CN105524102B - 含自由基聚合性基团的硅氧烷化合物及其制造方法 - Google Patents
含自由基聚合性基团的硅氧烷化合物及其制造方法 Download PDFInfo
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- CN105524102B CN105524102B CN201510667646.XA CN201510667646A CN105524102B CN 105524102 B CN105524102 B CN 105524102B CN 201510667646 A CN201510667646 A CN 201510667646A CN 105524102 B CN105524102 B CN 105524102B
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- siloxane compound
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- -1 Siloxane compound Chemical class 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000007788 liquid Substances 0.000 abstract description 20
- 230000009257 reactivity Effects 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 230000035699 permeability Effects 0.000 abstract description 11
- 125000005375 organosiloxane group Chemical group 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 150000003254 radicals Chemical class 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YICILWNDMQTUIY-UHFFFAOYSA-N 2-methylidenepentanamide Chemical compound CCCC(=C)C(N)=O YICILWNDMQTUIY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000001166 anti-perspirative effect Effects 0.000 description 2
- 239000003213 antiperspirant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 1
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- 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
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
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Abstract
本发明涉及含自由基聚合性基团的硅氧烷化合物及其制造方法。本发明课题的目的在于,提供在室温下为液体且处理性良好、具有良好的透氧性和反应性的含自由基聚合性基团的硅氧烷化合物及其制造方法。解决手段在于:本发明提供下述式(1)所示的硅氧烷化合物和该硅氧烷化合物的制造方法。[化1]
Description
技术领域
本发明涉及末端具有自由基聚合性基团的硅氧烷化合物及其制造方法。详细而言,涉及透氧性优异、在室温下的处理性良好的硅氧烷化合物及其制造方法。
背景技术
