JP2008266301A - New silicone compound, and raw material thereof and method for producing the silicone compound - Google Patents
New silicone compound, and raw material thereof and method for producing the silicone compound Download PDFInfo
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- JP2008266301A JP2008266301A JP2008056320A JP2008056320A JP2008266301A JP 2008266301 A JP2008266301 A JP 2008266301A JP 2008056320 A JP2008056320 A JP 2008056320A JP 2008056320 A JP2008056320 A JP 2008056320A JP 2008266301 A JP2008266301 A JP 2008266301A
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- silicone compound
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 107
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002994 raw material Substances 0.000 title description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 33
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 24
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 17
- 150000003377 silicon compounds Chemical class 0.000 claims description 16
- 239000012454 non-polar solvent Substances 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- 238000006243 chemical reaction Methods 0.000 description 39
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 28
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 239000012044 organic layer Substances 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- -1 silane compound Chemical class 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 101150065749 Churc1 gene Proteins 0.000 description 7
- 102100038239 Protein Churchill Human genes 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 230000010354 integration Effects 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010992 reflux Methods 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NUNPZNVZTQDOPX-UHFFFAOYSA-N (4-but-3-enylphenyl)-chloro-dimethylsilane Chemical compound C[Si](Cl)(C1=CC=C(C=C1)CCC=C)C NUNPZNVZTQDOPX-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 description 1
- CSBJCQMIXISILC-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl prop-2-enoate Chemical compound C[Si](C)(Cl)CCCOC(=O)C=C CSBJCQMIXISILC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WWZSYGZOOSSSIG-UHFFFAOYSA-N C[Si](Cl)(CC(CC(C)C)(C)C)C Chemical compound C[Si](Cl)(CC(CC(C)C)(C)C)C WWZSYGZOOSSSIG-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- WCEQVCWCZPWAJN-UHFFFAOYSA-N [chloro(dimethyl)silyl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](C)(C)Cl WCEQVCWCZPWAJN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical compound CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- KIGALSBMRYYLFJ-UHFFFAOYSA-N chloro-(2,3-dimethylbutan-2-yl)-dimethylsilane Chemical compound CC(C)C(C)(C)[Si](C)(C)Cl KIGALSBMRYYLFJ-UHFFFAOYSA-N 0.000 description 1
- ZRZLAQZGAAWEIF-UHFFFAOYSA-N chloro-(4-ethenylphenyl)-dimethylsilane Chemical compound C[Si](C)(Cl)C1=CC=C(C=C)C=C1 ZRZLAQZGAAWEIF-UHFFFAOYSA-N 0.000 description 1
- RTYNSTRFACIKRL-UHFFFAOYSA-N chloro-(4-methoxyphenyl)-dimethylsilane Chemical compound COC1=CC=C([Si](C)(C)Cl)C=C1 RTYNSTRFACIKRL-UHFFFAOYSA-N 0.000 description 1
- MEUXNEGJODESOX-UHFFFAOYSA-N chloro-cyclohexyl-dimethylsilane Chemical compound C[Si](C)(Cl)C1CCCCC1 MEUXNEGJODESOX-UHFFFAOYSA-N 0.000 description 1
- HKPQSAMLXJHFSU-UHFFFAOYSA-N chloro-cyclopentyl-dimethylsilane Chemical compound C[Si](C)(Cl)C1CCCC1 HKPQSAMLXJHFSU-UHFFFAOYSA-N 0.000 description 1
- ZLZGHBNDPINFKG-UHFFFAOYSA-N chloro-decyl-dimethylsilane Chemical compound CCCCCCCCCC[Si](C)(C)Cl ZLZGHBNDPINFKG-UHFFFAOYSA-N 0.000 description 1
- SFSURLOVKBVPAD-UHFFFAOYSA-N chloro-dimethyl-(2-methylpropyl)silane Chemical compound CC(C)C[Si](C)(C)Cl SFSURLOVKBVPAD-UHFFFAOYSA-N 0.000 description 1
- UTMBOOWVJPCANU-UHFFFAOYSA-N chloro-dimethyl-(4-methylphenyl)silane Chemical compound CC1=CC=C([Si](C)(C)Cl)C=C1 UTMBOOWVJPCANU-UHFFFAOYSA-N 0.000 description 1
- LNBWPBXZABQWBQ-UHFFFAOYSA-N chloro-dimethyl-(4-prop-1-en-2-ylphenyl)silane Chemical compound CC(=C)C1=CC=C([Si](C)(C)Cl)C=C1 LNBWPBXZABQWBQ-UHFFFAOYSA-N 0.000 description 1
- YBQPKOVSNHDRKD-UHFFFAOYSA-N chloro-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C[Si](C)(Cl)CCCOCC1CO1 YBQPKOVSNHDRKD-UHFFFAOYSA-N 0.000 description 1
- RZVDZQLEAUDZLO-UHFFFAOYSA-N chloro-dimethyl-naphthalen-1-ylsilane Chemical compound C1=CC=C2C([Si](C)(Cl)C)=CC=CC2=C1 RZVDZQLEAUDZLO-UHFFFAOYSA-N 0.000 description 1
- DFJITQMWZGWUJW-UHFFFAOYSA-N chloro-dimethyl-nonylsilane Chemical compound CCCCCCCCC[Si](C)(C)Cl DFJITQMWZGWUJW-UHFFFAOYSA-N 0.000 description 1
- DBKNGKYVNBJWHL-UHFFFAOYSA-N chloro-dimethyl-octylsilane Chemical compound CCCCCCCC[Si](C)(C)Cl DBKNGKYVNBJWHL-UHFFFAOYSA-N 0.000 description 1
- QZRWJJLUUOMZIT-UHFFFAOYSA-N chloro-dimethyl-pentylsilane Chemical compound CCCCC[Si](C)(C)Cl QZRWJJLUUOMZIT-UHFFFAOYSA-N 0.000 description 1
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 description 1
- YCXVDEMHEKQQCI-UHFFFAOYSA-N chloro-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)Cl YCXVDEMHEKQQCI-UHFFFAOYSA-N 0.000 description 1
- HXVPUKPVLPTVCQ-UHFFFAOYSA-N chloro-dimethyl-propylsilane Chemical compound CCC[Si](C)(C)Cl HXVPUKPVLPTVCQ-UHFFFAOYSA-N 0.000 description 1
- AVDUEHWPPXIAEB-UHFFFAOYSA-N chloro-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)Cl AVDUEHWPPXIAEB-UHFFFAOYSA-N 0.000 description 1
- ILASLZLYOTYKPR-UHFFFAOYSA-N chloro-heptyl-dimethylsilane Chemical compound CCCCCCC[Si](C)(C)Cl ILASLZLYOTYKPR-UHFFFAOYSA-N 0.000 description 1
- JQYKSDDVPXVEOL-UHFFFAOYSA-N chloro-hexyl-dimethylsilane Chemical compound CCCCCC[Si](C)(C)Cl JQYKSDDVPXVEOL-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- SIPHWXREAZVVNS-UHFFFAOYSA-N trichloro(cyclohexyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCCC1 SIPHWXREAZVVNS-UHFFFAOYSA-N 0.000 description 1
- FCMZRNUHEXJWGB-UHFFFAOYSA-N trichloro(cyclopentyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCC1 FCMZRNUHEXJWGB-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
Description
本発明は、新規な硬化性シリコーン化合物及びその原料、並びに硬化性シリコーン化合物の製造方法に関し、具体的には、硬化性官能基を複数有して、電子材料、光学材料、電子光学材料等として利用するのに適し、かつ、高分子材料に難燃性、耐熱性、電気絶縁性、表面特性、硬度、力学的強度、耐薬品性、透明性等を付与せしめるための添加剤としても利用可能な新規な硬化性シリコーン化合物及びその原料、並びにこのシリコーン化合物を得るための製造方法に関する。 The present invention relates to a novel curable silicone compound and a raw material thereof, and a method for producing the curable silicone compound. Specifically, the curable silicone compound has a plurality of curable functional groups and is used as an electronic material, an optical material, an electro-optical material, etc. Suitable for use, and can also be used as an additive to impart flame retardancy, heat resistance, electrical insulation, surface properties, hardness, mechanical strength, chemical resistance, transparency, etc. to polymer materials The present invention relates to a novel novel curable silicone compound, a raw material thereof, and a production method for obtaining the silicone compound.
一般式[ＲＳｉＯ3/2]nで表されるようなシルセスキオキサンに関しては、これまでに多くの研究が行われてきた。Chem. Rev. 1995, 95，1409にはBaneyらによるシルセスキオキサンに関する総説が記載されており、ラダー構造、完全縮合型構造及び不完全縮合構造のシルセスキオキサンのほかに、一定の構造を示さないアモルファス構造を有するシルセスキオキサン等が報告されている。また、Organometallics, 1991, 10, 2556によれば、シクロペンチルトリクロロシラン又はシクロへキシルトリクロロシランをアセトン中で加水分解することにより、不完全縮合構造のシルセスキオキサンが得られるとする。ここで、完全縮合型構造のシルセスキオキサンとは、複数の環状構造からなり、閉じた空間を形成するもの（いわゆるかご型シロキサン樹脂）を意味し、不完全縮合構造のシルセスキオキサンとは、完全縮合構造の少なくとも１箇所以上が塞がれておらず、空間が閉じていない
ものを意味する。
Many studies have been conducted on silsesquioxanes represented by the general formula [RSiO 3/2 ] n . Chem. Rev. 1995, 95, 1409 provides a review of silsesquioxane by Baney et al., In addition to the silsesquioxane of ladder structure, fully condensed structure and incompletely condensed structure, certain structures Silsesquioxane and the like having an amorphous structure that does not show the property have been reported. According to Organanometallics, 1991, 10, 2556, it is assumed that silsesquioxane having an incompletely condensed structure can be obtained by hydrolyzing cyclopentyltrichlorosilane or cyclohexyltrichlorosilane in acetone. Here, the silsesquioxane having a fully condensed structure means one having a plurality of cyclic structures and forming a closed space (so-called cage-type siloxane resin). Means that at least one part of the fully condensed structure is not blocked and the space is not closed.
