WO2013098966A1 - Silicone monomer and method for producing same - Google Patents
Silicone monomer and method for producing same Download PDFInfo
- Publication number
- WO2013098966A1 WO2013098966A1 PCT/JP2011/080311 JP2011080311W WO2013098966A1 WO 2013098966 A1 WO2013098966 A1 WO 2013098966A1 JP 2011080311 W JP2011080311 W JP 2011080311W WO 2013098966 A1 WO2013098966 A1 WO 2013098966A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- formula
- silicone
- ppm
- meth
- Prior art date
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 118
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- -1 acryloylamino Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 150000001413 amino acids Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 5
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000005259 measurement Methods 0.000 description 20
- 150000001875 compounds Chemical group 0.000 description 18
- 239000007983 Tris buffer Substances 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 125000005401 siloxanyl group Chemical group 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- BBNUYEDGTKFYIM-UHFFFAOYSA-N 3-iodopropyl-tris(trimethylsilyloxy)silane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)CCCI BBNUYEDGTKFYIM-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000002597 Solanum melongena Nutrition 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000002504 physiological saline solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- LENNEKIRYSQQJD-YFKPBYRVSA-N (2s)-3-hydroxy-2-(2-methylprop-2-enoylamino)propanoic acid Chemical compound CC(=C)C(=O)N[C@@H](CO)C(O)=O LENNEKIRYSQQJD-YFKPBYRVSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BYXKJWZJPAGNAD-UHFFFAOYSA-N (1,2-dihydroxy-6-silylhexan-3-yl) 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OC(C(O)CO)CCC[SiH3] BYXKJWZJPAGNAD-UHFFFAOYSA-N 0.000 description 1
- FQOWJGGXNSRNJS-YFKPBYRVSA-N (2s)-2-(2-methylprop-2-enoylamino)propanoic acid Chemical compound OC(=O)[C@H](C)NC(=O)C(C)=C FQOWJGGXNSRNJS-YFKPBYRVSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- BOURDYMMTZXVRY-UHFFFAOYSA-N 2-(2-methylprop-2-enoylamino)acetic acid Chemical compound CC(=C)C(=O)NCC(O)=O BOURDYMMTZXVRY-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- KLNANBDDZIFLBH-UHFFFAOYSA-N 2-[[2-(prop-2-enoylamino)acetyl]amino]acetic acid Chemical compound OC(=O)CNC(=O)CNC(=O)C=C KLNANBDDZIFLBH-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YVAQHFNMILVVNE-UHFFFAOYSA-N 3-(prop-2-enoylamino)propanoic acid Chemical compound OC(=O)CCNC(=O)C=C YVAQHFNMILVVNE-UHFFFAOYSA-N 0.000 description 1
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 description 1
- BKZOLCBOZIVAAA-UHFFFAOYSA-N 3-hydroxy-2-(2-methylprop-2-enoylamino)butanoic acid Chemical compound CC(O)C(C(O)=O)NC(=O)C(C)=C BKZOLCBOZIVAAA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- XMECSUBHXDPQDP-UHFFFAOYSA-N C(CC)OC(CCNC(C=C)=O)=O Chemical compound C(CC)OC(CCNC(C=C)=O)=O XMECSUBHXDPQDP-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 1
- 239000004473 Threonine Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 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
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LNALMWCZYULLHX-QMMMGPOBSA-N propyl (2S)-2-(2-methylprop-2-enoylamino)propanoate Chemical compound CCCOC(=O)[C@H](C)NC(=O)C(C)=C LNALMWCZYULLHX-QMMMGPOBSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- AJURYMCOXVKKFB-UHFFFAOYSA-M trimethyl(3-prop-2-enoyloxypropyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCOC(=O)C=C AJURYMCOXVKKFB-UHFFFAOYSA-M 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Definitions
- the present invention relates to a polymerizable silicone monomer that can be used in the production of ophthalmic devices such as contact lenses, intraocular lenses, and artificial corneas, a method for producing the same, a monomer composition using the silicone monomer, and a weight thereof. Regarding coalescence.
- Various articles including a biological device are formed from, for example, an organic silicon compound-containing material.
- One organosilicon compound material useful for biomedical devices such as soft contact lenses is a silicon-containing hydrogel material.
- silicon-based materials have higher oxygen permeability than water, and therefore, articles having higher oxygen permeability can be provided.
- Organosilicon compound materials conventionally used for hard contact lenses are highly oxygen permeable, but are harder than materials used for soft contact lenses. Also, since such organosilicon compound materials are hydrophobic, manufacturing lenses using them requires additional processing to provide a hydrophilic surface.
- TRIS tris (trimethylsiloxy) silyl] propyl methacrylate
- TRIS is also a hydrophobic monomer, when used as an ophthalmic lens material, for example, it may be copolymerized with a hydrophilic monomer.
- TRIS has poor compatibility with hydrophilic monomers such as HEMA (2-hydroxyethyl methacrylate).
- HEMA 2-hydroxyethyl methacrylate
- transparent polymers cannot be obtained and used as lens materials.
- many combinations with other hydrophilic monomers such as N-vinylpyrrolidone and N, N-dimethylacrylamide have a strong water repellency when containing water, so TRIS is difficult to use as a material for soft contact lenses. Are known.
- Patent Documents 2 and 3 propose SiGMA (methyldi (trimethylsiloxy) silylpropylglycerol methacrylate), which is used as a compatibilizer monomer in silicone hydrogel contact lens applications. Since SiGMA has an appropriate oxygen permeation performance, it also plays a role as an oxygen permeation preparation. Since this SiGMA has a hydroxyl group, it is known to express good hydrophilicity.
- SiGMA methyldi (trimethylsiloxy) silylpropylglycerol methacrylate
- a silicone monomer represented by the formula (1) is provided.
- R represents a hydrogen atom or a methyl group.
- X represents a group selected from the formulas (2a) to (2f).
- N represents 0 or 1)
- the silicone monomer represented by the above formula (1) comprising the step of reacting an N- (meth) acryloylamino acid obtained by reacting an amino acid and (meth) acrylic acid with an alkyl halide-modified silicone.
- a manufacturing method is provided.
- the silicone monomer is selected from the group consisting of 20 to 60% by mass and 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide or a mixture of two or more thereof.
- a monomer composition comprising 40-80% by weight of hydrophilic monomer is provided.
- a polymer obtained by polymerizing the monomer composition is provided.
- the silicone monomer of the present invention has a high silicone content, and since it has an amide group or an ester group derived from a hydrophilic amino acid in the molecule, it is highly hydrophilic, and other polymerizable monomers such as (meth) acrylic monomers Because of its high compatibility, when used for the purpose of copolymerization, it is considered that both transparency and oxygen permeability are satisfied at the same time, and it is useful as a silicone monomer used as a raw material for ophthalmic devices. In addition, since the monomer composition and polymer of the present invention utilize the silicone monomer of the present invention, they are useful for the production of ophthalmic devices such as contact lenses that satisfy both transparency and oxygen permeability.
- X represents a group selected from the above formulas (2a) to (2f).
- the ratio of the siloxanyl group in one molecule is as large as possible.
- X is a compound represented by the formula (2a)
- X is a formula (2c )
- a compound wherein X is formula (2d) is particularly preferred.
- X is the formula (2a)
- R is a methyl group
- the above reaction is preferably performed in the presence of a base in order to increase the reaction rate.
- Preferred bases include, for example, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and organic bases such as triethylamine and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU).
- a base More preferably, potassium carbonate and triethylamine are mentioned.
- the amount of the base used is about 1 mol to 3 mol with respect to 1 mol of the silicone compound represented by the formula (6).
- a polymerization inhibitor so that the (meth) acrylic group is not polymerized.
- the polymerization inhibitor include hydroquinone monomethyl ether, 1,4-dihydroxybenzene, dibutylhydroxytoluene and the like.
- the inhibitor is preferably added to the reaction solution in an amount of 100 ppm to 10,000 ppm.
- other monomers can be appropriately contained as required within a range not impairing the above-described properties of the silicone monomer of the present invention.
- examples of other monomers include 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate.
- the content ratio in the case of using the other monomer can be appropriately determined within the range not impairing the desired effect of the present invention, but the total amount is usually 40% by mass based on the total amount of the monomer composition. Hereinafter, it is preferably 30% by mass or less.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Provided are: a silicone monomer which has a high silicone content, may have high transparency and oxygen transmission rate when copolymerized with polymerizable monomers such as a (meth)acrylic monomer, and is suitable for application to the eye; a method for producing the same; and a monomer composition and a polymer using the monomer. This silicon monomer is represented by formula (1) (R: H or CH3, X: a group selected from formula (2a) - formula (2f), and n: 0 or 1.). The monomer is useful for producing eye devices such as contact lenses.
(1)
(2a)
(2b)
(2c)
(2d)
(2e)
(2f)
Description
本発明は、コンタクトレンズ、眼内レンズ、人工角膜等の眼科デバイスを製造する際に利用可能な、重合性を有するシリコーンモノマー、その製造方法、該シリコーンモノマーを用いた単量体組成物及び重合体に関する。
The present invention relates to a polymerizable silicone monomer that can be used in the production of ophthalmic devices such as contact lenses, intraocular lenses, and artificial corneas, a method for producing the same, a monomer composition using the silicone monomer, and a weight thereof. Regarding coalescence.
生体用デバイスを含む種々の物品は、例えば、有機ケイ素化合物含有材料から形成されている。ソフトコンタクトレンズなどの生体用デバイスに有用な有機ケイ素化合物材料の一つにケイ素含有ヒドロゲル材料が挙げられる。一般に、ケイ素系の材料は、水よりも高い酸素透過性を有するので、より高い酸素透過性を有する物品が提供できる。
従来ハードコンタクトレンズに用いられている有機ケイ素化合物材料は、高酸素透過性であるが、ソフトコンタクトレンズに用いられる材料よりも硬い。また、このような有機ケイ素化合物材料は疎水性であるため、これを用いてレンズを製造するには、親水性表面を提供するための追加の処理を必要とする。
眼科デバイスに用いられる眼用のシリコーンモノマーとして、例えば、下記ＴＲＩＳ（３－[トリス(トリメチルシロキシ)シリル]プロピルメタクリレート）が知られている（特許文献１）。 Various articles including a biological device are formed from, for example, an organic silicon compound-containing material. One organosilicon compound material useful for biomedical devices such as soft contact lenses is a silicon-containing hydrogel material. In general, silicon-based materials have higher oxygen permeability than water, and therefore, articles having higher oxygen permeability can be provided.
Organosilicon compound materials conventionally used for hard contact lenses are highly oxygen permeable, but are harder than materials used for soft contact lenses. Also, since such organosilicon compound materials are hydrophobic, manufacturing lenses using them requires additional processing to provide a hydrophilic surface.
As an ophthalmic silicone monomer used for an ophthalmic device, for example, the following TRIS (3- [tris (trimethylsiloxy) silyl] propyl methacrylate) is known (Patent Document 1).
従来ハードコンタクトレンズに用いられている有機ケイ素化合物材料は、高酸素透過性であるが、ソフトコンタクトレンズに用いられる材料よりも硬い。また、このような有機ケイ素化合物材料は疎水性であるため、これを用いてレンズを製造するには、親水性表面を提供するための追加の処理を必要とする。
眼科デバイスに用いられる眼用のシリコーンモノマーとして、例えば、下記ＴＲＩＳ（３－[トリス(トリメチルシロキシ)シリル]プロピルメタクリレート）が知られている（特許文献１）。 Various articles including a biological device are formed from, for example, an organic silicon compound-containing material. One organosilicon compound material useful for biomedical devices such as soft contact lenses is a silicon-containing hydrogel material. In general, silicon-based materials have higher oxygen permeability than water, and therefore, articles having higher oxygen permeability can be provided.
Organosilicon compound materials conventionally used for hard contact lenses are highly oxygen permeable, but are harder than materials used for soft contact lenses. Also, since such organosilicon compound materials are hydrophobic, manufacturing lenses using them requires additional processing to provide a hydrophilic surface.
As an ophthalmic silicone monomer used for an ophthalmic device, for example, the following TRIS (3- [tris (trimethylsiloxy) silyl] propyl methacrylate) is known (Patent Document 1).
ＴＲＩＳも疎水性のモノマーであるため、眼用レンズ素材として用いる場合には、例えば、親水性モノマーと共重合させることが考えられる。しかし、ＴＲＩＳは、ＨＥＭＡ(２－ヒドロキシエチルメタクリレート)のような親水性モノマーとの相溶性に劣り、このような親水性モノマーと共重合させた場合、透明ポリマーが得られず、レンズ素材として使用できない。また、Ｎ－ビニルピロリドンやＮ，Ｎ－ジメチルアクリルアミドなど、他の親水性モノマーとの組み合わせの多くは含水時に表面が強く撥水するために、ＴＲＩＳはソフトコンタクトレンズ用素材として使用しにくいことが知られている。
これを改善する目的で、特許文献２及び３には、ＳｉＧＭＡ（メチルジ（トリメチルシロキシ）シリルプロピルグリセロールメタクリレート）が提案され、シリコーンハイドロゲルコンタクトレンズ用途において相溶化剤モノマーとして使用されている。ＳｉＧＭＡは、適度な酸素透過性能を有するために酸素透過製剤としての役割も果たしている。該ＳｉＧＭＡは水酸基を有していることから良好な親水性を発現することが知られている。
Since TRIS is also a hydrophobic monomer, when used as an ophthalmic lens material, for example, it may be copolymerized with a hydrophilic monomer. However, TRIS has poor compatibility with hydrophilic monomers such as HEMA (2-hydroxyethyl methacrylate). When copolymerized with such hydrophilic monomers, transparent polymers cannot be obtained and used as lens materials. Can not. In addition, many combinations with other hydrophilic monomers such as N-vinylpyrrolidone and N, N-dimethylacrylamide have a strong water repellency when containing water, so TRIS is difficult to use as a material for soft contact lenses. Are known.
In order to improve this, Patent Documents 2 and 3 propose SiGMA (methyldi (trimethylsiloxy) silylpropylglycerol methacrylate), which is used as a compatibilizer monomer in silicone hydrogel contact lens applications. Since SiGMA has an appropriate oxygen permeation performance, it also plays a role as an oxygen permeation preparation. Since this SiGMA has a hydroxyl group, it is known to express good hydrophilicity.
これを改善する目的で、特許文献２及び３には、ＳｉＧＭＡ（メチルジ（トリメチルシロキシ）シリルプロピルグリセロールメタクリレート）が提案され、シリコーンハイドロゲルコンタクトレンズ用途において相溶化剤モノマーとして使用されている。ＳｉＧＭＡは、適度な酸素透過性能を有するために酸素透過製剤としての役割も果たしている。該ＳｉＧＭＡは水酸基を有していることから良好な親水性を発現することが知られている。
In order to improve this, Patent Documents 2 and 3 propose SiGMA (methyldi (trimethylsiloxy) silylpropylglycerol methacrylate), which is used as a compatibilizer monomer in silicone hydrogel contact lens applications. Since SiGMA has an appropriate oxygen permeation performance, it also plays a role as an oxygen permeation preparation. Since this SiGMA has a hydroxyl group, it is known to express good hydrophilicity.