以往开发了用于隐形眼镜材料的硅氧烷水凝胶,为了提高透氧性、或者出于对镜片赋予柔软性和改善机械强度的目的,作为原材料而采用具有聚合性基团的硅氧烷化合物(聚二甲基硅氧烷)(非专利文献1)。例如在美国专利第3808178号(专利文献1)中,作为用于眼科设备的硅氧烷单体而记载了3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基甲基丙烯酸酯(TRIS)。硅氧烷水凝胶是使亲水性单体与聚合性的硅氧烷化合物共聚而得到的,因此重要的是其与亲水性单体的相容性。但TRIS与亲水性单体的相容性差。为了提高其与亲水性单体的相容性,已知的是:向硅氧烷化合物中导入酰胺基、氨基甲酸酯基或羟基等极性官能团的方法(非专利文献1、专利文献2和3)。
专利文献4中记载了包含3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基丙烯酰胺(TRIS-A)作为单体成分的眼用镜片制造用组合物。TRIS-A具有丙烯酰基作为自由基聚合性基团,因此UV固化性优异,常用作隐形眼镜原材料之一。但是,TRIS-A在室温下是固体(熔点:约50℃),存在处理性差这一问题。
现有技术文献
专利文献
专利文献1:美国专利第3808178号
专利文献2:日本特开2007-186709号公报
专利文献3:日本特表2007-526364号公报
专利文献4:国际公开公报第2012/130956号
非专利文献
非专利文献1:先端生物材料手册(先端バイオマテリアルハンドブック)、秋吉一成、石原一彦、山冈哲二主编、第5章第5节P.528-533、《隐形眼镜材料》。
发明内容
发明要解决的问题
因此,本发明的目的在于,提供含自由基聚合性基团的硅氧烷化合物,其赋予具有优异透氧性的固化物、在室温下为液体且处理性良好、进而反应性也良好。
用于解决问题的方案
本发明人等为了解决上述课题而重复进行了深入研究,结果发现下述式(1)所示的硅氧烷化合物。即,本发明提供下述式(1)所示的硅氧烷化合物和该硅氧烷化合物的制造方法。
[化1]
(式(1)中,A彼此独立地为取代或未取代的、碳原子数1~6且可以具有支链结构的二价烃基,B彼此独立地为包含硅原子数是2~20个的有机硅氧烷的一价基团,X是具有自由基聚合性基团的一价基团。)。
发明效果
本发明的硅氧烷化合物在室温下可为液体、处理性良好、且赋予透氧性优异的固化物。进而反应性也良好。
具体实施方式
以下,针对本发明进行详细说明。
本发明为下述式(1)所示的硅氧烷化合物。
[化2]
(式(1)中,A彼此独立地为取代或未取代的、碳原子数1~6且可以具有支链结构的二价烃基,B彼此独立地为包含硅原子数是2~20个的有机硅氧烷的一价基团,X为具有自由基聚合性基团的一价基团。)
该硅氧烷化合物的特征在于,自由基聚合性基团(X)与硅氧烷链(B)通过氮原子进行了键合,该氮原子上键合有两个硅氧烷链。通过该结构,能够具有良好的透氧性。另外,本发明的化合物在室温下可为液体,处理性良好。这是因为:用于键合自由基聚合性基团(X)和硅氧烷链(B)的氮原子上不具有氢原子。
上述式中,A彼此独立地为取代或未取代的、碳原子数1~6且可以具有支链结构的二价烃基。作为该二价烃基,可列举出亚乙基、1,3-亚丙基、1-甲基亚丙基、1,1-二甲基亚丙基、2-甲基亚丙基、1,2-二甲基亚丙基、1,1,2-三甲基亚丙基、1,4-亚丁基、2-甲基-1,4-亚丁基、2、2-二甲基-1,4-亚丁基、3-甲基-1,4-亚丁基、2,3-二甲基-1,4-亚丁基、2,2,3-三甲基-1,4-亚丁基、1,5-亚戊基、1,6-亚己基(ヘキサニレン)。也可以是这些基团的碳原子上所键合的氢原子的一部分或全部被氯、氟等卤原子取代而得的卤化亚烷基等。优选为碳原子数2~5的直链结构的二价烃基。
上述式中,X为含有自由基聚合性基团的一价基团。作为自由基聚合性基团,可列举出(甲基)丙烯酰基、苯乙烯基、茚基、烯基、环烯基、降冰片基以及共轭或非共轭烷烃二烯基等。该X例如优选为下述(3)或(4)所示的基团。
[化3]