このような完全縮合型又は不完全縮合型構造を有するシルセスキオキサンについては、例えば熱可塑性樹脂の改質剤、高分子材料の難燃剤、耐熱性、耐候性、電気絶縁性、表面特性、硬度、力学的強度、耐薬品性等を向上させるための添加剤として利用されている。最近ではポリマーのビルディングブロックとして用いるために、他の樹脂との相溶性及び重合性を付与するために種々の官能基を導入する方法が検討されている。一般的には、末端にシラノール基（Si-OH）を有したシルセスキオキサンがよく知られており、シラノールの反応性を利用して新たなシルセスキオキサンを誘導することが行われている。また、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Si-ONaを反応性活性基として有する不完全縮合型構造シルセスキオキサンが合成され、目的に応じた官能基を有するクロロシランを反応させることで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及び２参照）。
For silsesquioxanes having such a fully condensed or incompletely condensed structure, for example, thermoplastic resin modifiers, polymeric material flame retardants, heat resistance, weather resistance, electrical insulation, surface properties, It is used as an additive for improving hardness, mechanical strength, chemical resistance and the like. Recently, in order to use as a building block of a polymer, a method of introducing various functional groups in order to impart compatibility with other resins and polymerizability has been studied. In general, silsesquioxanes having a silanol group (Si-OH) at the terminal are well known, and the silanol reactivity is used to derive a new silsesquioxane. Yes. Incompletely condensed structure having Si-ONa as a reactive active group by hydrolyzing a silane compound having a trifunctional hydrolyzable group in an organic solvent in the presence of a monovalent alkali metal hydroxide. Silsesquioxane has been synthesized, and a derivative of silsesquioxane has been proposed by reacting chlorosilane having a functional group according to the purpose (see
しかしながら、一般に、シルセスキオキサンの誘導体は他の樹脂との相溶性が悪く、均一に混合することができなかったり、また、塗膜にした場合に白化してしまったり、塗膜からブリードアウトするために添加量に制限があるなどの問題がある。更には、従来のシルセスキオキサンの誘導体は、電子材料や光学材料として用いる場合など、ポリマーのビルディングブロックとして利用するためには、誘導体自身が硬化性を有することが望まれるが、本発明者等が知る限りにおいて、このような特性を十分に備えたものは報告された例がない。
そこで、本発明者等は、他の樹脂との相溶性や硬化性等に関する従来のシルセスキオキサン誘導体が抱える問題点を解消するために鋭意検討した結果、分子量分布が制御され、かつ、所定の硬化性官能基を複数有した水酸基含有シルセスキオキサンの合成に成功し、この水酸基含有シルセスキオキサンを原料にして得た硬化性シリコーン化合物が、これらの問題をすべて解消することができることを見出し、本発明を完成した。 Therefore, the present inventors have intensively studied to solve the problems of conventional silsesquioxane derivatives related to compatibility and curability with other resins, and as a result, the molecular weight distribution is controlled and predetermined. Succeeding in the synthesis of a hydroxyl group-containing silsesquioxane having a plurality of curable functional groups, the curable silicone compound obtained from the hydroxyl group-containing silsesquioxane as a raw material can solve all of these problems. The present invention has been completed.
従って、本発明の目的は、他の樹脂との相溶性に優れると共に、硬化性にも優れた新規な硬化性シリコーン化合物を提供することにある。
また、本発明の別の目的は、上記硬化性シリコーン化合物を得るための原料になる水酸基含有シルセスキオキサン化合物を提供することにある。
更に、本発明の別の目的は、上記硬化性シリコーン化合物を短時間で、かつ、低コストで得ることができる硬化性シリコーン化合物の製造方法を提供することにある。
Accordingly, an object of the present invention is to provide a novel curable silicone compound that is excellent in compatibility with other resins and also excellent in curability.
Another object of the present invention is to provide a hydroxyl group-containing silsesquioxane compound as a raw material for obtaining the curable silicone compound.
Furthermore, another object of the present invention is to provide a method for producing a curable silicone compound capable of obtaining the curable silicone compound in a short time and at a low cost.
すなわち、本発明は、下記一般式（１）
[ＲＳｉＯ3/2]n[Ｒ1(ＣＨ3)2ＳｉＯ1/2]m （１）
で表される硬化性シリコーン化合物である。
〔但し、Ｒ及びＲ1は、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[RSiO 3/2 ] n [R 1 (CH 3 ) 2 SiO 1/2 ] m (1)
It is a curable silicone compound represented by.
[However, R and R 1 are a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, and a carbon number. 2-3 alkenyl groups or the following formulas (2) to (4)
また、本発明は、下記一般式（５）
[ＲＳｉＯ3/2]n [ＨＯ1/2]m （５）
で表される水酸基含有シルセスキオキサン化合物である。
〔但し、Ｒは、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[RSiO 3/2 ] n [HO 1/2 ] m (5)
It is a hydroxyl group containing silsesquioxane compound represented by these.
[However, R is a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2-3 carbon atoms. Or an alkenyl group of the following formulas (2) to (4)
更に、本発明は、上記の硬化性シリコーン化合物の製造方法であって、下記一般式（６）
ＲＳｉＸ3 （６）
〔但し、Ｒは、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[ＲＳｉＯ3/2]n [ＨＯ1/2]m （５）
（但し、Ｒは上記と同じである。ｎは６〜２０の整数、ｍは１〜６の整数を示し、ｎ／ｍが１〜１０の範囲である）で表される水酸基含有シルセスキオキサン化合物を生成した後、モノクロロシランと反応させることを特徴とする硬化性シリコーン化合物の製造方法である。
Furthermore, the present invention is a method for producing the above curable silicone compound, which comprises the following general formula (6):
RSix 3 (6)
[However, R is a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2-3 carbon atoms. Or an alkenyl group of the following formulas (2) to (4)
[RSiO 3/2 ] n [HO 1/2 ] m (5)
(Wherein R is the same as above, n is an integer of 6 to 20, m is an integer of 1 to 6, and n / m is in the range of 1 to 10). This is a method for producing a curable silicone compound characterized by reacting with monochlorosilane after producing a sun compound.
本発明における硬化性シリコーン化合物の製造方法では、先ず、上記一般式（６）で表されるケイ素化合物を所定の溶媒及び塩基性触媒の存在下で加水分解して、上記一般式（５）で表される水酸基含有シルセスキオキサン化合物を得て、この水酸基含有シルセスキオキサン化合物をモノクロロシラン類と反応させることで、上記一般式（１）の硬化性シリコーン化合物を得る。 In the method for producing a curable silicone compound in the present invention, first, the silicon compound represented by the general formula (6) is hydrolyzed in the presence of a predetermined solvent and a basic catalyst, and the general formula (5) By obtaining the hydroxyl group-containing silsesquioxane compound represented and reacting the hydroxyl group-containing silsesquioxane compound with monochlorosilanes, the curable silicone compound of the above general formula (1) is obtained.
ここで、一般式（６）及び後述する一般式（７）におけるケイ素化合物のそれぞれのＲについて、水素原子以外の置換基の具体例を挙げると、炭素数２〜３のアルケニルとしては、ビニル、アリル等を挙げることができる。１〜１０の直鎖状もしくは分岐状のアルキル基としては、メチル、エチル、プロピル、１−メチルエチル、ブチル、２−メチルプロピル、１，１−ジメチルエチル、ペンチル、へキシル、１，１，２−トリメチルプロピル、ヘプチル、オクチル、２，２，４−トリメチルペンチル、ノニル、デシル等を挙げることができる。炭素数４〜１０のシクロアルキル基としては、シクロペンチル、シクロへキシル等を挙げることができる。炭素数６〜１０のアリール含有基としては、フェニル、４−メチルフェニル、４−、メトキシフェニル、４−ビニルフェニル、４−（１−メチルビニル）フェニル、４−（３−ブテニル）フェニル、ナフチル等を挙げることができる。上記式（２）の例としては、メタクリロキシメチル、３−メタクリロキシプロピル、３−アクリロキシプロピル等を挙げることができる。上記式（３）の例としては３−グリシドキシプロピル等を挙げることができる。上記式（４）の例としては２−（３，４―エポキシシクロへキシル）エチル等を挙げることができる。尚、これらの官能基は一般的なものであってこれらに限定されるものではない。一般式（１）の硬化性シリコーン化合物は、少なくとも２以上の硬化性官能基を有する。即ち、一般式（１）の硬化性シリコーン化合物が、例えばケイ素１６個からなるとすると、少なくともすべてのＲの１２．５モル％以上が上記の硬化性官能基になるように一般式（６）及び（７）のケイ素化合物の仕込み量を調整するようにする。 Here, specific examples of substituents other than a hydrogen atom for each R of the silicon compound in the general formula (6) and the general formula (7) described later include vinyl, alkenyl having 2 to 3 carbon atoms, Examples include allyl. Examples of the linear or branched alkyl group of 1 to 10 include methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1, Examples thereof include 2-trimethylpropyl, heptyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl and the like. Examples of the cycloalkyl group having 4 to 10 carbon atoms include cyclopentyl and cyclohexyl. Examples of the aryl-containing group having 6 to 10 carbon atoms include phenyl, 4-methylphenyl, 4-, methoxyphenyl, 4-vinylphenyl, 4- (1-methylvinyl) phenyl, 4- (3-butenyl) phenyl, and naphthyl. Etc. Examples of the formula (2) include methacryloxymethyl, 3-methacryloxypropyl, 3-acryloxypropyl and the like. Examples of the formula (3) include 3-glycidoxypropyl. Examples of the formula (4) include 2- (3,4-epoxycyclohexyl) ethyl. In addition, these functional groups are general and are not limited to these. The curable silicone compound of the general formula (1) has at least two or more curable functional groups. That is, if the curable silicone compound of the general formula (1) is composed of, for example, 16 silicon, the general formula (6) and the curable functional group so that at least 12.5 mol% of all R are the above curable functional groups. The amount of silicon compound (7) is adjusted.
また、一般式（６）におけるＸは加水分解性基であり、その例としては塩素原子、または炭素数１〜４のアルキルオキシ基（アルコキシル基）が挙げられる。このうち、アルコキシル基としてはメトキシ基、エトキシ基、ｎ-プロポキシ基、ｉ-プロポキシ基、ｎ-ブトキシ基、ｉ-ブトキシ基、ｔ-ブトキシ基等が挙げられる。なかでも反応性が高いメトキシ基であるのが好ましい。 Moreover, X in General formula (6) is a hydrolysable group, and a chlorine atom or a C1-C4 alkyloxy group (alkoxyl group) is mentioned as the example. Among these, examples of the alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, and a t-butoxy group. Of these, a methoxy group having high reactivity is preferable.