レンズの装用感に悪影響を与えるオリゴマー架橋成分を低減する方法として、特許文献４にＳｉＧＭＡの新たな製造方法も提案されている。しかしながら、モノマー１分子内のシロキサニル基が占める質量割合をシリコーン含量と定義したとき、ＳｉＧＭＡはシリコーン含量が５２．４％（ＳｉＧＭＡの１分子中のシロキサニル基を構成する各原子の原子量の合計は２２１であり、ＳｉＧＭＡの分子量が４２２であるから、このときのシリコーン含量は、２２１／４２２×１００＝５２．４％と計算できる。）であり、ＴＲＩＳのシリコーン含量７２％と比較して、ケイ素含量が低いため、十分な酸素透過性を得ることが困難であった。
As a method for reducing oligomer crosslinking components that adversely affect the wearing feeling of the lens, Patent Document 4 proposes a new method for producing SiGMA. However, when the mass ratio of the siloxanyl group in one monomer molecule is defined as the silicone content, the SiGMA has a silicone content of 52.4% (the total atomic weight of each atom constituting the siloxanyl group in one molecule of SiGMA is 221). Since the molecular weight of SiGMA is 422, the silicone content at this time can be calculated as 221/422 × 100 = 52.4%.) Compared with the silicone content of TRIS of 72%, the silicon content Therefore, it was difficult to obtain sufficient oxygen permeability.
特許文献５には分子内にアミド結合を有する下記式で示されるシリコーンモノマーＴＭＳＡＡが提案されている。該シリコーンモノマーは、アミド基を有することからＴＲＩＳと比較して親水性が向上している。
しかし、十分な親水性を得るには至っておらず、これを用いてソフトコンタクトレンズを調製した際にはレンズ表面が疎水性になり、表面の親水化処理等を行なう必要がある。そのため、製造工程が複雑になるという問題があった。
Patent Document 5 proposes a silicone monomer TMSAA represented by the following formula having an amide bond in the molecule. Since the silicone monomer has an amide group, the hydrophilicity is improved as compared with TRIS.
However, sufficient hydrophilicity has not been obtained, and when a soft contact lens is prepared using this, the lens surface becomes hydrophobic, and it is necessary to perform a hydrophilic treatment on the surface. Therefore, there has been a problem that the manufacturing process becomes complicated.
しかし、十分な親水性を得るには至っておらず、これを用いてソフトコンタクトレンズを調製した際にはレンズ表面が疎水性になり、表面の親水化処理等を行なう必要がある。そのため、製造工程が複雑になるという問題があった。
However, sufficient hydrophilicity has not been obtained, and when a soft contact lens is prepared using this, the lens surface becomes hydrophobic, and it is necessary to perform a hydrophilic treatment on the surface. Therefore, there has been a problem that the manufacturing process becomes complicated.
特許文献６には、メタクリル酸ハライドとオリゴエチレングリコール変性直鎖シリコーンとの反応による新たなモノマーが提案されている。オリゴエチレングリコールは、分子内のエーテル基と共に末端の遊離水酸基が大きく親水性に寄与する。しかし、該モノマーの水酸基はエステル結合を形成しているため十分に機能せず、親水性を得るためには、エーテル構造の繰り返し単位を多くする必要がある。そのため、モノマー中のシリコーン含量は下がる傾向にあり、レンズの表面親水性と酸素透過性とを同時に満たすことは困難であった。
Patent Document 6 proposes a new monomer by reaction of methacrylic acid halide with oligoethylene glycol-modified linear silicone. Oligoethylene glycol has a large free hydroxyl group at the terminal as well as an ether group in the molecule and contributes to hydrophilicity. However, the hydroxyl group of the monomer does not function sufficiently because it forms an ester bond, and in order to obtain hydrophilicity, it is necessary to increase the number of repeating units of the ether structure. For this reason, the silicone content in the monomer tends to decrease, and it has been difficult to satisfy both the surface hydrophilicity and oxygen permeability of the lens.
特許文献７には、３級アミンとハロゲン化アルキルとの反応により得られる、式（３）で表される分子内に４級アンモニウムを有するシリコーンモノマーが提案されている。このモノマーは、重合によりレンズ表面の親水性は達成されるが、シリコーン含量は２９５／５８７＝５０．３％とＳｉＧＭＡと同程度であり、酸素透過性を満足することが困難である。また該モノマーはカチオン性であるため、これを用いたレンズではタンパク質吸着など、レンズ表面の白濁汚れが懸念される。
Patent Document 7 proposes a silicone monomer having a quaternary ammonium in the molecule represented by the formula (3), which is obtained by a reaction between a tertiary amine and an alkyl halide. This monomer achieves the hydrophilicity of the lens surface by polymerization, but the silicone content is 295/587 = 50.3%, which is similar to SiGMA, and it is difficult to satisfy oxygen permeability. Further, since the monomer is cationic, there is a concern that the lens surface using the monomer may cause white turbid contamination on the lens surface such as protein adsorption.
以上の事情から、眼科デバイスに用いられる眼用のシリコーンモノマーの分野では、新たな分子構造の親水性を有するシリコーンモノマーであって、製造が容易で、一日使い捨てレンズのような安価な用途にも使用可能な、且つモノマー１分子内にシロキサニル基が占める割合（シリコーン含量）が大きいシリコーンモノマーの開発が求められている。
From the above circumstances, in the field of ophthalmic silicone monomers used in ophthalmic devices, it is a silicone monomer having a hydrophilicity with a new molecular structure, which is easy to manufacture and is inexpensive for daily disposable lenses. There is a need to develop a silicone monomer that can be used and has a large proportion (silicone content) of siloxanyl groups in one monomer molecule.
本発明の課題は、シリコーン含量が大きく、（メタ）アクリル系モノマー等の重合性モノマーと共重合した際に、透明度及び酸素透過率が高いと想定される、眼に適用するのに好適なシリコーンモノマー、その製造方法、該シリコーンモノマーを用いた単量体組成物及び重合体を提供することにある。
An object of the present invention is a silicone suitable for application to the eye, which has a high silicone content and is assumed to have high transparency and high oxygen permeability when copolymerized with a polymerizable monomer such as a (meth) acrylic monomer. It is providing the monomer, its manufacturing method, the monomer composition and polymer using this silicone monomer.
本発明によれば、式（１）で表されるシリコーンモノマーが提供される。
(式（１）中、Ｒは水素原子又はメチル基を示す。Ｘは式(２a)～式(２f)から選ばれる基を示す。ｎは０または１を表す。)
According to the present invention, a silicone monomer represented by the formula (1) is provided.
(In the formula (1), R represents a hydrogen atom or a methyl group. X represents a group selected from the formulas (2a) to (2f). N represents 0 or 1)
また本発明によれば、アミノ酸及び（メタ）アクリル酸を反応させてなるＮ－（メタ）アクリロイルアミノ酸と、ハロゲン化アルキル変性シリコーンとを反応させる工程を含む上記式（１）で示されるシリコーンモノマーの製造方法が提供される。
更に本発明によれば、上記シリコーンモノマー２０～６０質量％と、２－ヒドロキシエチル（メタ）アクリレート、Ｎ－ビニルピロリドン、Ｎ，Ｎ－ジメチルアクリルアミドまたはこれら２種以上の混合物からなる群より選ばれる親水性モノマー４０～８０質量％とを含む単量体組成物が提供される。
更にまた本発明によれば、上記単量体組成物を重合させて得た重合体が提供される。 According to the present invention, the silicone monomer represented by the above formula (1) comprising the step of reacting an N- (meth) acryloylamino acid obtained by reacting an amino acid and (meth) acrylic acid with an alkyl halide-modified silicone. A manufacturing method is provided.
Further, according to the present invention, the silicone monomer is selected from the group consisting of 20 to 60% by mass and 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide or a mixture of two or more thereof. A monomer composition comprising 40-80% by weight of hydrophilic monomer is provided.
Furthermore, according to the present invention, there is provided a polymer obtained by polymerizing the monomer composition.
更に本発明によれば、上記シリコーンモノマー２０～６０質量％と、２－ヒドロキシエチル（メタ）アクリレート、Ｎ－ビニルピロリドン、Ｎ，Ｎ－ジメチルアクリルアミドまたはこれら２種以上の混合物からなる群より選ばれる親水性モノマー４０～８０質量％とを含む単量体組成物が提供される。
更にまた本発明によれば、上記単量体組成物を重合させて得た重合体が提供される。 According to the present invention, the silicone monomer represented by the above formula (1) comprising the step of reacting an N- (meth) acryloylamino acid obtained by reacting an amino acid and (meth) acrylic acid with an alkyl halide-modified silicone. A manufacturing method is provided.
Further, according to the present invention, the silicone monomer is selected from the group consisting of 20 to 60% by mass and 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide or a mixture of two or more thereof. A monomer composition comprising 40-80% by weight of hydrophilic monomer is provided.
Furthermore, according to the present invention, there is provided a polymer obtained by polymerizing the monomer composition.
本発明のシリコーンモノマーは、シリコーン含量が高く、また分子内に親水性アミノ酸に由来するアミド基、エステル基を有することから親水性が高く、他の（メタ）アクリル系モノマー等の重合性モノマーと相溶性が高いため、共重合させる目的で用いたとき、透明性と酸素透過性を同時に満足すると考えられ、眼科デバイスの原料に用いられるシリコーンモノマーとして有用である。また、本発明の単量体組成物及び重合体は、本発明のシリコーンモノマーを利用するので、透明性と酸素透過性を同時に満足するコンタクトレンズ等の眼科デバイスの製造に有用である。
The silicone monomer of the present invention has a high silicone content, and since it has an amide group or an ester group derived from a hydrophilic amino acid in the molecule, it is highly hydrophilic, and other polymerizable monomers such as (meth) acrylic monomers Because of its high compatibility, when used for the purpose of copolymerization, it is considered that both transparency and oxygen permeability are satisfied at the same time, and it is useful as a silicone monomer used as a raw material for ophthalmic devices. In addition, since the monomer composition and polymer of the present invention utilize the silicone monomer of the present invention, they are useful for the production of ophthalmic devices such as contact lenses that satisfy both transparency and oxygen permeability.
以下、本発明を更に詳細に説明する。
本発明のシリコーンモノマーは、上記式（１）で示されるアミノ酸誘導体のシリコーンモノマーである。ここで、アミノ酸とは、アミノ基とカルボキシル基の両方の官能基を持つ有機化合物を意味する。該モノマーは具体的には、アミノ酸が有するアミンとカルボン酸により、アミド基とエステル基を介して不飽和重合性基とシロキサニル基が化学結合しているモノマーである。
式（１）中、Ｒは水素原子又はメチル基を示す。ｎは０または１を表す。 Hereinafter, the present invention will be described in more detail.
The silicone monomer of the present invention is a silicone monomer of an amino acid derivative represented by the above formula (1). Here, the amino acid means an organic compound having both amino group and carboxyl group functional groups. Specifically, the monomer is a monomer in which an unsaturated polymerizable group and a siloxanyl group are chemically bonded via an amide group and an ester group by an amine and a carboxylic acid of an amino acid.
In the formula (1), R represents a hydrogen atom or a methyl group. n represents 0 or 1.
本発明のシリコーンモノマーは、上記式（１）で示されるアミノ酸誘導体のシリコーンモノマーである。ここで、アミノ酸とは、アミノ基とカルボキシル基の両方の官能基を持つ有機化合物を意味する。該モノマーは具体的には、アミノ酸が有するアミンとカルボン酸により、アミド基とエステル基を介して不飽和重合性基とシロキサニル基が化学結合しているモノマーである。
式（１）中、Ｒは水素原子又はメチル基を示す。ｎは０または１を表す。 Hereinafter, the present invention will be described in more detail.
The silicone monomer of the present invention is a silicone monomer of an amino acid derivative represented by the above formula (1). Here, the amino acid means an organic compound having both amino group and carboxyl group functional groups. Specifically, the monomer is a monomer in which an unsaturated polymerizable group and a siloxanyl group are chemically bonded via an amide group and an ester group by an amine and a carboxylic acid of an amino acid.
In the formula (1), R represents a hydrogen atom or a methyl group. n represents 0 or 1.
式（１）中、Ｘは上記式（２ａ）～（２ｆ）から選ばれる基を示す。
本発明のシリコーンモノマーは、１分子中に占めるシロキサニル基の割合がなるべく大きい方が好ましく、この観点から、例えば、式（１）において、Ｘが式（２ａ）である化合物、Ｘが式（２ｃ）である化合物、またはＸが式（２ｄ）である化合物が特に好ましく挙げられる。
式（１）において、Ｘが式（２ａ）であり、Ｒがメチル基、ｎ＝１で表される化合物は式（４ａ）で表される。 In the formula (1), X represents a group selected from the above formulas (2a) to (2f).
In the silicone monomer of the present invention, it is preferable that the ratio of the siloxanyl group in one molecule is as large as possible. From this viewpoint, for example, in the formula (1), X is a compound represented by the formula (2a), and X is a formula (2c ) Or a compound wherein X is formula (2d) is particularly preferred.
In the formula (1), X is the formula (2a), R is a methyl group, and the compound represented by n = 1 is represented by the formula (4a).
本発明のシリコーンモノマーは、１分子中に占めるシロキサニル基の割合がなるべく大きい方が好ましく、この観点から、例えば、式（１）において、Ｘが式（２ａ）である化合物、Ｘが式（２ｃ）である化合物、またはＸが式（２ｄ）である化合物が特に好ましく挙げられる。
式（１）において、Ｘが式（２ａ）であり、Ｒがメチル基、ｎ＝１で表される化合物は式（４ａ）で表される。 In the formula (1), X represents a group selected from the above formulas (2a) to (2f).
In the silicone monomer of the present invention, it is preferable that the ratio of the siloxanyl group in one molecule is as large as possible. From this viewpoint, for example, in the formula (1), X is a compound represented by the formula (2a), and X is a formula (2c ) Or a compound wherein X is formula (2d) is particularly preferred.
In the formula (1), X is the formula (2a), R is a methyl group, and the compound represented by n = 1 is represented by the formula (4a).
式（１）において、Ｘが式（２ｄ）であり、Ｒが水素原子、ｎ＝１で表される化合物は式（４ｂ）で表される。
式（４ｂ）で表されるモノマーの分子量は４９３であり、シロキサニル基を構成する各原子の原子量の合計は２９５であることから、このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。
In the formula (1), X is the formula (2d), R is a hydrogen atom, and the compound represented by n = 1 is represented by the formula (4b).
Since the molecular weight of the monomer represented by the formula (4b) is 493 and the total atomic weight of each atom constituting the siloxanyl group is 295, the silicone content of this monomer is 295/493 × 100 = 59.8%. It is.
