JP7007555B2 - Purification method and production method of unsaturated bond-containing silane compound - Google Patents
Purification method and production method of unsaturated bond-containing silane compound Download PDFInfo
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- JP7007555B2 JP7007555B2 JP2017152904A JP2017152904A JP7007555B2 JP 7007555 B2 JP7007555 B2 JP 7007555B2 JP 2017152904 A JP2017152904 A JP 2017152904A JP 2017152904 A JP2017152904 A JP 2017152904A JP 7007555 B2 JP7007555 B2 JP 7007555B2
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- Prior art keywords
- unsaturated bond
- silane compound
- containing silane
- group
- tetrahydrofuran
- Prior art date
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- -1 silane compound Chemical class 0.000 title claims description 166
- 229910000077 silane Inorganic materials 0.000 title claims description 129
- 238000000034 method Methods 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000746 purification Methods 0.000 title claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 262
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 130
- 239000000203 mixture Substances 0.000 claims description 111
- 238000009835 boiling Methods 0.000 claims description 95
- 239000002904 solvent Substances 0.000 claims description 92
- 238000004821 distillation Methods 0.000 claims description 38
- 239000007818 Grignard reagent Substances 0.000 claims description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 27
- 150000004795 grignard reagents Chemical class 0.000 claims description 25
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 22
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 22
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 claims description 18
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 15
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- 150000004756 silanes Chemical class 0.000 claims description 14
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- QQLFJFKDDGCTQJ-UHFFFAOYSA-N triethynyl(methyl)silane Chemical compound C#C[Si](C)(C#C)C#C QQLFJFKDDGCTQJ-UHFFFAOYSA-N 0.000 claims description 9
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- MBUNTPHHHPPWMA-UHFFFAOYSA-N methyl-tris(prop-2-ynoxy)silane Chemical compound C#CCO[Si](C)(OCC#C)OCC#C MBUNTPHHHPPWMA-UHFFFAOYSA-N 0.000 claims description 8
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 8
- PGHWHQUVLXTFLZ-UHFFFAOYSA-N trichloro(fluoro)silane Chemical compound F[Si](Cl)(Cl)Cl PGHWHQUVLXTFLZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 125000005372 silanol group Chemical group 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 6
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 3
- WJYMPXJVHNDZHD-UHFFFAOYSA-N 1,3,5-triethylbenzene Chemical compound CCC1=CC(CC)=CC(CC)=C1 WJYMPXJVHNDZHD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 3
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 claims 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 34
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 34
- 238000003756 stirring Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000706 filtrate Substances 0.000 description 22
- 238000001816 cooling Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 10
- JEHJZEUPJDGOQW-UHFFFAOYSA-N [Mg].C(=C)Cl Chemical compound [Mg].C(=C)Cl JEHJZEUPJDGOQW-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 4
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- LMVVLQVKKDFECD-UHFFFAOYSA-L [Cl-].[Mg+2].C(=C)Cl.[Cl-] Chemical compound [Cl-].[Mg+2].C(=C)Cl.[Cl-] LMVVLQVKKDFECD-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- INEFJGFWNOXUCE-UHFFFAOYSA-N O1CCCC1.[C-]#[C-].[Na+].[Na+] Chemical compound O1CCCC1.[C-]#[C-].[Na+].[Na+] INEFJGFWNOXUCE-UHFFFAOYSA-N 0.000 description 2
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 2
- SFDZETWZUCDYMD-UHFFFAOYSA-N monosodium acetylide Chemical compound [Na+].[C-]#C SFDZETWZUCDYMD-UHFFFAOYSA-N 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- CIHXIRAAMAUYLZ-UHFFFAOYSA-N [K+].[K+].[C-]#[C-] Chemical compound [K+].[K+].[C-]#[C-] CIHXIRAAMAUYLZ-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- RMGJCSHZTFKPNO-UHFFFAOYSA-M magnesium;ethene;bromide Chemical compound [Mg+2].[Br-].[CH-]=C RMGJCSHZTFKPNO-UHFFFAOYSA-M 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
本発明は、不飽和結合含有シラン化合物の純度を向上させる精製方法などに関するものである。 The present invention relates to a purification method for improving the purity of an unsaturated bond-containing silane compound.
不飽和結合含有シラン化合物は、ポリオレフィンのコモノマーとして使用される工業的に有用な製品であり、近年リチウムイオン電池用電解液の添加剤としても利用されつつある。 The unsaturated bond-containing silane compound is an industrially useful product used as a polyolefin comonomer, and has recently been used as an additive for an electrolytic solution for a lithium ion battery.
不飽和結合含有シラン化合物の製造方法として、さまざまな方法が提案されている。特許文献1では、典型元素金属および/または金属化合物類を触媒とする不均化反応によりヒドロシラン化合物からビニルシラン化合物を製造する方法が記載されている。 Various methods have been proposed as methods for producing unsaturated bond-containing silane compounds. Patent Document 1 describes a method for producing a vinylsilane compound from a hydrosilane compound by a disproportionation reaction catalyzed by a main group element metal and / or a metal compound.