一般式（６）で表されるケイ素化合物については、少なくとも１種のケイ素化合物のＲが、炭素数２〜３のアルケニル基、及び下記式（２）〜（４）からなる群から選ばれたいずれかの硬化性官能基である１種以上のケイ素化合物を用いるようにする。
また、一般式（６）で表されるケイ素化合物の加水分解反応で使用する塩基性触媒の使用量については、ケイ素化合物（ＲＳｉＸ3）と塩基性触媒との割合が、ＲＳｉＸ3：塩基性触媒＝４〜１０モル：１モルとなるようにする。塩基性触媒の使用量がこの範囲内であれば、高分子量のシルセスキオキサン化合物の生成が防止され、以下で説明するような不完全縮合型の水酸基含有シルセスキオキサン化合物を得ることができる。塩基性触媒の使用量が上記範囲より少なくなると、縮合反応が速くゲル化の原因となり、反対に、使用量が多くなると縮合反応が抑制されて、未反応のシラノール基が多く残存したまま反応が完結しない。 As for the amount of basic catalyst used in the hydrolysis reaction of silicon compound represented by the general formula (6), the ratio of silicon compound (RSiX 3) with a basic catalyst, RSiX 3: a basic catalyst = 4-10 mol: 1 mol. When the amount of the basic catalyst used is within this range, formation of a high molecular weight silsesquioxane compound is prevented, and an incompletely condensed hydroxyl group-containing silsesquioxane compound as described below can be obtained. it can. If the amount of the basic catalyst used is less than the above range, the condensation reaction will quickly cause gelation. Conversely, if the amount used is increased, the condensation reaction will be suppressed and the reaction will continue with many unreacted silanol groups remaining. Not complete.
一般式（６）で表されるケイ素化合物を加水分解する際に用いる塩基性触媒については、例えば、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等の水酸化アンモニウム塩を挙げることができる。なかでも、触媒活性が高いことからテトラメチルアンモニウムヒドロキシドが好ましく用いられる。なお、塩基性触媒は、通常、水溶液として使用される。 The basic catalyst used for hydrolyzing the silicon compound represented by the general formula (6) is, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyl Mention may be made of ammonium hydroxide salts such as triethylammonium hydroxide. Of these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity. The basic catalyst is usually used as an aqueous solution.
また、加水分解の際に用いる有機溶媒については、反応速度制御の観点から極性溶媒と非極性溶媒の２相系を用いて行うのが好ましい。このうち、極性溶媒について具体例を示すと、メタノール、エタノール、２−プロパノール等のアルコール類を挙げることができる。非極性溶媒について具体例を示すと、トルエン、キシレン、ベンゼン等を挙げることができる。これらのなかでも2-プロパノールとトルエンが好ましい。極性溶媒と非極性溶媒の体積比については、極性溶媒／非極性溶媒＝１／５〜５／１であるのが好ましく、１／２がより好ましい。 Moreover, about the organic solvent used in the case of a hydrolysis, it is preferable to carry out using the two phase system of a polar solvent and a nonpolar solvent from a viewpoint of reaction rate control. Among these, specific examples of polar solvents include alcohols such as methanol, ethanol, and 2-propanol. Specific examples of the nonpolar solvent include toluene, xylene, benzene and the like. Of these, 2-propanol and toluene are preferred. The volume ratio of the polar solvent to the nonpolar solvent is preferably polar solvent / nonpolar solvent = 1/5 to 5/1, and more preferably 1/2.
加水分解反応の反応条件については、反応温度は０〜６０℃が好ましく、２０〜４０℃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加水分解性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、６０℃より高いと反応速度が速すぎるために複雑な縮合反応が進行してしまい、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加水分解性基が未反応の状態で残存してしまう状態となる。 About the reaction conditions of a hydrolysis reaction, 0-60 degreeC is preferable and 20-40 degreeC is more preferable. If the reaction temperature is lower than 0 ° C, the reaction rate becomes slow and the hydrolyzable group remains in an unreacted state, resulting in a long reaction time. On the other hand, if the reaction temperature is higher than 60 ° C, the reaction rate is too high. Complicated condensation reaction proceeds, and as a result, high molecular weight of the hydrolysis product is promoted. 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 hydrolyzable group remains in an unreacted state.
上記加水分解反応では水の存在が必須であるが、これは塩基性触媒の水溶液から供給することもでき、別途水として加えてもよい。水の量は加水分解性基を加水分解するに足る量以上、好ましくは理論量の１．０〜１．５倍量であるのがよい。この範囲より少ないと加水分解性基が未反応の状態で残存してしまい、反対に多くなると反応の進行が速く、ゲル化の原因となる。 In the hydrolysis reaction, the presence of water is essential, but this can be supplied from an aqueous solution of a basic catalyst or added separately as water. The amount of water is not less than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. When the amount is less than this range, the hydrolyzable group remains in an unreacted state, while when the amount is larger, the reaction proceeds rapidly and causes gelation.
加水分解反応終了後は、例えば、弱酸性水溶液を用いて中和し、この溶液を食塩水等で洗浄し、系中の塩基性触媒、水分及びその他の不純物を十分に取り除いたのち、更に無水硫酸マグネシウム等の乾燥剤で乾燥し、減圧濃縮等の手段を用いることで水酸基含有シルセスキオキサン化合物を回収することができる。この際、完全に中和すためには弱酸性水溶液を過剰に加えることが好ましく、具体的には弱酸性水溶液を塩基性触媒のモル比に対して１.０〜１．５倍量が好ましく、１．２５倍量がより好ましい。少量でも塩基性触媒が残存すると、残存しているシラノール基が反応し高分子量化する。弱酸性水溶液としては硫酸希釈水溶液、塩酸希釈水溶液、クエン酸水溶液、酢酸水溶液、塩化アンモニウム水溶液、リンゴ酸水溶液、リン酸水溶液、シュウ酸水溶液等を用いることができる。 After completion of the hydrolysis reaction, for example, neutralize with a weakly acidic aqueous solution, wash this solution with a saline solution, etc., and after sufficiently removing the basic catalyst, moisture and other impurities in the system, further anhydrous The hydroxyl group-containing silsesquioxane compound can be recovered by drying with a desiccant such as magnesium sulfate and using means such as vacuum concentration. At this time, in order to completely neutralize, it is preferable to add a weakly acidic aqueous solution in excess. Specifically, the weakly acidic aqueous solution is preferably 1.0 to 1.5 times the molar ratio of the basic catalyst. 1.25 times the amount is more preferable. If the basic catalyst remains even in a small amount, the remaining silanol groups react to increase the molecular weight. As the weakly acidic aqueous solution, sulfuric acid diluted aqueous solution, hydrochloric acid diluted aqueous solution, citric acid aqueous solution, acetic acid aqueous solution, ammonium chloride aqueous solution, malic acid aqueous solution, phosphoric acid aqueous solution, oxalic acid aqueous solution and the like can be used.
上記で得られた水酸基含有シルセスキオキサン化合物は、次の一般式（５）で表すことができる。
[ＲＳｉＯ3/2]n[ＨＯ1/2]m （５）
〔但し、Ｒは、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[RSiO 3/2 ] n [HO 1/2 ] m (5)
[However, R is a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2-3 carbon atoms. Or an alkenyl group of the following formulas (2) to (4)
一般式（５）で表される水酸基含有シルセスキオキサン化合物は、末端に一部シラノール基を有して完全には閉じた空間を形成していないと考えられることから不完全縮合型のシルセスキオキサンである。 Since the hydroxyl group-containing silsesquioxane compound represented by the general formula (5) is considered to have a partly silanol group at the terminal and does not form a completely closed space, the incompletely condensed silyl Sesquioxane.