式（４ａ）または式（４ｂ）のシリコーンモノマーは、モノマー中のシリコーン含量の割合が約６０％と高く、得られる共重合体の酸素透過性を効果的に高められると考えられ、眼科デバイスの中でもコンタクトレンズ用のシリコーンモノマーとしての利用が期待できる。
The silicone monomer of formula (4a) or formula (4b) has a high proportion of silicone content in the monomer of about 60%, which is considered to effectively increase the oxygen permeability of the resulting copolymer. Among them, it can be expected to be used as a silicone monomer for contact lenses.
本発明のシリコーンモノマーは、アミノ酸及び（メタ）アクリル酸ハロゲン化物、例えば、（メタ）アクリル酸クロライドを反応させてなるＮ－（メタ）アクリロイルアミノ酸（誘導体）と、ハロゲン化アルキル変性シリコーン、例えば、３－ヨードプロピル［トリス（トリメチル）シロキシ］シランとを反応させる本発明の製造方法等により得ることができる。
具体的には、式（５）(式（５）中、Ｒは水素原子又はメチル基を示す。Ｘは酸素原子又は窒素原子を含んでいても良い炭素数１～６の２価の有機基を示し、例えば、上記式(２a)～式(２f)から選ばれる基が挙げられる。)で表される（メタ）アクリロイルアミノ酸と、式（６）（式（６）中、Ｙはハロゲンであり、好ましくはＢｒ、またはＩである。ｎは０または１を表す。）で表されるハロゲン化アルキル変性シリコーンとを反応させる方法により得られる。 The silicone monomer of the present invention includes an N- (meth) acryloyl amino acid (derivative) obtained by reacting an amino acid and a (meth) acrylic acid halide, for example, (meth) acrylic acid chloride, and a halogenated alkyl-modified silicone, for example, It can be obtained by the production method of the present invention in which 3-iodopropyl [tris (trimethyl) siloxy] silane is reacted.
Specifically, in the formula (5) (in the formula (5), R represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 6 carbon atoms which may contain an oxygen atom or a nitrogen atom. For example, a group selected from the above formulas (2a) to (2f)), and a formula (6) (wherein Y is a halogen in formula (6)). Yes, preferably Br, or I. n represents 0 or 1).
具体的には、式（５）(式（５）中、Ｒは水素原子又はメチル基を示す。Ｘは酸素原子又は窒素原子を含んでいても良い炭素数１～６の２価の有機基を示し、例えば、上記式(２a)～式(２f)から選ばれる基が挙げられる。)で表される（メタ）アクリロイルアミノ酸と、式（６）（式（６）中、Ｙはハロゲンであり、好ましくはＢｒ、またはＩである。ｎは０または１を表す。）で表されるハロゲン化アルキル変性シリコーンとを反応させる方法により得られる。 The silicone monomer of the present invention includes an N- (meth) acryloyl amino acid (derivative) obtained by reacting an amino acid and a (meth) acrylic acid halide, for example, (meth) acrylic acid chloride, and a halogenated alkyl-modified silicone, for example, It can be obtained by the production method of the present invention in which 3-iodopropyl [tris (trimethyl) siloxy] silane is reacted.
Specifically, in the formula (5) (in the formula (5), R represents a hydrogen atom or a methyl group. X represents a divalent organic group having 1 to 6 carbon atoms which may contain an oxygen atom or a nitrogen atom. For example, a group selected from the above formulas (2a) to (2f)), and a formula (6) (wherein Y is a halogen in formula (6)). Yes, preferably Br, or I. n represents 0 or 1).
上記反応は、例えば、式（５）で示される（メタ）アクリロイルアミノ酸５～６０質量％を含む有機溶媒中に、式（６）で示されるシリコーン化合物を式（５）で示される（メタ）アクリロイルアミノ酸のカルボン酸に対して、１０モル％～１００モル％混合し、恒温槽中、２０～１００℃の温度で行なうことが好ましい。
前記有機溶媒としては、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル等の非プロトン性極性溶媒が好ましく挙げられる。 In the above reaction, for example, a silicone compound represented by the formula (6) is represented by the formula (5) in an organic solvent containing 5 to 60% by mass of the (meth) acryloylamino acid represented by the formula (5). It is preferable to mix 10 mol% to 100 mol% with respect to the carboxylic acid of acryloylamino acid, and carry out at a temperature of 20 to 100 ° C. in a thermostatic bath.
Preferred examples of the organic solvent include aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile.
前記有機溶媒としては、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル等の非プロトン性極性溶媒が好ましく挙げられる。 In the above reaction, for example, a silicone compound represented by the formula (6) is represented by the formula (5) in an organic solvent containing 5 to 60% by mass of the (meth) acryloylamino acid represented by the formula (5). It is preferable to mix 10 mol% to 100 mol% with respect to the carboxylic acid of acryloylamino acid, and carry out at a temperature of 20 to 100 ° C. in a thermostatic bath.
Preferred examples of the organic solvent include aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile.
上記式（５）で示される（メタ）アクリロイルアミノ酸は、公知の方法により得られる。例えば、氷冷下、アミノ酸のナトリウム塩水溶液に塩化（メタ）アクリロイルを滴下することにより合成できる（Journal of Applied Polymer Science, 24, 1551, 1979、米国特許第4172934号明細書）。
上記式（６）で示されるシリコーン化合物は、得られるシリコーンモノマーの純度に影響するので高純度品であることが好ましく、例えば、Dokl. Akad. Nauk, SSSR, 1976, 227, 607～610、J. Organomet. Chem., 1988, 340, 31～36、特開2002－68930号公報に示される、トリアルコキシシランまたはトリクロロシランと、ヘキサメチルジシロキサンとから得ることができ、抽出や蒸留精製により高純度化することができる。 The (meth) acryloyl amino acid represented by the above formula (5) is obtained by a known method. For example, it can be synthesized by dropping (meth) acryloyl chloride into an aqueous sodium salt solution of an amino acid under ice cooling (Journal of Applied Polymer Science, 24, 1551, 1979, US Pat. No. 4,172,934).
The silicone compound represented by the above formula (6) is preferably a high-purity product because it affects the purity of the resulting silicone monomer. For example, Dokl. Akad. Nauk, SSSR, 1976, 227, 607 to 610, J Organomet. Chem., 1988, 340, 31-36, JP-A-2002-68930, can be obtained from trialkoxysilane or trichlorosilane and hexamethyldisiloxane, and can be obtained by extraction or distillation purification. Can be purified.
上記式（６）で示されるシリコーン化合物は、得られるシリコーンモノマーの純度に影響するので高純度品であることが好ましく、例えば、Dokl. Akad. Nauk, SSSR, 1976, 227, 607～610、J. Organomet. Chem., 1988, 340, 31～36、特開2002－68930号公報に示される、トリアルコキシシランまたはトリクロロシランと、ヘキサメチルジシロキサンとから得ることができ、抽出や蒸留精製により高純度化することができる。 The (meth) acryloyl amino acid represented by the above formula (5) is obtained by a known method. For example, it can be synthesized by dropping (meth) acryloyl chloride into an aqueous sodium salt solution of an amino acid under ice cooling (Journal of Applied Polymer Science, 24, 1551, 1979, US Pat. No. 4,172,934).
The silicone compound represented by the above formula (6) is preferably a high-purity product because it affects the purity of the resulting silicone monomer. For example, Dokl. Akad. Nauk, SSSR, 1976, 227, 607 to 610, J Organomet. Chem., 1988, 340, 31-36, JP-A-2002-68930, can be obtained from trialkoxysilane or trichlorosilane and hexamethyldisiloxane, and can be obtained by extraction or distillation purification. Can be purified.
上記反応は、反応速度を上げるために塩基の存在下行うことが好ましい。好ましい塩基としては、例えば、炭酸カリウム、炭酸ナトリウム、水酸化ナトリウム、水酸化カリウム等の無機塩基、トリエチルアミン、１，８－ジアザビシクロ［５，４，０］ウンデカ－７－エン（ＤＢＵ）等の有機塩基が挙げられる。より好ましくは炭酸カリウム、トリエチルアミンが挙げられる。
前記塩基の使用量は、式（６）で示されるシリコーン化合物１モルに対して、１モル～３モル程度である。 The above reaction is preferably performed in the presence of a base in order to increase the reaction rate. Preferred bases include, for example, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and organic bases such as triethylamine and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU). A base. More preferably, potassium carbonate and triethylamine are mentioned.
The amount of the base used is about 1 mol to 3 mol with respect to 1 mol of the silicone compound represented by the formula (6).
前記塩基の使用量は、式（６）で示されるシリコーン化合物１モルに対して、１モル～３モル程度である。 The above reaction is preferably performed in the presence of a base in order to increase the reaction rate. Preferred bases include, for example, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and organic bases such as triethylamine and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU). A base. More preferably, potassium carbonate and triethylamine are mentioned.
The amount of the base used is about 1 mol to 3 mol with respect to 1 mol of the silicone compound represented by the formula (6).
反応に際しては、（メタ）アクリル基が重合しないように重合禁止剤を用いるのが好ましい。重合禁止剤としては、例えばヒドロキノンモノメチルエーテル、１，４－ジヒドロキシベンゼン、ジブチルヒドロキシトルエン等が挙げられる。上記禁止剤は、反応液へ１００ｐｐｍ～１００００ｐｐｍ添加することが望ましい。
In the reaction, it is preferable to use a polymerization inhibitor so that the (meth) acrylic group is not polymerized. Examples of the polymerization inhibitor include hydroquinone monomethyl ether, 1,4-dihydroxybenzene, dibutylhydroxytoluene and the like. The inhibitor is preferably added to the reaction solution in an amount of 100 ppm to 10,000 ppm.
反応後に得られるシリコーンモノマーは高沸点を有する液体であり、再結晶や蒸留操作の利用が困難であるため、分液洗浄、吸着剤処理等による精製が望ましい。
洗浄により精製する場合は、反応液をｎ－ヘキサン、シクロヘキサン、ヘプタン、オクタン等の炭化水素に溶解させて得られる溶液（疎水相）を、イオン交換水、アルカリ水溶液、アルコール水溶液等（親水相）で洗浄することが望ましい。この時用いるアルカリとしては水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウムが望ましい。アルコール水溶液に用いるアルコールとしては、分液状態を形成するために極性が高いメタノール、エタノール、１－プロパノール、２－プロパノールから選択されるもの又はこれらの混合物を水と混合して用いることが望ましい。
前記疎水相を形成するために、反応液に対して炭化水素を質量比で０．５～３倍量加えるのが好ましい。０．５倍未満では分液させることが困難であり、３倍より多いと経済的に不利である。前記洗浄液の使用量は炭化水素と同程度が好ましい。 Since the silicone monomer obtained after the reaction is a liquid having a high boiling point and it is difficult to use recrystallization or distillation operation, purification by liquid separation washing, adsorbent treatment or the like is desirable.
When purifying by washing, a solution (hydrophobic phase) obtained by dissolving the reaction solution in a hydrocarbon such as n-hexane, cyclohexane, heptane, octane, etc. is replaced with ion-exchanged water, alkaline aqueous solution, alcohol aqueous solution, etc. (hydrophilic phase) It is desirable to wash with. The alkali used at this time is preferably sodium hydroxide, sodium carbonate, or sodium bicarbonate. As the alcohol used in the aqueous alcohol solution, it is desirable to use a highly polar one selected from methanol, ethanol, 1-propanol, 2-propanol or a mixture thereof with water in order to form a liquid separation state.
In order to form the hydrophobic phase, it is preferable to add 0.5 to 3 times the mass of hydrocarbon by mass ratio to the reaction solution. If it is less than 0.5 times, it is difficult to separate the liquid, and if it exceeds 3 times, it is economically disadvantageous. The amount of the cleaning liquid used is preferably about the same as that of hydrocarbon.
洗浄により精製する場合は、反応液をｎ－ヘキサン、シクロヘキサン、ヘプタン、オクタン等の炭化水素に溶解させて得られる溶液（疎水相）を、イオン交換水、アルカリ水溶液、アルコール水溶液等（親水相）で洗浄することが望ましい。この時用いるアルカリとしては水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウムが望ましい。アルコール水溶液に用いるアルコールとしては、分液状態を形成するために極性が高いメタノール、エタノール、１－プロパノール、２－プロパノールから選択されるもの又はこれらの混合物を水と混合して用いることが望ましい。
前記疎水相を形成するために、反応液に対して炭化水素を質量比で０．５～３倍量加えるのが好ましい。０．５倍未満では分液させることが困難であり、３倍より多いと経済的に不利である。前記洗浄液の使用量は炭化水素と同程度が好ましい。 Since the silicone monomer obtained after the reaction is a liquid having a high boiling point and it is difficult to use recrystallization or distillation operation, purification by liquid separation washing, adsorbent treatment or the like is desirable.
When purifying by washing, a solution (hydrophobic phase) obtained by dissolving the reaction solution in a hydrocarbon such as n-hexane, cyclohexane, heptane, octane, etc. is replaced with ion-exchanged water, alkaline aqueous solution, alcohol aqueous solution, etc. (hydrophilic phase) It is desirable to wash with. The alkali used at this time is preferably sodium hydroxide, sodium carbonate, or sodium bicarbonate. As the alcohol used in the aqueous alcohol solution, it is desirable to use a highly polar one selected from methanol, ethanol, 1-propanol, 2-propanol or a mixture thereof with water in order to form a liquid separation state.
In order to form the hydrophobic phase, it is preferable to add 0.5 to 3 times the mass of hydrocarbon by mass ratio to the reaction solution. If it is less than 0.5 times, it is difficult to separate the liquid, and if it exceeds 3 times, it is economically disadvantageous. The amount of the cleaning liquid used is preferably about the same as that of hydrocarbon.
上記洗浄後、無水硫酸ナトリウム、無水硫酸マグネシウム等の脱水剤を使用して、反応液中に含まれる少量の水を脱水し、固体をろ別した後、例えばエバポレータを使用して溶媒を除去することにより目的物を得ることができる。溶媒の除去は約５０℃以下で行い、真空ポンプにより１０mmHg以下で１時間程度行なうのが望ましい。
After the washing, using a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate, a small amount of water contained in the reaction solution is dehydrated, and after filtering off the solid, the solvent is removed using, for example, an evaporator. Thus, the target product can be obtained. It is desirable to remove the solvent at about 50 ° C. or less and for about 1 hour with a vacuum pump at 10 mmHg or less.
