JP5234909B2 - Alkoxy group-containing cage-type siloxane compound, silanol group-containing cage-type siloxane compound, and methods for producing them - Google Patents
Alkoxy group-containing cage-type siloxane compound, silanol group-containing cage-type siloxane compound, and methods for producing them Download PDFInfo
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- JP5234909B2 JP5234909B2 JP2007337059A JP2007337059A JP5234909B2 JP 5234909 B2 JP5234909 B2 JP 5234909B2 JP 2007337059 A JP2007337059 A JP 2007337059A JP 2007337059 A JP2007337059 A JP 2007337059A JP 5234909 B2 JP5234909 B2 JP 5234909B2
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- -1 siloxane compound Chemical class 0.000 title claims description 162
- 125000003545 alkoxy group Chemical group 0.000 title claims description 95
- 125000005372 silanol group Chemical group 0.000 title claims description 65
- 238000000034 method Methods 0.000 title description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 35
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000012454 non-polar solvent Substances 0.000 claims description 17
- 125000000466 oxiranyl group Chemical group 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 26
- 239000000203 mixture Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000010354 integration Effects 0.000 description 12
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 11
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 229910014033 C-OH Inorganic materials 0.000 description 4
- 229910014570 C—OH Inorganic materials 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 3
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- BQQGVSONEPNPAB-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound CCOC(OCC)[SiH2]CCCOC(=O)C(C)=C BQQGVSONEPNPAB-UHFFFAOYSA-N 0.000 description 1
- SLDXSSRFNABVCN-UHFFFAOYSA-N 3-diethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[SiH](OCC)CCCOC(=O)C(C)=C SLDXSSRFNABVCN-UHFFFAOYSA-N 0.000 description 1
- DACWUGOLTNQROR-UHFFFAOYSA-N 3-diethoxysilylpropyl prop-2-enoate Chemical compound CCO[SiH](OCC)CCCOC(=O)C=C DACWUGOLTNQROR-UHFFFAOYSA-N 0.000 description 1
- BZCWFJMZVXHYQA-UHFFFAOYSA-N 3-dimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C(C)=C BZCWFJMZVXHYQA-UHFFFAOYSA-N 0.000 description 1
- HNVMCAHOYIOFAQ-UHFFFAOYSA-N 3-dimethoxysilylpropyl prop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C=C HNVMCAHOYIOFAQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- CSXPRVTYIFRYPR-UHFFFAOYSA-N bis(ethenyl)-diethoxysilane Chemical compound CCO[Si](C=C)(C=C)OCC CSXPRVTYIFRYPR-UHFFFAOYSA-N 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、新規な籠型シロキサン化合物及びその製造方法に関し、詳しくは、アルコキシル基又はシラノール基を有する籠型シロキサン化合物及びその製造方法に関するものである。 The present invention relates to a novel cage-type siloxane compound and a method for producing the same, and more particularly to a cage-type siloxane compound having an alkoxyl group or a silanol group and a method for producing the same.
従来より、籠型シロキサンまたはその誘導体に関する研究が行われている(Chem. Rev. 1995, 95,1409)。中でも加水分解性基を有する籠型シロキサン誘導体は、加水分解性基の反応性を利用し、新たなシロキサン化合物を誘導することができる有用な化合物である。例えば、シラノール基を有する籠型シロキサン化合物としては、Feher等により、クロロシランを加水分解し、更に熟成させることで得られることが報告されている(Organometallics, 1991, 10, 2526)。 Conventionally, studies have been conducted on cage-type siloxane or its derivatives (Chem. Rev. 1995, 95, 1409). Among these, a cage-type siloxane derivative having a hydrolyzable group is a useful compound that can induce a new siloxane compound by utilizing the reactivity of the hydrolyzable group. For example, it has been reported that a cage-type siloxane compound having a silanol group can be obtained by hydrolyzing and further aging chlorosilane by Feher et al. (Organometallics, 1991, 10, 2526).
しかしながら、この方法は合成に長時間有し、副生成物が多く目的化合物の収率が低いといった問題点がある。このようにシラノール基を有する籠型シロキサン化合物の製造方法として、加水分解性基を有するモノシランから合成する方法では、加水分解と縮合反応を制御する必要があることに加え、シラノール基自体が非常に不安定であり、シラノール基の間での縮合反応が進行して分子量が経時的に変化してしまう問題などがある。故にシラノール基を任意にコントロールすることも実質的に不可能である。最近では、3官能の加水分解性基を有するシラン化合物を1価のアルカリ金属水酸化物の存在下、有機溶媒中で加水分解することでシラノール基(Si−OH)の代わりにSi-ONaを反応活性基として導入した前駆体を用いたシルセスキオキサンの誘導体が提案されている(特許文献1、2及び3参照)。
上述したように、シラノール基を有するシロキサンは、シラノール基の不安定さからシラノール基の量を制御した籠型シロキサンの製造が困難である。また、加水分解性基であるアルコキシル基を任意に籠型シロキサンに導入した製造方法はこれまで報告されていない。 As described above, siloxanes having silanol groups are difficult to produce cage siloxanes in which the amount of silanol groups is controlled due to the instability of silanol groups. In addition, a production method in which an alkoxyl group which is a hydrolyzable group is arbitrarily introduced into a cage siloxane has not been reported so far.
本発明の目的は、従来の欠点を解消して、分子構造の制御された籠型シロキサンに任意にアルコキシル基又はシラノール基を含有させた、アルコキシル基含有籠型シロキサン化合物又はシラノール基含有籠型シロキサン化合物を提供することにある。 An object of the present invention is to eliminate an alkoxyl group-containing cage-type siloxane compound or silanol group-containing cage-type siloxane in which an alkoxyl group or silanol group is optionally contained in a cage-type siloxane having a controlled molecular structure, eliminating conventional drawbacks. It is to provide a compound.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、特定の反応条件によりこれを解決し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies in order to solve the above problems, the present inventors have found that this can be solved under specific reaction conditions, and have completed the present invention.
すなわち、本発明は、下記一般式(1)
[R1SiO3/2]n (1)
(但し、R1はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1は互いに同じか異なるものであってもよく、nは8〜14の整数である。)で表される籠型シロキサン化合物に、
下記一般式(2)
R1R2Si(OR3) 2 (2)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。)で表されるジアルコキシシランを非極性溶媒及び塩基性触媒の存在下で付加させて得られることを特徴とするアルコキシル基含有籠型シロキサン化合物である。
That is, the present invention provides the following general formula (1)
[R 1 SiO 3/2 ] n (1)
(However, R 1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, R 1 may be the same or different from each other, and n is 8 Is an integer of ˜14).
The following general formula (2)
R 1 R 2 Si (OR 3 ) 2 (2)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 may be the same as or different from each other.) Is obtained by adding a dialkoxysilane represented by the above in the presence of a nonpolar solvent and a basic catalyst. It is a characteristic alkoxyl group-containing cage-type siloxane compound.
また、本発明は、上記アルコキシル基含有籠型シロキサン化合物を酸または塩基性触媒の存在下で加水分解して得られる下記一般式(4)
[(HO)R1R2SiO1/2]a − [R1SiO3/2]n − [O1/2H]b (4)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1又はR2において、各置換基は互いに同じか異なるものであってもよい。また、a及びbは0〜3の数であって1≦a + b≦4の関係を満たす。更にnは8〜14の整数である。)で表せるシラノール基含有籠型シロキサン化合物である。
The present invention also provides the following general formula (4) obtained by hydrolysis of the alkoxyl group-containing cage-type siloxane compound in the presence of an acid or a basic catalyst.
[(HO) R 1 R 2 SiO 1/2] a - [R 1 SiO 3/2] n - [O 1/2 H] b (4)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and in R 1 or R 2 , are each substituents the same as each other? And a and b are numbers from 0 to 3, satisfying the relationship 1 ≦ a + b ≦ 4, and n is an integer from 8 to 14.) This is a contained cage-type siloxane compound.
更に本発明は、下記一般式(1)
[R1SiO3/2]n (1)
(但し、R1はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1は互いに同じか異なるものであってもよく、nは8〜14の整数である。)で表される籠型シロキサン化合物と、
下記一般式(2)
R1R2Si(OR3) 2 (2)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。)で表されるジアルコキシシランとを[R1SiO3/2]n:R1R2Si(OR3) 2 =1モル:0.5〜2モルの範囲で混合し、非極性溶媒及び塩基性触媒の存在下で付加させることで、数平均分子量Mnが500〜2000の範囲であり、かつ、分子量分散度(重量平均分子量Mw/数平均分子量Mn)が1.0〜2.0であるアルコキシル基含有籠型シロキサン化合物を得ることを特徴とするアルコキシル基含有籠型シロキサン化合物の製造方法である。
Furthermore, the present invention provides the following general formula (1)
[R 1 SiO 3/2 ] n (1)
(However, R 1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, R 1 may be the same or different from each other, and n is 8籠 -type siloxane compound represented by
The following general formula (2)
R 1 R 2 Si (OR 3 ) 2 (2)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 , each substituent may be the same or different from each other.) And a dialkoxysilane represented by [R 1 SiO 3/2 ] n : R 1 R 2 Si (OR 3 ) 2 = 1 mol: mixed in the range of 0.5 to 2 mol, added in the presence of a nonpolar solvent and a basic catalyst, the number average molecular weight Mn is in the range of 500 to 2000, and An alkoxyl group-containing cage-type siloxane compound having a molecular weight dispersity (weight average molecular weight Mw / number-average molecular weight Mn) of 1.0 to 2.0 is obtained.
更にまた本発明は、下記一般式(1)
[R1SiO3/2]n (1)
(但し、R1はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1は互いに同じか異なるものであってもよく、nは8〜14の整数である。)で表される籠型シロキサン化合物と、
下記一般式(2)
R1R2Si(OR3) 2 (2)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。)で表されるジアルコキシシランとを[R1SiO3/2]n:R1R2Si(OR3) 2 =1モル:0.5〜2モルの範囲で混合し、 非極性溶媒及び塩基性触媒の存在下で付加させて得られる数平均分子量Mnが500〜2000の範囲であり、かつ、分子量分散度(重量平均分子量Mw/数平均分子量Mn)が1.0〜2.0のアルコキシル基含有籠型シロキサン樹脂を、酸または塩基触媒の存在下で加水分解することで、数平均分子量Mnが500〜2000の範囲であり、分子量分散度(重量平均分子量Mw/数平均分子量Mn)が1.0〜2.0であるシラノール基含有籠型シロキサン化合物を得ることを特徴とするシラノール基含有籠型シロキサン化合物の製造方法である。
Furthermore, the present invention provides the following general formula (1):
[R 1 SiO 3/2 ] n (1)
(However, R 1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, R 1 may be the same or different from each other, and n is 8籠 -type siloxane compound represented by
The following general formula (2)
R 1 R 2 Si (OR 3 ) 2 (2)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 , each substituent may be the same or different from each other.) And a dialkoxysilane represented by [R 1 SiO 3/2 ] n : R 1 R 2 Si (OR 3 ) 2 = 1 mol: mixed in the range of 0.5 to 2 mol, The number average molecular weight Mn obtained by addition in the presence of a nonpolar solvent and a basic catalyst is in the range of 500 to 2000, and the molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) is 1.0 to 2.0. By hydrolyzing the alkoxyl group-containing cage-type siloxane resin in the presence of an acid or base catalyst, the number average molecular weight Mn is in the range of 500 to 2000, and the molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) It is a manufacturing method of the silanol group containing cage type | mold siloxane compound characterized by obtaining the silanol group containing cage type siloxane compound whose is is 1.0-2.0.
