEYSASDBPHWTGR-UHFFFAOYSA-N 4-oxohex-5-ene-3-sulfonic acid Chemical compound CCC(S(O)(=O)=O)C(=O)C=C AEYSASDBPHWTGR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- QKLXQAAHFKAFNS-UHFFFAOYSA-N CC(C(OCC(COCCCNC)OC(C(C)=C)=O)=O)=C Chemical compound CC(C(OCC(COCCCNC)OC(C(C)=C)=O)=O)=C QKLXQAAHFKAFNS-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- KWSGODHUGLIESB-UHFFFAOYSA-N ethenyl ethaneperoxoate Chemical compound CC(=O)OOC=C KWSGODHUGLIESB-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005401 siloxanyl group Chemical group 0.000 description 1
- PQCHENNROHVIHO-UHFFFAOYSA-M silver;2-methylprop-2-enoate Chemical compound [Ag+].CC(=C)C([O-])=O PQCHENNROHVIHO-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- IXSPLXSQNNZJJU-UHFFFAOYSA-N trimethyl(silyloxy)silane Chemical compound C[Si](C)(C)O[SiH3] IXSPLXSQNNZJJU-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XAASNKQYFKTYTR-UHFFFAOYSA-N tris(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)O[Si](C)(C)C XAASNKQYFKTYTR-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、コンタクトレンズ、眼内レンズ、人工角膜などの眼用レンズに特に好適なポリマーを得ることができるシリコーン化合物の製造方法に関する。 The present invention relates to a method for producing a silicone compound capable of obtaining a polymer particularly suitable for ophthalmic lenses such as contact lenses, intraocular lenses and artificial corneas.
従来、眼用レンズ用モノマーとして、ケイ素基を有する化合物が知られている。 Conventionally, compounds having a silicon group are known as monomers for ophthalmic lenses.
そのような化合物の一つとして、上記式(c)または(c’)で表される化合物が知られている(例えば、特許文献1)。この化合物は分子内に水酸基を有することから親水性モノマーとの相溶性が得やすいという特長を有するが、これを上記特許文献1記載の方法で合成すると、副生成物として下記式(d) As one of such compounds, a compound represented by the above formula (c) or (c ′) is known (for example, Patent Document 1). Since this compound has a hydroxyl group in the molecule, it has a feature that compatibility with a hydrophilic monomer is easily obtained. When this compound is synthesized by the method described in Patent Document 1, the following formula (d) is obtained as a by-product.
で表される化合物が生成する。この副生成物(d)は分子内にシリコーン成分を有する架橋性モノマーであるため、例えば一般的に用いられる架橋剤の一つであるエチレングリコールジメタクリレートと比較すると、多量に用いても眼用レンズ用ポリマーの酸素透過性の低下を招かないという利点がある。しかしながら上記式(c)または(c’)で表される化合物の合成の際(d)は2%程度しか生成しないため、上記式(c)または(c’)を重合して得られるポリマーに十分な弾性率を与えることができなかった。
本発明は、一般式(z)または(z’)で表される架橋性シリコーン化合物を製造する方法を提供することを目的とする。 An object of this invention is to provide the method of manufacturing the crosslinkable silicone compound represented by general formula (z) or (z ').
上記の目的を達成するために、本発明は下記の構成を有する。
「(1)下記一般式(z)または(z’)
In order to achieve the above object, the present invention has the following configuration.
“(1) The following general formula (z) or (z ′)
で表されるシリコーン化合物を得る方法であって、
下記一般式(a)または(a’)
In a method for obtaining a silicone compound represented,
Under following general formula (a) or (a ')
で表されるシリコーン化合物に下記一般式(x) The silicone compound represented by the following general formula (x)
で表される化合物を作用せしめることを特徴とするシリコーン化合物の製造方法。
(Aはトリス(トリメチルシロキシ)シリル基、ビス(トリメチルシロキシ)メチルシリル基、トリメチルシロキシジメチルシリル基、ポリジメチルシロキサン基、ポリメチルシロキサン基またはポリ−コ−メチルシロキサン−ジメチルシロキサン基、Xは炭素数1〜20の2価の基を表す。R1〜R3はそれぞれ独立に水素、炭素数1〜20の置換基または−X−Aを表す。R4、R5はそれぞれ独立に少なくとも1つの重合性基を有する炭素数1〜20の置換基を表す。LはH−Lの水中でのpKaが20以下の基を表す。)
(2)前記基Lが炭素数1〜20のアルコキシ基、水酸基、フッ素、塩素、臭素、ヨウ素および下記一般式(g1)〜(g3)
A method for producing a silicone compound, characterized in that a compound represented by the formula:
(A is tris (trimethylsiloxy) silyl group, bis (trimethylsiloxy) methylsilyl group, trimethylsiloxydimethylsilyl group, polydimethylsiloxane group, polymethylsiloxane group or poly-co-methylsiloxane-dimethylsiloxane group, X is carbon number Represents a divalent group of 1 to 20. R 1 to R 3 each independently represents hydrogen, a substituent having 1 to 20 carbon atoms, or —XA, and R 4 and R 5 each independently represents at least one group. .L representing a substituent having 1 to 20 carbon atoms having a polymerizable group p Ka in water H-L represents a 20 following groups.)