上述式(3)和(4)中,R1为氢原子或甲基。优选的是,从反应性的观点出发,R1为氢原子即可。
上述式中,B彼此独立地为包含硅原子数是2~20个、优选硅原子数是2~10个的有机硅氧烷的一价基团。作为该硅氧烷的结构,可列举出直链状、支链状或环状。作为该B,可列举出例如下述(2)所示的有机硅氧烷结构。
[化4]
式中,R2、R3和R4彼此独立地为碳原子数1~10的烷基或碳原子数6~12的芳基,b为1~3的整数,c为1~3的整数,d为0~3的整数,g为0~10的整数,h为0~2的整数,a为0~3的整数,其中,a、h和g不同时为0。
其中,优选为g=0、h=0的下述式所示的短链支链结构。
[化5]
(a为2或3,特别优选为3。b为1~3的整数,优选为1~2的整数,特别优选为1。R2和R4如上所示。)
特别优选的是,从与其它单体的溶解性的观点出发,为下述所示的硅氧烷结构即可。
[化6]
上述式(1)所示的硅氧烷化合物优选用下述式(5)或(6)表示。
[化7]
(式中,R1为氢原子或甲基,特别优选为氢原子。R2和R4彼此独立地为碳原子数1~10的烷基,n为1~6的整数,m为1~6的整数,e彼此独立地为1、2或3,e优选为2或3,e特别优选为3。)。
[化8]
(式中,R1为氢原子或甲基,特别优选为氢原子。R2和R4彼此独立地为碳原子数1~10的烷基,n为1~6的整数,m为1~6的整数,e彼此独立地为1、2或3,e优选为2或3,e特别优选为3。)。
特别优选为下述式(5’)或(6’)所示的硅氧烷化合物。
[化9]
(式中,R1为氢原子或甲基,特别优选为氢原子。R4为甲基,n为1~6的整数,n优选为3。e为1、2或3,e优选为2或3,e特别优选为3。)。
[化10]
(式中,R1为氢原子或甲基,特别优选为氢原子。R4为甲基,n为1~6的整数,n优选为3。e为1、2或3,e优选为2或3,e特别优选为3。)。
尤其是,上述式中的R1为氢原子的含丙烯酰基的硅氧烷化合物的固化性(反应性)优异,故而优选。
本发明还提供上述式(1)所示的硅氧烷化合物的制造方法。该制造方法包含使下述式(8)所示的化合物与下述式(9)所示的化合物发生反应的工序。
[化11]
(式(8)中,Y为具有自由基聚合性基团的一价基团,Z为与胺发生反应的基团或卤原子。)。
[化12]
(式中,A和B如上所示)
通过经由前述工序,能够制造在室温下为液体的化合物。
在上述式(8)中,Y为具有自由基聚合性基团的一价基团。作为自由基聚合性基团,可列举出(甲基)丙烯酰基、苯乙烯基、茚基、烯基、环烯基、降冰片基、以及共轭或非共轭烷烃二烯基等。该Y例如优选为下述(3’)或(4’)所示的基团。
[化13]
上述式(3’)和(4’)中,R1为氢原子或甲基。优选的是,从反应性的观点出发,R1为氢原子即可。
上述式(8)中,Z为与胺发生反应的基团或卤原子。可列举出例如卤化烷基、酸酐基、酯基和异氰酸酯基等。作为卤原子,可列举出氯、溴、碘。其中,由于反应性和合成的容易度,故而优选氯原子或异氰酸酯基。
作为上述式(8)所示的化合物,可列举出(甲基)丙烯酰氯和(甲基)丙烯酸乙基异氰酸酯。尤其是从反应性(自由基聚合性)的观点出发,优选为丙烯酰氯或丙烯酸乙基异氰酸酯。
例如,下述式(5)所示的化合物可以使用(甲基)丙烯酰氯来制造。
[化14]
(式中,R1、R2、R4、n、m和e如上所示。)。
详细而言,上述式(5)所示的化合物可以通过使下述式(10)所示的(甲基)丙烯酰氯与下述式(11)所示的化合物发生反应来制造。
[化15]
(式中,R1为氢原子或甲基。)。
[化16]
(式中,R2、R4、n、m和e如上所示。)。
另外,下述式(6)所示的化合物可以使用(甲基)丙烯酸乙基异氰酸酯来制造。
[化17]
(式中,R1、R2、R4、n、m和e如上所示)。
详细而言,上述式(6)所示的化合物可以通过使下述式(12)所示的化合物与下述式(13)所示的化合物发生反应来制造。
[化18]
(式中,R1如上所示)。
[化19]
(式中,R2、R4、n、m和e如上所示。)。