本発明において、アルコキシル基含有籠型シロキサン化合物は、下記一般式(3)を用いて表すことができる。
[(R3O)R1R2SiO1/2]a − [R1SiO3/2]n − [O1/2R3]b (3)
ここで、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。また、a及びbは0〜3の数であって1≦a + b≦4の関係を満たす。更にnは8〜14の整数である。
In the present invention, the alkoxyl group-containing cage-type siloxane compound can be represented by the following general formula (3).
[(R 3 O) R 1 R 2 SiO 1/2 ] a − [R 1 SiO 3/2 ] n − [O 1/2 R 3 ] b (3)
Here, R 1 and R 2 are selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group, or a group having an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 , each substituent may be the same as or different from each other. A and b are numbers from 0 to 3 and satisfy the relationship of 1 ≦ a + b ≦ 4. Furthermore, n is an integer of 8-14.
アルコキシル基含有籠型シロキサン化合物の構造式の例を下記式(5)〜(13)にそれぞれ示す。構造式(5)はn=8, a=1, b=1、(6)はn=8, a=2, b=0、(7)はn=8, a=0, b=2、(8)はn=9, a=1, b=2、(9)はn=10, a=1, b=1、(10)はn=11, a=1, b=2、(11)はn=12, a=1, b=1、(12)はn=13, a=1, b=2、(13)はn=14, a=1, b=1である。なお、アルコキシル基含有シロキサン化合物は、n,a,b数の異なる組み合わせがありここに示す限りではない。また構造式(5)〜(13)においてR1、R2及びR3は一般式(3)と同じである。
本発明のアルコキシル基含有籠型シロキサン化合物の製造方法では、公知の方法により製造された上記一般式(1)で表される籠型シロキサン化合物と、上記一般式(2)で表せるジアルコキシシランとを非極性溶媒下で塩基性触媒を用いて付加させることにより得る。 In the method for producing an alkoxyl group-containing cage-type siloxane compound of the present invention, a cage-type siloxane compound represented by the general formula (1) produced by a known method, a dialkoxysilane represented by the formula (2), and Is obtained using a basic catalyst in a nonpolar solvent.
本発明に用いられる一般式(1)で表される籠型シロキサン化合物の例としては、n=8、10、12及び14に対応する構造式の例としてそれぞれ下記一般式(14)、(15)、(16)及び(17)が挙げられる。なお、下記構造式(14)〜(17)においてR1は一般式(1)と同じである。
一般式(1)で表せる籠型シロキサン化合物におけるnの値は8〜14の整数であり、好ましくはn=8、10、12であり、より好ましくは8である。本発明では、一般式(1)で表せる籠型シロキサン化合物がn=8〜14の整数である混合物を用いてもよいが、好ましくはnが単一の化合物を用いるのがよい。 The value of n in the cage siloxane compound represented by the general formula (1) is an integer of 8 to 14, preferably n = 8, 10, 12 and more preferably 8. In the present invention, a mixture in which the cage-type siloxane compound represented by the general formula (1) is an integer of n = 8 to 14 may be used, but preferably a compound having a single n is used.
また、本発明で用いる一般式(2)で表されるジアルコキシシランの好ましい化合物を示せば、ジメチルジメトキシシラン、ジエチルジメトキシシラン、フェニルメチルジメトキシシラン、ビニルメチルジメトキシシラン、エチルアリルジメトキシシラン、スチリルメチルジメトキシシラン、ジビニルジメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−メタクリロキシプロピルジメトキシシラン、3−アクリロキシプロピルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジエトキシシラン、フェニルメチルジエトキシシラン、ビニルメチルジエトキシシラン、エチルアリルジエトキシシラン、スチリルメチルジエトキシシラン、ジビニルジエトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、3−メタクリロキシプロピルジエトキシシラン、3−アクリロキシプロピルジエトキシシランなどが挙げられる。 Further, preferable compounds of dialkoxysilane represented by the general formula (2) used in the present invention are dimethyldimethoxysilane, diethyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, ethylallyldimethoxysilane, styrylmethyl. Dimethoxysilane, divinyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-acryloxypropyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, phenylmethyldiethoxysilane, vinyl Methyldiethoxysilane, ethylallyldiethoxysilane, styrylmethyldiethoxysilane, divinyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include 3-methacryloxypropyldiethoxysilane and 3-acryloxypropyldiethoxysilane.
また、一般式(1)で表される籠型シロキサン化合物と一般式(2)で表せるジアルコキシシランとを付加させる際に用いる非極性溶媒及び塩基性触媒について、先ず、非極性溶媒としては、水に対し溶解性の無い又は殆どないものであればよいが、好ましくは炭化水素系溶媒であるのがよい。炭化水素系溶媒のなかでもトルエン、ベンゼン、キシレンなどの比較的沸点の低い非極性溶媒であるのがよく、好ましくはトルエンを用いるのがよい。塩基性触媒としては、水酸化カリウム、水酸化ナトリウム、水酸化セシウムなどのアルカリ金属水酸化物、あるいはテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ベンジルトリエチルアンモニウムヒドロキシドなどの水酸化アンモニウム塩が例示される。これらの中でも、テトラアルキルアンモニウム等の非極性溶媒に可溶性の触媒が好ましい。中でも触媒活性が高い点からテトラメチルアンモニウムヒドロキシドがより好ましく用いられる。 Moreover, about the nonpolar solvent and basic catalyst used when adding the saddle type siloxane compound represented by General formula (1) and the dialkoxysilane represented by General formula (2), first, as a nonpolar solvent, Any solvent that is insoluble or hardly soluble in water may be used, but a hydrocarbon solvent is preferable. Among hydrocarbon solvents, nonpolar solvents having a relatively low boiling point such as toluene, benzene, xylene and the like are preferable, and toluene is preferably used. Basic catalysts include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl Illustrative are ammonium hydroxide salts such as triethylammonium hydroxide. Among these, a catalyst soluble in a nonpolar solvent such as tetraalkylammonium is preferable. Of these, tetramethylammonium hydroxide is more preferably used because of its high catalytic activity.
一般式(1)で表される籠型シロキサン化合物と一般式(2)で表せるジアルコキシシランとを非極性溶媒下で塩基性触媒を用いて付加させる反応については、次のように推測することができる。まず籠型シロキサンを構成するシロキサン結合が塩基性触媒によって切断される。次いで切断されたシロキサン結合末端が、ジアルコキシシランのアルコキシル基とアルコール交換反応により、シロキサン結合が生成しアルコキシル基が付加する反応(付加反応)と、籠型シロキサンの分子内および分子間で切断されたシロキサン結合末端同士が結合する反応(再結合反応)とが競争的に起こる。よって前者(付加反応)を優先的に行う必要がある。また、本発明における反応は基本的に平衡反応であることから、目的物のアルコキシル基含有籠型シロキサン化合物の数平均分子量Mn、収率、及び生成速度は、反応温度、反応時間、両原料の添加量比、塩基触媒量等によって自ずと決定されるため、以下に記した条件下で行うのが好ましい。 Regarding the reaction in which the cage siloxane compound represented by the general formula (1) and the dialkoxysilane represented by the general formula (2) are added using a basic catalyst in a non-polar solvent, the following assumption is made. Can do. First, the siloxane bond constituting the cage siloxane is cleaved by a basic catalyst. Next, the cleaved siloxane bond ends are cleaved between the reaction of the alkoxyl group of dialkoxysilane and the addition of the alkoxyl group by the alcohol exchange reaction (addition reaction), and within and between the molecules of the cage siloxane. A reaction (recombination reaction) in which the siloxane bond ends are bonded to each other occurs competitively. Therefore, it is necessary to preferentially perform the former (addition reaction). In addition, since the reaction in the present invention is basically an equilibrium reaction, the number average molecular weight Mn, yield, and production rate of the target alkoxyl group-containing cage-type siloxane compound are the reaction temperature, reaction time, and both raw materials. Since it is naturally determined by the ratio of addition amount, the amount of base catalyst, etc., it is preferably carried out under the conditions described below.
すなわち、一般式(1)で表される籠型シロキサン化合物と一般式(2)で表せるジアルコキシシランを非極性溶媒下で塩基性触媒を用いて付加させる反応の反応条件については、一般式(2)のアルコキシル基が反応系内の水分と反応してシラノール基への変換や加水分解縮合を抑える為、窒素ガスなどの不活性雰囲気で反応を行うことが好ましい。反応温度は一般式(2)で表されるジアルコキシシランの沸点以下であるのがよく、70〜200℃の範囲が好ましく、80〜130℃がより好ましい。反応温度が低すぎると付加反応をさせるために十分なドライビングフォースが得られず反応が進行しない。反応温度が高すぎるとビニル基や(メタ)アクリロイル基のような不飽和結合をもつ反応性の官能基を含む場合、自己重合反応を起こす可能性があるので、反応温度を抑制するか、或いは重合禁止剤などを添加する必要がある。 That is, the reaction conditions for the reaction of adding the cage siloxane compound represented by the general formula (1) and the dialkoxysilane represented by the general formula (2) using a basic catalyst in a nonpolar solvent are as follows. In order that the alkoxyl group of 2) reacts with moisture in the reaction system to suppress conversion to a silanol group and hydrolysis condensation, the reaction is preferably performed in an inert atmosphere such as nitrogen gas. The reaction temperature may be equal to or lower than the boiling point of the dialkoxysilane represented by the general formula (2), preferably in the range of 70 to 200 ° C, more preferably 80 to 130 ° C. If the reaction temperature is too low, a sufficient driving force for the addition reaction cannot be obtained and the reaction does not proceed. If the reaction temperature is too high, a reactive functional group having an unsaturated bond such as a vinyl group or a (meth) acryloyl group may cause a self-polymerization reaction. It is necessary to add a polymerization inhibitor.