(2) The group L is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, fluorine, chlorine, bromine, iodine and the following general formulas (g1) to (g3)
で表される基からなる群から選ばれたものであることを特徴とする上記(1)記載のシリコーン化合物の製造方法。」 Manufacturing method (1) silicone compounds, wherein the one in which in selected from the group consisting of groups represented. "
本発明によれば、一般式(z)または(z’)で表される架橋性シリコーン化合物を得ることができる。 According to the present invention, a crosslinkable silicone compound represented by the general formula (z) or (z ′) can be obtained.
一般式(z)または(z’)において、R1〜R3はそれぞれ独立に水素、炭素数1〜20の置換基または−X−Aを表す。 In general formula (z) or (z ′), R 1 to R 3 each independently represent hydrogen, a substituent having 1 to 20 carbon atoms, or —XA.
R4、R5はそれぞれ独立に少なくとも1つの重合性基を有する炭素数1〜20の置換基を表す。ここで重合性基とはラジカル重合可能な炭素−炭素二重結合を表す。R4、R5からなるカルボン酸であるR4−COOHおよびR5−COOHの例としては、ビニロキシ酢酸、アリロキシ酢酸、(メタ)アクリル酸、クロトン酸、2−(メタ)アクリロイルプロパン酸、3−(メタ)アクリロイルブタン酸、4−ビニル安息香酸などを挙げることができる。これらのうち、カルボン酸、カルボン酸塩、カルボン酸無水物のいずれも入手しやすいことから好ましいのは(メタ)アクリル酸である。 R 4, R 5 each independently represent a substituent having 1 to 20 carbon atoms and having at least one polymerizable group. Here, the polymerizable group represents a carbon-carbon double bond capable of radical polymerization. R 4, examples of a carboxylic acid consisting of R 5 R 4 -COOH and R 5 -COOH are, vinyloxy acetate, allyloxy acetate, (meth) acrylic acid, crotonic acid, 2- (meth) acryloylpropanesulfonic acid, 3 -(Meth) acryloylbutanoic acid, 4-vinylbenzoic acid and the like can be mentioned. Of these, (meth) acrylic acid is preferred because it is easy to obtain any of carboxylic acid, carboxylate, and carboxylic anhydride.
Xは炭素数1〜20の2価の脂肪族または芳香族置換基を表す。 X represents a C1-C20 divalent aliphatic or aromatic substituent .
Aはトリス(トリメチルシロキシ)シリル基、ビス(トリメチルシロキシ)メチルシリル基、トリメチルシロキシジメチルシリル基、ポリジメチルシロキサン基、ポリメチルシロキサン基またはポリ−コ−メチルシロキサン−ジメチルシロキサン基である。 A is a tris (trimethylsiloxy) silyl group, bis (trimethylsiloxy) methylsilyl group, trimethylsiloxydimethylsilyl group, polydimethylsiloxane group, polymethylsiloxane group or poly-co-methylsiloxane-dimethylsiloxane group .
本発明では一般式(a)または(a’)で表されるシリコーン化合物の水酸基に重合性基を有する式(x)で表される化合物を作用させてエステル化することにより、一般式(z)または(z’)で表される架橋性シリコーン化合物を得る。 In the present invention , the compound represented by the formula (x) having a polymerizable group is allowed to act on the hydroxyl group of the silicone compound represented by the general formula (a) or (a ′) to perform esterification, whereby the general formula (z ) Or (z ′) is obtained.