他に、特許文献2では、アセチレン化合物と少なくとも1つ水素を有するシラン化合物とをチタン化合物存在下で反応させることによる位置および立体選択性を制御したビニルシラン化合物の製造方法が記載されている。 In addition, Patent Document 2 describes a method for producing a vinylsilane compound in which the position and stereoselectivity are controlled by reacting an acetylene compound with a silane compound having at least one hydrogen in the presence of a titanium compound.
また、非特許文献1では、グリニャール反応を利用し、ハロゲン化シランとビニルマグネシウムクロリド(以下、ビニルグリニャール試薬とも呼ぶ)とを加熱還流してビニルシラン化合物を合成する方法が記載されている。 Further, Non-Patent Document 1 describes a method for synthesizing a vinylsilane compound by heating and refluxing halogenated silane and vinylmagnesium chloride (hereinafter, also referred to as vinyl Grignard reagent) using a Grignard reaction.
また、ハロゲン化シランをアルカリ金属アセチリドと反応させてエチニルシラン化合物を合成する方法が知られている。例えば、特許文献3には、ヨウ化シラン(SiH3I)をナトリウムアセチリド(NaC≡CH)と反応させることで、SiH3C≡CHを得ることができ、さらに、ヒドロシラン類とアセチレン類とを金属酸化物の存在下に反応させることにより、エチニルシラン化合物を製造する方法が記載されている。 Further, a method of reacting a halogenated silane with an alkali metal acetylide to synthesize an ethynylsilane compound is known. For example, in Patent Document 3, SiH 3 C ≡ CH can be obtained by reacting silane iodide (SiH 3 I) with sodium acetylide (NaC ≡ CH), and hydrosilanes and acetylenes are further described. A method for producing an ethynylsilane compound by reacting in the presence of a metal oxide is described.
また、特許文献4では、モノハロゲン化シランを溶媒中でアルカリ金属アルコキシドと反応させ、オルガノモノアルコキシシランを合成する方法が開示されている。 Further, Patent Document 4 discloses a method for synthesizing an organomonoalkoxysilane by reacting a monohalogenated silane with an alkali metal alkoxide in a solvent.
グリニャール反応を利用して不飽和結合含有シラン化合物を合成する場合、グリニャール試薬の合成はテトラヒドロフラン中で行われることが多い。同様に、アルカリ金属アセチリドやアルカリ金属アルコキシドも、テトラヒドロフラン中で合成されることが多い。そのため、テトラヒドロフラン存在下でグリニャール試薬や、アルカリ金属アセチリド、アルカリ金属アルコキシドを利用して得られた生成物は、不飽和結合含有シラン化合物とテトラヒドロフランと未反応物などの混合物となっている。その場合、未反応物等は蒸留により容易に除去できるが、不飽和結合含有シラン化合物とテトラヒドロフランとを蒸留によって分離することが難しいという問題点があった。 When synthesizing an unsaturated bond-containing silane compound using a Grignard reaction, the Grignard reagent is often synthesized in tetrahydrofuran. Similarly, alkali metal acetylides and alkali metal alkoxides are often synthesized in tetrahydrofuran. Therefore, the product obtained by using the Grignard reagent, the alkali metal acetylide, and the alkali metal alkoxide in the presence of tetrahydrofuran is a mixture of the unsaturated bond-containing silane compound, the tetrahydrofuran, and the unreacted product. In that case, the unreacted substance or the like can be easily removed by distillation, but there is a problem that it is difficult to separate the unsaturated bond-containing silane compound and tetrahydrofuran by distillation.
本発明は、不飽和結合含有シラン化合物とテトラヒドロフランを含む混合物から、高純度のシラン化合物を得ることが可能な精製方法を提供することを目的とする。 An object of the present invention is to provide a purification method capable of obtaining a high-purity silane compound from a mixture containing an unsaturated bond-containing silane compound and tetrahydrofuran.
本発明者らは、不飽和結合含有シラン化合物とテトラヒドロフランと、不飽和結合含有シラン化合物やテトラヒドロフランよりも沸点の高い高沸点溶媒の三成分系の混合物の蒸留を行うと、不飽和結合含有シラン化合物とテトラヒドロフランの二成分系の混合物を蒸留する場合よりも高純度の不飽和結合含有シラン化合物を得られることを見出し、本発明を着想した。 When the present inventors distill a mixture of an unsaturated bond-containing silane compound and tetrahydrofuran and an unsaturated bond-containing silane compound or a high-boiling solvent having a higher boiling point than tetrahydrofuran, the unsaturated bond-containing silane compound is distilled. We have found that an unsaturated bond-containing silane compound having a higher purity than that obtained by distilling a mixture of two components of and tetrahydrofuran can be obtained, and have conceived the present invention.