本発明のシリコーンモノマーは、例えば、眼科デバイスを形成するポリマーの原料として使用することができる。該シリコーンモノマーを用いて眼科デバイスを製造するには、例えば、本発明のシリコーンモノマーと共重合可能な、(メタ)アクリロイル基、スチリル基、アリル基、ビニル基などの炭素－炭素不飽和結合を有する他のモノマー、好ましくは得られる重合体表面の十分な親水性がさらに改善される、水酸基、アミド基、両性イオン等の親水基を有する他のモノマーと混合し、重合させることにより得ることができる。
眼科デバイスを製造する際の本発明のシリコーンモノマーの使用量は、用いる他のモノマーの種類等により異なるが、得られる眼科デバイスの表面親水性の改善や、柔軟性をコントロールするために、原料モノマー中１０～８０質量％が好ましい。 The silicone monomer of the present invention can be used, for example, as a raw material for polymers that form ophthalmic devices. In order to produce an ophthalmic device using the silicone monomer, for example, a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a styryl group, an allyl group, or a vinyl group, which can be copolymerized with the silicone monomer of the present invention. It can be obtained by mixing and polymerizing with other monomers having a hydrophilic group such as a hydroxyl group, amide group, zwitterion, etc., in which sufficient hydrophilicity of the obtained polymer surface is further improved. it can.
The amount of the silicone monomer of the present invention used for producing an ophthalmic device varies depending on the type of other monomers used, but in order to improve the surface hydrophilicity of the obtained ophthalmic device and to control flexibility, the raw material monomer The content is preferably 10 to 80% by mass.
眼科デバイスを製造する際の本発明のシリコーンモノマーの使用量は、用いる他のモノマーの種類等により異なるが、得られる眼科デバイスの表面親水性の改善や、柔軟性をコントロールするために、原料モノマー中１０～８０質量％が好ましい。 The silicone monomer of the present invention can be used, for example, as a raw material for polymers that form ophthalmic devices. In order to produce an ophthalmic device using the silicone monomer, for example, a carbon-carbon unsaturated bond such as a (meth) acryloyl group, a styryl group, an allyl group, or a vinyl group, which can be copolymerized with the silicone monomer of the present invention. It can be obtained by mixing and polymerizing with other monomers having a hydrophilic group such as a hydroxyl group, amide group, zwitterion, etc., in which sufficient hydrophilicity of the obtained polymer surface is further improved. it can.
The amount of the silicone monomer of the present invention used for producing an ophthalmic device varies depending on the type of other monomers used, but in order to improve the surface hydrophilicity of the obtained ophthalmic device and to control flexibility, the raw material monomer The content is preferably 10 to 80% by mass.
本発明の単量体組成物は、上述の本発明のシリコーンモノマーと、例えば、２－ヒドロキシエチル（メタ）アクリレート、Ｎ－ビニルピロリドン、Ｎ，Ｎ－ジメチルアクリルアミド、２－（メタクリロイルオキシエチル）－２－（トリメチルアンモニオエチル）ホスフェートまたはこれら２種以上の混合物からなる群より選ばれる親水性モノマーとを含み、コンタクトレンズ等の眼用デバイスの重合用組成物として用いることができる。
本発明の単量体組成物において、本発明のシリコーンモノマーの含有割合は、組成物全量基準で２０～６０質量％であり、上記親水性モノマーの合計の含有割合は、組成物全量基準で４０～８０質量％である。本発明のシリコーンモノマーの含有割合が２０質量％未満では、重合して得られる重合体の酸素透過性が低い恐れがあり、６０質量％を超える場合には重合して得られる重合体の表面濡れ性が低下する恐れがある。 The monomer composition of the present invention comprises the above-described silicone monomer of the present invention and, for example, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide, 2- (methacryloyloxyethyl)- It contains a hydrophilic monomer selected from the group consisting of 2- (trimethylammonioethyl) phosphate or a mixture of two or more thereof, and can be used as a composition for polymerization of ophthalmic devices such as contact lenses.
In the monomer composition of the present invention, the content of the silicone monomer of the present invention is 20 to 60% by mass based on the total amount of the composition, and the total content of the hydrophilic monomers is 40% based on the total amount of the composition. ~ 80% by mass. If the content of the silicone monomer of the present invention is less than 20% by mass, the polymer obtained by polymerization may have low oxygen permeability, and if it exceeds 60% by mass, the surface wettability of the polymer obtained by polymerization May be reduced.
本発明の単量体組成物において、本発明のシリコーンモノマーの含有割合は、組成物全量基準で２０～６０質量％であり、上記親水性モノマーの合計の含有割合は、組成物全量基準で４０～８０質量％である。本発明のシリコーンモノマーの含有割合が２０質量％未満では、重合して得られる重合体の酸素透過性が低い恐れがあり、６０質量％を超える場合には重合して得られる重合体の表面濡れ性が低下する恐れがある。 The monomer composition of the present invention comprises the above-described silicone monomer of the present invention and, for example, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide, 2- (methacryloyloxyethyl)- It contains a hydrophilic monomer selected from the group consisting of 2- (trimethylammonioethyl) phosphate or a mixture of two or more thereof, and can be used as a composition for polymerization of ophthalmic devices such as contact lenses.
In the monomer composition of the present invention, the content of the silicone monomer of the present invention is 20 to 60% by mass based on the total amount of the composition, and the total content of the hydrophilic monomers is 40% based on the total amount of the composition. ~ 80% by mass. If the content of the silicone monomer of the present invention is less than 20% by mass, the polymer obtained by polymerization may have low oxygen permeability, and if it exceeds 60% by mass, the surface wettability of the polymer obtained by polymerization May be reduced.
前記単量体組成物には、本発明のシリコーンモノマーの上記特性を損なわない範囲で、必要に応じて、他のモノマーを適宜含有させることもできる。他のモノマーとしては、例えば、２－ヒドロキシブチル(メタ)アクリレート、４－ヒドロキシブチル(メタ)アクリレート、グリセロール(メタ)クリレート、(メタ)アクリルアミド、ポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコール(メタ)アクリレート等の非イオン性単量体；(メタ)アクリル酸、(メタ)アクリロイルオキシエチルコハク酸、スチレンスルホン酸、(メタ)アクリロイルオキシホスホン酸等の酸を含有するアニオン性単量体；２－ヒドロキシ－３－(メタ)アクリロイルオキシプロピルトリメチルアンモニウムクロライド、アミノエチルメタクリレート、Ｎ，Ｎ－ジメチルアミノエチル(メタ)アクリレート等のアミノ基又はアンモニウム基を含有するカチオン性単量体；Ｎ－メタクリロイルオキシエチル－Ｎ，Ｎ－ジメチルアンモニウム－α－Ｎ－メチルカルボキシベタイン、３－［［２－(メタクリロイルオキシ)エチル］(ジメチル)アンモニオ］－１－プロパンスルホネート等の両性イオン単量体が挙げられ、これらの１種又は２種以上を用いることができる。
上記他のモノマーを用いる場合の含有割合は、本発明の所望の効果を損なわない範囲で、適宜決定することができるが、単量体組成物全量基準で、その合計量が、通常４０質量％以下、好ましくは３０質量％以下である。 In the monomer composition, other monomers can be appropriately contained as required within a range not impairing the above-described properties of the silicone monomer of the present invention. Examples of other monomers include 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. Nonionic monomers such as: anionic monomers containing acids such as (meth) acrylic acid, (meth) acryloyloxyethyl succinic acid, styrene sulfonic acid, (meth) acryloyloxyphosphonic acid; 2-hydroxy -Cationic monomer containing amino group or ammonium group such as 3- (meth) acryloyloxypropyltrimethylammonium chloride, aminoethyl methacrylate, N, N-dimethylaminoethyl (meth) acrylate; N-methacryloyloxyethyl- N, N-di Zwitterionic monomers such as methylammonium-α-N-methylcarboxybetaine, 3-[[2- (methacryloyloxy) ethyl] (dimethyl) ammonio] -1-propanesulfonate, and one or two of these More than seeds can be used.
The content ratio in the case of using the other monomer can be appropriately determined within the range not impairing the desired effect of the present invention, but the total amount is usually 40% by mass based on the total amount of the monomer composition. Hereinafter, it is preferably 30% by mass or less.
上記他のモノマーを用いる場合の含有割合は、本発明の所望の効果を損なわない範囲で、適宜決定することができるが、単量体組成物全量基準で、その合計量が、通常４０質量％以下、好ましくは３０質量％以下である。 In the monomer composition, other monomers can be appropriately contained as required within a range not impairing the above-described properties of the silicone monomer of the present invention. Examples of other monomers include 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. Nonionic monomers such as: anionic monomers containing acids such as (meth) acrylic acid, (meth) acryloyloxyethyl succinic acid, styrene sulfonic acid, (meth) acryloyloxyphosphonic acid; 2-hydroxy -Cationic monomer containing amino group or ammonium group such as 3- (meth) acryloyloxypropyltrimethylammonium chloride, aminoethyl methacrylate, N, N-dimethylaminoethyl (meth) acrylate; N-methacryloyloxyethyl- N, N-di Zwitterionic monomers such as methylammonium-α-N-methylcarboxybetaine, 3-[[2- (methacryloyloxy) ethyl] (dimethyl) ammonio] -1-propanesulfonate, and one or two of these More than seeds can be used.
The content ratio in the case of using the other monomer can be appropriately determined within the range not impairing the desired effect of the present invention, but the total amount is usually 40% by mass based on the total amount of the monomer composition. Hereinafter, it is preferably 30% by mass or less.
本発明の重合体は、本発明の単量体組成物を重合させて得られたものであり、例えば、コンタクトレンズ等の眼用デバイスの製造に利用することができる。
前記重合は、例えば、熱重合、光重合、モールド重合等の任意の重合方法を利用して、公知の条件や方法に準じて行うことができる。この際、重合法に応じて適宜公知の重合開始剤を用いることができる。 The polymer of the present invention is obtained by polymerizing the monomer composition of the present invention, and can be used, for example, for the production of ophthalmic devices such as contact lenses.
The said polymerization can be performed according to well-known conditions and methods using arbitrary polymerization methods, such as thermal polymerization, photopolymerization, mold polymerization, for example. At this time, a known polymerization initiator can be appropriately used depending on the polymerization method.
前記重合は、例えば、熱重合、光重合、モールド重合等の任意の重合方法を利用して、公知の条件や方法に準じて行うことができる。この際、重合法に応じて適宜公知の重合開始剤を用いることができる。 The polymer of the present invention is obtained by polymerizing the monomer composition of the present invention, and can be used, for example, for the production of ophthalmic devices such as contact lenses.
The said polymerization can be performed according to well-known conditions and methods using arbitrary polymerization methods, such as thermal polymerization, photopolymerization, mold polymerization, for example. At this time, a known polymerization initiator can be appropriately used depending on the polymerization method.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されない。
尚、例中の各測定は以下の機器等を用いて行った。
１）シリコーンモノマー純度測定法(ＧＣ法)
ガスクロマトグラフ：Agilent社製GC system 7890A、
キャピラリーカラム：J＆W社 HP-1(0.53mm、30m、2.65μm)、
注入口温度：２５０℃、
昇温プログラム：８０℃(０分)→２０℃／分→２５０℃(２０分)、
検出器：FID、２５０℃、キャリアガス：ヘリウム(５ml／分)、スプリット比： ５：１、注入量：２μｌ。
２）1Ｈ－ＮＭＲ測定法
日本電子社製JNM-AL400、溶媒；ＣＤＣｌ3又はＣＤ3ＯＤ(ＴＭＳ基準)。
３）赤外線吸収(ＩＲ)測定法
測定法：液膜法、積算回数：１６回
４）質量測定法(ＬＣ－ＭＳ法)
LC部：Waters社 2695 Separations Module、
MS部；Waters 2695 Q-micro、
LC溶離液条件：アセトニトリル／５０mM酢酸アンモニウム水溶液（９／１）。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In addition, each measurement in an example was performed using the following apparatuses.
1) Silicone monomer purity measurement method (GC method)
Gas chromatograph: Agilent GC system 7890A,
Capillary column: J & W Company HP-1 (0.53mm, 30m, 2.65μm),
Inlet temperature: 250 ° C
Temperature rising program: 80 ° C (0 minutes) → 20 ° C / minute → 250 ° C (20 minutes)
Detector: FID, 250 ° C., carrier gas: helium (5 ml / min), split ratio: 5: 1, injection volume: 2 μl.
2) 1 H-NMR measurement method JNM-AL400 manufactured by JEOL Ltd., solvent: CDCl 3 or CD 3 OD (TMS standard).
3) Infrared absorption (IR) measurement method Measurement method: liquid film method, integration number: 16 times 4) Mass measurement method (LC-MS method)
LC: Waters 2695 Separations Module,
MS: Waters 2695 Q-micro,
LC eluent conditions: acetonitrile / 50 mM ammonium acetate aqueous solution (9/1).
尚、例中の各測定は以下の機器等を用いて行った。
１）シリコーンモノマー純度測定法(ＧＣ法)
ガスクロマトグラフ：Agilent社製GC system 7890A、
キャピラリーカラム：J＆W社 HP-1(0.53mm、30m、2.65μm)、
注入口温度：２５０℃、
昇温プログラム：８０℃(０分)→２０℃／分→２５０℃(２０分)、
検出器：FID、２５０℃、キャリアガス：ヘリウム(５ml／分)、スプリット比： ５：１、注入量：２μｌ。
２）1Ｈ－ＮＭＲ測定法
日本電子社製JNM-AL400、溶媒；ＣＤＣｌ3又はＣＤ3ＯＤ(ＴＭＳ基準)。
３）赤外線吸収(ＩＲ)測定法
測定法：液膜法、積算回数：１６回
４）質量測定法(ＬＣ－ＭＳ法)
LC部：Waters社 2695 Separations Module、
MS部；Waters 2695 Q-micro、
LC溶離液条件：アセトニトリル／５０mM酢酸アンモニウム水溶液（９／１）。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In addition, each measurement in an example was performed using the following apparatuses.
1) Silicone monomer purity measurement method (GC method)
Gas chromatograph: Agilent GC system 7890A,
Capillary column: J & W Company HP-1 (0.53mm, 30m, 2.65μm),
Inlet temperature: 250 ° C
Temperature rising program: 80 ° C (0 minutes) → 20 ° C / minute → 250 ° C (20 minutes)
Detector: FID, 250 ° C., carrier gas: helium (5 ml / min), split ratio: 5: 1, injection volume: 2 μl.
2) 1 H-NMR measurement method JNM-AL400 manufactured by JEOL Ltd., solvent: CDCl 3 or CD 3 OD (TMS standard).
3) Infrared absorption (IR) measurement method Measurement method: liquid film method, integration number: 16 times 4) Mass measurement method (LC-MS method)
LC: Waters 2695 Separations Module,
MS: Waters 2695 Q-micro,
LC eluent conditions: acetonitrile / 50 mM ammonium acetate aqueous solution (9/1).