一般式(x)において、LはH−LのpKaが20以下の基を表す。その例として炭素数1〜20のアルコキシ基、水酸基、フッ素、塩素、臭素、ヨウ素および下記一般式
(g1)〜(g3)
In the general formula (x), L represents a group having a pKa of HL of 20 or less. Examples thereof include an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, fluorine, chlorine, bromine, iodine, and the following general formulas (g1) to (g3).
で表される基などが挙げられる。これらのうち、入手のしやすさから好ましいのは炭素数1〜20のアルコキシ基、水酸基、塩素、(g1)〜(g3)であり、反応性の高さから塩素、(g1)がより好ましい。 Group represented by these. Among these, the alkoxy group having 1 to 20 carbon atoms, the hydroxyl group, and chlorine (g1) to (g3) are preferable from the viewpoint of availability, and chlorine and (g1) are more preferable because of high reactivity. .
反応後に発生するH−LのpKaが3以下の場合、H−Lの酸性によりシロキサニル基が分解してしまうため、塩基を加えるのが好ましい。加える塩基の例としては、アンモニア、トリメチルアミン、トリエチルアミン、トリ−n−プロピルアミン、トリイソプロピルアミン、トリ−n−ブチルアミンなどのアミン類や水酸化ナトリウム、水酸化カリウム、水酸化カルシウムなどの水酸化物類などが挙げられる。 When the pKa of HL generated after the reaction is 3 or less, since the siloxanyl group is decomposed by the acidity of HL, it is preferable to add a base. Examples of bases to be added include amines such as ammonia, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, and hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide. And the like.
本発明においては、触媒を使用してもよい。特にH−LのpKaが7以下の場合は化合物(x)の反応性が下がるので用いた方がよい。用いる触媒の例としては、ピリジン、N,N−ジメチルアミノピリジン、N,N−ジシクロヘキシルカルボジイミド、塩化鉄(III)、チタン(IV)イソプロポキシド、ジルコニウム(IV)ブトキシドなどが挙げられる。 In the present invention , a catalyst may be used. In particular, when the pKa of HL is 7 or less, the reactivity of the compound (x) decreases, so it is better to use it. Examples of the catalyst used include pyridine, N, N-dimethylaminopyridine, N, N-dicyclohexylcarbodiimide, iron (III) chloride, titanium (IV) isopropoxide, zirconium (IV) butoxide and the like .
本発明のシリコーン化合物の製造方法で得られたシリコーン化合物は必要に応じてさらにシリカゲルカラム精製、蒸留精製などの精製を行ってもよい。 The silicone compound obtained by the method for producing a silicone compound of the present invention may be further purified by silica gel column purification, distillation purification or the like, if necessary.
本発明の製造方法により得られるシリコーン化合物を重合して得られるポリマーは、コンタクトレンズ、眼内レンズ、人工角膜などの眼用レンズとして特に好適である。 The polymer obtained by polymerizing the silicone compound obtained by the production method of the present invention is particularly suitable as an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea.
以下、実施例により本発明を具体的に説明するが、本発明はこれによって限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
<測定方法>
ガスクロマトグラフ(GC)測定は本体に島津製作所社製GC−18A(FID検出器)、キャピラリーカラムにJ&W社DB−5(0.25mm×30m×1μm)を用いた。キャリアガスはヘリウム(138kPa)、注入口温度280℃、検出器温度280℃、昇温プログラムは60℃(5分)→10℃/分→325℃(19分)で測定した。サンプルは測定試料100μLをイソプロピルアルコール1mLに溶解して調製し、1μL注入した。
<Measurement method>
For the gas chromatograph (GC) measurement, GC-18A (FID detector) manufactured by Shimadzu Corporation was used for the main body, and DB-5 (0.25 mm × 30 m × 1 μm) for J & W was used for the capillary column. The carrier gas was helium (138 kPa), the inlet temperature was 280 ° C., the detector temperature was 280 ° C., and the temperature raising program was 60 ° C. (5 minutes) → 10 ° C./minute→325° C. (19 minutes). A sample was prepared by dissolving 100 μL of a measurement sample in 1 mL of isopropyl alcohol, and 1 μL was injected.