本発明は、下記一般式(1)で示される少なくとも1種の不飽和結合含有シラン化合物と、テトラヒドロフランと、前記不飽和結合含有シラン化合物及びテトラヒドロフランより沸点の高い高沸点溶媒と、の混合物に対して、蒸留を行うことを特徴とする不飽和結合含有シラン化合物の精製方法である。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕
The present invention relates to a mixture of at least one unsaturated bond-containing silane compound represented by the following general formula (1), tetrahydrofuran, the unsaturated bond-containing silane compound, and a high-boiling solvent having a boiling point higher than that of tetrahydrofuran. This is a method for purifying an unsaturated bond-containing silane compound, which comprises performing distillation.
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
本発明では、シラン化合物とテトラヒドロフランの二成分系でなく、さらに高沸点溶媒を含む三成分系とすることで、シラン化合物とテトラヒドロフランの相対揮発度を変化させ、蒸留で分離しにくいシラン化合物とテトラヒドロフランを分離しやすくすることができ、高純度のシラン化合物の組成物を得ることができる。さらに、高沸点溶媒がシラン化合物やテトラヒドロフランよりも沸点が高いため、蒸留時に高沸点溶媒が釜に残り、蒸留操作が容易となる。 In the present invention, by adopting a three-component system containing a high boiling point solvent instead of the two-component system of the silane compound and the tetrahydrofuran, the relative volatility of the silane compound and the tetrahydrofuran is changed, and the silane compound and the tetrahydrofuran which are difficult to separate by distillation are used. Can be easily separated, and a composition of a high-purity silane compound can be obtained. Further, since the high boiling point solvent has a higher boiling point than the silane compound or tetrahydrofuran, the high boiling point solvent remains in the kettle during distillation, facilitating the distillation operation.
本発明により、不飽和結合含有シラン化合物とテトラヒドロフランを含む混合物から、高純度の不飽和結合含有シラン化合物を得ることが可能な精製方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a purification method capable of obtaining a high-purity unsaturated bond-containing silane compound from a mixture containing an unsaturated bond-containing silane compound and tetrahydrofuran.
以下、本発明について詳細に説明するが、以下に記載する構成要件の説明は本発明の実施形態の一例であり、これらの具体的内容に限定はされない。その要旨の範囲内で種々変形して実施することができる。 Hereinafter, the present invention will be described in detail, but the description of the constituent elements described below is an example of an embodiment of the present invention, and the specific contents thereof are not limited thereto. It can be modified in various ways within the scope of the gist.
本発明は、下記一般式(1)で示される少なくとも1種の不飽和結合含有シラン化合物と、テトラヒドロフランと、前記不飽和結合含有シラン化合物及びテトラヒドロフランより沸点の高い高沸点溶媒と、の混合物に対して、蒸留を行うことを特徴とする不飽和結合含有シラン化合物の精製方法である。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕
The present invention relates to a mixture of at least one unsaturated bond-containing silane compound represented by the following general formula (1), tetrahydrofuran, the unsaturated bond-containing silane compound, and a high-boiling solvent having a boiling point higher than that of tetrahydrofuran. This is a method for purifying an unsaturated bond-containing silane compound, which comprises performing distillation.
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
蒸留の際には、混合物を高沸点溶媒の沸点未満の温度に加熱する。なお、1回の蒸留で必要な純度まで到達しない場合、複数回の蒸留を行ってもよい。 During distillation, the mixture is heated to a temperature below the boiling point of the high boiling solvent. If the required purity is not reached by one distillation, a plurality of distillations may be performed.
なお、本発明では、不飽和結合含有シラン化合物の分解を抑制するために、低温でも蒸留できるように5kPa以上50kPa以下の減圧度の減圧環境で蒸留を行うことが好ましい。 In the present invention, in order to suppress the decomposition of the unsaturated bond-containing silane compound, it is preferable to perform distillation in a reduced pressure environment at a reduced pressure of 5 kPa or more and 50 kPa or less so that distillation can be performed even at a low temperature.
不飽和結合含有シラン化合物がテトラヒドロフランよりも沸点が高い場合、最初にテトラヒドロフランが蒸発し、その後、不飽和結合含有シラン化合物が蒸発し、本留として精製された不飽和結合含有シラン化合物が得られる。高沸点溶媒は釜残となるため、不飽和結合含有シラン化合物の蒸発中に液体の高沸点溶媒が残り、加熱を効率的に行うことができる。特に、蒸留の初期は、減圧度を高め(例えば、25kPa以上50kPa以下など)かつ温度を低め(例えば、25℃以上100℃以下)に設定して、主にテトラヒドロフランを除去し、次第に減圧度を下げながら温度を上げ、蒸留の終期には減圧度を低め(例えば、5kPa以上25kPa以下など)かつ温度を高め(例えば、100℃以上150℃以下)に設定することが好ましい。 When the unsaturated bond-containing silane compound has a higher boiling point than tetrahydrofuran, the tetrahydrofuran evaporates first, and then the unsaturated bond-containing silane compound evaporates to obtain an unsaturated bond-containing silane compound purified as a main distillate. Since the high boiling point solvent remains in the kettle, the liquid high boiling point solvent remains during the evaporation of the unsaturated bond-containing silane compound, and heating can be performed efficiently. In particular, in the initial stage of distillation, the degree of decompression is increased (for example, 25 kPa or more and 50 kPa or less) and the temperature is set low (for example, 25 ° C or more and 100 ° C or less) to mainly remove tetrahydrofuran, and the degree of decompression is gradually increased. It is preferable to raise the temperature while lowering the temperature, lower the degree of decompression (for example, 5 kPa or more and 25 kPa or less) and raise the temperature (for example, 100 ° C. or higher and 150 ° C. or lower) at the end of distillation.