そして、一般式（５）で表される水酸基含有シルセスキオキサン化合物にモノクロロシランを反応させるようにする。この際に用いるモノクロロシランは、好ましくは下記一般式（７）
一般式（７）で表されるモノクロロシランの具体例を挙げると、ジメチルビニルクロロシラン、ジメチルアリルクロロシラン、トリメチルクロロシラン、ジメチルエチルクロロシラン、ジメチルプロピルクロロシラン、ジメチル−１−メチルエチルクロロシラン、ジメチルブチルクロロシラン、ジメチル−２−メチルプロピルクロロシラン、ジメチル−１，１−ジメチルエチルクロロシラン、ジメチルペンチルクロロシラン、ジメチルへキシルクロロシラン、ジメチル−１，１，２−トリメチルプロピルクロロシラン、ジメチルヘプチルクロロシラン、ジメチルオクチルクロロシラン、ジメチル−２，２，４−トリメチルペンチルクロロシラン、ジメチルノニルクロロシラン、ジメチルデシルクロロシラン、ジメチルシクロペンチルクロロシラン、ジメチルシクロへキシルクロロシラン、ジメチルフェニルクロロシラン、ジメチル−４−メチルフェニルクロロシラン、ジメチル−４−メトキシフェニルクロロシラン、ジメチル−４−ビニルフェニルクロロシラン、ジメチル−４−（１−メチルビニル）フェニルクロロシラン、ジメチル−４−（３−ブテニル）フェニルクロロシラン、ジメチルナフチルクロロシラン、ジメチルメタクリロキシメチルクロロシラン、ジメチル−３−メタクリロキシプロピルクロロシラン、ジメチル−３−アクリロキシプロピルクロロシラン、ジメチル−３−グリシドキシプロピルクロロシラン、ジメチル−２−（３，４−エポキシシクロへキシル）エチルクロロシラン、ジメチルクロロシラン等を例示することができる。ここで、一般式（１）の硬化性シリコーン化合物は、少なくとも２以上の硬化性官能基を有する。例えば、一般式（１）の硬化性シリコーン化合物がケイ素１６個からなるとすると、少なくともすべてのＲ及びＲ1の１２．５モル％以上が炭素数２〜３のアルケニル基、及び式（２）〜（４）からなる群から選ばれたいずれかの硬化性官能基になるように一般式（６）及び（７）のケイ素化合物の仕込み量を調整する。すなわち、一般式（６）及び（７）のケイ素化合物においては、必要に応じそれぞれの置換基Ｒ及びＲ1が異なる２種以上の混合物を用いるようにすればよい。 Specific examples of the monochlorosilane represented by the general formula (7) include dimethylvinylchlorosilane, dimethylallylchlorosilane, trimethylchlorosilane, dimethylethylchlorosilane, dimethylpropylchlorosilane, dimethyl-1-methylethylchlorosilane, dimethylbutylchlorosilane, dimethyl -2-methylpropylchlorosilane, dimethyl-1,1-dimethylethylchlorosilane, dimethylpentylchlorosilane, dimethylhexylchlorosilane, dimethyl-1,1,2-trimethylpropylchlorosilane, dimethylheptylchlorosilane, dimethyloctylchlorosilane, dimethyl-2, 2,4-trimethylpentylchlorosilane, dimethylnonylchlorosilane, dimethyldecylchlorosilane, dimethylcyclopentylchlorosilane , Dimethylcyclohexylchlorosilane, dimethylphenylchlorosilane, dimethyl-4-methylphenylchlorosilane, dimethyl-4-methoxyphenylchlorosilane, dimethyl-4-vinylphenylchlorosilane, dimethyl-4- (1-methylvinyl) phenylchlorosilane, dimethyl -4- (3-butenyl) phenylchlorosilane, dimethylnaphthylchlorosilane, dimethylmethacryloxymethylchlorosilane, dimethyl-3-methacryloxypropylchlorosilane, dimethyl-3-acryloxypropylchlorosilane, dimethyl-3-glycidoxypropylchlorosilane, dimethyl Examples include -2- (3,4-epoxycyclohexyl) ethylchlorosilane, dimethylchlorosilane, and the like. Here, the curable silicone compound of the general formula (1) has at least two curable functional groups. For example, when the curable silicone compound of the general formula (1) is composed of 16 silicons, at least 12.5 mol% of all R and R 1 are alkenyl groups having 2 to 3 carbon atoms, and the formulas (2) to The amount of the silicon compound of the general formulas (6) and (7) is adjusted so as to be any curable functional group selected from the group consisting of (4). That is, in the silicon compounds of the general formulas (6) and (7), a mixture of two or more different substituents R and R 1 may be used as necessary.
また、一般式（５）の水酸基含有シルセスキオキサン化合物とモノクロロシランとの反応は、好ましくは塩基性条件下で行うようにするのがよい。塩基性条件については特に制限されず、公知の反応方法を利用することができ、例えば、有機溶媒としてテトラヒドロフランを使用し、塩基としてトリエチルアミン存在下で一般式（５）の水酸基含有シルセスキオキサン化合物とモノクロロシランとを反応させてもよく、或いは、溶媒兼塩基としてピリジンを用いて水酸基含有シルセスキオキサン化合物とモノクロロシランとを反応させてもよい。 The reaction between the hydroxyl group-containing silsesquioxane compound of the general formula (5) and monochlorosilane is preferably carried out under basic conditions. The basic conditions are not particularly limited, and a known reaction method can be used. For example, tetrahydrofuran is used as an organic solvent, and a hydroxyl group-containing silsesquioxane compound of the general formula (5) in the presence of triethylamine as a base. And monochlorosilane may be reacted, or a hydroxyl group-containing silsesquioxane compound and monochlorosilane may be reacted using pyridine as a solvent and base.
上記水酸基含有シルセスキオキサン化合物とモノクロロシランとの反応条件については、例えば水酸基含有シルセスキオキサン化合物を０．１〜２．０Ｍのテトラヒドロフランに溶解し、水酸基に対して１当量以上のトリエチルアミンを使用するか、或いは溶媒兼塩基として水酸基含有シルセスキオキサンを水酸基含有シルセスキオキサンに対して０．１〜２．０Ｍのピリジンに溶解した混合液を窒素等の不活性ガス雰囲気下、室温でモノクロロシランを１時間かけて滴下し、その後、室温で２時間以上撹拌を行う。この際、反応時間が短いと、反応が完結しない場合がある。反応終了後、トルエンと水を加え、一般式（１）の硬化性シリコーン化合物をトルエンに溶解し、反応によって生じた塩を水層に溶解し除去する。有機層を硫酸マグネシウム等の乾燥剤を用いて乾燥し、使用した塩基及び溶媒を減圧濃縮によって除去することで、一般式（１）の硬化性シリコーン化合物を得ることができる。 Regarding the reaction conditions of the hydroxyl group-containing silsesquioxane compound and monochlorosilane, for example, the hydroxyl group-containing silsesquioxane compound is dissolved in 0.1 to 2.0 M tetrahydrofuran, and 1 equivalent or more of triethylamine is added to the hydroxyl group. A mixed solution prepared by dissolving a hydroxyl group-containing silsesquioxane as a solvent and base in 0.1 to 2.0 M pyridine with respect to the hydroxyl group-containing silsesquioxane as a solvent and base, under an inert gas atmosphere such as nitrogen, at room temperature Then, monochlorosilane is added dropwise over 1 hour, followed by stirring at room temperature for 2 hours or more. At this time, if the reaction time is short, the reaction may not be completed. After completion of the reaction, toluene and water are added, the curable silicone compound of the general formula (1) is dissolved in toluene, and the salt generated by the reaction is dissolved in the aqueous layer and removed. The organic layer is dried using a drying agent such as magnesium sulfate, and the used base and solvent are removed by concentration under reduced pressure, whereby the curable silicone compound of the general formula (1) can be obtained.
モノクロロシランの使用量については、例えば一般式（７）で表されるモノクロロシランの場合、一般式（５）で表される水酸基含有シルセスキオキサン化合物のシラノール基を捕捉するにたる量以上、好ましくは理論量の１．０〜１．５倍量であるのがよい。過剰に加えても問題はないが、後処理の際、未反応モノクロロシランが残存しているとジシロキサンが生成するため精製が困難になる。なお、後処理の際生じるジシロキサンは沸点の低いものであれば減圧濃縮により除去できる。沸点の高いものは理論量で反応を行い、未反応モノクロロシランを残存させないようにしジシロキサンが生成しないようにすればよい。 For the amount of monochlorosilane used, for example, in the case of monochlorosilane represented by the general formula (7), the amount used to capture the silanol group of the hydroxyl group-containing silsesquioxane compound represented by the general formula (5) is more than, The amount is preferably 1.0 to 1.5 times the theoretical amount. Although there is no problem if it is added excessively, if unreacted monochlorosilane remains during post-treatment, purification is difficult because disiloxane is formed. In addition, if the disiloxane produced in the post-treatment has a low boiling point, it can be removed by concentration under reduced pressure. Those having a high boiling point may be reacted in a theoretical amount so that unreacted monochlorosilane does not remain and disiloxane is not generated.
そして、上記水酸基含有シルセスキオキサン化合物とモノクロロシランとの反応により、下記一般式（１）で表される硬化性シリコーン化合物を得ることができる。
[ＲＳｉＯ3/2]n[Ｒ1(ＣＨ3)2ＳｉＯ1/2]m （１）
〔但し、Ｒ及びＲ1は、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は上記式（２）〜（４）（但し、式中のlは１〜３の整数であり、Ｒ2は水素原子又はメチル基を示す）から選ばれ、Ｒ及びＲ1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が、少なくとも一般式（１）で表される１分子中には、炭素数２〜３のアルケニル基、及び式（２）〜（４）からなる群から選ばれたいずれかの硬化性官能基を２以上有し、かつ、Ｒのうち少なくとも１つが上記硬化性官能基である。また、ｎは６〜２０の整数、ｍは１〜６の整数を示し、ｎ／ｍが１〜１０の範囲である。更に、Ｍｗ＝５００〜５０００であり、Ｍｗ／Ｍｎ＝１．０〜１．５の範囲である。〕１分子中に硬化性官能基を２以上含まないとポリマーのビルディングブロックとして用いる場合、架橋により十分なネットワークを広げることができないため好ましくない。
And the curable silicone compound represented by following General formula (1) can be obtained by reaction of the said hydroxyl-containing silsesquioxane compound and monochlorosilane.
[RSiO 3/2 ] n [R 1 (CH 3 ) 2 SiO 1/2 ] m (1)
[However, R and R 1 are a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, and a carbon number. 2 to 3 alkenyl groups or the above formulas (2) to (4) (wherein l is an integer of 1 to 3 and R 2 represents a hydrogen atom or a methyl group) In R 1 , each substituent may be the same as or different from each other, but at least in one molecule represented by the general formula (1), the alkenyl group having 2 to 3 carbon atoms and the formula (2) It has two or more curable functional groups selected from the group consisting of (4) and at least one of R is the curable functional group. Moreover, n shows the integer of 6-20, m shows the integer of 1-6, n / m is the range of 1-10. Furthermore, it is Mw = 500-5000 and is the range of Mw / Mn = 1.0-1.5. When two or more curable functional groups are not contained in one molecule, it is not preferable when used as a polymer building block because a sufficient network cannot be expanded by crosslinking.
一般式（１）で表されるシリコーン化合物は、一般式（５）で表される不完全縮合型のシルセスキオキサンから誘導されているため、籠型シロキサンと類似した構造をとっている。即ち、一般式（１）で表されるシリコーン化合物は籠型シロキサンの特性を保持しており、且つ、他の樹脂との相溶性に優れる。 Since the silicone compound represented by the general formula (1) is derived from the incompletely condensed silsesquioxane represented by the general formula (5), it has a structure similar to that of the cage siloxane. That is, the silicone compound represented by the general formula (1) retains the characteristics of cage-type siloxane and is excellent in compatibility with other resins.
また、一般式（１）の硬化性シリコーン化合物は、原料として上記一般式（５）の水酸基含有シルセスキオキサン化合物より合成していることから、分子量分布が制御され、得られたシリコーン化合物のＭｗは５００〜５０００、好ましくは５００〜２０００であり、分子量の分布を表すＭｗ／Ｍｎは１．０〜１．５の範囲内である（Mw：重量平均分子量、Mn：数平均分子量）。 Moreover, since the curable silicone compound of the general formula (1) is synthesized from the hydroxyl group-containing silsesquioxane compound of the general formula (5) as a raw material, the molecular weight distribution is controlled and the obtained silicone compound Mw is 500 to 5000, preferably 500 to 2000, and Mw / Mn representing the distribution of molecular weight is in the range of 1.0 to 1.5 (Mw: weight average molecular weight, Mn: number average molecular weight).