比較例1
300mLのナスフラスコに下式(c1)
Comparative Example 1
In a 300 mL eggplant flask, the following formula (c1)
で表されるエポキシシラン30g(89mmol)、メタクリル酸30.66g(356mmol)、メタクリル酸ナトリウム2.89g(27mmol)、p−メトキシフェノール0.14g(1mmol)、メタクリル酸無水物16.49g(107mmol)を加え、空気雰囲気下で100℃に加熱して攪拌した。GCでエポキシシラン(c1)の面積%が0.1%以下になるのを確認した後、反応液を室温まで冷却した。反応液にヘキサン50mLを加え、0.5N水酸化ナトリウム水溶液50mLで7回、2.6%食塩水35mLで3回洗浄し、有機層に硫酸ナトリウムを加えて乾燥し、ろ過してエバポレータで溶媒を留去して架橋性シリコーン化合物(d)を得た。GCで純度を測定したところ、表1のような結果が得られた。 30 g (89 mmol) of epoxysilane represented by the following formula: 30.66 g (356 mmol) of methacrylic acid, 2.89 g (27 mmol) of sodium methacrylate, 0.14 g (1 mmol) of p-methoxyphenol, 16.49 g (107 mmol) of methacrylic anhydride And heated to 100 ° C. in an air atmosphere and stirred. After confirming that the area percentage of the epoxysilane (c1) was 0.1% or less by GC, the reaction solution was cooled to room temperature. Add 50 mL of hexane to the reaction solution, wash 7 times with 50 mL of 0.5N aqueous sodium hydroxide solution and 3 times with 35 mL of 2.6% brine, dry the organic layer by adding sodium sulfate, filter and remove the solvent with an evaporator. Was distilled off to obtain a crosslinkable silicone compound (d). When the purity was measured by GC, the results shown in Table 1 were obtained.
合成例1
メタクリル酸無水物を加えない以外は比較例1と同様の方法で実験を行い、
Synthesis example 1
Except without added methacrylic anhydride experimented in the same manner as in Comparative Example 1,
で表されるシリコーン化合物を得た。この化合物を原料に以下の合成を行った。 The silicone compound represented by these was obtained. The following synthesis was performed using this compound as a raw material.
実施例1
200mLナスフラスコに上記実施例2で得たシリコーン化合物(c)または(c’)30g(71mmol)、トリエチルアミン8.62g(85mmol)、酢酸エチル30mLを加え、氷浴中で10分間攪拌した後、滴下ロートからメタクリル酸塩化物8.90g(85mmol)を滴下した。室温まで戻しながら6時間攪拌した後、0.5N水酸化ナトリウム水溶液50mLで3回、2.6%食塩水35mLで3回洗浄し、有機層に硫酸ナトリウムを加えて乾燥し、ろ過してエバポレータで溶媒を留去した。得られた液体のGC純度を測定したところ、表1のような結果が得られた。
Example 1
To a 200 mL eggplant flask, 30 g (71 mmol) of the silicone compound (c) or (c ′) obtained in Example 2 above, 8.62 g (85 mmol) of triethylamine, and 30 mL of ethyl acetate were added and stirred for 10 minutes in an ice bath. From the dropping funnel, 8.90 g (85 mmol) of methacrylic acid chloride was added dropwise. The mixture was stirred for 6 hours while returning to room temperature, then washed 3 times with 50 mL of 0.5N aqueous sodium hydroxide solution and 3 times with 35 mL of 2.6% brine, dried by adding sodium sulfate to the organic layer, filtered and evaporated. The solvent was distilled off. When the GC purity of the obtained liquid was measured, the results shown in Table 1 were obtained.
比較例2
上記合成例1で得られたシリコーン化合物(c)または(c’)30g(71mmol)に、メタクリル酸無水物16.41g(106mmol)を加えて100℃に加熱し、16時間攪拌した。反応液にヘキサン50mLを加え、0.5N水酸化ナトリウム水溶液50mLで5回、2.6%食塩水35mLで3回洗浄し、有機層に硫酸ナトリウムを加えて乾燥し、ろ過してエバポレータで溶媒を留去して架橋性シリコーン化合物(d)を得た。GC純度は表1の通りであった。
Comparative Example 2
Synthesis Example 1 in the resulting silicone compound (c) or (c ') 30g (71mmol) , was added methacrylic anhydride 16.41 g (106 mmol) was heated to 100 ° C., and stirred for 16 hours. Add 50 mL of hexane to the reaction solution, wash 5 times with 50 mL of 0.5N aqueous sodium hydroxide solution and 3 times with 35 mL of 2.6% brine, dry the organic layer by adding sodium sulfate, filter and remove the solvent with an evaporator. Was distilled off to obtain a crosslinkable silicone compound (d). The GC purity was as shown in Table 1.