シラン化合物の一般式(1)中のR1が、ビニル基(即ち、H2C=CH-で表されるエテニル基である)、アリル基(即ち、H2C=CH-CH2-で表される2-プロペニル基である)、エチニル基(HC≡C-で表される)、プロパルギル基(即ち、HC≡C-CH2-で表される2-プロピニル基である)、1-プロピニル基(H3C-C≡C-で表される)、トリメチルシリルエチニル基((H3C)3-Si-C≡C-で表される)、及びプロパルギルオキシ基(即ち、HC≡C-CH2-O-で表される2-プロピニルオキシ基)からなる群から選ばれるいずれか一種以上であることが好ましい。特にR1が、ビニル基、エチニル基及び2-プロピニルオキシ基からなる群から選ばれるいずれか一種以上であることが特に好ましい。 R 1 in the general formula (1) of the silane compound is a vinyl group (that is, an ethenyl group represented by H 2 C = CH-) and an allyl group (that is, H 2 C = CH-CH 2- ). Represented 2-propenyl group), ethynyl group (represented by HC≡C-), propargyl group (ie, 2 -propynyl group represented by HC≡C-CH2-), 1- A propynyl group (represented by H 3C -C≡C-), a trimethylsilylethynyl group (represented by (H 3C ) 3 -Si-C≡C-), and a propargyloxy group (ie, HC≡C). It is preferably at least one selected from the group consisting of (2-propynyloxy group represented by -CH2 -O-). In particular, it is particularly preferable that R 1 is at least one selected from the group consisting of a vinyl group, an ethynyl group and a 2-propynyloxy group.
一般式(1)で示される不飽和結合含有シラン化合物としては、より具体的には以下の化合物が挙げられる。例えば、化合物(1-2)であるトリビニルメチルシラン(沸点101~102℃)、化合物(1-6)であるテトラビニルシラン(沸点130℃)、化合物(1-20)であるトリビニルフルオロシラン(沸点107℃)、化合物(1-27)であるトリエチニルメチルシラン、化合物(1-33)であるトリ(2-プロピニルオキシ)メチルシランを用いることができる。但し、本発明で用いられるシラン化合物は、以下の例示によりなんら制限を受けるものではない。 Specific examples of the unsaturated bond-containing silane compound represented by the general formula (1) include the following compounds. For example, compound (1-2) trivinylmethylsilane (boiling point 101-102 ° C.), compound (1-6) tetravinylsilane (boiling point 130 ° C.), and compound (1-20) trivinylfluorosilane. (Boiled at 107 ° C.), triethynylmethylsilane which is compound (1-27), and tri (2-propynyloxy) methylsilane which is compound (1-33) can be used. However, the silane compound used in the present invention is not limited by the following examples.
上記一般式(1)で示される不飽和結合含有シラン化合物は、シラノール基又は加水分解性基を有するシラン化合物と、炭素-炭素不飽和結合を有するグリニャール試薬を反応させて、シラノール基又は加水分解性基を炭素-炭素不飽和結合を有する基に置換して製造することができる。加水分解性基としては、加水分解してシラノール基を生じる置換基であれば特に限定されないが、一例としてクロロ基を挙げることができる。例えば、不飽和結合含有シラン化合物としてトリビニルメチルシラン、トリビニルフルオロシラン、テトラビニルシランを合成する場合、それぞれ、トリクロロメチルシラン、トリクロロフルオロシラン、テトラクロロシランにビニルグリニャール試薬を反応させて得ることができる。ビニルグリニャール試薬は、マグネシウムと塩化ビニルを反応させることで得ることができる。また、ビニルグリニャール試薬として、臭素を利用したビニルマグネシウムブロミドを使用することもできる。 The unsaturated bond-containing silane compound represented by the general formula (1) is a silanol group or hydrolysis by reacting a silane compound having a silanol group or a hydrolyzable group with a Grinard reagent having a carbon-carbon unsaturated bond. It can be produced by substituting a sex group with a group having a carbon-carbon unsaturated bond. The hydrolyzable group is not particularly limited as long as it is a substituent that hydrolyzes to form a silanol group, and examples thereof include a chloro group. For example, when trivinylmethylsilane, trivinylfluorosilane, and tetravinylsilane are synthesized as unsaturated bond-containing silane compounds, they can be obtained by reacting trichloromethylsilane, trichlorofluorosilane, and tetrachlorosilane with vinyl Grignard reagents, respectively. .. The vinyl Grignard reagent can be obtained by reacting magnesium with vinyl chloride. Further, as a vinyl Grignard reagent, vinyl magnesium bromide using bromine can also be used.