本発明によれば、硬化性官能基を２つ以上含む硬化性シリコーン化合物を高収率で得ることができる。さらに、この硬化性シリコーン化合物はシリコーン系硬化性樹脂や有機硬化性樹脂との相溶性があり、ヒドロシリル化、ラジカル重合性樹脂組成物の原料として広く使用でき、また、高分子材料の難燃性、耐熱性、電気絶縁性、表面特性、硬度、力学的強度、耐薬品性等を向上させるための添加剤としても利用できる。 According to the present invention, a curable silicone compound containing two or more curable functional groups can be obtained in high yield. Furthermore, this curable silicone compound is compatible with silicone-based curable resins and organic curable resins, and can be widely used as a raw material for hydrosilylation and radical polymerizable resin compositions. It can also be used as an additive for improving heat resistance, electrical insulation, surface characteristics, hardness, mechanical strength, chemical resistance, and the like.
また、本発明における水酸基含有シルセスキオキサン化合物は反応性に高い水酸基を有しているため、上記のような特性を持つ有用な新規な硬化性シリコーン化合物を誘導することができ、かつ、収率良く合成する手段として利用できる。 In addition, since the hydroxyl group-containing silsesquioxane compound in the present invention has a highly reactive hydroxyl group, it is possible to derive a useful novel curable silicone compound having the above-mentioned characteristics and It can be used as a means of combining efficiently.
以下、実施例及び比較例に基づいて本発明を更に詳細に説明する。なお、本発明はこれらの実施例等によりその範囲を限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples. The scope of the present invention is not limited by these examples.
撹拌機及び滴下ロートを備えた反応容器に、溶媒として２−プロパノール(ＩＰＡ)２０５ｍＬ及びトルエン４１１ｍＬを入れ、塩基性触媒として２６％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）５４．９ｇ（１５６ミリモル）を装入した。また、滴下ロートにＩＰＡ１３６ｍＬ、トリメトキシメチルシラン（東レ・ダウコーニング・シリコーン株式会社製ＳＺ−６０７０）４６．６ｇ（３４２ミリモル）、及びトリメトキシビニルシラン（信越化学工業株式会社製ＫＢＭ−１００３）５０．７ｇ（３４２ミリモル）を入れて、反応容器を撹拌しながら、室温で３時間かけて滴下した。滴下終了後、室温で５時間撹拌した。５時間撹拌後、１０％クエン酸水溶液を加え２時間撹拌して中和した。水層をトルエンで抽出し、有機層を飽和食塩水で２回洗浄し、有機層を硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで加水分解生成物（水酸基含有シルセスキオキサン化合物）を４６．１ｇ（回収率８６％）得た。この水酸基含有シルセスキオキサン化合物は種々の有機溶剤に可溶な無色粘性液体であった。 In a reaction vessel equipped with a stirrer and a dropping funnel, 205 mL of 2-propanol (IPA) and 411 mL of toluene were placed, and 54.9 g (156 mmol) of 26% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) was used as a basic catalyst. Was loaded. In addition, 136 mL of IPA, 46.6 g (342 mmol) of trimethoxymethylsilane (SZ-6070 manufactured by Toray Dow Corning Silicone Co., Ltd.), and trimethoxyvinylsilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) 50. 7 g (342 mmol) was added, and the reaction vessel was added dropwise at room temperature over 3 hours while stirring. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, a 10% aqueous citric acid solution was added and the mixture was stirred for 2 hours for neutralization. The aqueous layer was extracted with toluene, the organic layer was washed twice with saturated brine, and the organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 46.1 g (recovery rate: 86%) of a hydrolysis product (hydroxyl group-containing silsesquioxane compound). This hydroxyl group-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.
上記で得た水酸基含有シルセスキオキサン化合物[ＣＨ3ＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[ＨＯ1/2]mのＧＰＣを測定した結果を図１に示す。図１から、Ｍｗ＝１１８８、Ｍｗ／Ｍｎ＝１．３２６であった。 FIG. 1 shows the results of GPC measurement of the hydroxyl group-containing silsesquioxane compound [CH 3 SiO 3/2 ] k [CH 2 ═CHSiO 3/2 ] j [HO 1/2 ] m obtained above. From FIG. 1, it was Mw = 1188 and Mw / Mn = 1.326.
また、この水酸基含有シルセスキオキサン化合物[ＣＨ3ＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[ＨＯ1/2]mの1Ｈ−ＮＭＲを測定した結果を図２に示す。図２から、ビニル基、メチル基及びシラノール基のピークを確認した。[ＣＨ3ＳｉＯ3/2]k：[ＣＨ2＝ＣＨＳｉＯ3/2]j：[ＨＯ1/2]mの積分比を比較したところ、２．９８９：３．０００：１．０６７であり、その官能基比率は０．９６６：１．０００：１．０６７であった。従って、ｎはｋとｊの和であることから、ｎ／ｍ＝１．８４３であった。また、Ｍｗ＝１１８８及びｎ／ｍ＝１．８４から導かれるｋ：ｊ：ｍの比は７．４７９：７．７５３：８．２２６であると計算され、Ｓｉが１５の縮合体であり、水酸基を８つ、硬化性官能基を８つ含むことが確認された。 The results of 1 H-NMR measurement of this hydroxyl group-containing silsesquioxane compound [CH 3 SiO 3/2 ] k [CH 2 = CHSiO 3/2 ] j [HO 1/2 ] m are shown in FIG. . From FIG. 2, peaks of vinyl group, methyl group and silanol group were confirmed. When the integration ratio of [CH 3 SiO 3/2 ] k : [CH 2 = CHSiO 3/2 ] j : [HO 1/2 ] m was compared, it was 2.989: 3.000: 1.067, The functional group ratio was 0.966: 1.000: 1.067. Therefore, n is the sum of k and j, so n / m = 1.443. Also, the k: j: m ratio derived from Mw = 1188 and n / m = 1.84 is calculated to be 7.479: 7.753: 8.226, and is a condensate with 15 Si, It was confirmed that 8 hydroxyl groups and 8 curable functional groups were contained.
次に撹拌機及び滴下ロートを備えた反応容器に、上記で得られた水酸基含有シルセスキオキサン化合物３６．３ｇ（３１ミリモル）とピリジン２０７ｍＬをはかり込み窒素置換した。滴下ロートにトリメチルクロロシラン（東レ・ダウコーニング・シリコーン株式会社製ＰＲＸ−２４）３６．０ｇ（３３１ミリモル）を入れ、室温で１時間かけて滴下した。滴下終了後室温で２時間撹拌した。２時間撹拌後、トルエン２０７ｍＬと純水２０７ｍＬを加え、有機層と水層を分離した。有機層を飽和食塩水で洗浄した後、有機層を無水硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで、硬化性シリコーン化合物を４５．７ｇ（回収率９７％）得た。この硬化性シリコーン化合物は種々の有機溶剤に可溶な無色液体であった。 Next, 36.3 g (31 mmol) of the hydroxyl group-containing silsesquioxane compound obtained above and 207 mL of pyridine were placed in a reaction vessel equipped with a stirrer and a dropping funnel and purged with nitrogen. 36.0 g (331 mmol) of trimethylchlorosilane (PRX-24 manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to the dropping funnel and added dropwise at room temperature over 1 hour. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 207 mL of toluene and 207 mL of pure water were added, and the organic layer and the aqueous layer were separated. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 45.7 g of a curable silicone compound (recovery rate 97%). This curable silicone compound was a colorless liquid soluble in various organic solvents.
この硬化性シリコーン化合物[ＣＨ3ＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[（ＣＨ3）3ＳｉＯ1/2]mのＧＰＣを測定した結果を図３に示す。ＧＰＣの測定の結果（図３）から、Ｍｗ＝１５２０、Ｍｗ／Ｍｎ＝１．２７０であった。 FIG. 3 shows the result of GPC measurement of this curable silicone compound [CH 3 SiO 3/2 ] k [CH 2 ═CHSiO 3/2 ] j [(CH 3 ) 3 SiO 1/2 ] m . From the GPC measurement results (FIG. 3), Mw = 1520 and Mw / Mn = 1.270.
この硬化性シリコーン化合物[ＣＨ3ＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[（ＣＨ3）3ＳｉＯ1/2]m の1Ｈ―ＮＭＲを測定した結果を図４に示す。図４から[ＣＨ2＝ＣＨＳｉＯ3/2]j：[ＣＨ3ＳｉＯ3/2]k＋[（ＣＨ3）3ＳｉＯ1/2]mの積分比を比較したところ３．０００：８．６９９であり、ｋ：ｊ：ｍの積分比は２．９８９：３．０００：５．８０１であり、ｋ：ｊ：ｍの比率は０．９６６：１．０００：０．６４５であった。従って、ｎはｋとｊの和であることから、ｎ／ｍ＝３．０５であった。なお、水酸基含有シルセスキオキサン化合物の水酸基とこの硬化性シリコーン化合物のトリメチルシリル基の数が異なるのは、ピリジン存在下でシラノール基同士が一部分縮合したためであると考えられる。 The results of 1 H-NMR measurement of this curable silicone compound [CH 3 SiO 3/2 ] k [CH 2 ═CHSiO 3/2 ] j [(CH 3 ) 3 SiO 1/2 ] m are shown in FIG. . FIG. 4 shows that the integration ratio of [CH 2 = CHSiO 3/2 ] j : [CH 3 SiO 3/2 ] k + [(CH 3 ) 3 SiO 1/2 ] m is compared to 3.000: 8.699. The integration ratio of k: j: m was 2.989: 3.000: 5.801, and the ratio of k: j: m was 0.966: 1.000: 0.645. Therefore, n is the sum of k and j, so n / m = 3.05. The reason why the number of the hydroxyl groups of the hydroxyl group-containing silsesquioxane compound and the trimethylsilyl group of the curable silicone compound is different is considered to be that the silanol groups are partially condensed in the presence of pyridine.