比較例3
上記合成例1で得られた化合物(c)または(c’)30g(71mmol)に、メタクリル酸メチル71.05g(710mmol)、チタン(IV)イソプロポキシド6g(21mmol)を加え、室温で8時間攪拌して架橋性シリコーン化合物(d)を得た。GC純度は表1の通りであった。
Comparative Example 3
To 30 g (71 mmol) of the compound (c) or (c ′) obtained in Synthesis Example 1 above, 71.05 g (710 mmol) of methyl methacrylate and 6 g (21 mmol) of titanium (IV) isopropoxide were added. The mixture was stirred for a time to obtain a crosslinkable silicone compound (d). The GC purity was as shown in Table 1.
比較例4
100mL3つ口フラスコに還流冷却管、メカニカルスターラ、塩化カルシウムを充填した乾燥管をつけ、上記合成例1で得られた化合物(c)または(c’)30g(71mmol)にN−ニトロソフェニルヒドロキシルアミンアルミニウム0.3g(1重量%)を加え、150℃、20時間加熱して、架橋性シリコーン化合物(d)を得た。GC純度は表1の通りであった。
Comparative Example 4
A 100 mL three-necked flask was equipped with a reflux condenser, a mechanical stirrer, and a drying tube filled with calcium chloride, and N-nitrosophenylhydroxylamine was added to 30 g (71 mmol) of the compound (c) or (c ′) obtained in Synthesis Example 1 above. 0.3 g (1% by weight) of aluminum was added and heated at 150 ° C. for 20 hours to obtain a crosslinkable silicone compound (d). The GC purity was as shown in Table 1.
比較例5
(c1)で表されるエポキシシラン30g(89mmol)にギ酸8.20g(178mmol)、水酸化ナトリウム0.53g(13mmol)を加え、100℃で5時間攪拌した後、0.5N水酸化ナトリウム水溶液、飽和食塩水で洗浄した。硫酸ナトリウムで乾燥した後、溶媒を留去した。得られた液体に1当量の炭酸カリウムとメタノールを溶媒として加え、室温で一時間放置した後、飽和食塩水で洗浄した。硫酸ナトリウムで乾燥した後、溶媒を留去して下式(c2)で表されるジオールを得た。
Comparative Example 5
After adding 8.20 g (178 mmol) of formic acid and 0.53 g (13 mmol) of sodium hydroxide to 30 g (89 mmol) of the epoxysilane represented by (c1) and stirring at 100 ° C. for 5 hours, 0.5N aqueous sodium hydroxide solution And washed with saturated brine. After drying with sodium sulfate, the solvent was distilled off. 1 equivalent of potassium carbonate and methanol were added as solvents to the obtained liquid, and the mixture was allowed to stand at room temperature for 1 hour, and then washed with saturated brine. After drying with sodium sulfate, the solvent was distilled off to obtain a diol represented by the following formula (c2).
得られたジオールをシリカゲルカラム精製して用い、メタクリル酸塩化物およびトリエチルアミンをジオールに対して2倍モル量加える以外は実施例1と同様の方法により、目的の架橋性シリコーン化合物を得た。GC純度は表1の通りであった。 The obtained diol was used after purification on a silica gel column, and the target crosslinkable silicone compound was obtained in the same manner as in Example 1 except that methacrylic acid chloride and triethylamine were added in a 2-fold molar amount with respect to the diol. The GC purity was as shown in Table 1.
比較例6
エポキシシランのかわりにアリルグリシジルエーテルを用いる以外は比較例1と同様の方法で合成を行って下記式(c3)で表される化合物を得た。
Comparative Example 6
Synthesis was carried out in the same manner as in Comparative Example 1 except that allyl glycidyl ether was used instead of epoxy silane to obtain a compound represented by the following formula (c3).