非極性溶媒の使用量は特に限定されないが籠型シロキサン化合物の重量に対して、撹拌効率や釜効率を考慮すると1〜5倍の重量を用いることが好ましい。ジアルコキシシランの添加量は、籠型シロキサン化合物1モルに対して0.5〜2.0モルの範囲で加えることが好ましい。ジアルコキシシランの添加量を調節することで、アルコキシル基含有籠型シロキサン化合物のアルコキシル基の量を調節することが可能である。例えば、籠型シロキサン化合物1モルに対して、1モルのジアルコキシシランを添加し反応させた場合、下記一般式(3)で表せるアルコキシル基含有籠型シロキサン化合物
[(R3O)R1R2SiO1/2]a − [R1SiO3/2]n − [O1/2R3]b (3)
はa+b=2の、籠構造単位に2個アルコキシル基を含有する籠型シロキサン化合物が混合物として得られる。また用いる籠型シロキサン化合物が混合物である場合、nの平均値に対してジアルコキシシランの添加量を調整することで籠構造単位当りのアルコキシル基の含有量を調整することができる。一方ジアルコキシシランの添加量が籠型シロキサン化合物1モルに対して0.5〜2.0モルの範囲より多いと、籠構造を形成するシロキサン結合がより多く切断し、アルコキシル基の付加が起こるため籠構造が分解されてしまう。
Although the usage-amount of a nonpolar solvent is not specifically limited, It is preferable to use 1 to 5 times the weight with respect to the weight of a cage-type siloxane compound, when stirring efficiency and pot efficiency are considered. The amount of dialkoxysilane added is preferably in the range of 0.5 to 2.0 moles per mole of cage siloxane compound. By adjusting the amount of dialkoxysilane added, it is possible to adjust the amount of alkoxyl groups in the alkoxyl group-containing cage-type siloxane compound. For example, when 1 mole of dialkoxysilane is added to 1 mole of cage siloxane compound and reacted, the alkoxyl group-containing cage siloxane compound represented by the following general formula (3)
[(R 3 O) R 1 R 2 SiO 1/2 ] a − [R 1 SiO 3/2 ] n − [O 1/2 R 3 ] b (3)
Is a mixture of が -type siloxane compounds having a + b = 2 and containing two alkoxyl groups in the 籠 structural unit. Moreover, when the cage type | mold siloxane compound to be used is a mixture, content of the alkoxyl group per cage | basket structure unit can be adjusted by adjusting the addition amount of dialkoxysilane with respect to the average value of n. On the other hand, when the amount of dialkoxysilane added is more than the range of 0.5 to 2.0 moles per mole of saddle type siloxane compound, more siloxane bonds forming the saddle structure are cleaved and alkoxyl groups are added. Therefore, the heel structure will be decomposed.
また、塩基性触媒の使用量については、籠型シロキサン化合物1モルに対し、塩基性触媒を0.01〜0.15モル、好ましくは0.06〜0.1モルとなるように加えるのがよい。また用いる籠型シロキサン化合物が混合物である場合、nの平均値に対して塩基性触媒を0.01〜0.15モル、好ましくは0.06〜0.1モルとなるように加えるのがよい。 The basic catalyst is used in an amount of 0.01 to 0.15 mol, preferably 0.06 to 0.1 mol, based on 1 mol of the cage siloxane compound. Moreover, when the cage type | mold siloxane compound to be used is a mixture, it is good to add a basic catalyst so that it may become 0.01-0.15 mol with respect to the average value of n, Preferably it is 0.06-0.1 mol.
本発明によって得られるアルコキシル基含有籠型シロキサン化合物は、用いる籠型シロキサン化合物の種類及び純度、ジアルコキシシラン化合物の添加量、種類、純度、並びに反応条件や重縮合物の状態により異なるが、一般式(3)のa及びbは0〜3の数であり、1≦ a + b ≦4を満たし、nは8〜14の整数で表される複数種のアルコキシル基含有籠型シロキサン化合物の混合物として得られる場合が多い。 The alkoxyl group-containing cage-type siloxane compound obtained by the present invention varies depending on the type and purity of the cage-type siloxane compound to be used, the addition amount, type and purity of the dialkoxysilane compound, and the reaction conditions and the state of the polycondensate. A and b in Formula (3) are numbers of 0 to 3, satisfying 1 ≦ a + b ≦ 4, and n is a mixture of a plurality of alkoxyl group-containing cage-type siloxane compounds represented by an integer of 8 to 14 It is often obtained as.
本発明におけるシラノール基含有籠型シロキサン化合物は、上記一般式(3)で表されるアルコキシル基含有籠型シロキサン化合物を酸または塩基触媒存在下加水分解して得ることができ、得られるシラノール基含有籠型シロキサン化合物は下記一般式(4)
[(HO)R1R2SiO1/2]a − [R1SiO3/2]n − [O1/2H]b (4)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1又はR2において、各置換基は互いに同じか異なるものであってもよい。またa及びbは0〜3の数であり、1≦ a + b ≦4を満たし、更にnは8〜14の整数である。)で表すことができる。
The silanol group-containing cage-type siloxane compound in the present invention can be obtained by hydrolyzing the alkoxyl group-containing cage-type siloxane compound represented by the above general formula (3) in the presence of an acid or base catalyst, and the resulting silanol group-containing product The cage-type siloxane compound has the following general formula (4)
[(HO) R 1 R 2 SiO 1/2] a - [R 1 SiO 3/2] n - [O 1/2 H] b (4)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and in R 1 or R 2 , are each substituents the same as each other? A and b are numbers from 0 to 3, satisfying 1 ≦ a + b ≦ 4, and n is an integer of 8 to 14.
シラノール基含有籠型シロキサン化合物の構造式の例は、基本的には上述したアルコキシル基含有籠型シロキサン化合物の構造式の例(5)〜(13)におけるR3が水素原子に置き換わったものに対応する。すなわち構造式(5)はn=8, a=1, b=1、(6)はn=8, a=2, b=0、(7)はn=8, a=0, b=2、(8)はn=9, a=1, b=2、(9)はn=10, a=1, b=1、(10)はn=11, a=1, b=2、(11)はn=12, a=1, b=1、(12)はn=13, a=1, b=2、(13)はn=14, a=1, b=1である。なお、シラノール基含有シロキサン化合物は、n,a,b数の異なる組み合わせがあるためこれらに示す限りではない。また構造式(5)〜(13)においてR1及びR2は一般式(4)と同じである。 Examples of structural formulas of silanol group-containing cage-type siloxane compounds are basically those in which R 3 in the structural formula examples (5) to (13) of the alkoxyl group-containing cage-type siloxane compounds described above is replaced with hydrogen atoms. Correspond. That is, structural formula (5) is n = 8, a = 1, b = 1, (6) is n = 8, a = 2, b = 0, (7) is n = 8, a = 0, b = 2 , (8) n = 9, a = 1, b = 2, (9) n = 10, a = 1, b = 1, (10) n = 11, a = 1, b = 2, ( 11) is n = 12, a = 1, b = 1, (12) is n = 13, a = 1, b = 2, and (13) is n = 14, a = 1, b = 1. Note that silanol group-containing siloxane compounds are not limited to these because they have different combinations of n, a, and b numbers. In the structural formulas (5) to (13), R 1 and R 2 are the same as those in the general formula (4).
シラノール基含有籠型シロキサン化合物を製造するために用いる酸性触媒の例としては、塩酸、硫酸、酢酸、蟻酸、トリフロオロメタンスルホン酸等が挙げられる。また塩基性触媒としては水酸化カリウム、水酸化ナトリウム、水酸化セシウムなどのアルカリ金属水酸化物、あるいはテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ベンジルトリエチルアンモニウムヒドロキシドなどの水酸化アンモニウム塩が例示される。 Examples of the acidic catalyst used for producing the silanol group-containing cage-type siloxane compound include hydrochloric acid, sulfuric acid, acetic acid, formic acid, trifluoromethanesulfonic acid and the like. Basic catalysts include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl Illustrative are ammonium hydroxide salts such as triethylammonium hydroxide.
加水分解に必要な水は、酸又は塩基性触媒に含まれる水分を使用してもよく、別途加えてもよい。水の量としては使用するアルコキシル基含有籠型シロキサン化合物のアルコキシル基1モルに対して1〜3モルが好ましく、より好ましくは1〜1.5モルがよい。水の量が少なすぎるとアルコキシル基からシラノール基の変換が完全に行われず、多すぎるとシロキサン結合が切断するといった悪影響を及ぼす可能性がある。 The water necessary for the hydrolysis may be water contained in the acid or basic catalyst, or may be added separately. The amount of water is preferably 1 to 3 moles, more preferably 1 to 1.5 moles per mole of alkoxyl groups of the alkoxyl group-containing cage-type siloxane compound to be used. If the amount of water is too small, conversion of the alkoxyl group to the silanol group is not performed completely, and if it is too much, there is a possibility that the siloxane bond is broken.
酸または塩基触媒の使用量は、使用するアルコキシル基含有籠型シロキサン化合物のアルコキシル基1モルに対して0.1〜1.5モルが好ましい。触媒の使用量が多すぎるとシロキサン結合が切断され籠構造が分解されてしまう。 The amount of the acid or base catalyst used is preferably 0.1 to 1.5 moles per mole of alkoxyl groups of the alkoxyl group-containing cage-type siloxane compound to be used. If the amount of the catalyst used is too large, the siloxane bond is broken and the soot structure is decomposed.
加水分解反応条件については、反応温度は0〜40℃が好ましく、10〜30℃がより好ましい。反応温度が0℃より低いと、反応速度が遅くなりアルコキシル基が未反応の状態で残存してしまい反応時間を多く費やす結果となる、一方、40℃より高いと加水分解に加え、シラノール基の縮合反応が進行し結果として加水分解生成物の高分子量化が促進される。また、反応時間は2時間以上が好ましい。反応時間が2時間に満たないと、加水分解反応が十分に進行せずアルコキシル基が未反応の状態で残存してしまう状態となる。 Regarding the hydrolysis reaction conditions, the reaction temperature is preferably 0 to 40 ° C, more preferably 10 to 30 ° C. When the reaction temperature is lower than 0 ° C, the reaction rate becomes slow and the alkoxyl group remains in an unreacted state, resulting in a long reaction time. On the other hand, when the reaction temperature is higher than 40 ° C, in addition to hydrolysis, the silanol group The condensation reaction proceeds, and as a result, the hydrolysis product is increased in molecular weight. The reaction time is preferably 2 hours or more. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the alkoxyl group remains in an unreacted state.
加水分解時には非極性溶媒と極性溶媒のうちの1つもしくは両方合わせて使用するのがよく、好ましくは両方用いるか、極性溶媒のみ用いるのがよい。極性溶媒としてはメタノール、エタノール、2-プロパノールなどのアルコール類、或いは他の極性溶媒を用いることができ、好ましくは水に対し溶解性のある炭素数1〜6の低級アルコール類であるのがよく、2-プロパノールを用いることがより好ましい。非極性溶媒のみを用いると反応系が均一にならず加水分解が十分に進行しない。なお、非極性溶媒についてはアルコキシル基含有籠型シロキサン化合物の製造方法において例に挙げたものを用いることができる。 At the time of hydrolysis, one or both of a nonpolar solvent and a polar solvent may be used in combination, preferably both are used, or only a polar solvent is used. As the polar solvent, alcohols such as methanol, ethanol and 2-propanol, or other polar solvents can be used, preferably lower alcohols having 1 to 6 carbon atoms which are soluble in water. It is more preferable to use 2-propanol. If only a nonpolar solvent is used, the reaction system will not be uniform and hydrolysis will not proceed sufficiently. In addition, about the nonpolar solvent, what was mentioned in the example in the manufacturing method of an alkoxyl group containing cage type | mold siloxane compound can be used.
加水分解反応終了後は、トルエンなどの極性溶媒を加えて、使用した触媒により異なるが、反応溶液を弱塩基または弱酸性溶液で中和し、水又は水含有反応溶媒を分離する。水又は水含有反応溶媒の分離は、この溶液を食塩水等で洗浄し水分やその他の不純物を十分に除去し、その後無水硫酸マグネシウム等の乾燥剤で乾燥させる等の手段が採用できる。 After completion of the hydrolysis reaction, a polar solvent such as toluene is added, and depending on the catalyst used, the reaction solution is neutralized with a weak base or a weakly acidic solution, and water or a water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate.