また、Ｍｗ＝１５２０及びｎ／ｍ＝３．０５から導かれるｋ：ｊ：ｍの比は７．４６９：７．７４３：５．０２０であると計算され、Ｓｉが２０の縮合体であり、硬化性官能基を８つ含むことが確認された。 The ratio of k: j: m derived from Mw = 1520 and n / m = 3.05 is calculated to be 7.469: 7.743: 5.020, and Si is a condensate of 20, It was confirmed to contain 8 curable functional groups.
撹拌機及び滴下ロートを備えた反応容器に、溶媒として２−プロパノール(ＩＰＡ)６０ｍＬ及びトルエン１２０ｍＬを入れ、塩基性触媒として２６％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）１６．１ｇ（４５．９ミリモル）を装入した。また、滴下ロートにＩＰＡ４０ｍLとトリメトキシビニルシラン（信越化学工業株式会社製ＫＢＭ−１００３）２９．６ｇ（２００ミリモル）を入れ、反応容器を撹拌しながら、室温で３時間かけて滴下した。滴下終了後、室温で５時間撹拌した。５時間撹拌後、１０％クエン酸水溶液を加え２時間撹拌して中和した。水層をトルエンで抽出し、有機層を飽和食塩水で２回洗浄した。有機層を硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで加水分解生成物（水酸基含有シルセスキオキサン化合物）を１４、３ｇ（回収率９２％）得た。この水酸基含有シルセスキオキサン化合物は種々の有機溶剤に可溶な無色粘性液体であった。 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 60 mL of 2-propanol (IPA) and 120 mL of toluene as a solvent, and 16.1 g (45.9) of a 26% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. Mmol) was charged. Further, 40 mL of IPA and 29.6 g (200 mmol) of trimethoxyvinylsilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) were added to the dropping funnel, and the mixture was added dropwise at room temperature over 3 hours while stirring the reaction vessel. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, a 10% aqueous citric acid solution was added and the mixture was stirred for 2 hours for neutralization. The aqueous layer was extracted with toluene, and the organic layer was washed twice with saturated brine. The organic layer was dried with magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 14, 3 g of a hydrolysis product (hydroxyl group-containing silsesquioxane compound) (recovery rate: 92%). This hydroxyl group-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.
この水酸基含有シルセスキオキサン化合物 [ＣＨ2＝ＣＨＳｉＯ3/2]n[ＨＯ1/2]mのＧＰＣを測定した結果を図５に示す。ＧＰＣ測定結果（図５）から、Ｍｗ＝８５０、Ｍｗ／Ｍｎ＝１．１６２であった。 This hydroxyl-containing silsesquioxane compound FIG. 5 shows the results of GPC measurement of [CH 2 = CHSiO 3/2 ] n [HO 1/2 ] m . From the GPC measurement result (FIG. 5), it was Mw = 850 and Mw / Mn = 1.162.
次に、撹拌機及び滴下ロートを備えた反応容器に、水酸基含有シルセスキオキサン化合物１０．８ｇ（１２．７ミリモル）とピリジン８２．５ｍＬをはかり込み窒素置換した。滴下ロートにジメチルビニルクロロシラン（東レ・ダウコーニング・シリコーン株式会社製）２０．７ｇ（１７２ミリモル）を入れ、室温で１時間かけて滴下した。滴下終了後室温で２時間撹拌した。２時間撹拌後、トルエン８２．５ｍＬと純水８２．５ｍＬを加え、有機層と水層を分離した。有機層を飽和食塩水で洗浄した後、有機層を無水硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで、硬化性シリコーン化合物を１４．１ｇ（回収率９０）得た。この硬化性シリコーン化合物は種々の有機溶剤に可溶な無色液体であった。 Next, 10.8 g (12.7 mmol) of a hydroxyl group-containing silsesquioxane compound and 82.5 mL of pyridine were weighed into a reaction vessel equipped with a stirrer and a dropping funnel and replaced with nitrogen. Into the dropping funnel, 20.7 g (172 mmol) of dimethylvinylchlorosilane (manufactured by Toray Dow Corning Silicone Co., Ltd.) was added and dropped at room temperature over 1 hour. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 82.5 mL of toluene and 82.5 mL of pure water were added, and the organic layer and the aqueous layer were separated. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 14.1 g of curable silicone compound (recovery rate 90). This curable silicone compound was a colorless liquid soluble in various organic solvents.
この硬化性シリコーン化合物[ＣＨ2＝ＣＨＳｉＯ3/2]n[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mのＧＰＣを測定した結果を図６に示す。ＧＰＣ測定の結果（図６）から、Ｍｗ＝１２２６であり、Ｍｗ／Ｍｎ＝１．１３３であった。 FIG. 6 shows the result of GPC measurement of this curable silicone compound [CH 2 ═CHSiO 3/2 ] n [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m . From the result of GPC measurement (FIG. 6), Mw = 1226 and Mw / Mn = 1.133.
この硬化性シリコーン化合物[ＣＨ2＝ＣＨＳｉＯ3/2]n[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mの1Ｈ−ＮＭＲを測定した結果を図７に示す。図７から[ＣＨ2＝ＣＨＳｉＯ3/2]n：[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mの積分比を比較したところ１１．３７５：６．０００であった。従って、ｎ：ｍの比率は１．０００：０．３５８となり、ｎ／ｍ＝２．７９であった。 FIG. 7 shows the results of 1 H-NMR measurement of this curable silicone compound [CH 2 ═CHSiO 3/2 ] n [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m . From FIG. 7, the integration ratio of [CH 2 ═CHSiO 3/2 ] n : [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m was compared to be 11.375: 6.0000. Therefore, the ratio of n: m was 1.000: 0.358, and n / m = 2.79.
また、Ｍｗ＝１２２６及びｎ／ｍ＝２．７９から導かれるｎ：ｍの比は７．１１４：２．５４７であることが計算され、Ｓｉが９の縮合体であり、硬化性官能基を９つ含むことが確認された。 Also, the n: m ratio derived from Mw = 1226 and n / m = 2.79 was calculated to be 7.114: 2.547, Si was a 9 condensate, and the curable functional group was It was confirmed that 9 were included.
撹拌機及び滴下ロートを備えた反応容器に、溶媒として２−プロパノール(ＩＰＡ)４８ｍＬ及びトルエン１９４ｍＬを入れ、塩基性触媒として２６％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）９．６ｇ（２７ミリモル）を装入した。また、滴下ロートにＩＰＡ３２ｍL、トリメトキシビニルシラン（信越化学工業株式会社製ＫＢＭ１００３）１１．９ｇ（８０ミリモル）、及び３−グリシドキシプロピルトリメトキシシラン（信越化学工業株式会社製ＬＳ−２９４０）２０．０ｇ（８０ミリモル）を入れ、反応容器を撹拌しながら、室温で３時間かけて滴下した。滴下終了後、室温で５時間撹拌した。５時間撹拌後、１０％クエン酸水溶液を加え２時間撹拌して中和した。水層をトルエンで抽出し、有機層を飽和食塩水で２回洗浄した。有機層を硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで加水分解生成物（水酸基含有シルセスキオキサン化合物）を１７．８ｇ（回収率８９％）得た。この水酸基含有シルセスキオキサン化合物は種々の有機溶剤に可溶な無色粘性液体であった。 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 48 mL of 2-propanol (IPA) and 194 mL of toluene as a solvent, and 9.6 g (27 mmol) of a 26% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. Was loaded. Further, IPA 32 mL, trimethoxyvinylsilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) 11.9 g (80 mmol), and 3-glycidoxypropyltrimethoxysilane (LS-2940 manufactured by Shin-Etsu Chemical Co., Ltd.) 20. 0 g (80 mmol) was added, and the reaction vessel was added dropwise at room temperature over 3 hours while stirring. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, a 10% aqueous citric acid solution was added and the mixture was stirred for 2 hours for neutralization. The aqueous layer was extracted with toluene, and the organic layer was washed twice with saturated brine. The organic layer was dried with magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 17.8 g (recovery rate 89%) of a hydrolysis product (hydroxyl group-containing silsesquioxane compound). This hydroxyl group-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.
この水酸基含有シルセスキオキサン化合物 [ＣＨ2（Ｏ）ＣＨＣＨ2Ｏ（ＣＨ2）3ＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[ＨＯ1/2]mのＧＰＣを測定した結果を図８に示す。ＧＰＣ測定結果（図８）から、Ｍｗ＝１３７９、Ｍｗ／Ｍｎ＝１．２８２であった。 This hydroxyl-containing silsesquioxane compound FIG. 8 shows the result of GPC measurement of [CH 2 (O) CHCH 2 O (CH 2 ) 3 SiO 3/2 ] k [CH 2 = CHSiO 3/2 ] j [HO 1/2 ] m . From the GPC measurement result (FIG. 8), it was Mw = 1379 and Mw / Mn = 1.282.
次に、撹拌機及び滴下ロートを備えた反応容器に、水酸基含有シルセスキオキサン化合物１０．８ｇ（８ミリモル）とピリジン８２ｍＬをはかり込み窒素置換した。滴下ロートにジメチルビニルクロロシラン（東レ・ダウコーニング・シリコーン株式会社製）２０．７ｇ（１７１ミリモル）を入れ、室温で１時間かけて滴下した。滴下終了後室温で２時間撹拌した。２時間撹拌後、トルエン８２Ｌと純水８２ｍＬを加え、有機層と水層を分離した。有機層を飽和食塩水で洗浄した後、有機層を無水硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで、硬化性シリコーン化合物を１１．７ｇ、回収率９１％で得た。この硬化性シリコーン化合物は種々の有機溶剤に可溶な無色液体であった。 Next, 10.8 g (8 mmol) of a hydroxyl group-containing silsesquioxane compound and 82 mL of pyridine were weighed into a reaction vessel equipped with a stirrer and a dropping funnel and replaced with nitrogen. Into the dropping funnel, 20.7 g (171 mmol) of dimethylvinylchlorosilane (manufactured by Toray Dow Corning Silicone Co., Ltd.) was added and dropped at room temperature over 1 hour. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 82 L of toluene and 82 mL of pure water were added, and the organic layer and the aqueous layer were separated. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 11.7 g of a curable silicone compound at a recovery rate of 91%. This curable silicone compound was a colorless liquid soluble in various organic solvents.