比較例7
2Lナスフラスコに(c3)214g(1mol)、2,6−ジ−tert−ブチル−4−メチルフェノール220mg(1mmol)、トルエン500mL、塩化白金(IV)酸六水和物518mg(1mmol)を加え、トリクロロシラン135.5g(1mol)を滴下した。室温で8時間攪拌した後、減圧蒸留により精製して下記式(c4)で表される化合物を得た。
Comparative Example 7
To a 2 L eggplant flask was added 214 g (1 mol) of (c3), 220 mg (1 mmol) of 2,6-di-tert-butyl-4-methylphenol, 500 mL of toluene, and 518 mg (1 mmol) of platinum chloride (IV) acid hexahydrate. Then, 135.5 g (1 mol) of trichlorosilane was added dropwise. The mixture was stirred at room temperature for 8 hours and purified by distillation under reduced pressure to obtain a compound represented by the following formula (c4).
比較例8
1Lナスフラスコ中の水160mL−メタノール80mL−ヘキサン80mL混合溶媒に、(c4)152g(0.43mol)とメトキシトリメチルシラン272g(2.6mol)の混合液を滴下した。室温で8時間攪拌した後、攪拌を止め、水層を捨てて、有機層を飽和炭酸水素ナトリウム水溶液で3回、飽和食塩水で3回洗浄した。硫酸ナトリウムで乾燥した後、溶媒を留去して下記式(c5)で表される架橋性シリコーン化合物を得た。GC純度は表1の通りであった。
Comparative Example 8
A mixed solution of 152 g (0.43 mol) of (c4) and 272 g (2.6 mol) of methoxytrimethylsilane was added dropwise to a mixed solvent of 160 mL of water, 80 mL of methanol, and 80 mL of hexane in a 1 L eggplant flask. After stirring at room temperature for 8 hours, stirring was stopped, the aqueous layer was discarded, and the organic layer was washed 3 times with saturated aqueous sodium hydrogen carbonate solution and 3 times with saturated brine. After drying with sodium sulfate, the solvent was distilled off to obtain a crosslinkable silicone compound represented by the following formula (c5). The GC purity was as shown in Table 1.
比較例9
トリクロロシランのかわりにトリス(トリメチルシロキシ)シランを用いる以外は比較例7と同様にして合成を行い、(c5)で表される架橋性シリコーン化合物を得た。
Comparative Example 9
Synthesis was carried out in the same manner as in Comparative Example 7 except that tris (trimethylsiloxy) silane was used instead of trichlorosilane to obtain a crosslinkable silicone compound represented by (c5).
比較例10
メタクリル酸塩化物のかわりに2−ブロモイソブチリルブロミドを用いて合成を行い下記式(c6)で表される化合物を得た。
Comparative Example 10
Synthesis was carried out using 2-bromoisobutyryl bromide instead of methacrylic acid chloride to obtain a compound represented by the following formula (c6).
比較例11
還流冷却管と滴下漏斗をつけた500mLの三ツ口フラスコに(c6)72.5g(0.10mol)、ジエチルエーテル200mLを加えて還流しながら攪拌し、滴下漏斗からトリエチルアミン24.3g(0.24mol)のジエチルエーテル(30mL)溶液を滴下した。還流しながら24時間攪拌した後、沈殿をろ過し、溶媒を留去して(c5)で表される架橋性シリコーン化合物を得た。GC純度は表1の通りであった。
Comparative Example 11
To a 500 mL three-necked flask equipped with a reflux condenser and a dropping funnel, 72.5 g (0.10 mol) of (c6) and 200 mL of diethyl ether were added and stirred while refluxing, and 24.3 g (0.24 mol) of triethylamine was added from the dropping funnel. Of diethyl ether (30 mL) was added dropwise. After stirring for 24 hours while refluxing, the precipitate was filtered and the solvent was distilled off to obtain a crosslinkable silicone compound represented by (c5). The GC purity was as shown in Table 1.
比較例12
3−アリロキシプロピルトリス(トリメチルシロキシ)シラン39.4g(0.1mol)の300mLベンゼン溶液にメタクリル酸銀38.6g(0.2mol)、ヨウ素25.4g(0.1mol)を加え、16時間還流した。反応終了後、沈殿をろ過して除き、ろ液を飽和炭酸ナトリウム水溶液で5回、飽和食塩水で3回洗浄した。硫酸ナトリウムで乾燥し、溶媒を留去して(c5)で表される架橋性シリコーン化合物を得た。GC純度は表1の通りであった。
Comparative Example 12
To a 300 mL benzene solution of 39.4 g (0.1 mol) of 3-allyloxypropyltris (trimethylsiloxy) silane, 38.6 g (0.2 mol) of silver methacrylate and 25.4 g (0.1 mol) of iodine were added for 16 hours. Refluxed. After completion of the reaction, the precipitate was removed by filtration, and the filtrate was washed 5 times with a saturated aqueous sodium carbonate solution and 3 times with a saturated saline solution. It dried with sodium sulfate, the solvent was distilled off, and the crosslinkable silicone compound represented by (c5) was obtained. The GC purity was as shown in Table 1.