本発明におけるアルコキシル基含有籠型シロキサン化合物の製造方法やシラノール基含有籠型シロキサン化合物の製造方法を用いれば、アルコキシル基やシラノール基の籠構造当りの含有量が調整された、分子量分散度の低い構造制御されたアルコキシル基含有籠型シロキサン化合物又はシラノール基含有籠型シロキサン化合物を高収率で製造することができる。 If the production method of the alkoxyl group-containing cage-type siloxane compound or the production method of silanol group-containing cage-type siloxane compound in the present invention is used, the content of alkoxyl groups or silanol groups per cage structure is adjusted, and the molecular weight dispersion is low. A structure-controlled alkoxyl group-containing cage-type siloxane compound or silanol group-containing cage-type siloxane compound can be produced in a high yield.
以下、実施例等に基づき本発明の好適な実施の形態を説明するが、本発明は下記の内容に制限されるものではない。 Hereinafter, preferred embodiments of the present invention will be described based on examples and the like, but the present invention is not limited to the following contents.
<参考例1>
[籠型フェニルシロキサン化合物の合成]
本合成例は特公昭40−15989号公報に記載された方法を使用して構造式 (C6 H5 SiO3/2 )8 を有する籠型オクタフェニルシルセスキオキサンの製造例を示す。反応容器にトルエン500mlとフェニルトリクロロシラン105gを装入し、0℃に冷却した。水を滴下し、加水分解が完了するまで撹拌した。加水分解生成物を水洗後市販の30%ベンジルトリメチルアンモニウムヒドロキサイド溶液16.6mlを加え、この混合物を4時間還流温度に加熱した。次いで全体を冷却し、約96時間放置した。この時間経過後得られたスラリーを再び24時間還流温度に加熱し次いで冷却し濾過を行い、白色の粉末を75g得た。得られた白色粉末の質量分析を行い籠型オクタフェニルシルセスキオキサンであることを確認した。
<Reference Example 1>
[Synthesis of cage-type phenylsiloxane compounds]
This synthesis example shows a production example of a cage octaphenylsilsesquioxane having the structural formula (C 6 H 5 SiO 3/2 ) 8 by using the method described in Japanese Patent Publication No. 40-15989. A reaction vessel was charged with 500 ml of toluene and 105 g of phenyltrichlorosilane, and cooled to 0 ° C. Water was added dropwise and stirred until hydrolysis was complete. After the hydrolysis product was washed with water, 16.6 ml of a commercially available 30% benzyltrimethylammonium hydroxide solution was added, and the mixture was heated to reflux for 4 hours. The whole was then cooled and left for about 96 hours. The slurry obtained after the lapse of time was heated again to the reflux temperature for 24 hours, then cooled and filtered to obtain 75 g of a white powder. The obtained white powder was subjected to mass spectrometry, and confirmed to be saddle type octaphenylsilsesquioxane.
[籠型シロキサン化合物として籠型オクタフェニルシルセスキオキサン(C6 H5 SiO3/2 )8とジアルコキシシランとして3-メタクリロキシプロピルメチルジエトキシシラン〔RMeSi(OEt) 2〕(但しRは3-メタクリロキシプロピル基である)を用いたアルコキシル基含有籠型シロキサン化合物Aの合成]
ディンスターク、及び冷却管を備えた反応容器にトルエン100ml、水酸化テトラメチルアンモニウム123mg(1.35mmol、25%のメタノール溶液として0.49g)、参考例1で得たオクタフェニルシルセスキオキサン20.29g(19.7mmol)、及び3-メタクリロキシプロピルジエトキシメチルシラン5.12g(19.7mmol)を入れ、80℃で1時間加熱しメタノールを留去した。次いで100℃に加熱し2時間後、室温に戻し反応を終了とした。反応溶液はオクタフェニルシルセスキオキサンの白色粉末が消え、完全に反応が進行したと判断できた。反応溶液を10%クエン酸水溶液で中和した後、水で洗浄し無水硫酸マグネシウムで脱水した。無水硫酸マグネシウムをろ別し、濃縮することで目的のアルコキシル基含有籠型シロキサン化合物A を無色透明の粘性液体として19.7g、収率78%で得た。
[籠 -type octaphenylsilsesquioxane (C 6 H 5 SiO 3/2 ) 8 as a cage-type siloxane compound and 3-methacryloxypropylmethyldiethoxysilane [RMeSi (OEt) 2 ] as a dialkoxysilane (where R is Synthesis of alkoxy group-containing cage-type siloxane compound A using 3-methacryloxypropyl group]
In a reaction vessel equipped with a Din Stark and a condenser, 100 ml of toluene, 123 mg of tetramethylammonium hydroxide (1.35 mmol, 0.49 g as a 25% methanol solution), 20.29 g of octaphenylsilsesquioxane obtained in Reference Example 1 ( 19.7 mmol) and 5.12 g (19.7 mmol) of 3-methacryloxypropyldiethoxymethylsilane were added and heated at 80 ° C. for 1 hour to distill off methanol. Subsequently, it heated at 100 degreeC, and after 2 hours, it returned to room temperature and complete | finished reaction. In the reaction solution, it was judged that the white powder of octaphenylsilsesquioxane disappeared and the reaction was completely progressed. The reaction solution was neutralized with 10% aqueous citric acid solution, washed with water, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 19.7 g of the objective alkoxyl group-containing cage-type siloxane compound A as a colorless transparent viscous liquid in a yield of 78%.
得られたアルコキシル基含有籠型シロキサン化合物AのGPCを測定した結果、数平均分子量(Mn)=1212、重量平均分子量(Mw)=1405、Mw/Mn=1.159であった。また1H-NMRよりオクタフェニルシルセスキオキサンのフェニル基40H に帰属される7〜8ppmのシグナルの積分比をS(Ph)=40とし、メタクリル基のアルケン2Hに帰属される5.4と6.0ppmのシグナルの積分比S(M)、エトキシ基のメチレン2Hに帰属される3.7ppmのシグナルの積分比S(E)としたとき、S(Ph):S(M):S(E)=40:1.9:3.8であり、得られたアルコキシル基含有籠型シロキサン化合物A は下記式(3A)
[(EtO)MeRSiO1/2]a − [PhSiO3/2]8 − [O1/2Et]b (3A)
(但しRは3-メタクリロキシプロピル基である)におけるa=0.95及びb=0.95で表せられることが分った。更に、液体クロマトグラフィ大気圧イオン化分析計(LC/APCI-MS)による質量分析を行った結果、式(3A)のa=1,b=1のアンモニウムイオンが付加したスペクトルm/z1311.9が検出された。これらのことからアルコキシル基含有籠型シロキサン化合物Aは籠型オクタフェニルシルセスキオキサン一分子にメトキシ基が2つ付加したアルコキシル基含有籠型シロキサン化合物といえる。
As a result of measuring GPC of the obtained alkoxyl group-containing cage-type siloxane compound A, it was found that the number average molecular weight (Mn) = 1212, the weight average molecular weight (Mw) = 1405, and Mw / Mn = 1.159. Also, from 1H-NMR, the integration ratio of the signal of 7-8 ppm attributed to the phenyl group 40H of octaphenylsilsesquioxane was S (Ph) = 40, and 5.4 and 6.0 ppm attributed to the alkene 2H of the methacryl group. S (Ph): S (M): S (E) = 40, where signal integration ratio S (M) and signal integration ratio S (E) of 3.7 ppm attributed to ethoxy group methylene 2H 1.9: 3.8, and the obtained alkoxyl group-containing cage-type siloxane compound A is represented by the following formula (3A)
[(EtO) MeRSiO 1/2 ] a − [PhSiO 3/2 ] 8 − [O 1/2 Et] b (3A)
It was found that a = 0.95 and b = 0.95 in (wherein R is a 3-methacryloxypropyl group). Furthermore, as a result of mass spectrometry using a liquid chromatography atmospheric pressure ionization analyzer (LC / APCI-MS), a spectrum m / z 1311.9 added with ammonium ions with a = 1 and b = 1 in formula (3A) was detected. It was done. From these facts, it can be said that the alkoxyl group-containing cage-type siloxane compound A is an alkoxyl group-containing cage-type siloxane compound in which two methoxy groups are added to one molecule of the cage-type octaphenylsilsesquioxane.
[アルコキシル基含有籠型シロキサン化合物Aを用いたシラノール基含有籠型シロキサン化合物A-OHの合成]
滴下ロートを備えた反応容器に2-プロパノール10ml、トルエン7ml、及び実施例1で得たアルコキシル基含有籠型シロキサン化合物A 1.23g(式3Aのa=1,b=1の分子量1292として計算 0.95mmol)を装入した。反応溶液に2%塩酸38mg(HCl:0.02mmol,H2O:2.09mmol)を室温で滴下し、室温で24時間撹拌した。反応溶液を炭酸水素ナトリウム水溶液で中和、水で洗浄し無水硫酸マグネシウムで脱水した。無水硫酸マグネシウムをろ別し、濃縮することで目的のシラノール基含有籠型シロキサン化合物A-OH を無色透明の粘性液体として1.07g、収率91%で得た。
[Synthesis of silanol group-containing cage-type siloxane compound A-OH using alkoxyl group-containing cage-type siloxane compound A]
In a reaction vessel equipped with a dropping funnel, 10 ml of 2-propanol, 7 ml of toluene, and 1.23 g of the alkoxyl group-containing cage-type siloxane compound A obtained in Example 1 (calculated as molecular weight 1292 of a = 1, b = 1 of formula 3A 0.95 mmol) was charged. To the reaction solution, 38 mg of 2% hydrochloric acid (HCl: 0.02 mmol, H2O: 2.09 mmol) was added dropwise at room temperature, and the mixture was stirred at room temperature for 24 hours. The reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, washed with water, and dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 1.07 g of the objective silanol group-containing cage-type siloxane compound A-OH as a colorless transparent viscous liquid in a yield of 91%.
得られたシラノール基含有籠型シロキサン化合物A-OHのGPCを測定した結果、数平均分子量(Mn)=1165、重量平均分子量(Mw)=1349、Mw/Mn=1.158であった。また1H-NMRよりエトキシ基に帰属されるシグナルは無く、IRからシラノールに帰属される3310cm-1付近のブロードのピークが観測された。更に、液体クロマトグラフィ大気圧イオン化分析計(LC/APCI-MS)による質量分析を行った結果、下記式(4A)
[(HO)MeRSiO1/2]a − [PhSiO3/2]8 − [O1/2H]b (4A)
(但しRはメタクリロキシプロピル基である。)のa=1,b=1のプロトンイオンが付加したスペクトルm/z1238.8質量が検出された。これらのことからシラノール基含有籠型シロキサン化合物A-OHは籠型オクタフェニルシルセスキオキサン一分子にシラノール基が2つ付加したシラノール基含有籠型シロキサン化合物といえる。
As a result of measuring GPC of the obtained silanol group-containing cage-type siloxane compound A-OH, it was found that the number average molecular weight (Mn) = 1165, the weight average molecular weight (Mw) = 1349, and Mw / Mn = 1.158. From 1H-NMR, there was no signal attributed to the ethoxy group, and a broad peak around 3310 cm-1 attributed to silanol was observed from IR. Furthermore, as a result of mass spectrometry using a liquid chromatography atmospheric pressure ionization analyzer (LC / APCI-MS), the following formula (4A)
[(HO) MeRSiO 1/2] a - [PhSiO 3/2] 8 - [O 1/2 H] b (4A)
A mass of spectrum m / z 1238.8 added with proton ions of a = 1 and b = 1 of R (wherein R is a methacryloxypropyl group) was detected. Therefore, it can be said that the silanol group-containing cage-type siloxane compound A-OH is a silanol group-containing cage-type siloxane compound in which two silanol groups are added to one molecule of the cage-type octaphenylsilsesquioxane.