この硬化性シリコーン化合物[ＣＨ2（Ｏ）ＣＨＣＨ2Ｏ（ＣＨ2）3ＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mのＧＰＣを測定した結果を図９に示す。ＧＰＣ測定の結果（図９）から、Ｍｗ＝１６２４であり、Ｍｗ／Ｍｎ＝１．２９３であった。
The curable silicone compound [CH 2 (O) CHCH 2 O (CH 2) 3
この硬化性シリコーン化合物[ＣＨ2（Ｏ）ＣＨＣＨ2ＯＳｉＯ3/2]k[ＣＨ2＝ＣＨＳｉＯ3/2]j[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mの1Ｈ−ＮＭＲを測定した結果を図１０に示す。図１０から[ＣＨ2（Ｏ）ＣＨＣＨ2ＣＨ2ＣＨ2ＳｉＯ3/2]k：[ＣＨ2＝ＣＨＳｉＯ3/2]j：[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mの積分比を比較したところ２．０００：３．０００：１．４９６であった。従って、ｎはｋとｊの和であることからｋ：ｊ：ｍの比率は１：１：０．２４９となり、ｎ／ｍ＝８．０３２であった。 1 H-NMR of this curable silicone compound [CH 2 (O) CHCH 2 OSiO 3/2 ] k [CH 2 ═CHSiO 3/2 ] j [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m The result of measuring is shown in FIG. From FIG. 10, [CH 2 (O) CHCH 2 CH 2 CH 2 SiO 3/2 ] k : [CH 2 = CHSiO 3/2 ] j : [CH 2 = CH (CH 3 ) 2 O 1/2 ] m When the integration ratio was compared, it was 2.000: 3.000: 1.496. Therefore, since n is the sum of k and j, the ratio of k: j: m was 1: 1: 0.249, and n / m = 8.032.
また、Ｍｗ＝１１３６及びｎ／ｍ＝８．０３から導かれるｎ：ｍの比は６．０２８：６．０２８：１．５０１であることが計算され、Ｓｉが１４の縮合体であり、硬化性官能基を１４つ含むことが確認された。 Further, the ratio of n: m derived from Mw = 1136 and n / m = 8.03 was calculated to be 6.028: 6.028: 1.501, and Si was a condensate of 14 and cured. It was confirmed that 14 functional groups were included.
撹拌機及び滴下ロートを備えた反応容器に、溶媒として２−プロパノール(ＩＰＡ)１８２ｍＬ及びトルエン３６３ｍＬを入れ、塩基性触媒として２６％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）３５．９ｇ（１０２ミリモル）を装入した。また、滴下ロートにＩＰＡ１２１ｍL、トリメトキシビニルシラン（信越化学工業株式会社製ＫＢＭ１００３）４４．８ｇ（３０３ミリモル）、及びトリメトキシフェニルシラン６０．０ｇ（３０３ミリモル）を入れ、反応容器を撹拌しながら、室温で３時間かけて滴下した。滴下終了後、室温で５時間撹拌した。５時間撹拌後、１０％クエン酸水溶液を加え２時間撹拌して中和した。水層をトルエンで抽出し、有機層を飽和食塩水で２回洗浄した。有機層を硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで加水分解生成物（水酸基含有シルセスキオキサン化合物）を５６．８ｇ（回収率８８％）得た。この水酸基含有シルセスキオキサン化合物は種々の有機溶剤に可溶な無色粘性液体であった。 A reaction vessel equipped with a stirrer and a dropping funnel was charged with 182 mL of 2-propanol (IPA) and 363 mL of toluene as a solvent, and 35.9 g (102 mmol) of 26% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst. Was loaded. Further, 121 mL of IPA, 44.8 g (303 mmol) of trimethoxyvinylsilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.), and 60.0 g (303 mmol) of trimethoxyphenylsilane were placed in a dropping funnel, and the reaction vessel was stirred at room temperature. For 3 hours. After completion of dropping, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, a 10% aqueous citric acid solution was added and the mixture was stirred for 2 hours for neutralization. The aqueous layer was extracted with toluene, and the organic layer was washed twice with saturated brine. The organic layer was dried with magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 56.8 g (recovery rate 88%) of a hydrolysis product (hydroxyl group-containing silsesquioxane compound). This hydroxyl group-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.
この水酸基含有シルセスキオキサン化合物 [ＣＨ2＝ＣＨＳｉＯ3/2]k[ＰｈＳｉＯ3/2]j[ＨＯ1/2]mのＧＰＣを測定した結果を図１１に示す。ＧＰＣ測定結果（図１１）から、Ｍｗ＝１４９２、Ｍｗ／Ｍｎ＝１．４３６であった。 This hydroxyl-containing silsesquioxane compound FIG. 11 shows the results of GPC measurement of [CH 2 = CHSiO 3/2 ] k [PhSiO 3/2 ] j [HO 1/2 ] m . From the GPC measurement result (FIG. 11), it was Mw = 1492 and Mw / Mn = 1.436.
次に、撹拌機及び滴下ロートを備えた反応容器に、水酸基含有シルセスキオキサン化合物５３．０ｇ（３６ミリモル）とピリジン３０４ｍＬをはかり込み窒素置換した。滴下ロートにジメチルビニルクロロシラン（東レ・ダウコーニング・シリコーン株式会社製）４４．１ｇ（３６６ミリモル）を入れ、室温で１時間かけて滴下した。滴下終了後室温で２時間撹拌した。２時間撹拌後、トルエン３０５ｍＬと純水３０５ｍＬを加え、有機層と水層を分離した。有機層を飽和食塩水で洗浄した後、有機層を無水硫酸マグネシウムで乾燥した。無水硫酸マグネシウムをろ別し、濃縮することで、硬化性シリコーン化合物を５５．２ｇ（回収率９１％）で得た。この硬化性シリコーン化合物は種々の有機溶剤に可溶な無色液体であった。 Next, 53.0 g (36 mmol) of a hydroxyl group-containing silsesquioxane compound and 304 mL of pyridine were weighed into a reaction vessel equipped with a stirrer and a dropping funnel and replaced with nitrogen. Into the dropping funnel, 44.1 g (366 mmol) of dimethylvinylchlorosilane (manufactured by Toray Dow Corning Silicone Co., Ltd.) was added and added dropwise at room temperature over 1 hour. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 305 mL of toluene and 305 mL of pure water were added, and the organic layer and the aqueous layer were separated. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 55.2 g of a curable silicone compound (recovery rate: 91%). This curable silicone compound was a colorless liquid soluble in various organic solvents.
この硬化性シリコーン化合物[ＣＨ2＝ＣＨＳｉＯ3/2]k[ＰｈＳｉＯ3/2]j[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mのＧＰＣを測定した結果を図１２に示す。ＧＰＣ測定の結果（図１２）から、Ｍｗ＝１６８５であり、Ｍｗ／Ｍｎ＝１．４２６であった。 FIG. 12 shows the results of GPC measurement of this curable silicone compound [CH 2 ═CHSiO 3/2 ] k [PhSiO 3/2 ] j [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m . From the result of the GPC measurement (FIG. 12), Mw = 1687 and Mw / Mn = 1.426.
この硬化性シリコーン化合物[ＣＨ2＝ＣＨＳｉＯ3/2]k[ＰｈＳｉＯ3/2]j[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mの1Ｈ−ＮＭＲを測定した結果を図１３に示す。図１３から[ＣＨ2＝ＣＨＳｉＯ3/2]k：[ＰｈＳｉＯ3/2]j：[ＣＨ2＝ＣＨ（ＣＨ3）2Ｏ1/2]mの積分比を比較したところ１３．８３１：２０．００４：６．０００であった。従って、ｋ：ｊ：ｍの比率は４．６１０：４．００１：１．０００となり、ｎはｋとｊの和であることからｎ／ｍ＝７．２２であった。 The results of 1 H-NMR measurement of this curable silicone compound [CH 2 ═CHSiO 3/2 ] k [PhSiO 3/2 ] j [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m are shown in FIG. Shown in FIG. 13 shows that the integration ratio of [CH 2 ═CHSiO 3/2 ] k : [PhSiO 3/2 ] j : [CH 2 ═CH (CH 3 ) 2 O 1/2 ] m is compared to 13.831: 20. .004: 6.000. Therefore, the ratio of k: j: m was 4.610: 4.001: 1.000, and n was the sum of k and j, so n / m = 7.22.
また、Ｍｗ＝１６８５及びｋ＋ｊ／ｍ＝７．２２から導かれるｋ：ｊ：ｍの比は７．１９８：７．１９８：１．９９４であることが計算され、Ｓｉが１７の縮合体であり、硬化性官能基を８つ含むことが確認された。 Further, the ratio of k: j: m derived from Mw = 1585 and k + j / m = 7.22 is calculated to be 7.198: 7.198: 1.994, and it is a condensate having 17 Si. It was confirmed to contain 8 curable functional groups.