また、上記一般式(1)で示される不飽和結合含有シラン化合物のうち、エチニル基がシリコン原子と結合するシラン化合物は、ハロゲン化シラン化合物と、アルカリ金属アセチリドを反応させて、ハロゲン基を炭素-炭素不飽和結合を有する基に置換して製造することができる。アルカリ金属アセチリドとしては、リチウムアセチリド、ナトリウムアセチリド、カリウムアセチリドを使用することができる。 Further, among the unsaturated bond-containing silane compounds represented by the above general formula (1), the silane compound in which the ethynyl group is bonded to the silicon atom is obtained by reacting the halogenated silane compound with the alkali metal acetylide to convert the halogen group into carbon. -Can be produced by substituting with a group having a carbon unsaturated bond. As the alkali metal acetylide, lithium acetylide, sodium acetylide, and potassium acetylide can be used.
また、上記一般式(1)で示される不飽和結合含有シラン化合物のうち、炭素-炭素不飽和結合を有するアルコキシ基がシリコン原子と結合するシラン化合物は、ハロゲン化シラン化合物と、炭素-炭素不飽和結合を有するアルコキシ基のアルカリ金属アルコキシドを反応させて、ハロゲン基を炭素-炭素不飽和結合を有するアルコキシ基に置換して製造することができる。アルカリ金属アルコキシドは、アルコールに水素化アルカリ金属を反応させて得ることができる。アルカリ金属アルコキシドとしては、リチウムアセチリド、ナトリウムアルコキシド、カリウムアルコキシドを使用できる。 Among the unsaturated bond-containing silane compounds represented by the above general formula (1), the silane compounds in which an alkoxy group having a carbon-carbon unsaturated bond is bonded to a silicon atom are a halogenated silane compound and a carbon-carbon unsaturated. It can be produced by reacting an alkali metal alkoxide of an alkoxy group having a saturated bond to replace the halogen group with an alkoxy group having a carbon-carbon unsaturated bond. The alkali metal alkoxide can be obtained by reacting an alcohol with a hydrogenated alkali metal. As the alkali metal alkoxide, lithium acetylide, sodium alkoxide, and potassium alkoxide can be used.
前記不飽和結合含有シラン化合物及びテトラヒドロフラン(沸点66℃)より沸点の高い高沸点溶媒が、エーテル系溶媒又は炭化水素系溶媒であることが好ましい。エーテル系溶媒としては、シクロペンチルメチルエーテル(沸点106℃)、ジエチレングリコールジメチルエーテル(沸点162℃)、ジエチレングリコールジエチルエーテル(沸点188℃)、ジエチレングリコールジブチルエーテル(沸点255℃)、トリエチレングリコールジメチルエーテル(沸点216℃、トリグライムとも呼ばれる)などを使用でき、炭化水素系溶媒としては、1,3,5-トリメチルベンゼン(沸点165℃、メシチレンとも呼ばれる)、1,2,4-トリメチルベンゼン(沸点169℃)、ジエチルベンゼン(オルト体(沸点183℃)、メタ体(沸点182℃)、パラ体(沸点184℃)のいずれも使用できこれらの混合物も使用できる。)、ブチルベンゼン(n-ブチルベンゼン(沸点183℃)とtert-ブチルベンゼン(169℃)のいずれも使用できこれらの混合物も使用できる)、1,3,5-トリエチルベンゼン(沸点212~222℃)、ジイソプロピルベンゼン(オルト体(沸点204℃)、メタ体(沸点203℃)、パラ体(沸点210℃)のいずれも使用できこれらの混合物も使用できる。)などを使用できる。なお、以上に記載した沸点の値は大気圧(1atm)での値であり、減圧環境での沸点の値は上記の値よりも小さくなる。また、高沸点溶媒は、蒸留にて分離を容易にするため、不飽和結合含有シラン化合物の沸点よりも20℃以上、好ましくは30℃以上高い沸点を持つ溶媒を使用することが好ましい。 It is preferable that the unsaturated bond-containing silane compound and a high boiling point solvent having a boiling point higher than that of tetrahydrofuran (boiling point 66 ° C.) are an ether solvent or a hydrocarbon solvent. Examples of the ether solvent include cyclopentylmethyl ether (boiling point 106 ° C.), diethylene glycol dimethyl ether (boiling point 162 ° C.), diethylene glycol diethyl ether (boiling point 188 ° C.), diethylene glycol dibutyl ether (boiling point 255 ° C.), triethylene glycol dimethyl ether (boiling point 216 ° C., Triglime (also called triglime) can be used, and as the hydrocarbon solvent, 1,3,5-trimethylbenzene (boiling point 165 ° C., also called mesitylene), 1,2,4-trimethylbenzene (boiling point 169 ° C.), diethylbenzene (boiling point 169 ° C.) can be used. Ortho-form (boiling point 183 ° C.), meta-form (boiling point 182 ° C.), para-form (boiling point 184 ° C.) can be used, and a mixture thereof can also be used), butylbenzene (n-butylbenzene (boiling point 183 ° C.)) and Any of tert-butylbenzene (169 ° C.) can be used and a mixture thereof can also be used), 1,3,5-triethylbenzene (boiling point 212-222 ° C.), diisopropylbenzene (ortho-form (boiling point 204 ° C.), meta-form. (Boiling point 203 ° C.), para-form (boiling point 210 ° C.) can be used, and a mixture thereof can also be used.) And the like can be used. The boiling point value described above is a value at atmospheric pressure (1 atm), and the boiling point value in a reduced pressure environment is smaller than the above value. Further, as the high boiling point solvent, it is preferable to use a solvent having a boiling point of 20 ° C. or higher, preferably 30 ° C. or higher, higher than the boiling point of the unsaturated bond-containing silane compound in order to facilitate separation by distillation.