[籠型シロキサン化合物として籠型オクタフェニルシルセスキオキサン(C6 H5 SiO3/2 )8とジアルコキシシランとしてビニルメチルジメトキシシラン〔RMeSi(OEt) 2〕(但しRはビニル基)を用いたアルコキシル基含有籠型シロキサン化合物Bの合成]
実施例1と同様な操作をトルエン50ml、水酸化テトラメチルアンモニウム60mg(0.66 mmol、25%のメタノール溶液として0.24g)、参考例1で得たオクタフェニルシルセスキオキサン10.00g(9.69mmol)、及びビニルメチルジメトキシシラン1.55g(9.69mmol)の仕込み量に変更して行い、アルコキシル基含有籠型シロキサン化合物B を無色透明の粘性液体として8.87g、収率77%で得た。
[籠 -octaphenylsilsesquioxane (C 6 H 5 SiO 3/2 ) 8 as cage-type siloxane compound and vinylmethyldimethoxysilane [RMeSi (OEt) 2 ] (where R is a vinyl group) as dialkoxysilane Of Alkoxy group-containing cage-type siloxane compound B]
The same operation as in Example 1 was carried out using 50 ml of toluene, 60 mg of tetramethylammonium hydroxide (0.66 mmol, 0.24 g as a 25% methanol solution), 10.00 g (9.69 mmol) of octaphenylsilsesquioxane obtained in Reference Example 1, In addition, the amount was changed to 1.55 g (9.69 mmol) of vinylmethyldimethoxysilane, and 8.87 g of an alkoxyl group-containing cage-type siloxane compound B was obtained as a colorless transparent viscous liquid in a yield of 77%.
得られたアルコキシル基含有籠型シロキサン化合物BのGPCを測定した結果、数平均分子量(Mn)=1095、重量平均分子量(Mw)=1207、Mw/Mn=1.159であった。また1H-NMRよりオクタフェニルシルセスキオキサンのフェニル基40Hに帰属される7〜8ppmのシグナルの積分比をS(Ph)=40とし、ビニル基3Hに帰属される5.9ppm付近のシグナルの積分比S(V)、エトキシ基のメチレン2Hに帰属される3.7ppmのシグナルの積分比S(E)としたとき、S(Ph):S(M):S(E)=40:2.9:3.8であり、得られたアルコキシル基含有籠型シロキサン化合物Bは下記式(3B)
[(EtO)MeRSiO1/2]a − [PhSiO3/2]8 − [O1/2Et]b (3B)
(但しRはビニル基でありa=0.97、b=0.95)で表されることが分かった。
As a result of measuring GPC of the obtained alkoxyl group-containing cage-type siloxane compound B, it was found that the number average molecular weight (Mn) was 1095, the weight average molecular weight (Mw) was 1207, and Mw / Mn was 1.159. Also, from 1H-NMR, the integration ratio of the signal of 7-8ppm attributed to the phenyl group 40H of octaphenylsilsesquioxane is S (Ph) = 40, and the signal around 5.9ppm attributed to the vinyl group 3H is integrated. S (Ph): S (M): S (E) = 40: 2.9: 3.8, where S (V) is the integration ratio S (E) of the signal of 3.7 ppm attributed to methylene 2H of the ethoxy group The obtained alkoxyl group-containing cage-type siloxane compound B is represented by the following formula (3B)
[(EtO) MeRSiO 1/2 ] a − [PhSiO 3/2 ] 8 − [O 1/2 Et] b (3B)
(However, R is a vinyl group, and a = 0.97, b = 0.95).
[アルコキシル基含有籠型シロキサン化合物Bを用いたシラノール基含有籠型シロキサン化合物B-OHの合成]
実施例2と同様な操作をアルコキシル基含有籠型シロキサン化合物Aの代わりにアルコキシル基含有籠型シロキサン化合物B 1.13g(式3Aのa=1,b=1の分子量1192として計算 0.95mmol)を用いて行ない、シラノール基含有籠型シロキサン化合物B-OHを無色透明の粘性液体として1.07g、収率91%で得た。得られたシラノール基含有籠型シロキサン化合物B-OHのGPCを測定した結果、数平均分子量(Mn)=1147、重量平均分子量(Mw)=1255、Mw/Mn=1.094であった。また1H-NMRよりエトキシ基に帰属されるシグナルは無く、IRからシラノールに帰属される3310cm-1付近のブロードのピークが観測された。これらのことからシラノール基含有籠型シロキサン化合物B-OHはアルコキシル基含有籠型シロキサン化合物Bのアルコキシル基がシラノール基に変換されたシラノール基含有籠型シロキサン化合物といえる。
[Synthesis of silanol group-containing cage-type siloxane compound B-OH using alkoxyl group-containing cage-type siloxane compound B]
The same operation as in Example 2 was used instead of alkoxyl group-containing cage-type siloxane compound A using 1.13 g of alkoxyl-group-containing cage-type siloxane compound B (calculated as molecular weight 1192 of a = 1, b = 1 in formula 3A, 0.95 mmol). As a result, 1.07 g of a silanol group-containing cage-type siloxane compound B-OH was obtained as a colorless and transparent viscous liquid in a yield of 91%. As a result of measuring GPC of the obtained silanol group-containing cage-type siloxane compound B-OH, it was found that the number average molecular weight (Mn) = 1147, the weight average molecular weight (Mw) = 1255, and Mw / Mn = 1.94. From 1H-NMR, there was no signal attributed to the ethoxy group, and a broad peak around 3310 cm-1 attributed to silanol was observed from IR. From these facts, the silanol group-containing cage-type siloxane compound B-OH can be said to be a silanol group-containing cage-type siloxane compound in which the alkoxyl group of the alkoxyl group-containing cage-type siloxane compound B is converted to a silanol group.
<参考例2>
[籠型ビニルシロキサン化合物の合成]
本合成例は先に出願した特開2004-143449号公報に記載された方法を参考に使用して構造式 (H2C=CH-SiO3/2 )n を有する籠型ポリビニルシルセスキオキサンの製造例を示す。
反応容器に、トルエン150ml、2-プロパノール85ml、及び5%テトラメチルアンモニウムヒドロキシド水溶液(TMAH水溶液)37.2gを装入した。トルエン25mlとビニルトリメトキシシラン50.3gの溶液を室温で反応容器へ撹拌しながら、3時間かけ滴下した。滴下終了後、室温で2時間撹拌後に攪拌を停止して1日静置した。反応溶液を10%クエン酸水溶液23.0gで中和した後、飽和食塩水で洗浄し無水硫酸マグネシウムで脱水、濃縮することでビニルトリメトキシシランの加水分解重縮合物を20.6g得た。
<Reference Example 2>
[Synthesis of vertical vinylsiloxane compounds]
This synthesis example uses a method described in Japanese Patent Application Laid-Open No. 2004-143449 filed earlier as a reference, and a cage-type polyvinylsilsesquioxane having the structural formula (H 2 C═CH—SiO 3/2 ) n The example of manufacture of is shown.
A reaction vessel was charged with 150 ml of toluene, 85 ml of 2-propanol, and 37.2 g of 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution). While stirring, a solution of 25 ml of toluene and 50.3 g of vinyltrimethoxysilane was added dropwise to the reaction vessel at room temperature over 3 hours. After completion of the dropping, the mixture was stirred at room temperature for 2 hours, and then the stirring was stopped and the mixture was allowed to stand for 1 day. The reaction solution was neutralized with 23.0 g of 10% aqueous citric acid solution, washed with saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to obtain 20.6 g of a hydrolyzed polycondensate of vinyltrimethoxysilane.
次に、ディンスターク及び冷却管を備えた反応容器に先得られたビニルトリメトキシシランの加水分解重縮合物15.0gとトルエン380mlと5%TMAH水溶液1.72gとを入れ120℃で水を留去しながら還流加熱を3時間行った。室温に冷却し、10%クエン酸23.0gで中和にした後、飽和食塩水で洗浄し無水硫酸マグネシウムで脱水、濃縮することで籠型ポリビニルシルセスキオキサンを14.5g得た。得られた籠型ポリビニルシルセスキオキサンは、NMR測定及びIR測定ではメトキシ基、及びシラノール基は確認されず、GPCおよび液体クロマトグラフィ大気圧イオン化分析計(LC/APCI-MS)による質量分析より構造式(H2C=CH-SiO3/2 )nのn=8,10,12,14を主に含み、平均してn=10の籠型ビニルシロキサン混合物であると確認された。 Next, 15.0 g of the vinyltrimethoxysilane hydrolyzed polycondensate obtained above, 380 ml of toluene, and 1.72 g of 5% TMAH aqueous solution were placed in a reaction vessel equipped with a Dinsterk and a cooling tube, and water was distilled off at 120 ° C. Reflux heating was performed for 3 hours. The mixture was cooled to room temperature, neutralized with 23.0 g of 10% citric acid, washed with saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to obtain 14.5 g of a caged polyvinylsilsesquioxane. The obtained cocoon-type polyvinylsilsesquioxane was confirmed by mass spectrometry using GPC and a liquid chromatography atmospheric pressure ionization analyzer (LC / APCI-MS) without methoxy group and silanol group being confirmed by NMR measurement and IR measurement. The formula (H 2 C═CH—SiO 3/2 ) n was confirmed to be mainly a n-type vinyl siloxane mixture containing n = 8, 10, 12, 14 and n = 10 on average.
[籠型シロキサン化合物として参考例2で合成した籠型ポリビニルシルセスキオキサン(H2C=CH-SiO3/2 )n(但しn=8,10,12,14を主に含み平均してn=10の籠型ビニルシロキサン混合物)とジアルコキシシランとして、ジメチルジエトキシシランMe2Si(OEt) 2を用いたアルコキシル基含有籠型シロキサン化合物Cの合成]
実施例1と同様な操作をトルエン50ml、水酸化テトラメチルアンモニウム78mg(0.86 mmol、25%のメタノール溶液として0.31g)、参考例2で得た籠型ビニルシロキサン混合物(H2C=CH-SiO3/2 )n(但しn=8,10,12,14を主に含み平均してn=10)10.00g(n=10として12.7mmol)、及びジメチルジメトキシシラン1.88g(12.7mmol)の仕込み量に変更して行い、アルコキシル基含有籠型シロキサン化合物Cを無色透明の粘性液体として10.01g、回収率84%で得た。
[Saddle-type polyvinylsilsesquioxane (H 2 C═CH—SiO 3/2 ) n (where n = 8, 10, 12, 14 is mainly included and averaged as a cage-type siloxane compound synthesized in Reference Example 2) Synthesis of alkoxyl group-containing cage-type siloxane compound C using dimethyldiethoxysilane Me 2 Si (OEt) 2 as dialkoxysilane and n = 10 cage-type vinylsiloxane mixture]
The same operation as in Example 1 was carried out using 50 ml of toluene, 78 mg of tetramethylammonium hydroxide (0.86 mmol, 0.31 g as a 25% methanol solution), and the vertical vinylsiloxane mixture obtained in Reference Example 2 (H 2 C═CH—SiO 2). 3/2 ) n (provided that n = 8, 10, 12, 14 are mainly included and averaged n = 10) 10.00 g (12.7 mmol as n = 10) and 1.88 g (12.7 mmol) of dimethyldimethoxysilane The amount of the alkoxide group-containing cage-type siloxane compound C was changed to 10.01 g as a colorless and transparent viscous liquid with a recovery rate of 84%.