在上述制造方法中,式(8)所示的化合物(包括上述式(10)和(12))的配合量适当选择即可。优选的是,相对于上述式(9)所示的化合物(包括上述式(11)和(13))1摩尔,式(8)所示的化合物为1~3摩尔、进一步优选为1.05~2摩尔即可。少于上述下限值时,式(9)所示的化合物的未反应物大量残留在产物中、目标物的纯度降低。另外,多于上述上限值时,成本有可能变高。
上述反应可以在碱金属盐和碱土金属盐的水溶液的共存下进行。通过在碱金属盐和碱土金属盐水溶液的共存下进行反应,容易去除未反应的含自由基聚合性基团的化合物、其副产物。作为碱金属盐和碱土金属盐,可列举出例如氢氧化锂、碳酸锂、碳酸氢锂、氢氧化钠、碳酸钠、碳酸氢钠、硼氢化钠、氢化钾、氢氧化钾、碳酸钾、碳酸氢钾、磷酸氢二钾等碱金属盐;或者氢氧化镁、碳酸镁、氢氧化钙、碳酸钙、氢氧化锶、碳酸锶、氢氧化钡、碳酸钡等。其中,由于获取容易性、处理性、反应性和反应体系中的化合物的稳定性,故而优选为氢氧化钠、碳酸钠和碳酸钾,更优选为碳酸钠。碳酸钠的添加量相对于具有自由基聚合性基团的化合物1摩尔优选为1摩尔以上、更优选为2摩尔以上。
反应温度没有特别限定,优选为-20~60℃、特别优选为0~20℃。温度为-20℃以下时,反应需要特殊的装置。另外,温度超过60℃时,自由基聚合性基团有可能发生聚合反应。
为了防止自由基聚合性基团的聚合反应,上述反应中可以添加各种阻聚剂。所添加的阻聚剂没有特别限定,可列举出氢醌、氢醌单甲醚、4,4’-丁叉基双(6-叔丁基间甲酚)、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、2,6-二叔丁基对甲酚、2,5-二叔戊基氢醌、2,5-二叔丁基氢醌等。
另外,本发明的硅氧烷化合物也可以如下制造:预先合成下述式所示那样的导入有自由基聚合性基团的烷氧基硅烷化合物,然后使该烷氧基硅烷化合物与具有卤代甲硅烷基或烷氧基甲硅烷基的硅氧烷化合物或硅烷化合物发生反应,从而制造。
[化20]
(上述各式中,R1、R4、n和e如上所示,R为碳原子数1~3的烷基。)。
但是,该制造方法中,预先导入的自由基聚合性基团有可能由于反应过程中或纯化阶段的加热而反应从而产生着色或增稠或者凝胶化。该问题尤其在自由基聚合性基团为丙烯酰基时变得显著。这是因为丙烯酰基的反应性高。因此,为了得到在室温下为液体的化合物,如上所述,优选最后导入自由基聚合性基团。
如上所示,本发明的硅氧烷化合物的熔点低,在室温可为液体。因此处理性优异。另外,本发明的硅氧烷化合物会赋予具有良好透氧性的固化物。进而,与其它单体成分的相容性优异、具有良好的反应性。尤其是,本发明的硅氧烷化合物中的自由基聚合性基团(X)为丙烯酰基的化合物与自由基聚合性基团(X)为甲基丙烯酰基的化合物相比,固化性良好,故而更优选。
与本发明的硅氧烷化合物进行聚合的其它单体化合物没有特别限定,可以根据后述用途使用现有公知的化合物。可列举出例如N-乙烯基吡咯烷酮、N,N-二甲基丙烯酰胺和N-甲基-3-次甲基吡咯烷酮等含氮原子单体;甲基丙烯酸和(甲基)丙烯酸羟乙酯等亲水性单体。
使本发明的硅氧烷化合物与其它单体化合物相容而得到的组合物例如可适合地用作眼用设备组合物、涂料或化妆品组合物。作为化妆品组合物,可列举出例如护肤用、毛发用、止汗剂用、脱臭剂用、彩妆用或防紫外线用化妆品。
实施例
以下示出实施例和比较例来进一步详细说明本发明,但本发明不限定于下述实施例。
在以下的实施例中,分子结构使用核磁共振光谱法(1H-NMR)进行测定来确定。以下示出实施例中使用的测定装置。
1H-NMR:AVANCE III(Bruker BioSpin K.K.)。
[实施例1]
向安装有温度计、滴液漏斗、氮气导入管的烧瓶中添加下述式(I)的含有硅氧烷的胺0.1mol、己烷200ml和10%碳酸钠水170g,一边搅拌一边在5℃下滴加丙烯酰氯1.2mol。
[化21]
滴加后,在室温下持续搅拌5小时后,将有机层用纯水清洗。接着,向清洗后的溶液中添加对甲氧基苯酚(阻聚剂)0.008g,在减压下(60℃、5torr)蒸馏去除挥发成分,在室温(25℃)下得到淡黄色透明液状的产物。利用1H-NMR测定进行鉴定,结果为下述式(II)所示的化合物。收率为96.9%。