実施例１－１
ＭＡｇｌｙＳ（３－[トリス(トリメチルシロキシ)シリル]プロピル－Ｎ－メタクリロイルグリシネート）の合成（シリコーン含量５９．８％）
１Ｌナスフラスコに、ジメチルスルホキシド７０１．７ｇ、メタクリロイルグリシン５５．４ｇ（０．３８７モル）、ｐ－メトキシフェノール（以下、ＭＱと記す）０．３５ｇを入れ攪拌した後、炭酸カリウム３５．７ｇ（０．２５８モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．２５８モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン７００ｇで希釈し、ヘプタン相を、１％重曹水３５０ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液７００ｇで洗浄した。洗浄後、ヘプタン相へメタノール８００ｇを混合してメタノール相へ抽出し、メタノールを減圧除去して透明液体１０１．８ｇを得た（収率８２％）。ＧＣによる得られたシリコーン化合物の純度は９４％であった。各測定結果を以下、並びに図１及び図２に示す。 Example 1-1
Synthesis of MAglyS (3- [tris (trimethylsiloxy) silyl] propyl-N-methacryloyl glycinate) (silicone content 59.8%)
In a 1 L eggplant flask, 701.7 g of dimethyl sulfoxide, 55.4 g (0.387 mol) of methacryloylglycine and 0.35 g of p-methoxyphenol (hereinafter referred to as MQ) were added and stirred, and then 35.7 g (0 .258 mol) was added and the reaction was warmed to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 350 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, 800 g of methanol was mixed with the heptane phase and extracted into the methanol phase, and methanol was removed under reduced pressure to obtain 101.8 g of a transparent liquid (yield 82%). The purity of the silicone compound obtained by GC was 94%. Each measurement result is shown below and in FIG.1 and FIG.2.
ＭＡｇｌｙＳ（３－[トリス(トリメチルシロキシ)シリル]プロピル－Ｎ－メタクリロイルグリシネート）の合成（シリコーン含量５９．８％）
１Ｌナスフラスコに、ジメチルスルホキシド７０１．７ｇ、メタクリロイルグリシン５５．４ｇ（０．３８７モル）、ｐ－メトキシフェノール（以下、ＭＱと記す）０．３５ｇを入れ攪拌した後、炭酸カリウム３５．７ｇ（０．２５８モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．２５８モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン７００ｇで希釈し、ヘプタン相を、１％重曹水３５０ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液７００ｇで洗浄した。洗浄後、ヘプタン相へメタノール８００ｇを混合してメタノール相へ抽出し、メタノールを減圧除去して透明液体１０１．８ｇを得た（収率８２％）。ＧＣによる得られたシリコーン化合物の純度は９４％であった。各測定結果を以下、並びに図１及び図２に示す。 Example 1-1
Synthesis of MAglyS (3- [tris (trimethylsiloxy) silyl] propyl-N-methacryloyl glycinate) (silicone content 59.8%)
In a 1 L eggplant flask, 701.7 g of dimethyl sulfoxide, 55.4 g (0.387 mol) of methacryloylglycine and 0.35 g of p-methoxyphenol (hereinafter referred to as MQ) were added and stirred, and then 35.7 g (0 .258 mol) was added and the reaction was warmed to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 350 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, 800 g of methanol was mixed with the heptane phase and extracted into the methanol phase, and methanol was removed under reduced pressure to obtain 101.8 g of a transparent liquid (yield 82%). The purity of the silicone compound obtained by GC was 94%. Each measurement result is shown below and in FIG.1 and FIG.2.
1Ｈ－ＮＭＲ測定
ＣＨ2＝Ｃ－：５．７８ｐｐｍ（１Ｈ）、５．４３ｐｐｍ（１Ｈ）、－ＣＨ2－：４．９２ｐｐｍ（２Ｈ）、４．００ｐｐｍ（２Ｈ）、１．７０ｐｐｍ（２Ｈ）、０．５０ｐｐｍ（２Ｈ）、－ＣＨ3：１．９６ｐｐｍ（３Ｈ）、０．１０ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３３４５ｃｍ-1、３０９０ｃｍ-1、２９６０ｃｍ-1、１７４５ｃｍ-1、１６７０ｃｍ-1、１６２５ｃｍ-1、１４５５ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる分子量測定の結果、分子量４９３であることから、上記式（４ａ）で表される化合物(ＭＡｇｌｙＳ)であることが特定された。このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。 1 H-NMR measurement CH 2 ═C—: 5.78 ppm (1H), 5.43 ppm (1H), —CH 2 —: 4.92 ppm (2H), 4.00 ppm (2H), 1.70 ppm (2H) 0.50 ppm (2H), —CH 3 : 1.96 ppm (3H), 0.10 ppm (27H).
IR measurement results 3345 cm −1 , 3090 cm −1 , 2960 cm −1 , 1745 cm −1 , 1670 cm −1 , 1625 cm −1 , 1455 cm −1 , 1255 cm −1 , 1065 cm −1 , 840 cm −1 .
As a result of measuring the molecular weight by LC-MS, the molecular weight was 493. Thus, it was identified as the compound (MAglyS) represented by the above formula (4a). The silicone content of this monomer is 295/493 × 100 = 59.8%.
ＣＨ2＝Ｃ－：５．７８ｐｐｍ（１Ｈ）、５．４３ｐｐｍ（１Ｈ）、－ＣＨ2－：４．９２ｐｐｍ（２Ｈ）、４．００ｐｐｍ（２Ｈ）、１．７０ｐｐｍ（２Ｈ）、０．５０ｐｐｍ（２Ｈ）、－ＣＨ3：１．９６ｐｐｍ（３Ｈ）、０．１０ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３３４５ｃｍ-1、３０９０ｃｍ-1、２９６０ｃｍ-1、１７４５ｃｍ-1、１６７０ｃｍ-1、１６２５ｃｍ-1、１４５５ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる分子量測定の結果、分子量４９３であることから、上記式（４ａ）で表される化合物(ＭＡｇｌｙＳ)であることが特定された。このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。 1 H-NMR measurement CH 2 ═C—: 5.78 ppm (1H), 5.43 ppm (1H), —CH 2 —: 4.92 ppm (2H), 4.00 ppm (2H), 1.70 ppm (2H) 0.50 ppm (2H), —CH 3 : 1.96 ppm (3H), 0.10 ppm (27H).
IR measurement results 3345 cm −1 , 3090 cm −1 , 2960 cm −1 , 1745 cm −1 , 1670 cm −1 , 1625 cm −1 , 1455 cm −1 , 1255 cm −1 , 1065 cm −1 , 840 cm −1 .
As a result of measuring the molecular weight by LC-MS, the molecular weight was 493. Thus, it was identified as the compound (MAglyS) represented by the above formula (4a). The silicone content of this monomer is 295/493 × 100 = 59.8%.
実施例１－２
ＭａｌａＳ（３－[トリス(トリメチルシロキシ)シリル]プロピル－Ｎ－メタクリロイルアラニネート）の合成（シリコーン含量５８．２％）
１Ｌナスフラスコに、Ｎ，Ｎ－ジメチルホルムアミド７０１．７ｇ、メタクリロイルアラニン６０．８７ｇ（０．３８７モル）、ＭＱ０．１８ｇを入れ攪拌した後、炭酸カリウム３５．７ｇ（０．３８７モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．２５８モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン７００ｇで希釈し、ヘプタン相を、１％重曹水７００ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液７００ｇで洗浄した。洗浄後、ヘプタン相を減圧除去してＭａｌａＳ １０８．０ｇを得た（収率８５％）。ＧＣによる該シリコーン化合物の純度は９３％であった。各測定結果を以下、並びに図３及び図４に示す。 Example 1-2
Synthesis of MalaS (3- [tris (trimethylsiloxy) silyl] propyl-N-methacryloylalaninate) (silicone content 58.2%)
To a 1 L eggplant flask, 701.7 g of N, N-dimethylformamide, 60.87 g (0.387 mol) of methacryloylalanine and 0.18 g of MQ were added and stirred, and then 35.7 g (0.387 mol) of potassium carbonate was added. The reaction was warmed to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 700 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 108.0 g of MalaS (yield 85%). The purity of the silicone compound by GC was 93%. Each measurement result is shown below and in FIG.3 and FIG.4.
ＭａｌａＳ（３－[トリス(トリメチルシロキシ)シリル]プロピル－Ｎ－メタクリロイルアラニネート）の合成（シリコーン含量５８．２％）
１Ｌナスフラスコに、Ｎ，Ｎ－ジメチルホルムアミド７０１．７ｇ、メタクリロイルアラニン６０．８７ｇ（０．３８７モル）、ＭＱ０．１８ｇを入れ攪拌した後、炭酸カリウム３５．７ｇ（０．３８７モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．２５８モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン７００ｇで希釈し、ヘプタン相を、１％重曹水７００ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液７００ｇで洗浄した。洗浄後、ヘプタン相を減圧除去してＭａｌａＳ １０８．０ｇを得た（収率８５％）。ＧＣによる該シリコーン化合物の純度は９３％であった。各測定結果を以下、並びに図３及び図４に示す。 Example 1-2
Synthesis of MalaS (3- [tris (trimethylsiloxy) silyl] propyl-N-methacryloylalaninate) (silicone content 58.2%)
To a 1 L eggplant flask, 701.7 g of N, N-dimethylformamide, 60.87 g (0.387 mol) of methacryloylalanine and 0.18 g of MQ were added and stirred, and then 35.7 g (0.387 mol) of potassium carbonate was added. The reaction was warmed to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 700 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 108.0 g of MalaS (yield 85%). The purity of the silicone compound by GC was 93%. Each measurement result is shown below and in FIG.3 and FIG.4.
1Ｈ－ＮＭＲ測定
ＣＨ2＝Ｃ－：５．７５ｐｐｍ（１Ｈ）、５．４３ｐｐｍ（１Ｈ）、
－ＣＨ2－：４．０９ｐｐｍ（２Ｈ）、１．７１ｐｐｍ（２Ｈ）、０．５１ｐｐｍ（２Ｈ）、－ＣＨ3：１．９６ｐｐｍ（３Ｈ）、１．４４ｐｐｍ（３Ｈ）、０．１３ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３３３５ｃｍ-1、３０９０ｃｍ-1、２９６０ｃｍ-1、１７４０ｃｍ-1、１６６０ｃｍ-1、１６２５ｃｍ-1、１５５０ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる分子量測定の結果、分子量５０７であることから、ＭａｌａＳは、式（７）で表されることが特定された。このモノマーのシリコーン含量は２９５／５０７×１００＝５８．２％である。 1 H-NMR measurement CH 2 ═C—: 5.75 ppm (1H), 5.43 ppm (1H),
—CH 2 —: 4.09 ppm (2H), 1.71 ppm (2H), 0.51 ppm (2H), —CH 3 : 1.96 ppm (3H), 1.44 ppm (3H), 0.13 ppm (27H) .
IR measurements 3335cm -1, 3090cm -1, 2960cm -1 , 1740cm -1, 1660cm -1, 1625cm -1, 1550cm -1, 1255cm -1, 1065cm -1, 840cm -1.
As a result of measuring the molecular weight by LC-MS, the molecular weight was 507. Therefore, it was specified that MalaS was represented by the formula (7). The silicone content of this monomer is 295/507 × 100 = 58.2%.
ＣＨ2＝Ｃ－：５．７５ｐｐｍ（１Ｈ）、５．４３ｐｐｍ（１Ｈ）、
ＩＲ測定結果
３３３５ｃｍ-1、３０９０ｃｍ-1、２９６０ｃｍ-1、１７４０ｃｍ-1、１６６０ｃｍ-1、１６２５ｃｍ-1、１５５０ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる分子量測定の結果、分子量５０７であることから、ＭａｌａＳは、式（７）で表されることが特定された。このモノマーのシリコーン含量は２９５／５０７×１００＝５８．２％である。 1 H-NMR measurement CH 2 ═C—: 5.75 ppm (1H), 5.43 ppm (1H),
IR measurements 3335cm -1, 3090cm -1, 2960cm -1 , 1740cm -1, 1660cm -1, 1625cm -1, 1550cm -1, 1255cm -1, 1065cm -1, 840cm -1.
As a result of measuring the molecular weight by LC-MS, the molecular weight was 507. Therefore, it was specified that MalaS was represented by the formula (7). The silicone content of this monomer is 295/507 × 100 = 58.2%.
実施例１－３
ＡｂａｌＳ（３－[トリス(トリメチルシロキシ)シリル]プロピル－Ｎ－アクリロイル－β－アラニネート）の合成（シリコーン含量５９．８％）
１Ｌナスフラスコに、ジメチルスルホキシド７０１．７ｇ、アクリロイル－β－アラニン５５．４３ｇ（０．３８７モル）、ＭＱ０．１８ｇを入れ攪拌した後、炭酸カリウム３５．７ｇ（０．３８７モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．２５８モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン７００ｇで希釈し、ヘプタン相を、１％重曹水７００ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液７００ｇで洗浄した。洗浄後、ヘプタン相を減圧除去してＡｂａｌＳ １０５．５ｇを得た（収率８５％）。ＧＣによる該シリコーン化合物の純度は９３％であった。各測定結果を以下、並びに図５及び図６に示す。 Example 1-3
Synthesis of AbalS (3- [Tris (trimethylsiloxy) silyl] propyl-N-acryloyl-β-alaninate) (silicone content 59.8%)
To a 1 L eggplant flask, 701.7 g of dimethyl sulfoxide, 55.43 g (0.387 mol) of acryloyl-β-alanine, and 0.18 g of MQ were added and stirred, and then 35.7 g (0.387 mol) of potassium carbonate was added to the reaction. The liquid was heated to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 700 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 105.5 g of AbalS (yield 85%). The purity of the silicone compound by GC was 93%. Each measurement result is shown below, and in FIG.5 and FIG.6.
ＡｂａｌＳ（３－[トリス(トリメチルシロキシ)シリル]プロピル－Ｎ－アクリロイル－β－アラニネート）の合成（シリコーン含量５９．８％）
１Ｌナスフラスコに、ジメチルスルホキシド７０１．７ｇ、アクリロイル－β－アラニン５５．４３ｇ（０．３８７モル）、ＭＱ０．１８ｇを入れ攪拌した後、炭酸カリウム３５．７ｇ（０．３８７モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．２５８モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン７００ｇで希釈し、ヘプタン相を、１％重曹水７００ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液７００ｇで洗浄した。洗浄後、ヘプタン相を減圧除去してＡｂａｌＳ １０５．５ｇを得た（収率８５％）。ＧＣによる該シリコーン化合物の純度は９３％であった。各測定結果を以下、並びに図５及び図６に示す。 Example 1-3
Synthesis of AbalS (3- [Tris (trimethylsiloxy) silyl] propyl-N-acryloyl-β-alaninate) (silicone content 59.8%)
To a 1 L eggplant flask, 701.7 g of dimethyl sulfoxide, 55.43 g (0.387 mol) of acryloyl-β-alanine, and 0.18 g of MQ were added and stirred, and then 35.7 g (0.387 mol) of potassium carbonate was added to the reaction. The liquid was heated to 40 ° C. Further, 120.0 g (0.258 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added, and the mixture was stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 700 g of heptane, and the heptane phase was washed with 700 g of 1% sodium bicarbonate, followed by 700 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 105.5 g of AbalS (yield 85%). The purity of the silicone compound by GC was 93%. Each measurement result is shown below, and in FIG.5 and FIG.6.