不飽和結合含有シラン化合物とテトラヒドロフランと高沸点溶媒の混合物中の、高沸点溶媒の含有量が、混合物中の不飽和結合含有シラン化合物の含有量よりも多いことが好ましく、質量比で2倍以上であることがより好ましい。高沸点溶媒の量が不飽和結合含有シラン化合物より少なすぎると、十分に蒸留を行えず、蒸留した不飽和結合含有シラン化合物の純度が低くなる。 The content of the high boiling point solvent in the mixture of the unsaturated bond-containing silane compound, tetrahydrofuran and the high boiling point solvent is preferably higher than the content of the unsaturated bond-containing silane compound in the mixture, and is more than twice by mass ratio. Is more preferable. If the amount of the high boiling point solvent is too smaller than that of the unsaturated bond-containing silane compound, sufficient distillation cannot be performed and the purity of the distilled unsaturated bond-containing silane compound becomes low.
不飽和結合含有シラン化合物とテトラヒドロフランと高沸点溶媒の混合物中のテトラヒドロフランの含有量が、1質量%以上90質量%以下であることが好ましく、10質量%以上80質量%以下であることがより好ましい。テトラヒドロフランの量を少なくするためには、グリニャール試薬の合成や保管、不飽和結合含有シラン化合物の合成に特別な方法を用いる必要があり、効率的でない。一方で、テトラヒドロフランの量が多すぎると、蒸留に必要なエネルギーが過大となる。 The content of tetrahydrofuran in the mixture of the unsaturated bond-containing silane compound, tetrahydrofuran and the high boiling point solvent is preferably 1% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. .. In order to reduce the amount of tetrahydrofuran, it is necessary to use a special method for the synthesis and storage of Grignard reagent and the synthesis of unsaturated bond-containing silane compound, which is not efficient. On the other hand, if the amount of tetrahydrofuran is too large, the energy required for distillation becomes excessive.
蒸留により得られた不飽和結合含有シラン化合物の組成物中の不飽和結合含有シラン化合物の含有量が90質量%以上であることが好ましく、95質量%以上であることがより好ましく、99質量%以上であることがさらに好ましい。組成物にテトラヒドロフランや高沸点溶媒が含まれても、その合計の含有量が10質量ppm以上10質量%以下であることが好ましく、100質量ppm以上1質量%以下であることがより好ましい。テトラヒドロフランと高沸点溶媒のそれぞれの含有量を1質量ppm未満にまで精製するためには、蒸留を複数回繰り返す必要があるなど、不飽和結合含有シラン化合物の組成物を得るためのコストが高くなるため、通常は組成物中にテトラヒドロフランと高沸点溶媒のそれぞれの含有量が1質量ppm以上である。一方、合計の含有量が多すぎる場合、不飽和結合含有シラン化合物をリチウムイオン電池用電解液の添加剤として用いる場合、テトラヒドロフランや高沸点溶媒がリチウムイオン電池に悪影響を与える可能性がある。 The content of the unsaturated bond-containing silane compound in the composition of the unsaturated bond-containing silane compound obtained by distillation is preferably 90% by mass or more, more preferably 95% by mass or more, and 99% by mass. The above is more preferable. Even if the composition contains tetrahydrofuran or a high boiling point solvent, the total content thereof is preferably 10% by mass or more and 10% by mass or less, and more preferably 100% by mass or more and 1% by mass or less. In order to purify the respective contents of tetrahydrofuran and the high boiling point solvent to less than 1 mass ppm, it is necessary to repeat distillation multiple times, and the cost for obtaining the composition of the unsaturated bond-containing silane compound becomes high. Therefore, usually, the content of each of the tetrahydrofuran and the high boiling point solvent in the composition is 1 mass ppm or more. On the other hand, when the total content is too large, when an unsaturated bond-containing silane compound is used as an additive for an electrolytic solution for a lithium ion battery, tetrahydrofuran or a high boiling point solvent may adversely affect the lithium ion battery.