得られたアルコキシル基含有籠型シロキサン化合物CのGPCを測定した結果、数平均分子量(Mn)=986、重量平均分子量(Mw)=1315、Mw/Mn=1.334であった。また1H-NMRより籠型ビニルシロキサンのビニル基30Hに帰属される5.8〜6.2ppmのシグナルの積分比をS(cV)=30とし、メチル基3Hに帰属される0.1ppm付近のシグナルの積分比S(Me)、エトキシ基のメチレン2Hに帰属される3.7ppmのシグナルの積分比S(E)としたとき、S(cV):S(Me):S(E)=30:6:3.9であり、得られたアルコキシル基含有籠型シロキサン化合物Cは下記式(3C) [(EtO)Me2SiO1/2]a − [H2C=CH-SiO3/2]n − [O1/2Et]b (3C)
におけるn=10、a=1.00、及びb=0.95で表されることが分かった。
As a result of measuring GPC of the obtained alkoxyl group-containing cage-type siloxane compound C, the number average molecular weight (Mn) was 986, the weight average molecular weight (Mw) was 1315, and Mw / Mn was 1.334. Also, from 1H-NMR, the integral ratio of the signal of 5.8 to 6.2 ppm attributed to vinyl group 30H of cage vinyl siloxane is S (cV) = 30, and the integral ratio of the signal around 0.1 ppm attributed to methyl group 3H S (Me), when the integration ratio S (E) of the signal of 3.7 ppm attributed to methylene 2H of the ethoxy group is S (cV): S (Me): S (E) = 30: 6: 3.9 And the obtained alkoxyl group-containing cage-type siloxane compound C has the following formula (3C) [(EtO) Me 2 SiO 1/2 ] a − [H 2 C═CH—SiO 3/2 ] n − [O 1 / 2 Et] b (3C)
N = 10, a = 1.00, and b = 0.95.
[アルコキシル基含有籠型シロキサン化合物Cを用いたシラノール基含有籠型シロキサン化合物C-OHの合成]
滴下ロートを備えた反応容器に2-プロパノール10ml、トルエン7ml、及びアルコキシル基含有籠型シロキサン化合物C 1.0g(式3Cのa=1,b=1の分子量734として計算 1.36mmol)を装入し、反応溶液に水酸化テトラメチルアンモニウム260mg(2.86mmol、25%のメタノール溶液として1.04g)、イオン交換水59mg(3.27mmol)及び2-プロパノール6mlの混合溶液を滴下し、室温で3時間撹拌した。反応溶液にトルエン20mlを加え、撹拌し、続けて10%クエン酸水溶液で中和した後、飽和食塩水で洗浄し無水硫酸マグネシウムで脱水、濃縮することでシラノール基含有籠型シロキサン化合物C-OHを6.2g、収率92%で得た。
[Synthesis of silanol group-containing cage-type siloxane compound C-OH using alkoxyl group-containing cage-type siloxane compound C]
Charge a reaction vessel equipped with a dropping funnel with 10 ml of 2-propanol, 7 ml of toluene, and 1.0 g of an alkoxyl-containing cage-type siloxane compound C (calculated as a molecular weight of 734 where a = 1 and b = 1 in formula 3C, 1.36 mmol). Then, a mixed solution of tetramethylammonium hydroxide 260 mg (2.86 mmol, 1.04 g as a 25% methanol solution), ion-exchanged water 59 mg (3.27 mmol) and 2-propanol 6 ml was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 3 hours. . To the reaction solution was added 20 ml of toluene, stirred, and then neutralized with 10% aqueous citric acid solution, washed with saturated brine, dehydrated with anhydrous magnesium sulfate, and concentrated to give a silanol group-containing cage-type siloxane compound C-OH. Was obtained in a yield of 92%.
得られたシラノール基含有籠型シロキサン化合物C-OHのGPCを測定した結果、数平均分子量(Mn)=577、重量平均分子量(Mw)=641、Mw/Mn=1.111であった。また1H-NMRよりエトキシ基に帰属されるシグナルは無く、IRからシラノールに帰属される3310cm-1付近のブロードのピークが観測された。これらのことからシラノール基含有籠型シロキサン化合物C-OHはアルコキシル基含有籠型シロキサン化合物Cのアルコキシル基がシラノール基に変換されたシラノール基含有籠型シロキサン化合物といえる。 As a result of measuring GPC of the obtained silanol group-containing cage-type siloxane compound C-OH, it was found that the number average molecular weight (Mn) = 577, the weight average molecular weight (Mw) = 641, and Mw / Mn = 1.111. From 1H-NMR, there was no signal attributed to the ethoxy group, and a broad peak around 3310 cm-1 attributed to silanol was observed from IR. From these facts, the silanol group-containing cage-type siloxane compound C-OH can be said to be a silanol group-containing cage-type siloxane compound in which the alkoxyl group of the alkoxyl group-containing cage-type siloxane compound C is converted to a silanol group.
[籠型シロキサン化合物として参考例2で合成した籠型ポリビニルシルセスキオキサン(H2C=CH-SiO3/2 )n(但しn=8,10,12,14を主に含み平均してn=10の籠型ビニルシロキサン混合物)とジアルコキシシランとして、3-メタクリロキシプロピルメチルジエトキシシラン〔RMeSi(OEt) 2〕(但しRは3-メタクリロキシプロピル基)を用いたアルコキシル基含有籠型シロキサン化合物Dの合成]
実施例1と同様な操作をトルエン50ml、水酸化テトラメチルアンモニウム78mg(0.86 mmol、25%のメタノール溶液として0.31g)、参考例2で得た籠型ビニルシロキサン混合物(H2C=CH-SiO3/2 )n(但しn=8,10,12,14を主に含み平均してn=10)10.00g(n=10として12.7mmol)、及び3-メタクリロキシプロピルメチルジエトキシシラン3.30g(12.7mmol)の仕込み量に変更して行い、アルコキシル基含有籠型シロキサン化合物Dを無色透明の粘性液体として11.84g、回収率89%で得た。
[Saddle-type polyvinylsilsesquioxane (H 2 C═CH—SiO 3/2 ) n (where n = 8, 10, 12, 14 is mainly contained as an average and contains an average as a cage-type siloxane compound) n = 10 vertical vinylsiloxane mixture) and dialkoxysilane containing 3-methacryloxypropylmethyldiethoxysilane [RMeSi (OEt) 2 ] (where R is a 3-methacryloxypropyl group) Synthesis of Type Siloxane Compound D]
The same operation as in Example 1 was carried out using 50 ml of toluene, 78 mg of tetramethylammonium hydroxide (0.86 mmol, 0.31 g as a 25% methanol solution), and the vertical vinylsiloxane mixture obtained in Reference Example 2 (H 2 C═CH—SiO 2). 3/2 ) n (where n = 8, 10, 12, 14 are mainly included and n = 10 on average) 10.00 g (12.7 mmol as n = 10), and 3.30 g of 3-methacryloxypropylmethyldiethoxysilane The amount was changed to (12.7 mmol), and 11.84 g of an alkoxyl group-containing cage-type siloxane compound D was obtained as a colorless and transparent viscous liquid with a recovery rate of 89%.
得られたアルコキシル基含有籠型シロキサン化合物DのGPCを測定した結果、数平均分子量(Mn)=1110、重量平均分子量(Mw)=1521、Mw/Mn=1.370であった。また1H-NMRより籠型ビニルシロキサンのビニル基30Hとメタクリル基のアルケン2Hうち1Hに帰属される5.8〜6.2ppmのシグナルの積分比をS(cV+M)=31とし、メタクリル基のアルケンの残り1Hに帰属される5.5ppmのシグナルの積分比S(M)、エトキシ基のメチレン2Hに帰属される3.7ppmのシグナルの積分比S(E)としたとき、S(cV+M):S(M):S(E)=31:0.89:3.8であり、得られたアルコキシル基含有籠型シロキサン化合物Dは下記式(3D)
[(EtO)RMeSiO1/2]a − [H2C=CH-SiO3/2]n − [O1/2Et]b (3D)
(但しRはメタクリロキシプロピル基である。)におけるn=10、a=0.89、b=1.01で表されることが分った。
As a result of measuring GPC of the obtained alkoxyl group-containing cage-type siloxane compound D, it was found that the number average molecular weight (Mn) = 1110, the weight average molecular weight (Mw) = 1521, and Mw / Mn = 1.370. Also, from 1H-NMR, the integral ratio of the signal of 5.8-6.2ppm attributed to 1H out of 2H of vinyl group 30H and alkene alkene 2H of caged vinyl siloxane is S (cV + M) = 31, and the remaining 1H of methacrylic alkene S (cV + M): S (M) where the integration ratio S (M) of the signal of 5.5 ppm attributed to ## EQU2 ## and the integration ratio S (E) of the signal of 3.7 ppm attributed to methylene 2H of the ethoxy group ): S (E) = 31: 0.89: 3.8, and the obtained alkoxyl group-containing cage-type siloxane compound D has the following formula (3D)
[(EtO) RMeSiO 1/2 ] a − [H 2 C═CH—SiO 3/2 ] n − [O 1/2 Et] b (3D)
It was found that n = 10, a = 0.89, and b = 1.01 in (wherein R is a methacryloxypropyl group).
[アルコキシル基含有籠型シロキサン化合物Dを用いたシラノール基含有籠型シロキサン化合物D-OHの合成]
アルコキシル基含有籠型シロキサン化合物C 1.0gの代わりに実施例7で合成したアルコキシル基含有籠型シロキサン化合物D 1.43g(式3Dのa=1,b=1の分子量1050として計算 1.36mmol)を用い実施例6と同様の操作を行い、シラノール基含有籠型シロキサン化合物D-OHを0.91g、収率92%で得た。
[Synthesis of silanol group-containing cage-type siloxane compound D-OH using alkoxyl group-containing cage-type siloxane compound D]
In place of 1.0 g of the alkoxyl group-containing cage-type siloxane compound C, 1.43 g of the alkoxyl-group-containing cage-type siloxane compound D synthesized in Example 7 (calculated as a molecular weight 1050 of a = 1, b = 1 in Formula 3D) was used. The same operation as in Example 6 was performed to obtain 0.91 g of a silanol group-containing cage-type siloxane compound D-OH in a yield of 92%.