［比較例１］
撹拌機、滴下ロートを備えた反応容器に、溶媒としてトルエン２００ｍＬを入れ、塩基性触媒として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）３９．０ｇ（２１ミリモル）を装入した。滴下ロートにトルエン６０ｍＬ、トリメトキシメチルシラン（東レ・ダウコーニング・シリコーン株式会社製ＳＺ−６０７０）２４．５ｇ（１７９ミリモル）、及びトリメトキシビニルシラン（信越化学株式会社製ＫＢＭ１００３）２６．７ｇ（１７９ミリモル）を入れ、反応容器を撹拌しながら、室温でトリメトキシビニルシランのトルエン溶液を２時間かけて滴下した。トリメトキシビニルシラン滴下終了後、加熱することなく２時間撹拌し、この反応溶液を1日静置し、その後、後再縮合を行った。滴下ロートを取り外して反応容器にディンスターク、冷却管を備えつけ、液温７５℃まで加熱して副生成物のメタノールを除去した後、液温１０５℃でトルエンを還流加熱した。３時間撹拌還流後、室温に戻して反応を終了とした。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した。無水硫酸マグネシウムをろ別し、濃縮することで下記再縮合物（８）を３３．７ｇ、収率７２％で得た。この再縮合物は種々の有機溶剤に難溶な白色固体であった。得られた下記再縮合物（８）のＧＰＣチャートを図１４に示す。なお、ここで言う再縮合とは、トリアルコキシシランを有機極性溶媒および塩基性触媒存在下、加水分解、重縮合し、得られた加水分解生成物を再び、非極性溶媒及び塩基性触媒存在下で縮合することであり、完全縮合型のシルセスキオキサン（かご型シルセスキオキサン樹脂）の製造方法である（特開2004-143449号公報）。
[ＣＨ3ＳｉＯ3/2]i[ＣＨ2＝ＣＨＳｉＯ3/2]h （８）
[Comparative Example 1]
In a reaction vessel equipped with a stirrer and a dropping funnel, 200 mL of toluene was added as a solvent, and 39.0 g (21 mmol) of 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) was charged as a basic catalyst. To the dropping funnel, 60 mL of toluene, 24.5 g (179 mmol) of trimethoxymethylsilane (SZ-6070 manufactured by Toray Dow Corning Silicone Co., Ltd.), and 26.7 g (179 mmol) of trimethoxyvinylsilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) ) And a toluene solution of trimethoxyvinylsilane was added dropwise over 2 hours at room temperature while stirring the reaction vessel. After completion of the dropwise addition of trimethoxyvinylsilane, the mixture was stirred for 2 hours without heating, and this reaction solution was allowed to stand for 1 day, and then post-recondensation was performed. After removing the dropping funnel, the reaction vessel was equipped with a Din Stark and cooling tube, heated to a liquid temperature of 75 ° C. to remove methanol as a by-product, and then heated to reflux at a liquid temperature of 105 ° C. After stirring and refluxing for 3 hours, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 23.0 g of 10% aqueous citric acid solution, washed with saturated brine, and dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 33.7 g of the following recondensate (8) in a yield of 72%. This recondensate was a white solid hardly soluble in various organic solvents. The GPC chart of the following recondensate (8) obtained is shown in FIG. The term "recondensation" as used herein means hydrolysis and polycondensation of trialkoxysilane in the presence of an organic polar solvent and a basic catalyst, and the resulting hydrolysis product is again in the presence of a nonpolar solvent and a basic catalyst. This is a method for producing a fully condensed silsesquioxane (cage-type silsesquioxane resin) (Japanese Patent Laid-Open No. 2004-143449).
[CH 3 SiO 3/2 ] i [CH 2 = CHSiO 3/2 ] h (8)
［比較例２］
撹拌機、滴下ロートを備えた反応容器に、溶媒としてトルエン２００ｍＬを入れ、塩基性触媒として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）３９．０ｇ（２１ミリモル）を装入した。滴下ロートにトルエン６０ｍＬとトリメトキシビニルシラン（信越化学株式会社製ＫＢＭ１００３）５３．０ｇ（３５８モル）を入れ、反応容器を撹拌しながら、室温でトリメトキシビニルシランのトルエン溶液を２時間かけて滴下した。トリメトキシビニルシラン滴下終了後、加熱することなく２時間撹拌し、この反応溶液を1日静置し、その後、再縮合を行った。滴下ロートを取り外して反応容器にディンスターク、冷却管を備えつけ、液温７５℃まで加熱して副生成物のメタノールを除去した後、液温１０５℃でトルエンを還流加熱した。３時間撹拌還流後、室温に戻して反応を終了とした。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した。無水硫酸マグネシウムをろ別し、濃縮することで下記再縮合物（９）を３０．３ｇ、収率８３％で得た。この再縮合物は種々の有機溶剤に難溶な白色固体であった。得られた下記再縮合物（９）のＧＰＣチャートを図１５に示す。
[ＣＨ2＝ＣＨＳｉＯ3/2]g （９）
[Comparative Example 2]
In a reaction vessel equipped with a stirrer and a dropping funnel, 200 mL of toluene was added as a solvent, and 39.0 g (21 mmol) of 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) was charged as a basic catalyst. To the dropping funnel, 60 mL of toluene and 53.0 g (358 mol) of trimethoxyvinylsilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and a toluene solution of trimethoxyvinylsilane was added dropwise over 2 hours at room temperature while stirring the reaction vessel. After completion of the dropwise addition of trimethoxyvinylsilane, the mixture was stirred for 2 hours without heating, and the reaction solution was allowed to stand for 1 day, and then recondensed. After removing the dropping funnel, the reaction vessel was equipped with a Din Stark and cooling tube, heated to a liquid temperature of 75 ° C. to remove methanol as a by-product, and then heated to reflux at a liquid temperature of 105 ° C. After stirring and refluxing for 3 hours, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 23.0 g of 10% aqueous citric acid solution, washed with saturated brine, and dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 30.3 g of the following recondensate (9) in a yield of 83%. This recondensate was a white solid hardly soluble in various organic solvents. A GPC chart of the following recondensate (9) obtained is shown in FIG.
[CH 2 = CHSiO 3/2 ] g (9)
［相溶性試験］
上記実施例１〜４で得られた硬化性シリコーン化合物と下記（１０）〜（１４）で表されるシリコーン系硬化性樹脂を重量比１：１で混合して相溶性を評価した。また、上記比較例１及び２で得られたものについても同様に評価した。結果を表１に示す。なお、評価は目視で行い、透明の場合を○、白濁が認められた場合を×とした。
The curable silicone compounds obtained in Examples 1 to 4 and the silicone-based curable resins represented by the following (10) to (14) were mixed at a weight ratio of 1: 1 to evaluate the compatibility. Moreover, it evaluated similarly about what was obtained in the said comparative examples 1 and 2. FIG. The results are shown in Table 1. In addition, evaluation was performed visually, the case where it was transparent was set to (circle), and the case where cloudiness was recognized was set to x.
Claims (3)
[ＲＳｉＯ3/2]n[Ｒ1(ＣＨ3)2ＳｉＯ1/2]m （１）
で表される硬化性シリコーン化合物。
〔但し、Ｒ及びＲ1は、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[RSiO 3/2 ] n [R 1 (CH 3 ) 2 SiO 1/2 ] m (1)
A curable silicone compound represented by:
[However, R and R 1 are a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, and a carbon number. 2-3 alkenyl groups or the following formulas (2) to (4)
[ＲＳｉＯ3/2]n [ＨＯ1/2]m （５）
で表される水酸基含有シルセスキオキサン化合物。
〔但し、Ｒは、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[RSiO 3/2 ] n [HO 1/2 ] m (5)
A hydroxyl group-containing silsesquioxane compound represented by:
[However, R is a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2-3 carbon atoms. Or an alkenyl group of the following formulas (2) to (4)
ＲＳｉＸ3 （６）
〔但し、Ｒは、水素原子、炭素数６〜１０のアリール含有基、炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、炭素数４〜１０のシクロアルキル基、炭素数２〜３のアルケニル基、又は下記式（２）〜（４）
[ＲＳｉＯ3/2]n [ＨＯ1/2]m （５）
（但し、Ｒは上記と同じである。ｎは６〜２０の整数、ｍは１〜６の整数を示し、ｎ／ｍが１〜１０の範囲である）で表される水酸基含有シルセスキオキサン化合物を生成した後、モノクロロシランと反応させることを特徴とする硬化性シリコーン化合物の製造方法。 It is a manufacturing method of the curable silicone compound of Claim 1, Comprising: The following general formula (6)
RSix 3 (6)
[However, R is a hydrogen atom, an aryl-containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 2-3 carbon atoms. Or an alkenyl group of the following formulas (2) to (4)
[RSiO 3/2 ] n [HO 1/2 ] m (5)
(Wherein R is the same as above, n is an integer of 6 to 20, m is an integer of 1 to 6, and n / m is in the range of 1 to 10). A method for producing a curable silicone compound, characterized by reacting monochlorosilane after producing a sun compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008056320A JP2008266301A (en) | 2007-03-26 | 2008-03-06 | New silicone compound, and raw material thereof and method for producing the silicone compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007079417 | 2007-03-26 | ||
| JP2008056320A JP2008266301A (en) | 2007-03-26 | 2008-03-06 | New silicone compound, and raw material thereof and method for producing the silicone compound |
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| JP2008266301A true JP2008266301A (en) | 2008-11-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2008056320A Withdrawn JP2008266301A (en) | 2007-03-26 | 2008-03-06 | New silicone compound, and raw material thereof and method for producing the silicone compound |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2008266301A (en) |
| KR (1) | KR20080087741A (en) |
| CN (1) | CN101397306A (en) |
| TW (1) | TW200916507A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009099099A1 (en) * | 2008-02-07 | 2009-08-13 | Nippon Steel Chemical Co., Ltd. | Silicone resins and manufacturing method thereof, as well as curable resin compositions that comprise said silicone resins |
| WO2009119253A1 (en) * | 2008-03-28 | 2009-10-01 | 新日鐵化学株式会社 | Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition |
| EP2177556A2 (en) | 2008-10-15 | 2010-04-21 | Shinetsu Chemical Co., Ltd. | Silicone for preparing ophthalmic devices |
-
2008
- 2008-03-06 JP JP2008056320A patent/JP2008266301A/en not_active Withdrawn
- 2008-03-18 TW TW097109529A patent/TW200916507A/en unknown
- 2008-03-26 KR KR1020080028002A patent/KR20080087741A/en not_active Application Discontinuation
- 2008-03-26 CN CNA2008101785259A patent/CN101397306A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009099099A1 (en) * | 2008-02-07 | 2009-08-13 | Nippon Steel Chemical Co., Ltd. | Silicone resins and manufacturing method thereof, as well as curable resin compositions that comprise said silicone resins |
| US8754181B2 (en) | 2008-02-07 | 2014-06-17 | Nippon Steel & Sumikin Chemical Co., Ltd. | Silicone resin, process for producing the same, and curable resin composition comprising the same |
| WO2009119253A1 (en) * | 2008-03-28 | 2009-10-01 | 新日鐵化学株式会社 | Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition |
| EP2177556A2 (en) | 2008-10-15 | 2010-04-21 | Shinetsu Chemical Co., Ltd. | Silicone for preparing ophthalmic devices |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200916507A (en) | 2009-04-16 |
| CN101397306A (en) | 2009-04-01 |
| KR20080087741A (en) | 2008-10-01 |
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