本発明の精製方法を適用することで、純度90質量%以上の高純度な不飽和結合含有シラン化合物の組成物を得ることができる。また、精製工程を非水系で行うことで、不飽和結合含有シラン化合物の組成物の含水量を低減することができ、リチウムイオン電池用電解液の添加剤として適した不飽和含有シラン化合物の組成物を得ることができる。 By applying the purification method of the present invention, a composition of a high-purity unsaturated bond-containing silane compound having a purity of 90% by mass or more can be obtained. Further, by performing the purification step in a non-aqueous system, the water content of the composition of the unsaturated bond-containing silane compound can be reduced, and the composition of the unsaturated-containing silane compound suitable as an additive for the electrolytic solution for lithium ion batteries. You can get things.
また、蒸留装置の釜が空焚きになる事を防ぐため、不飽和結合含有シラン化合物とテトラヒドロフランの二成分系の混合物を蒸留する場合、不飽和結合含有シラン化合物を一部残さないといけないが、高沸点溶媒を含む三成分系では、釜に高沸点溶媒が残るため、不飽和結合含有シラン化合物を全て留出することができ、収率を高くすることができる。 In addition, in order to prevent the kettle of the distillation apparatus from becoming empty, when distilling a mixture of an unsaturated bond-containing silane compound and a two-component system of tetrahydrofuran, a part of the unsaturated bond-containing silane compound must be left. In the three-component system containing the high boiling point solvent, since the high boiling point solvent remains in the kettle, all the unsaturated bond-containing silane compounds can be distilled off, and the yield can be increased.
また、不飽和結合含有シラン化合物とテトラヒドロフランと、不飽和結合含有シラン化合物よりも沸点の低い低沸点溶媒の三成分系では、蒸留時に不飽和結合含有シラン化合物とテトラヒドロフランだけでなく低沸点溶媒も揮発させなくてはならないため、多量のエネルギーが必要となるが、高沸点溶媒を用いた三成分系では、テトラヒドロフランと不飽和結合含有シラン化合物だけを揮発させればよいため、蒸留に必要なエネルギーを節約することが可能である。 Further, in the three-component system of the unsaturated bond-containing silane compound and tetrahydrofuran and the low boiling point solvent having a lower boiling point than the unsaturated bond-containing silane compound, not only the unsaturated bond-containing silane compound and tetrahydrofuran but also the low boiling point solvent volatilize during distillation. A large amount of energy is required because this must be done, but in a three-component system using a high-boiling solvent, only tetrahydrofuran and the unsaturated bond-containing silane compound need to be volatilized, so the energy required for distillation can be obtained. It is possible to save.
上述の蒸留工程を含む不飽和結合含有シラン化合物の製造方法の一例として、以下の三つの方法を挙げることができる。 As an example of the method for producing an unsaturated bond-containing silane compound including the above-mentioned distillation step, the following three methods can be mentioned.
[第1の方法]
第1の不飽和結合含有シラン化合物の製造方法では、不飽和結合含有シラン化合物をテトラヒドロフラン中で合成する工程と、さらに高沸点溶媒を加える工程により混合物を得た後に、この混合物を蒸留する。
[First method]
In the first method for producing an unsaturated bond-containing silane compound, a mixture is obtained by a step of synthesizing the unsaturated bond-containing silane compound in tetrahydrofuran and a step of further adding a high boiling point solvent, and then the mixture is distilled.
不飽和結合含有シラン化合物の合成においては、炭素-炭素不飽和結合を有するグリニャール試薬のテトラヒドロフラン溶液に対して、シラノール基又は加水分解性基を有するシラン化合物を供給して反応させて合成する方法を用いることができる。第1の方法では、グリニャール試薬がテトラヒドロフラン中で安定であるため、保管条件や反応条件などを厳密に制御しなくても不飽和結合含有シラン化合物を得ることができる。 In the synthesis of unsaturated bond-containing silane compounds, a method of supplying a silane compound having a silanol group or a hydrolyzable group to a tetrahydrofuran solution of a Grignard reagent having a carbon-carbon unsaturated bond and reacting them to synthesize the compound is performed. Can be used. In the first method, since the Grignard reagent is stable in tetrahydrofuran, an unsaturated bond-containing silane compound can be obtained without strictly controlling storage conditions and reaction conditions.
また、不飽和結合含有シラン化合物のR1がエチニル基である場合、アルカリ金属アセチリドのテトラヒドロフラン溶液に対して、ハロゲン化シランを供給して反応させて合成する方法を用いることができる。 When R 1 of the unsaturated bond-containing silane compound is an ethynyl group, a method of supplying silane halide to a tetrahydrofuran solution of alkali metal acetylide and reacting them can be used.
また、不飽和結合含有シラン化合物のR1が炭素-炭素不飽和結合を有するアルコキシ基である場合、炭素-炭素不飽和結合を有するアルコキシ基のアルカリ金属アルコキシドのテトラヒドロフラン溶液に対して、ハロゲン化シランを供給して反応させて合成する方法を用いることができる。 When R 1 of the unsaturated bond-containing silane compound is an alkoxy group having a carbon-carbon unsaturated bond, halogenated silane with respect to a tetrahydrofuran solution of an alkali metal alkoxide of an alkoxy group having a carbon-carbon unsaturated bond. Can be used for synthesizing by supplying and reacting with each other.