[化22]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.06(s,54H)、0.33~0.50(m,4H)、1.49~1.67(m,4H)、3.18~3.38(m,4H)、5.61(dd,1H)、6.32(ddd,1H)、6.55(dd,1H)。
[实施例2]
除了使用下述式(III)所示的化合物来代替上述式(I)所示的化合物之外,重复实施例1的方法,在室温(25℃)下得到淡黄色透明液状的产物。
[化23]
利用1H-NMR测定进行鉴定,结果为下述式(IV)所示的硅氧烷化合物。收率为97.3%。
[化24]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.00(s,6H)、0.07(s,36H)、0.34~0.48(m,4H)、1.49~1.67(m,4H)、3.18~3.39(m,4H)、5.62(dd,1H)、6.32(ddd,1H)、6.53(dd,1H)。
[实施例3]
除了使用2-丙烯酰氧基乙基异氰酸酯来代替丙烯酰氯之外,重复实施例1的方法,在室温(25℃)下得到淡黄色透明液状的产物。利用1H-NMR测定进行鉴定,结果为下述式(V)所示的硅氧烷化合物。收率为95.2%。
[化25]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.07(s,54H)、0.34~0.45(m,4H)、1.49~1.68(m,4H)、3.08~3.20(m,4H)、3.49~3.59(m,2H)、4.18~4.28(m,2H)、4.72(br,1H)、5.82(dd,1H)、6.15(ddd,1H)、6.39(dd,1H)。
[实施例4]
除了使用2-甲基丙烯酰氧基乙基异氰酸酯来代替丙烯酰氯之外,重复实施例1的方法,在室温(25℃)下得到淡黄色透明液状的产物。利用1H-NMR测定进行鉴定,结果为下述式(VI)所示的硅氧烷化合物。收率为96.5%。
[化26]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.07(s,54H)、0.34~0.42(m,4H)、1.49~1.69(m,4H)、1.93(m,3H)、3.06~3.18(m,4H)、3.48~3.58(m,2H)、4.19~4.30(m,2H)、4.74(br,1H)、5.55(s,1H)、6.09(s,1H)。
[实施例5]
除了使用甲基丙烯酰氯来代替丙烯酰氯之外,重复实施例2的方法,在室温(25℃)下得到淡黄色透明液状的产物。利用1H-NMR测定进行鉴定,结果为下述式(VII)所示的硅氧烷化合物。收率为97.4%。
[化27]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.00(s,6H)、0.07(s,36H)、0.34~0.48(m,4H)、1.49~1.67(m,4H)、1.96(m,3H)、3.16~3.37(m,4H)、5.05(s,1H)、5.20(s,1H)。
[参考例1]
向安装有温度计、滴液漏斗、氮气导入管的烧瓶中添加下述式(IX)所示的含胺基烷氧基硅烷0.1mol、甲苯200ml和三乙胺0.12mol,一边搅拌一边在5℃下滴加丙烯酰氯0.11mol。
[化28]
滴加后,在室温下持续搅拌5小时后,添加甲醇0.3mol并进一步搅拌30分钟。接着,将有机层用纯水清洗,向清洗后的溶液中添加对甲氧基苯酚(阻聚剂)0.008g,在减压下(60℃、5torr)蒸馏去除挥发成分,从而得到黄色液状的产物。利用1H-NMR测定进行鉴定,结果为下述式(X)所示的化合物。收率为92.9%。
[化29]
接着,向安装有温度计、滴液漏斗、氮气导入管的烧瓶中添加水20ml、甲醇20ml和己烷40ml,在5℃下滴加上述化合物(X)0.03mol与三甲基氯硅烷0.27mol的混合物。滴加结束后,在室温下搅拌3小时后,将有机层用纯水清洗,向清洗后的溶液中添加对甲氧基苯酚(阻聚剂)0.003g。在减压下(60℃、5torr)蒸馏去除挥发成分的期间,所得反应液发生凝胶化。