1Ｈ－ＮＭＲ測定結果
ＣＨ2＝ＣＨ－：６．２１ｐｐｍ（２Ｈ）、５．６３ｐｐｍ（１Ｈ）、－ＣＨ2－：４．０４ｐｐｍ（２Ｈ）、３．５１ｐｐｍ（２Ｈ）、２．５８ｐｐｍ（２Ｈ）、１．６７ｐｐｍ（２Ｈ）、０．４８ｐｐｍ（２Ｈ）、－ＣＨ3：０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３２９０ｃｍ-1、３０７５ｃｍ-1、２９５５ｃｍ-1、１７４０ｃｍ-1、１６８０ｃｍ-1、１６３０ｃｍ-1、１４４０ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1
ＬＣ－ＭＳによる分子量測定の結果、分子量５０７であることから、上記式（４ｂ）で表される化合物(ＡｂａｌＳ)であることが特定された。このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。 1 H-NMR measurement result CH 2 ═CH—: 6.21 ppm (2H), 5.63 ppm (1H), —CH 2 —: 4.04 ppm (2H), 3.51 ppm (2H), 2.58 ppm (2H) ), 1.67 ppm (2H), 0.48 ppm (2H), —CH 3 : 0.11 ppm (27H).
IR measurement result 3290cm -1, 3075cm -1, 2955cm -1 , 1740cm -1, 1680cm -1, 1630cm -1, 1440cm -1, 1255cm -1, 1065cm -1, 840cm -1
As a result of measuring the molecular weight by LC-MS, the molecular weight was 507, and thus the compound (AbalS) represented by the above formula (4b) was identified. The silicone content of this monomer is 295/493 × 100 = 59.8%.
ＣＨ2＝ＣＨ－：６．２１ｐｐｍ（２Ｈ）、５．６３ｐｐｍ（１Ｈ）、－ＣＨ2－：４．０４ｐｐｍ（２Ｈ）、３．５１ｐｐｍ（２Ｈ）、２．５８ｐｐｍ（２Ｈ）、１．６７ｐｐｍ（２Ｈ）、０．４８ｐｐｍ（２Ｈ）、－ＣＨ3：０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３２９０ｃｍ-1、３０７５ｃｍ-1、２９５５ｃｍ-1、１７４０ｃｍ-1、１６８０ｃｍ-1、１６３０ｃｍ-1、１４４０ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1
ＬＣ－ＭＳによる分子量測定の結果、分子量５０７であることから、上記式（４ｂ）で表される化合物(ＡｂａｌＳ)であることが特定された。このモノマーのシリコーン含量は２９５／４９３×１００＝５９．８％である。 1 H-NMR measurement result CH 2 ═CH—: 6.21 ppm (2H), 5.63 ppm (1H), —CH 2 —: 4.04 ppm (2H), 3.51 ppm (2H), 2.58 ppm (2H) ), 1.67 ppm (2H), 0.48 ppm (2H), —CH 3 : 0.11 ppm (27H).
IR measurement result 3290cm -1, 3075cm -1, 2955cm -1 , 1740cm -1, 1680cm -1, 1630cm -1, 1440cm -1, 1255cm -1, 1065cm -1, 840cm -1
As a result of measuring the molecular weight by LC-MS, the molecular weight was 507, and thus the compound (AbalS) represented by the above formula (4b) was identified. The silicone content of this monomer is 295/493 × 100 = 59.8%.
実施例１－４
ＡｇｌｙｇｌｙＳ（Ｎ－[３－トリス(トリメチルシロキシ)シリルプロピル]アクリロイルグリシルグリシン）の合成（シリコーン含量５６．５％）
３００ｍＬナスフラスコに、ジメチルスルホキシド６５．６ｇ、Ｎ－（Ｎ－アクリロイルグリシル）グリシン６．４１ｇ（０．０３４４モル）、ＭＱ０．０８２ｇを入れ攪拌した後、炭酸カリウム２．９７ｇ（０．０２１５モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１０．０ｇ（０．０２１５モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン６５．６ｇで希釈し、ヘプタン相を、１％重曹水６５．６ｇ、続いて３０％エタノール（ｗ／ｗ）水溶液６５．６ｇで洗浄した。洗浄後、ヘプタン相を減圧除去して白色固体６．８ｇを得た（収率６０％）。ＧＣによる該シリコーン化合物の純度は８２％であった。各測定結果を以下、並びに図７及び図８に示す。 Example 1-4
Synthesis of AglylyS (N- [3-tris (trimethylsiloxy) silylpropyl] acryloylglycylglycine) (silicone content 56.5%)
In a 300 mL eggplant flask, 65.6 g of dimethyl sulfoxide, 6.41 g (0.0344 mol) of N- (N-acryloylglycyl) glycine and 0.082 g of MQ were added and stirred, and then 2.97 g (0.0215 mol) of potassium carbonate. ), And the temperature of the reaction solution was raised to 40 ° C. Further, 10.0 g (0.0215 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 65.6 g of heptane, and the heptane phase was diluted with 65.6 g of 1% sodium bicarbonate water followed by 65.6 g of 30% ethanol (w / w) aqueous solution. Washed. After washing, the heptane phase was removed under reduced pressure to obtain 6.8 g of a white solid (yield 60%). The purity of the silicone compound by GC was 82%. Each measurement result is shown below and in FIG.7 and FIG.8.
ＡｇｌｙｇｌｙＳ（Ｎ－[３－トリス(トリメチルシロキシ)シリルプロピル]アクリロイルグリシルグリシン）の合成（シリコーン含量５６．５％）
３００ｍＬナスフラスコに、ジメチルスルホキシド６５．６ｇ、Ｎ－（Ｎ－アクリロイルグリシル）グリシン６．４１ｇ（０．０３４４モル）、ＭＱ０．０８２ｇを入れ攪拌した後、炭酸カリウム２．９７ｇ（０．０２１５モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１０．０ｇ（０．０２１５モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン６５．６ｇで希釈し、ヘプタン相を、１％重曹水６５．６ｇ、続いて３０％エタノール（ｗ／ｗ）水溶液６５．６ｇで洗浄した。洗浄後、ヘプタン相を減圧除去して白色固体６．８ｇを得た（収率６０％）。ＧＣによる該シリコーン化合物の純度は８２％であった。各測定結果を以下、並びに図７及び図８に示す。 Example 1-4
Synthesis of AglylyS (N- [3-tris (trimethylsiloxy) silylpropyl] acryloylglycylglycine) (silicone content 56.5%)
In a 300 mL eggplant flask, 65.6 g of dimethyl sulfoxide, 6.41 g (0.0344 mol) of N- (N-acryloylglycyl) glycine and 0.082 g of MQ were added and stirred, and then 2.97 g (0.0215 mol) of potassium carbonate. ), And the temperature of the reaction solution was raised to 40 ° C. Further, 10.0 g (0.0215 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 65.6 g of heptane, and the heptane phase was diluted with 65.6 g of 1% sodium bicarbonate water followed by 65.6 g of 30% ethanol (w / w) aqueous solution. Washed. After washing, the heptane phase was removed under reduced pressure to obtain 6.8 g of a white solid (yield 60%). The purity of the silicone compound by GC was 82%. Each measurement result is shown below and in FIG.7 and FIG.8.
1Ｈ－ＮＭＲ測定
ＣＨ2＝ＣＨ－：６．２８ｐｐｍ（２Ｈ）、５．６９ｐｐｍ（１Ｈ）、－ＣＨ2－：４．０８ｐｐｍ（２Ｈ）、３．９７ｐｐｍ（４Ｈ）、１．６９ｐｐｍ（２Ｈ）、０．４９ｐｐｍ（２Ｈ）、－ＣＨ3：０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３２９５ｃｍ-1、３０８０ｃｍ-1、２９６０ｃｍ-1、１７４５ｃｍ-1、１６６５ｃｍ-1、１６３０ｃｍ-1、１４４０ｃｍ-1、１２５５ｃｍ-1、１０５２ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる構造特定の結果、分子量５０７であることから、式（８）で表されるＡｇｌｙｇｌｙＳであることが特定された。このモノマーのシリコーン含量は２９５／５２２×１００＝５６．５％である。 1 H-NMR measurement CH 2 ═CH—: 6.28 ppm (2H), 5.69 ppm (1H), —CH 2 —: 4.08 ppm (2H), 3.97 ppm (4H), 1.69 ppm (2H) , 0.49ppm (2H), - CH 3: 0.11ppm (27H).
IR measurements 3295cm -1, 3080cm -1, 2960cm -1 , 1745cm -1, 1665cm -1, 1630cm -1, 1440cm -1, 1255cm -1, 1052cm -1, 840cm -1.
As a result of specifying the structure by LC-MS, the molecular weight was 507. Therefore, it was specified to be AglylyS represented by the formula (8). The silicone content of this monomer is 295/522 × 100 = 56.5%.
ＣＨ2＝ＣＨ－：６．２８ｐｐｍ（２Ｈ）、５．６９ｐｐｍ（１Ｈ）、－ＣＨ2－：４．０８ｐｐｍ（２Ｈ）、３．９７ｐｐｍ（４Ｈ）、１．６９ｐｐｍ（２Ｈ）、０．４９ｐｐｍ（２Ｈ）、－ＣＨ3：０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３２９５ｃｍ-1、３０８０ｃｍ-1、２９６０ｃｍ-1、１７４５ｃｍ-1、１６６５ｃｍ-1、１６３０ｃｍ-1、１４４０ｃｍ-1、１２５５ｃｍ-1、１０５２ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる構造特定の結果、分子量５０７であることから、式（８）で表されるＡｇｌｙｇｌｙＳであることが特定された。このモノマーのシリコーン含量は２９５／５２２×１００＝５６．５％である。 1 H-NMR measurement CH 2 ═CH—: 6.28 ppm (2H), 5.69 ppm (1H), —CH 2 —: 4.08 ppm (2H), 3.97 ppm (4H), 1.69 ppm (2H) , 0.49ppm (2H), - CH 3: 0.11ppm (27H).
IR measurements 3295cm -1, 3080cm -1, 2960cm -1 , 1745cm -1, 1665cm -1, 1630cm -1, 1440cm -1, 1255cm -1, 1052cm -1, 840cm -1.
As a result of specifying the structure by LC-MS, the molecular weight was 507. Therefore, it was specified to be AglylyS represented by the formula (8). The silicone content of this monomer is 295/522 × 100 = 56.5%.
実施例１－５
ＭＡｓｅｒＳ（Ｎ－[３－トリス(トリメチルシロキシ)シリルプロピル]メタクリロイルセリン）の合成（シリコーン含量５８．０％）
１Ｌナスフラスコに、ジメチルスルホキシド９６．１ｇ、Ｎ－メタクリロイルセリン８．３８ｇ（０．０４８４モル）、ＭＱ０．０１２ｇを入れ攪拌した後、炭酸カリウム４．４６ｇ（０．０３２３モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１５．０ｇ（０．０３２３モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン１２０ｇで希釈し、ヘプタン相を、１％重曹水１２０ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液１２０ｇで洗浄した。洗浄後、ヘプタン相を減圧除去して粘調性液体１３．２ｇを得た（収率８０％）。ＧＣによる該シリコーン化合物の純度は９０％であった。各測定結果を以下、並びに図９及び図１０に示す。 Example 1-5
Synthesis of MAserS (N- [3-tris (trimethylsiloxy) silylpropyl] methacryloylserine) (silicone content 58.0%)
To a 1 L eggplant flask, 96.1 g of dimethyl sulfoxide, 8.38 g (0.0484 mol) of N-methacryloylserine and 0.012 g of MQ were added and stirred. Then, 4.46 g (0.0323 mol) of potassium carbonate was added and the reaction solution was added. The temperature was raised to 40 ° C. Further, 15.0 g (0.0323 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 120 g of heptane, and the heptane phase was washed with 120 g of 1% aqueous sodium bicarbonate followed by 120 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 13.2 g of viscous liquid (yield 80%). The purity of the silicone compound by GC was 90%. Each measurement result is shown below, and in FIG.9 and FIG.10.
ＭＡｓｅｒＳ（Ｎ－[３－トリス(トリメチルシロキシ)シリルプロピル]メタクリロイルセリン）の合成（シリコーン含量５８．０％）
１Ｌナスフラスコに、ジメチルスルホキシド９６．１ｇ、Ｎ－メタクリロイルセリン８．３８ｇ（０．０４８４モル）、ＭＱ０．０１２ｇを入れ攪拌した後、炭酸カリウム４．４６ｇ（０．０３２３モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１５．０ｇ（０．０３２３モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン１２０ｇで希釈し、ヘプタン相を、１％重曹水１２０ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液１２０ｇで洗浄した。洗浄後、ヘプタン相を減圧除去して粘調性液体１３．２ｇを得た（収率８０％）。ＧＣによる該シリコーン化合物の純度は９０％であった。各測定結果を以下、並びに図９及び図１０に示す。 Example 1-5
Synthesis of MAserS (N- [3-tris (trimethylsiloxy) silylpropyl] methacryloylserine) (silicone content 58.0%)
To a 1 L eggplant flask, 96.1 g of dimethyl sulfoxide, 8.38 g (0.0484 mol) of N-methacryloylserine and 0.012 g of MQ were added and stirred. Then, 4.46 g (0.0323 mol) of potassium carbonate was added and the reaction solution was added. The temperature was raised to 40 ° C. Further, 15.0 g (0.0323 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 120 g of heptane, and the heptane phase was washed with 120 g of 1% aqueous sodium bicarbonate followed by 120 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 13.2 g of viscous liquid (yield 80%). The purity of the silicone compound by GC was 90%. Each measurement result is shown below, and in FIG.9 and FIG.10.
1Ｈ－ＮＭＲ測定
ＣＨ2＝ＣＨ－：５．８１ｐｐｍ（２Ｈ）、５．４６ｐｐｍ（１Ｈ）、－ＣＨ－：４．５０ｐｐｍ（１Ｈ）、４．３２ｐｐｍ（１Ｈ）、－ＣＨ2－：４．１１ｐｐｍ（２Ｈ）、１．７１ｐｐｍ（２Ｈ）、０．５１ｐｐｍ（２Ｈ）、－ＣＨ3：１．９９ｐｐｍ（３Ｈ）、１．２０ｐｐｍ（３Ｈ）、０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３４３５ｃｍ-1、３０９０ｃｍ-1、２９５５ｃｍ-1、１７４０ｃｍ-1、１６８０ｃｍ-1、１６２５ｃｍ-1、１４５５ｃｍ-1、１２５５ｃｍ-1、１０６０ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる構造特定の結果、分子量５０９であることから、式（９）で表されるＭＡｓｅｒＳであることが特定された。このモノマーのシリコーン含量は２９５／５０９×１００＝５８．０％である。 1 H-NMR measurement CH 2 ═CH—: 5.81 ppm (2H), 5.46 ppm (1H), —CH—: 4.50 ppm (1H), 4.32 ppm (1H), —CH 2 —: 4. 11 ppm (2H), 1.71 ppm (2H), 0.51 ppm (2H), —CH 3 : 1.99 ppm (3H), 1.20 ppm (3H), 0.11 ppm (27H).