得られたシラノール基含有籠型シロキサン化合物D-OHのGPCを測定した結果、数平均分子量(Mn)=1283、重量平均分子量(Mw)=1511、Mw/Mn=1.178であった。また1H-NMRよりエトキシ基に帰属されるシグナルは無く、IRからシラノールに帰属される3310cm-1付近のブロードのピークが観測された。これらのことからシラノール基含有籠型シロキサン化合物D-OHはアルコキシル基含有籠型シロキサン化合物Cのアルコキシル基がシラノール基に変換されたシラノール基含有籠型シロキサン化合物といえる。 As a result of measuring GPC of the obtained silanol group-containing cage-type siloxane compound D-OH, it was found that the number average molecular weight (Mn) = 1283, the weight average molecular weight (Mw) = 1511, and Mw / Mn = 1.178. From 1H-NMR, there was no signal attributed to the ethoxy group, and a broad peak around 3310 cm-1 attributed to silanol was observed from IR. From these facts, the silanol group-containing cage-type siloxane compound D-OH can be said to be a silanol group-containing cage-type siloxane compound in which the alkoxyl group of the alkoxyl group-containing cage-type siloxane compound C is converted to a silanol group.
[籠型シロキサン化合物として参考例2で合成した籠型ポリビニルシルセスキオキサン(H2C=CH-SiO3/2 )n(但しn=8,10,12,14を主に含み平均してn=10の籠型ビニルシロキサン混合物)とジアルコキシシランとして、3-グリシドキシプロピルメチルジエトキシシラン〔RMeSi(OEt) 2〕(但しRは3-グリシドキシプロピル基)を用いたアルコキシル基含有籠型シロキサン化合物Eの合成]
実施例1と同様な操作をトルエン50ml、水酸化テトラメチルアンモニウム78mg(0.86 mmol、25%のメタノール溶液として0.31g)、参考例2で得た籠型ビニルシロキサン混合物(H2C=CH-SiO3/2 )n(但しn=8,10,12,14を主に含み平均してn=10)10.00g(n=10として12.7mmol)、及び3-グリシドキシプロピルメチルジエトキシシラン3.15g(12.7mmol) の仕込み量に変更して行い、アルコキシル基含有籠型シロキサン化合物Dを無色透明の粘性液体として11.17g、回収率85%で得た。
[Saddle-type polyvinylsilsesquioxane (H 2 C═CH—SiO 3/2 ) n (where n = 8, 10, 12, 14 is mainly included and averaged as a cage-type siloxane compound synthesized in Reference Example 2) n = 10 vertical vinyl siloxane mixture) and dialkoxysilane as alkoxyl group using 3-glycidoxypropylmethyldiethoxysilane [RMeSi (OEt) 2 ] (where R is 3-glycidoxypropyl group) Synthesis of caged siloxane compound E]
The same operation as in Example 1 was carried out using 50 ml of toluene, 78 mg of tetramethylammonium hydroxide (0.86 mmol, 0.31 g as a 25% methanol solution), and the vertical vinylsiloxane mixture obtained in Reference Example 2 (H 2 C═CH—SiO 2). 3/2 ) n (where n = 8, 10, 12, and 14 mainly, average n = 10) 10.00 g (12.7 mmol as n = 10), and 3-glycidoxypropylmethyldiethoxysilane 3.15 The amount was changed to a charged amount of g (12.7 mmol) to obtain 11.17 g of an alkoxyl group-containing cage-type siloxane compound D as a colorless transparent viscous liquid with a recovery rate of 85%.
得られたアルコキシル基含有籠型シロキサン化合物DのGPCを測定した結果、数平均分子量(Mn)=1138、重量平均分子量(Mw)=1578、Mw/Mn=1.387であった。また1H-NMRより籠型ビニルシロキサンのビニル基30Hに帰属される5.8〜6.2ppmのシグナルの積分比をS(cV)=30とし、グリシジル基の2Hに帰属される2.45と2.6ppmのシグナルの積分比S(G)、エトキシ基のメチル3Hに帰属される1.2ppmのシグナルの積分比S(E)としたとき、S(cV):S(G):S(E)=30:1.99:5.98であり、得られたアルコキシル基含有籠型シロキサン化合物Eは下記式(3E)
[(EtO)RMeSiO1/2]a − [H2C=CH-SiO3/2]n − [O1/2Et]b (3E)
(但しRは3-グリシドキシプロピル基である。)におけるn=10、a=1.00、b=1.00で表されることが分った。
As a result of measuring GPC of the obtained alkoxyl group-containing cage-type siloxane compound D, it was found that the number average molecular weight (Mn) = 1138, the weight average molecular weight (Mw) = 1578, and Mw / Mn = 1.387. From 1H-NMR, the integral ratio of the signal of 5.8-6.2 ppm attributed to vinyl group 30H of cage vinyl siloxane is S (cV) = 30, and the signals of 2.45 and 2.6 ppm attributed to 2H of glycidyl group are S (cV): S (G): S (E) = 30: 1.99, where the integration ratio S (G) is the integration ratio S (E) of the signal of 1.2 ppm attributed to methyl 3H of the ethoxy group. 5. The obtained alkoxyl group-containing cage-type siloxane compound E is represented by the following formula (3E)
[(EtO) RMeSiO 1/2 ] a − [H 2 C═CH—SiO 3/2 ] n − [O 1/2 Et] b (3E)
It was found that n = 10, a = 1.00, and b = 1.00 in (where R is a 3-glycidoxypropyl group).
[アルコキシル基含有籠型シロキサン化合物Dを用いたシラノール基含有籠型シロキサン化合物E-OHの合成]
アルコキシル基含有籠型シロキサン化合物C 1.0gの代わりに実施例9で合成したアルコキシル基含有籠型シロキサン化合物D1.41g(式3Eのa=1,b=1の分子量1038として計算 1.36mmol)を用い実施例6と同様の操作を行い、シラノール基含有籠型シロキサン化合物E-OHを0.86g、収率88%で得た。
[Synthesis of silanol group-containing cage-type siloxane compound E-OH using alkoxyl group-containing cage-type siloxane compound D]
In place of 1.0 g of alkoxyl group-containing cage-type siloxane compound C, 1.41 g of alkoxyl-group-containing cage-type siloxane compound D 1.41 g (calculated as a molecular weight of 1038 where a = 1 and b = 1 in formula 3E is 1.36 mmol) synthesized in Example 9 was used. The same operation as in Example 6 was performed to obtain 0.86 g of silanol group-containing cage-type siloxane compound E-OH in a yield of 88%.
得られたシラノール基含有籠型シロキサン化合物E-OHのGPCを測定した結果、数平均分子量(Mn)=1220、重量平均分子量(Mw)=1579、Mw/Mn=1.294であった。また1H-NMRよりエトキシ基に帰属されるシグナルは無く、IRからシラノールに帰属される3310cm-1付近のブロードのピークが観測された。これらのことからシラノール基含有籠型シロキサン化合物E-OHはアルコキシル基含有籠型シロキサン化合物Eのアルコキシル基がシラノール基に変換されたシラノール基含有籠型シロキサン化合物といえる。 As a result of measuring GPC of the obtained silanol group-containing cage-type siloxane compound E-OH, it was found that the number average molecular weight (Mn) = 1220, the weight average molecular weight (Mw) = 1579, and Mw / Mn = 1.294. From 1H-NMR, there was no signal attributed to the ethoxy group, and a broad peak around 3310 cm-1 attributed to silanol was observed from IR. From these facts, it can be said that the silanol group-containing cage-type siloxane compound E-OH is a silanol group-containing cage-type siloxane compound in which the alkoxyl group of the alkoxyl group-containing cage-type siloxane compound E is converted to a silanol group.
<参考例3>
参考例2と同様な操作をトリメトキシビニルシラン(50.3g:0.34mol)の代わりに、トリメトキシエチルシラン(25.2g:0.17mol)とトリメトキシビニルシラン((25.5g:0.17mol)を混合して用い行い、籠型ポリ(ビニル‐エチル)シルセスキオキサンを得た。参考例2と同様の分析から、構造式 [R1SiO3/2]nのn=8,10,12,14を主に含み、R1がビニル基とエチル基からなる平均してn=10の籠型ポリ(ビニルーエチル)シロキサン混合物であることが分った。
<Reference Example 3>
The same procedure as in Reference Example 2 was used instead of trimethoxyvinylsilane (50.3 g: 0.34 mol) mixed with trimethoxyethylsilane (25.2 g: 0.17 mol) and trimethoxyvinylsilane ((25.5 g: 0.17 mol)). To obtain cage-type poly (vinyl-ethyl) silsesquioxane, which was analyzed in the same manner as in Reference Example 2 and the main structural formulas [R 1 SiO 3/2 ] n were n = 8, 10, 12, and 14. It was found that R 1 is a vertical poly (vinyl-ethyl) siloxane mixture consisting of a vinyl group and an ethyl group with an average of n = 10.
[籠型シロキサン化合物として参考例3で合成した籠型ポリ(ビニルーエチル)シロキサン混合物[R1SiO3/2]n(但しn=8,10,12,14を主に含み平均してn=10の籠型ビニルシロキサン混合物)とジアルコキシシランとして、3-メタクリロキシプロピルメチルジエトキシシラン〔RMeSi(OEt) 2〕(但しRは3-メタクリロキシプロピル基)を用いたアルコキシル基含有籠型シロキサン化合物Fの合成]
実施例1と同様な操作をトルエン50ml、水酸化テトラメチルアンモニウム78mg(0.86 mmol、25%のメタノール溶液として0.31g)、参考例3で合成した籠型ポリ(ビニルーエチル)シロキサン混合物[R1SiO3/2]n(但しn=8,10,12,14を主に含み平均してn=10の籠型ビニルシロキサン混合物)10.00g(n=10でR1にビニル基とエチル基が同数含まれるとして12.7mmol)、及び3-メタクリロキシプロピルメチルジエトキシシラン3.30g(12.7mmol)の仕込み量に変更して行い、アルコキシル基含有籠型シロキサン化合物Fを無色透明の粘性液体として12.64g、回収率95%で得た。
[A cage-type poly (vinyl-ethyl) siloxane mixture synthesized in Reference Example 3 as a cage-type siloxane compound [R 1 SiO 3/2 ] n (where n = 8, 10, 12, 14 is mainly included and n = 10 on average) Alkoxy-containing siloxane compound using 3-methacryloxypropylmethyldiethoxysilane [RMeSi (OEt) 2 ] (where R is a 3-methacryloxypropyl group) as dialkoxysilane. Synthesis of F]
The same operation as in Example 1 was carried out using 50 ml of toluene, 78 mg of tetramethylammonium hydroxide (0.86 mmol, 0.31 g as a 25% methanol solution), and a caged poly (vinyl-ethyl) siloxane mixture synthesized in Reference Example 3 [R 1 SiO 3 / 2 ] n (however, n-type vertical vinyl siloxane mixture mainly containing n = 8, 10, 12, 14 and n = 10 on average) 10.00g (n = 10 and R 1 contains the same number of vinyl groups and ethyl groups) 12.7 mmol), and 3.30 g (12.7 mmol) of 3-methacryloxypropylmethyldiethoxysilane were changed to 12.64 g of an alkoxyl group-containing cage-type siloxane compound F as a colorless transparent viscous liquid. Obtained at a rate of 95%.