Claims (2)
下記一般式(a)または(a’)
(Aはトリス(トリメチルシロキシ)シリル基、ビス(トリメチルシロキシ)メチルシリル基、トリメチルシロキシジメチルシリル基、ポリジメチルシロキサン基、ポリメチルシロキサン基またはポリ−コ−メチルシロキサン−ジメチルシロキサン基、Xは炭素数1〜20の2価の基を表す。R1〜R3はそれぞれ独立に水素、炭素数1〜20の置換基または−X−Aを表す。R4、R5はそれぞれ独立に少なくとも1つの重合性基を有する炭素数1〜20の置換基を表す。LはH−Lの水中でのpKaが20以下の基を表す。) The following general formula (z) or (z ′)
The following general formula (a) or (a ′)
(A is tris (trimethylsiloxy) silyl group, bis (trimethylsiloxy) methylsilyl group, trimethylsiloxydimethylsilyl group, polydimethylsiloxane group, polymethylsiloxane group or poly-co-methylsiloxane-dimethylsiloxane group, X is carbon number Represents a divalent group of 1 to 20. R 1 to R 3 each independently represents hydrogen, a substituent having 1 to 20 carbon atoms, or —XA, and R 4 and R 5 each independently represents at least one group. .L representing a substituent having 1 to 20 carbon atoms having a polymerizable group p Ka in water H-L represents a 20 following groups.)
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JPH0474184A (en) * | 1990-07-13 | 1992-03-09 | Toshiba Silicone Co Ltd | Siloxane compound having di(meth)acryloxyalkyl group |
JP2002371116A (en) * | 2001-03-30 | 2002-12-26 | Toray Ind Inc | Monomer, polymer, ocular lens and contact lens each using the polymer |
JP2003505557A (en) * | 1999-07-22 | 2003-02-12 | スリーエム エスペ アクチェンゲゼルシャフト | Hydrolyzable and polymerizable silane with low viscosity and use thereof |
JP2003277506A (en) * | 2001-11-15 | 2003-10-02 | Korea Inst Of Chemical Technology | Novel crosslinking agent and crosslinking type solid polymer electrolyte containing it |
JP2003277560A (en) * | 2002-03-25 | 2003-10-02 | Asahi Kasei Corp | Hydrogenated copolymer composition |
JP2007521302A (en) * | 2003-06-30 | 2007-08-02 | ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド | Process for producing esters from epoxides |
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2003
- 2003-10-29 JP JP2003368529A patent/JP4645016B2/en not_active Expired - Lifetime
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Publication number | Priority date | Publication date | Assignee | Title |
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JPS63196629A (en) * | 1987-02-06 | 1988-08-15 | テーハー ゴルトシユミツト アクチエンゲゼルシヤフト | Polysiloxane |
JPH0474184A (en) * | 1990-07-13 | 1992-03-09 | Toshiba Silicone Co Ltd | Siloxane compound having di(meth)acryloxyalkyl group |
JP2003505557A (en) * | 1999-07-22 | 2003-02-12 | スリーエム エスペ アクチェンゲゼルシャフト | Hydrolyzable and polymerizable silane with low viscosity and use thereof |
JP2002371116A (en) * | 2001-03-30 | 2002-12-26 | Toray Ind Inc | Monomer, polymer, ocular lens and contact lens each using the polymer |
JP2003277506A (en) * | 2001-11-15 | 2003-10-02 | Korea Inst Of Chemical Technology | Novel crosslinking agent and crosslinking type solid polymer electrolyte containing it |
JP2003277560A (en) * | 2002-03-25 | 2003-10-02 | Asahi Kasei Corp | Hydrogenated copolymer composition |
JP2007521302A (en) * | 2003-06-30 | 2007-08-02 | ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド | Process for producing esters from epoxides |
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