[参考例2]
除了使用2-丙烯酰氧基乙基异氰酸酯来代替上述参考例1中的丙烯酰氯之外,重复参考例1的方法。与参考例1同样地,所得反应液在纯化的期间发生凝胶化。
[比较例1]
3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基丙烯酰胺(TRIS-A)的合成
除了使用[(CH3)3SiO]3Si(CH2)3-NH2来代替上述式(I)所示的化合物的之外,重复实施例1的方法,得到在室温(25℃)下为白色固体状的产物。利用1H-NMR测定进行鉴定,结果为下述式(VIII)所示的硅氧烷化合物。收率为93.1%。
[化30]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.09(s,27H)、0.45~0.50(m,2H)、1.59(m,2H)、3.32(m,2H)、5.58(br,1H)、5.62(dd,1H)、6.06(ddd,1H)、6.25(dd,1H)
将实施例1~5和比较例1中得到的硅氧烷化合物在室温(25℃)下的状态总结于下述表1。
[表1]
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | |
25℃下的性状 | 液体 | 液体 | 液体 | 液体 | 液体 | 固体 |
比较例1中得到的化合物(3-[三(三甲基甲硅烷氧基)甲硅烷基]丙基丙烯酰胺(TRIS-A))的熔点为51℃,在室温(25℃)下为固体。与此相对,本发明的硅氧烷化合物在室温(25℃)下为液体,处理性良好。
[比较例2]
除了使用[(CH3)3SiO]3Si(CH2)3-NH-C6H13来代替上述式(I)所示的化合物之外,重复实施例1的方法,得到在室温(25℃)下为淡黄色液体的产物。利用1H-NMR测定进行鉴定,结果为下述式(XI)所示的硅氧烷化合物。收率为91.0%。
[化31]
以下示出1H-NMR的光谱。
1H-NMR(400MHz,CDCl3):δ 0.09(s,27H)、0.35-0.46(m,2H)、0.85-0.93(m,3H)、1.23-1.36(m,6H)、1.12-1.52(m,4H)、3.21-3.33(m,2H)、3.33-3.40(m,2H)、5.63(dd,1H)、6.34(ddd,1H)、6.54(dd,1H)。
[固化物的制造]
向反应容器中投入实施例和比较例中得到的各化合物(65质量份)、N,N-二甲基丙烯酰胺(34质量份)、三乙二醇二甲基丙烯酸酯(1质量份)、DAROCUR 1173(Ciba SpecialtyChemicals Inc.制、0.5质量份),进行混合搅拌。将所得混合物进行脱气后,注入至乙烯-乙烯醇树脂制模具中,在氮气气氛下使用金属卤化物灯进行固化。针对包含各化合物的混合物,将固化所需的能量记载于表2。
将上述得到的各固化物在异丙醇中浸渍10小时。其后,在水/异丙醇=1:1的溶液中浸渍10小时、进而在纯水中浸渍20小时。针对浸渍后的各固化物,使用膜透氧率计K-316(Tsukuba Rika Seiki Co., Ltd.制)测定透氧率。将结果记载于表2。
[表2]
与比较例1的硅氧烷化合物(Tris-A)和比较例2的硅氧烷化合物相比,本发明的硅氧烷化合物能够赋予具有高透氧性的固化物。另外,与其它单体成分的相容性优异、反应性也良好。
工业适用性
本发明的硅氧烷化合物能够赋予透氧性高的固化物。另外,熔点低、在室温下可为液体,因此处理性良好。进而反应性也良好。本发明的硅氧烷化合物对于眼用设备组合物、涂料和护肤、毛发、止汗剂、脱臭剂、彩妆或防紫外线用化妆品组合物等是有用的。
Claims (3)
2.根据权利要求1所述的硅氧烷化合物,其中,n和m为3。
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