得られたアルコキシル基含有籠型シロキサン化合物FのGPCを測定した結果、数平均分子量(Mn)=1176、重量平均分子量(Mw)=1543、Mw/Mn=1.312であった。また1H-NMRより籠型ポリ(ビニルーエチル)シロキサン混合物のエチル基のメチレン(n=10でR1にビニル基とエチル基が同数含まれるとして10H)0.6ppmのシグナルの積分比をS(cEt)=10とし、メタクリル基のアルケンの1Hに帰属される5.5ppmのシグナルの積分比S(M)、エトキシ基のメチレン2Hに帰属される3.7ppmのシグナルの積分比S(E)としたとき、S(cEt):S(M):S(E)=10:1.01:4.00であり、得られたアルコキシル基含有籠型シロキサン化合物Fは下記式(3F)
[(EtO)RMeSiO1/2]a − [R1SiO3/2]n − [O1/2Et]b (3F)
(但しRはメタクリロキシプロピル基であり、R1は同数のビニル基とエチル基である。)におけるn=10、a=1.01、b=0.99で表されることが分った。
As a result of measuring GPC of the obtained alkoxyl group-containing cage-type siloxane compound F, the number average molecular weight (Mn) = 1176, the weight average molecular weight (Mw) = 1543, and Mw / Mn = 1.112. In addition, from 1H-NMR, the integral ratio of 0.6 ppm signal of the methylene of the ethyl group in the cage poly (vinyl-ethyl) siloxane mixture (n = 10 and 10 H assuming that R 1 contains the same number of vinyl groups and ethyl groups) is S (cEt) = 10, the integration ratio S (M) of the signal of 5.5 ppm attributed to 1H of the alkene of the methacryl group, and the integration ratio S (E) of the signal of 3.7 ppm attributed to 2H of the ethoxy group methylene S (cEt): S (M): S (E) = 10: 1.01: 4.00, and the obtained alkoxyl group-containing cage-type siloxane compound F has the following formula (3F)
[(EtO) RMeSiO 1/2] a - [R 1 SiO 3/2] n - [O 1/2 Et] b (3F)
It was found that n = 10, a = 1.01, and b = 0.99 in R (wherein R is a methacryloxypropyl group and R 1 is the same number of vinyl groups and ethyl groups).
[アルコキシル基含有籠型シロキサン化合物Fを用いたシラノール基含有籠型シロキサン化合物F-OHの合成]
アルコキシル基含有籠型シロキサン化合物C 1.0gの代わりに実施例11で合成したアルコキシル基含有籠型シロキサン化合物F1.42g(式3FのRはメタクリロキシプロピル基でR1が同数のビニル基とエチル基でありa=1,b=1の分子量1045として計算 1.36mmol)を用い実施例6と同様の操作を行い、シラノール基含有籠型シロキサン化合物F-OHを0.89g、収率90%で得た。
[Synthesis of silanol group-containing cage-type siloxane compound F-OH using alkoxyl group-containing cage-type siloxane compound F]
Alkoxy group-containing cage-type siloxane compound C 1.0 g instead of alkoxyl group-containing cage-type siloxane compound F1.42 g synthesized in Example 11 (R in formula 3F is a methacryloxypropyl group and R 1 is the same number of vinyl and ethyl groups) And a calculation similar to that in Example 6 was performed using a molecular weight of 1045 with a = 1 and b = 1 and a molecular weight of 1045, and 0.89 g of silanol group-containing cage-type siloxane compound F-OH was obtained in a yield of 90%. .
得られたシラノール基含有籠型シロキサン化合物F-OHのGPCを測定した結果、数平均分子量(Mn)=1150、重量平均分子量(Mw)=1520、Mw/Mn=1.322であった。また1H-NMRよりエトキシ基に帰属されるシグナルは無く、IRからシラノールに帰属される3310cm-1付近のブロードのピークが観測された。これらのことからシラノール基含有籠型シロキサン化合物F-OHはアルコキシル基含有籠型シロキサン化合物Fのアルコキシル基がシラノール基に変換されたシラノール基含有籠型シロキサン化合物といえる。 As a result of measuring GPC of the obtained silanol group-containing cage-type siloxane compound F-OH, it was found that the number average molecular weight (Mn) = 1150, the weight average molecular weight (Mw) = 1520, and Mw / Mn = 1.322. From 1H-NMR, there was no signal attributed to the ethoxy group, and a broad peak around 3310 cm-1 attributed to silanol was observed from IR. From these facts, the silanol group-containing cage-type siloxane compound F-OH can be said to be a silanol group-containing cage-type siloxane compound in which the alkoxyl group of the alkoxyl group-containing cage-type siloxane compound F is converted to a silanol group.
Claims (7)
[R1SiO3/2]n (1)
(但し、R1はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1は互いに同じか異なるものであってもよく、nは8〜14の整数である。)で表される籠型シロキサン化合物に、
下記一般式(2)
R1R2Si(OR3) 2 (2)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。)で表されるジアルコキシシランを非極性溶媒及び塩基性触媒の存在下で付加させて得られることを特徴とするアルコキシル基含有籠型シロキサン化合物。 The following general formula (1)
[R 1 SiO 3/2 ] n (1)
(However, R 1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, R 1 may be the same or different from each other, and n is 8 Is an integer of ˜14).
The following general formula (2)
R 1 R 2 Si (OR 3 ) 2 (2)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 may be the same as or different from each other.) Is obtained by adding a dialkoxysilane represented by the above in the presence of a nonpolar solvent and a basic catalyst. An alkoxyl group-containing cage-type siloxane compound characterized by the above.
[(R3O)R1R2SiO1/2]a − [R1SiO3/2]n − [O1/2R3]b (3)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。また、a及びbは0〜3の数であって1≦a + b≦4の関係を満たす。更にnは8〜14の整数である。)で表される請求項1記載のアルコキシル基含有籠型シロキサン化合物。 The alkoxyl group-containing cage-type siloxane compound is represented by the following general formula (3)
[(R 3 O) R 1 R 2 SiO 1/2] a - [R 1 SiO 3/2] n - [O 1/2 R 3] b (3)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 , the substituents may be the same or different from each other, and a and b are 0 to 3 and satisfy the relationship 1 ≦ a + b ≦ 4. n is an integer of 8-14.) The alkoxyl group containing cage-type siloxane compound of Claim 1 represented by these.
[(HO)R1R2SiO1/2]a − [R1SiO3/2]n − [O1/2H]b (4)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1又はR2において、各置換基は互いに同じか異なるものであってもよい。また、a及びbは0〜3の数であって1≦a + b≦4の関係を満たす。更にnは8〜14の整数である。)で表せるシラノール基含有籠型シロキサン化合物。 The following general formula (4) obtained by hydrolyzing the alkoxyl group-containing cage-type siloxane compound according to any one of claims 1 to 3 in the presence of an acid or a basic catalyst.
[(HO) R 1 R 2 SiO 1/2] a - [R 1 SiO 3/2] n - [O 1/2 H] b (4)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, and in R 1 or R 2 , are each substituents the same as each other? And a and b are numbers from 0 to 3, satisfying the relationship 1 ≦ a + b ≦ 4, and n is an integer from 8 to 14.) Containing cage-type siloxane compound.
[R1SiO3/2]n (1)
(但し、R1はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1は互いに同じか異なるものであってもよく、nは8〜14の整数である。)で表される籠型シロキサン化合物と、
下記一般式(2)
R1R2Si(OR3) 2 (2)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。)で表されるジアルコキシシランとを[R1SiO3/2]n:R1R2Si(OR3) 2 =1モル:0.5〜2モルの範囲で混合し、非極性溶媒及び塩基性触媒の存在下で付加させることで、数平均分子量Mnが500〜2000の範囲であり、かつ、分子量分散度(重量平均分子量Mw/数平均分子量Mn)が1.0〜2.0であるアルコキシル基含有籠型シロキサン化合物を得ることを特徴とするアルコキシル基含有籠型シロキサン化合物の製造方法。 The following general formula (1)
[R 1 SiO 3/2 ] n (1)
(However, R 1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, R 1 may be the same or different from each other, and n is 8籠 -type siloxane compound represented by
The following general formula (2)
R 1 R 2 Si (OR 3 ) 2 (2)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 , each substituent may be the same or different from each other.) And a dialkoxysilane represented by [R 1 SiO 3/2 ] n : R 1 R 2 Si (OR 3 ) 2 = 1 mol: mixed in the range of 0.5 to 2 mol, added in the presence of a nonpolar solvent and a basic catalyst, the number average molecular weight Mn is in the range of 500 to 2000, and An alkoxyl group-containing cage-type siloxane compound having a molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.0 to 2.0 is obtained.
[R1SiO3/2]n (1)
(但し、R1はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R1は互いに同じか異なるものであってもよく、nは8〜14の整数である。)で表される籠型シロキサン化合物と、
下記一般式(2)
R1R2Si(OR3) 2 (2)
(但し、R1及びR2はビニル基、アルキル基、フェニル基、(メタ)アクリロイル基、アリル基又はオキシラン環を有する基から選ばれ、R3はメチル基またはエチル基から選ばれ、R1、R2又はR3において、各置換基は互いに同じか異なるものであってもよい。)で表されるジアルコキシシランとを[R1SiO3/2]n:R1R2Si(OR3) 2 =1モル:0.5〜2モルの範囲で混合し、 非極性溶媒及び塩基性触媒の存在下で付加させて得られる数平均分子量Mnが500〜2000の範囲であり、かつ、分子量分散度(重量平均分子量Mw/数平均分子量Mn)が1.0〜2.0のアルコキシル基含有籠型シロキサン樹脂を、酸または塩基触媒の存在下で加水分解することで、数平均分子量Mnが500〜2000の範囲であり、分子量分散度(重量平均分子量Mw/数平均分子量Mn)が1.0〜2.0であるシラノール基含有籠型シロキサン化合物を得ることを特徴とするシラノール基含有籠型シロキサン化合物の製造方法。 The following general formula (1)
[R 1 SiO 3/2 ] n (1)
(However, R 1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or a group having an oxirane ring, R 1 may be the same or different from each other, and n is 8籠 -type siloxane compound represented by
The following general formula (2)
R 1 R 2 Si (OR 3 ) 2 (2)
(However, R 1 and R 2 are selected from a group having a vinyl group, an alkyl group, a phenyl group, a (meth) acryloyl group, an allyl group or an oxirane ring, R 3 is selected from a methyl group or an ethyl group, and R 1 , R 2 or R 3 , each substituent may be the same or different from each other.) And a dialkoxysilane represented by [R 1 SiO 3/2 ] n : R 1 R 2 Si (OR 3 ) 2 = 1 mol: mixed in the range of 0.5 to 2 mol, The number average molecular weight Mn obtained by addition in the presence of a nonpolar solvent and a basic catalyst is in the range of 500 to 2000, and the molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) is 1.0 to 2.0. By hydrolyzing the alkoxyl group-containing cage-type siloxane resin in the presence of an acid or base catalyst, the number average molecular weight Mn is in the range of 500 to 2000, and the molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) A method for producing a silanol group-containing cage-type siloxane compound, characterized in that a silanol group-containing cage-type siloxane compound having a valence of 1.0 to 2.0 is obtained.
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TW097150700A TWI499619B (en) | 2007-12-27 | 2008-12-25 | Containing a curable poly cage-shaped structure of silicon oxide copolymer and its manufacturing method and use of the cage structure-containing curable silicon oxide copolymer of poly curable resin composition and cured |
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