IR measurements 3435cm -1, 3090cm -1, 2955cm -1 , 1740cm -1, 1680cm -1, 1625cm -1, 1455cm -1, 1255cm -1, 1060cm -1, 840cm -1.
As a result of specifying the structure by LC-MS, the molecular weight was 509, so that it was specified to be MAserS represented by the formula (9). The silicone content of this monomer is 295/509 × 100 = 58.0%.
ＣＨ2＝ＣＨ－：５．８１ｐｐｍ（２Ｈ）、５．４６ｐｐｍ（１Ｈ）、－ＣＨ－：４．５０ｐｐｍ（１Ｈ）、４．３２ｐｐｍ（１Ｈ）、－ＣＨ2－：４．１１ｐｐｍ（２Ｈ）、１．７１ｐｐｍ（２Ｈ）、０．５１ｐｐｍ（２Ｈ）、－ＣＨ3：１．９９ｐｐｍ（３Ｈ）、１．２０ｐｐｍ（３Ｈ）、０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３４３５ｃｍ-1、３０９０ｃｍ-1、２９５５ｃｍ-1、１７４０ｃｍ-1、１６８０ｃｍ-1、１６２５ｃｍ-1、１４５５ｃｍ-1、１２５５ｃｍ-1、１０６０ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる構造特定の結果、分子量５０９であることから、式（９）で表されるＭＡｓｅｒＳであることが特定された。このモノマーのシリコーン含量は２９５／５０９×１００＝５８．０％である。 1 H-NMR measurement CH 2 ═CH—: 5.81 ppm (2H), 5.46 ppm (1H), —CH—: 4.50 ppm (1H), 4.32 ppm (1H), —CH 2 —: 4. 11 ppm (2H), 1.71 ppm (2H), 0.51 ppm (2H), —CH 3 : 1.99 ppm (3H), 1.20 ppm (3H), 0.11 ppm (27H).
IR measurements 3435cm -1, 3090cm -1, 2955cm -1 , 1740cm -1, 1680cm -1, 1625cm -1, 1455cm -1, 1255cm -1, 1060cm -1, 840cm -1.
As a result of specifying the structure by LC-MS, the molecular weight was 509, so that it was specified to be MAserS represented by the formula (9). The silicone content of this monomer is 295/509 × 100 = 58.0%.
実施例１－６
ＭＡｔｈｒＳ（Ｎ－[３－トリス(トリメチルシロキシ)シリルプロピル]メタクリロイルトレオニン）の合成（シリコーン含量５６．４％）
１Ｌナスフラスコに、ジメチルスルホキシド９６．１ｇ、メタクリロイル－ＤＬ－トレオニン９．０６ｇ（０．０４８４モル）、ＭＱ０．０１２ｇを入れ攪拌した後、炭酸カリウム４．４６ｇ（０．０３２３モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．０３２３モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン９６ｇで希釈し、ヘプタン相を、イオン交換水９６ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液９６ｇで洗浄した。洗浄後、ヘプタン相を減圧除去して粘調性液体１３．５ｇを得た（収率８０％）。ＧＣによる該シリコーン化合物の純度は９２％であった。各測定結果を以下、並びに図１１及び図１２に示す。 Example 1-6
Synthesis of MAthrS (N- [3-tris (trimethylsiloxy) silylpropyl] methacryloyl threonine) (silicone content 56.4%)
To a 1 L eggplant flask, 96.1 g of dimethyl sulfoxide, 9.06 g (0.0484 mol) of methacryloyl-DL-threonine, and 0.012 g of MQ were added and stirred, and then 4.46 g (0.0323 mol) of potassium carbonate was added and reacted. The liquid was heated to 40 ° C. Further, 120.0 g (0.0323 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 96 g of heptane, and the heptane phase was washed with 96 g of ion-exchanged water and subsequently with 96 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 13.5 g of viscous liquid (yield 80%). The purity of the silicone compound by GC was 92%. Each measurement result is shown below, and in FIG.11 and FIG.12.
ＭＡｔｈｒＳ（Ｎ－[３－トリス(トリメチルシロキシ)シリルプロピル]メタクリロイルトレオニン）の合成（シリコーン含量５６．４％）
１Ｌナスフラスコに、ジメチルスルホキシド９６．１ｇ、メタクリロイル－ＤＬ－トレオニン９．０６ｇ（０．０４８４モル）、ＭＱ０．０１２ｇを入れ攪拌した後、炭酸カリウム４．４６ｇ（０．０３２３モル）を加え、反応液を４０℃まで昇温した。さらに３－ヨードプロピルトリス（トリメチルシロキシ）シラン１２０．０ｇ（０．０３２３モル）を加え、４０℃にて６時間攪拌を行った。冷却後、３Ｌ分液ロートへ反応液を移した後、ヘプタン９６ｇで希釈し、ヘプタン相を、イオン交換水９６ｇ、続いて５０％エタノール（ｗ／ｗ）水溶液９６ｇで洗浄した。洗浄後、ヘプタン相を減圧除去して粘調性液体１３．５ｇを得た（収率８０％）。ＧＣによる該シリコーン化合物の純度は９２％であった。各測定結果を以下、並びに図１１及び図１２に示す。 Example 1-6
Synthesis of MAthrS (N- [3-tris (trimethylsiloxy) silylpropyl] methacryloyl threonine) (silicone content 56.4%)
To a 1 L eggplant flask, 96.1 g of dimethyl sulfoxide, 9.06 g (0.0484 mol) of methacryloyl-DL-threonine, and 0.012 g of MQ were added and stirred, and then 4.46 g (0.0323 mol) of potassium carbonate was added and reacted. The liquid was heated to 40 ° C. Further, 120.0 g (0.0323 mol) of 3-iodopropyltris (trimethylsiloxy) silane was added and stirred at 40 ° C. for 6 hours. After cooling, the reaction solution was transferred to a 3 L separatory funnel, diluted with 96 g of heptane, and the heptane phase was washed with 96 g of ion-exchanged water and subsequently with 96 g of 50% ethanol (w / w) aqueous solution. After washing, the heptane phase was removed under reduced pressure to obtain 13.5 g of viscous liquid (yield 80%). The purity of the silicone compound by GC was 92%. Each measurement result is shown below, and in FIG.11 and FIG.12.
1Ｈ－ＮＭＲ測定
ＣＨ2＝ＣＨ－：５．８１ｐｐｍ（２Ｈ）、５．４６ｐｐｍ（１Ｈ）、－ＣＨ－：４．５０ｐｐｍ（１Ｈ）、４．３２ｐｐｍ（１Ｈ）、－ＣＨ2－：４．１１ｐｐｍ（２Ｈ）、１．７１ｐｐｍ（２Ｈ）、０．５１ｐｐｍ（２Ｈ）、－ＣＨ3：１．９９ｐｐｍ（３Ｈ）、１．２０ｐｐｍ（３Ｈ）、０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３４４０ｃｍ-1、３０８５ｃｍ-1、２９６０ｃｍ-1、１７４０ｃｍ-1、１６８０ｃｍ-1、１６２５ｃｍ-1、１４５５ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる構造特定の結果、分子量５２３であることから、式（１０）で表されるＭＡｔｈｒＳであることが特定された。このモノマーのシリコーン含量は２９５／５２３×１００＝５６．４％である。 1 H-NMR measurement CH 2 ═CH—: 5.81 ppm (2H), 5.46 ppm (1H), —CH—: 4.50 ppm (1H), 4.32 ppm (1H), —CH 2 —: 4. 11 ppm (2H), 1.71 ppm (2H), 0.51 ppm (2H), —CH 3 : 1.99 ppm (3H), 1.20 ppm (3H), 0.11 ppm (27H).
IR measurements 3440cm -1, 3085cm -1, 2960cm -1 , 1740cm -1, 1680cm -1, 1625cm -1, 1455cm -1, 1255cm -1, 1065cm -1, 840cm -1.
As a result of structure identification by LC-MS, the molecular weight was 523, and therefore, it was identified as MAthrS represented by the formula (10). The silicone content of this monomer is 295/523 × 100 = 56.4%.
ＣＨ2＝ＣＨ－：５．８１ｐｐｍ（２Ｈ）、５．４６ｐｐｍ（１Ｈ）、－ＣＨ－：４．５０ｐｐｍ（１Ｈ）、４．３２ｐｐｍ（１Ｈ）、－ＣＨ2－：４．１１ｐｐｍ（２Ｈ）、１．７１ｐｐｍ（２Ｈ）、０．５１ｐｐｍ（２Ｈ）、－ＣＨ3：１．９９ｐｐｍ（３Ｈ）、１．２０ｐｐｍ（３Ｈ）、０．１１ｐｐｍ（２７Ｈ）。
ＩＲ測定結果
３４４０ｃｍ-1、３０８５ｃｍ-1、２９６０ｃｍ-1、１７４０ｃｍ-1、１６８０ｃｍ-1、１６２５ｃｍ-1、１４５５ｃｍ-1、１２５５ｃｍ-1、１０６５ｃｍ-1、８４０ｃｍ-1。
ＬＣ－ＭＳによる構造特定の結果、分子量５２３であることから、式（１０）で表されるＭＡｔｈｒＳであることが特定された。このモノマーのシリコーン含量は２９５／５２３×１００＝５６．４％である。 1 H-NMR measurement CH 2 ═CH—: 5.81 ppm (2H), 5.46 ppm (1H), —CH—: 4.50 ppm (1H), 4.32 ppm (1H), —CH 2 —: 4. 11 ppm (2H), 1.71 ppm (2H), 0.51 ppm (2H), —CH 3 : 1.99 ppm (3H), 1.20 ppm (3H), 0.11 ppm (27H).
IR measurements 3440cm -1, 3085cm -1, 2960cm -1 , 1740cm -1, 1680cm -1, 1625cm -1, 1455cm -1, 1255cm -1, 1065cm -1, 840cm -1.
As a result of structure identification by LC-MS, the molecular weight was 523, and therefore, it was identified as MAthrS represented by the formula (10). The silicone content of this monomer is 295/523 × 100 = 56.4%.
実施例２－１
ヒドロキシエチルアクリレート（ＨＥＡ）３０質量部、実施例１－１で調製した式（４ａ）で表される化合物（ＭＡｇｌｙＳ）４０質量部、Ｎ－ビニルピロリドン（Ｖｐ）３０質量部、エチレングリコールジメタクリレート（ＥＤＭＡ）０．２７質量部、及びアゾビスイソブチロニトリル（ＡＩＢＮ）０．０４質量部を混合し、均一溶解させた。厚さ１ｍｍのポリエチレンテレフタレートシートをスペーサーとしてポリプロピレン板で挟んで作製したセルに混合物を流し込み、窒素置換したオーブン内で１００℃、２時間放置することにより重合体を得た。得られた重合体を生理食塩水へ浸漬し、膨潤させ、透明なゲル状重合体を得た。得られた重合体について以下の評価及び測定を行った。結果を表１に示す。 Example 2-1
30 parts by mass of hydroxyethyl acrylate (HEA), 40 parts by mass of the compound represented by the formula (4a) prepared in Example 1-1 (MAGlyS), 30 parts by mass of N-vinylpyrrolidone (Vp), ethylene glycol dimethacrylate ( EDMA) 0.27 parts by mass and azobisisobutyronitrile (AIBN) 0.04 parts by mass were mixed and dissolved uniformly. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. The obtained polymer was immersed in physiological saline and swollen to obtain a transparent gel polymer. The following evaluation and measurement were performed on the obtained polymer. The results are shown in Table 1.
ヒドロキシエチルアクリレート（ＨＥＡ）３０質量部、実施例１－１で調製した式（４ａ）で表される化合物（ＭＡｇｌｙＳ）４０質量部、Ｎ－ビニルピロリドン（Ｖｐ）３０質量部、エチレングリコールジメタクリレート（ＥＤＭＡ）０．２７質量部、及びアゾビスイソブチロニトリル（ＡＩＢＮ）０．０４質量部を混合し、均一溶解させた。厚さ１ｍｍのポリエチレンテレフタレートシートをスペーサーとしてポリプロピレン板で挟んで作製したセルに混合物を流し込み、窒素置換したオーブン内で１００℃、２時間放置することにより重合体を得た。得られた重合体を生理食塩水へ浸漬し、膨潤させ、透明なゲル状重合体を得た。得られた重合体について以下の評価及び測定を行った。結果を表１に示す。 Example 2-1
30 parts by mass of hydroxyethyl acrylate (HEA), 40 parts by mass of the compound represented by the formula (4a) prepared in Example 1-1 (MAGlyS), 30 parts by mass of N-vinylpyrrolidone (Vp), ethylene glycol dimethacrylate ( EDMA) 0.27 parts by mass and azobisisobutyronitrile (AIBN) 0.04 parts by mass were mixed and dissolved uniformly. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. The obtained polymer was immersed in physiological saline and swollen to obtain a transparent gel polymer. The following evaluation and measurement were performed on the obtained polymer. The results are shown in Table 1.
［配合物均一性確認方法］
重合前の混合物を無色透明な容器へ入れ、以下の評価基準で目視確認を行なった。
(A)：透明、(B)：白濁又は沈殿。
［透明性評価方法］
膨潤させて得られたゲル状の重合体の透明性を以下の評価基準で目視確認した。
(a)：透明、(b)：微濁、(c)：白濁。
［表面濡れ性］
膨潤させて得られたゲル状の重合体を生理食塩水から引き上げ、表面の水膜が切れるまでの時間を計測した。判断基準を以下に示す。
(X)：30秒以上、(Y)：30秒未満。
［酸素透過性測定方法］
酸素透過率測定装置（２０１Ｔ、Ｒｅｈｄｅｒ社）の平面電極セルを使用して、ＩＳＯ１８３６９－４（ＦＡＴＴ法）に定められている方法により酸素透過係数（Ｄｋ）を測定した。 [Method of confirming uniformity of compound]
The mixture before polymerization was put into a colorless and transparent container and visually confirmed according to the following evaluation criteria.
(A): transparent, (B): cloudy or precipitated.
[Transparency evaluation method]
The transparency of the gel-like polymer obtained by swelling was visually confirmed according to the following evaluation criteria.
(a): Transparent, (b): Slight turbidity, (c): White turbidity.
[Surface wettability]
The gel-like polymer obtained by swelling was pulled up from the physiological saline, and the time until the water film on the surface was cut was measured. Judgment criteria are shown below.
(X): 30 seconds or more, (Y): less than 30 seconds.
[Oxygen permeability measurement method]
An oxygen transmission coefficient (Dk) was measured by a method defined in ISO18369-4 (FATT method) using a planar electrode cell of an oxygen transmission rate measuring apparatus (201T, Rehder).
重合前の混合物を無色透明な容器へ入れ、以下の評価基準で目視確認を行なった。
(A)：透明、(B)：白濁又は沈殿。
［透明性評価方法］
膨潤させて得られたゲル状の重合体の透明性を以下の評価基準で目視確認した。
(a)：透明、(b)：微濁、(c)：白濁。
［表面濡れ性］
膨潤させて得られたゲル状の重合体を生理食塩水から引き上げ、表面の水膜が切れるまでの時間を計測した。判断基準を以下に示す。
(X)：30秒以上、(Y)：30秒未満。
［酸素透過性測定方法］
酸素透過率測定装置（２０１Ｔ、Ｒｅｈｄｅｒ社）の平面電極セルを使用して、ＩＳＯ１８３６９－４（ＦＡＴＴ法）に定められている方法により酸素透過係数（Ｄｋ）を測定した。 [Method of confirming uniformity of compound]
The mixture before polymerization was put into a colorless and transparent container and visually confirmed according to the following evaluation criteria.
(A): transparent, (B): cloudy or precipitated.
[Transparency evaluation method]
The transparency of the gel-like polymer obtained by swelling was visually confirmed according to the following evaluation criteria.
(a): Transparent, (b): Slight turbidity, (c): White turbidity.
[Surface wettability]
The gel-like polymer obtained by swelling was pulled up from the physiological saline, and the time until the water film on the surface was cut was measured. Judgment criteria are shown below.
(X): 30 seconds or more, (Y): less than 30 seconds.
[Oxygen permeability measurement method]
An oxygen transmission coefficient (Dk) was measured by a method defined in ISO18369-4 (FATT method) using a planar electrode cell of an oxygen transmission rate measuring apparatus (201T, Rehder).
実施例２－２～２－５
実施例２－１と同様の方法で重合し、生理食塩水へ浸漬させることで透明なゲル状重合体を得た。各モノマーの配合比率を表１に示す。 Examples 2-2 to 2-5
Polymerization was performed in the same manner as in Example 2-1, and the gel was immersed in physiological saline to obtain a transparent gel polymer. Table 1 shows the blending ratio of each monomer.
実施例２－１と同様の方法で重合し、生理食塩水へ浸漬させることで透明なゲル状重合体を得た。各モノマーの配合比率を表１に示す。 Examples 2-2 to 2-5
Polymerization was performed in the same manner as in Example 2-1, and the gel was immersed in physiological saline to obtain a transparent gel polymer. Table 1 shows the blending ratio of each monomer.
比較例１
ＨＥＡ ３０質量部、ＭＡｇｌｙＳ ７０質量部、ＥＤＭＡ ０．２７質量部及びＡＩＢＮ ０．０４質量部を混合し、均一溶解させた。厚さ１ｍｍのポリエチレンテレフタレートシートをスペーサーとしてポリプロピレン板で挟んで作製したセルに混合物を流し込み、窒素置換したオーブン内で１００℃、２時間放置することにより重合体を得た。得られた重合体を生理食塩水へ浸漬し、膨潤させ、透明なゲル状重合体を得た。この重合体は十分な表面親水性を得られなかった。 Comparative Example 1
30 parts by weight of HEA, 70 parts by weight of MAglyS, 0.27 parts by weight of EDMA and 0.04 parts by weight of AIBN were mixed and uniformly dissolved. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. The obtained polymer was immersed in physiological saline and swollen to obtain a transparent gel polymer. This polymer could not obtain sufficient surface hydrophilicity.
ＨＥＡ ３０質量部、ＭＡｇｌｙＳ ７０質量部、ＥＤＭＡ ０．２７質量部及びＡＩＢＮ ０．０４質量部を混合し、均一溶解させた。厚さ１ｍｍのポリエチレンテレフタレートシートをスペーサーとしてポリプロピレン板で挟んで作製したセルに混合物を流し込み、窒素置換したオーブン内で１００℃、２時間放置することにより重合体を得た。得られた重合体を生理食塩水へ浸漬し、膨潤させ、透明なゲル状重合体を得た。この重合体は十分な表面親水性を得られなかった。 Comparative Example 1
30 parts by weight of HEA, 70 parts by weight of MAglyS, 0.27 parts by weight of EDMA and 0.04 parts by weight of AIBN were mixed and uniformly dissolved. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. The obtained polymer was immersed in physiological saline and swollen to obtain a transparent gel polymer. This polymer could not obtain sufficient surface hydrophilicity.
比較例２
ＨＥＡ ９０質量部、ＭＡｇｌｙＳ １０質量部、ＥＤＭＡ ０．２７質量部、ＡＩＢＮ ０．０４質量部を混合し、均一溶解させた。厚さ１ｍｍのポリエチレンテレフタレートシートをスペーサーとしてポリプロピレン板で挟んで作製したセルに混合物を流し込み、窒素置換したオーブン内で１００℃、２時間放置することにより重合体を得た。得られた重合体を生理食塩水へ浸漬し、膨潤させたが、得られたゲル状重合体は白濁していた。 Comparative Example 2
90 parts by mass of HEA, 10 parts by mass of MAglyS, 0.27 parts by mass of EDMA, and 0.04 parts by mass of AIBN were mixed and uniformly dissolved. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. Although the obtained polymer was immersed in physiological saline and swollen, the obtained gel polymer was cloudy.
ＨＥＡ ９０質量部、ＭＡｇｌｙＳ １０質量部、ＥＤＭＡ ０．２７質量部、ＡＩＢＮ ０．０４質量部を混合し、均一溶解させた。厚さ１ｍｍのポリエチレンテレフタレートシートをスペーサーとしてポリプロピレン板で挟んで作製したセルに混合物を流し込み、窒素置換したオーブン内で１００℃、２時間放置することにより重合体を得た。得られた重合体を生理食塩水へ浸漬し、膨潤させたが、得られたゲル状重合体は白濁していた。 Comparative Example 2
90 parts by mass of HEA, 10 parts by mass of MAglyS, 0.27 parts by mass of EDMA, and 0.04 parts by mass of AIBN were mixed and uniformly dissolved. The mixture was poured into a cell prepared by sandwiching a polyethylene terephthalate sheet having a thickness of 1 mm with a polypropylene plate as a spacer, and left in an oven purged with nitrogen at 100 ° C. for 2 hours to obtain a polymer. Although the obtained polymer was immersed in physiological saline and swollen, the obtained gel polymer was cloudy.
比較例３
ＭＡｇｌｙＳの替わりに３－［トリス（トリメチルシロキシ）シリル］プロピルメタクリレート（ＴＲＩＳ）を使用した以外は実施例２－１と同様にモノマーを混合したが、均一溶解しなかった。 Comparative Example 3
Monomers were mixed in the same manner as in Example 2-1, except that 3- [tris (trimethylsiloxy) silyl] propyl methacrylate (TRIS) was used instead of MAglyS, but uniform dissolution did not occur.
ＭＡｇｌｙＳの替わりに３－［トリス（トリメチルシロキシ）シリル］プロピルメタクリレート（ＴＲＩＳ）を使用した以外は実施例２－１と同様にモノマーを混合したが、均一溶解しなかった。 Comparative Example 3
Monomers were mixed in the same manner as in Example 2-1, except that 3- [tris (trimethylsiloxy) silyl] propyl methacrylate (TRIS) was used instead of MAglyS, but uniform dissolution did not occur.
ＴＲＩＳ：３－［トリス（トリメチルシロキシ）シリル］プロピルメタクリレート、
ＤＭＡ：Ｎ，Ｎ－ジメチルアクリルアミド、
ＨＥＡ：ヒドロキシエチルアクリレート、
Ｖｐ：Ｎ－ビニルピロリドン、
ＥＤＭＡ：エチレングリコールジメタクリレート、
ＡＩＢＮ：α,α'‐アゾビスイソブチロニトリル、
DK：酸素透過係数（単位は、×10-11 (cm2/sec)・(mlO2/ml×mmHg)）。
TRIS: 3- [Tris (trimethylsiloxy) silyl] propyl methacrylate,
DMA: N, N-dimethylacrylamide,
HEA: hydroxyethyl acrylate,
Vp: N-vinylpyrrolidone,
EDMA: ethylene glycol dimethacrylate,
AIBN: α, α′-azobisisobutyronitrile,
DK: Oxygen permeability coefficient (unit: × 10 -11 (cm 2 / sec) · (mlO 2 / ml × mmHg)).
本発明のシリコーンモノマー、単量体組成物及び重合体は、コンタクトレンズ等の眼用デバイスの製造に好適に使用される。
The silicone monomer, monomer composition and polymer of the present invention are suitably used for the production of ophthalmic devices such as contact lenses.
Claims (4)
- 式（１）で表されるシリコーンモノマー。
- アミノ酸及び（メタ）アクリル酸クロライドを反応させてなる式（５）(式（５）中、Ｒは水素原子又はメチル基を示す。Ｘは酸素原子又は窒素原子を含んでいても良い炭素数１～６の２価の有機基を示る。)で表される（メタ）アクリロイルアミノ酸と、式（６）（式（６）中、Ｙはハロゲンであり、ｎは０または１を表す。）で表されるハロゲン化アルキル変性シリコーンとを反応させる工程を含む請求項１記載の式（１）で示されるシリコーンモノマーの製造方法。
- 請求項１記載のシリコーンモノマー２０～６０質量％と、２－ヒドロキシエチル（メタ）アクリレート、Ｎ－ビニルピロリドン、Ｎ，Ｎ－ジメチルアクリルアミド、２－（メタクリロイルオキシエチル）－２－（トリメチルアンモニオエチル）ホスフェートまたはこれら２種以上の混合物からなる群より選ばれる親水性モノマー４０～８０質量％とを含む単量体組成物。 A silicone monomer of 20 to 60% by mass according to claim 1, 2-hydroxyethyl (meth) acrylate, N-vinylpyrrolidone, N, N-dimethylacrylamide, 2- (methacryloyloxyethyl) -2- (trimethylammonioethyl) ) A monomer composition comprising 40 to 80% by mass of a hydrophilic monomer selected from the group consisting of phosphate or a mixture of two or more thereof.
- 請求項３に記載の単量体組成物を重合させて得た重合体。 A polymer obtained by polymerizing the monomer composition according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2011/080311 WO2013098966A1 (en) | 2011-12-27 | 2011-12-27 | Silicone monomer and method for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2011/080311 WO2013098966A1 (en) | 2011-12-27 | 2011-12-27 | Silicone monomer and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013098966A1 true WO2013098966A1 (en) | 2013-07-04 |
Family
ID=48696531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2011/080311 WO2013098966A1 (en) | 2011-12-27 | 2011-12-27 | Silicone monomer and method for producing same |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2013098966A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014093751A3 (en) * | 2012-12-14 | 2014-08-28 | Novartis Ag | Amphiphilic siloxane-containing vinylic monomers and uses thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191730A (en) * | 1998-12-24 | 2000-07-11 | Toray Ind Inc | Monomer for ophthalmic lens, polymer for ophthalmic lens and contact lens using the same |
| JP2000212223A (en) * | 1999-01-21 | 2000-08-02 | Toray Ind Inc | Monomer, polymer therefrom, and plastic molding |
| JP2001323024A (en) * | 2000-05-12 | 2001-11-20 | Toray Ind Inc | Monomer, polymer and ophthalmic lens using the same |
| JP2002088119A (en) * | 2000-09-14 | 2002-03-27 | Toray Ind Inc | Monomer, polymer, lens for eye and contact lens |
| JP2007526364A (en) * | 2004-02-11 | 2007-09-13 | 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 | Hydroxy and silicone functional group-containing (meth) acrylamide monomers and polymers produced therefrom |
| JP2011528816A (en) * | 2008-07-21 | 2011-11-24 | ノバルティス アーゲー | Silicone-containing polymer material having hydrolyzable groups |
| JP2012017285A (en) * | 2010-07-07 | 2012-01-26 | Nof Corp | Silicone monomer, method of producing the same, monomer composition and polymer |
-
2011
- 2011-12-27 WO PCT/JP2011/080311 patent/WO2013098966A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191730A (en) * | 1998-12-24 | 2000-07-11 | Toray Ind Inc | Monomer for ophthalmic lens, polymer for ophthalmic lens and contact lens using the same |
| JP2000212223A (en) * | 1999-01-21 | 2000-08-02 | Toray Ind Inc | Monomer, polymer therefrom, and plastic molding |
| JP2001323024A (en) * | 2000-05-12 | 2001-11-20 | Toray Ind Inc | Monomer, polymer and ophthalmic lens using the same |
| JP2002088119A (en) * | 2000-09-14 | 2002-03-27 | Toray Ind Inc | Monomer, polymer, lens for eye and contact lens |
| JP2007526364A (en) * | 2004-02-11 | 2007-09-13 | 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 | Hydroxy and silicone functional group-containing (meth) acrylamide monomers and polymers produced therefrom |
| JP2011528816A (en) * | 2008-07-21 | 2011-11-24 | ノバルティス アーゲー | Silicone-containing polymer material having hydrolyzable groups |
| JP2012017285A (en) * | 2010-07-07 | 2012-01-26 | Nof Corp | Silicone monomer, method of producing the same, monomer composition and polymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014093751A3 (en) * | 2012-12-14 | 2014-08-28 | Novartis Ag | Amphiphilic siloxane-containing vinylic monomers and uses thereof |
| US9103965B2 (en) | 2012-12-14 | 2015-08-11 | Novartis Ag | Amphiphilic siloxane-containing vinylic monomers and uses thereof |
| US9541676B2 (en) | 2012-12-14 | 2017-01-10 | Novartis Ag | Amphiphilic siloxane-containing vinylic monomers and uses thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1968986B1 (en) | Process for making cationic hydrophilic siloxanyl monomers | |
| EP2076523B1 (en) | Hydrolysis-resistant silicone compounds | |
| JP5699931B2 (en) | Silicone monomer | |
| EP2076522B1 (en) | Process of producing hydrolysis-resistant silicone compounds | |
| WO2009006285A1 (en) | Soluble silicone prepolymers | |
| EP3663302A1 (en) | Siloxane compound and production method for same | |
| JPWO2019194264A1 (en) | Phosphorylcholine group-containing polysiloxane monomer | |
| JP2012017285A (en) | Silicone monomer, method of producing the same, monomer composition and polymer | |
| WO2020218220A1 (en) | Monomer composition for contact lenses, polymer for contact lenses and method for producing same, and contact lens and method for producing same | |
| JP2015096471A (en) | Monomers for ophthalmic device production | |
| JP5505313B2 (en) | Silicone monomer | |
| WO2013098966A1 (en) | Silicone monomer and method for producing same | |
| WO2020246313A1 (en) | Siloxane and method for producing same | |
| JPH09221530A (en) | Ophthalmic lens material | |
| EP2955208B1 (en) | Silicone compound and a use thereof | |
| JP5526845B2 (en) | Silicone monomer | |
| JP5402934B2 (en) | Silicone monomer, its production method and use | |
| JP2016102159A (en) | Copolymer and ophthalmologic device | |
| JP2016102158A (en) | Monomer for producing ophthalmologic device | |
| TW201326187A (en) | Silicone monomer, preparation method thereof, monomer composition and polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11879094 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11879094 Country of ref document: EP Kind code of ref document: A1 |