[第2の方法]
第2の不飽和結合含有シラン化合物の製造方法では、不飽和結合含有シラン化合物を、テトラヒドロフランと高沸点溶媒の混合溶媒中で合成する工程により混合物を得た後に、この混合物を蒸留する。
[Second method]
In the second method for producing an unsaturated bond-containing silane compound, the unsaturated bond-containing silane compound is synthesized in a mixed solvent of tetrahydrofuran and a high boiling point solvent to obtain a mixture, and then the mixture is distilled.
不飽和結合含有シラン化合物の合成においては、炭素-炭素不飽和結合を有するグリニャール試薬のテトラヒドロフランと高沸点溶媒の混合溶媒の溶液に対して、シラノール基又は加水分解性基を有するシラン化合物を供給して反応させて合成する。第2の方法では、第1の方法よりもテトラヒドロフランの量が減るため、蒸留に必要なエネルギーを減らすことができる。 In the synthesis of unsaturated bond-containing silane compounds, a silane compound having a silanol group or a hydrolyzable group is supplied to a solution of a mixed solvent of a Grignard reagent having a carbon-carbon unsaturated bond and a high boiling point solvent. To react and synthesize. In the second method, the amount of tetrahydrofuran is reduced as compared with the first method, so that the energy required for distillation can be reduced.
また、不飽和結合含有シラン化合物のR1がエチニル基である場合、アルカリ金属アセチリドのテトラヒドロフランと高沸点溶媒の混合溶媒の溶液に対して、ハロゲン化シランを供給して反応させて、不飽和結合含有シラン化合物を合成することができる。 When R 1 of the unsaturated bond-containing silane compound is an ethynyl group, silane halide is supplied to a solution of a mixed solvent of tetrahydrofuran of alkali metal acetylide and a high boiling point solvent to cause an unsaturated bond. The contained silane compound can be synthesized.
また、不飽和結合含有シラン化合物のR1が炭素-炭素不飽和結合を有するアルコキシ基である場合、炭素-炭素不飽和結合を有するアルコキシ基のアルカリ金属アルコキシドの、テトラヒドロフランと高沸点溶媒の混合溶媒の溶液に対して、ハロゲン化シランを供給して反応させて、不飽和結合含有シラン化合物を合成することができる。 When R 1 of the unsaturated bond-containing silane compound is an alkoxy group having a carbon-carbon unsaturated bond, a mixed solvent of tetrahydrofuran and a high boiling point solvent of an alkali metal alkoxide of an alkoxy group having a carbon-carbon unsaturated bond. The unsaturated bond-containing silane compound can be synthesized by supplying silane halide and reacting with the solution of.
[第3の方法]
第3の不飽和結合含有シラン化合物の製造方法では、炭素-炭素不飽和結合を有するグリニャール試薬をテトラヒドロフラン中で合成する工程と、グリニャール試薬の溶媒を高沸点溶媒に置換する工程と、高沸点溶媒及び残余のテトラヒドロフランの混合溶媒中で、シラノール基又は加水分解性基を有するシラン化合物とグリニャール試薬とを反応させて、不飽和結合含有シラン化合物を合成する工程により混合物を得た後に、この混合物を蒸留する。
[Third method]
In the third method for producing an unsaturated bond-containing silane compound, a step of synthesizing a Grignard reagent having a carbon-carbon unsaturated bond in tetrahydrofuran, a step of replacing the Grignard reagent solvent with a high boiling solvent, and a high boiling solvent. And the Grignard reagent is reacted with a silane compound having a silanol group or a hydrolyzable group in a mixed solvent of the residue of tetrahydrofuran to obtain a mixture by a step of synthesizing an unsaturated bond-containing silane compound, and then this mixture is prepared. Distill.
また、不飽和結合含有シラン化合物のR1がエチニル基である場合、アルカリ金属アセチリドをテトラヒドロフラン中で合成する工程と、アルカリ金属アセチリドの溶媒を高沸点溶媒に置換する工程と、高沸点溶媒及び残余のテトラヒドロフランの混合溶媒中で、ハロゲン化シランとアルカリ金属アセチリドとを反応させて、不飽和結合含有シラン化合物を合成する工程により混合物を得た後に、この混合物を蒸留する方法でも、不飽和結合含有シラン化合物を得ることができる。 When R 1 of the unsaturated bond-containing silane compound is an ethynyl group, a step of synthesizing the alkali metal acetylide in tetrahydrofuran, a step of substituting the solvent of the alkali metal acetylide with a high boiling point solvent, a high boiling point solvent and a residue. A method of reacting a silane halide with an alkali metal acetylide in a mixed solvent of tetrahydrofuran to obtain a mixture by synthesizing an unsaturated bond-containing silane compound, and then distilling this mixture also contains an unsaturated bond. A silane compound can be obtained.
また、不飽和結合含有シラン化合物のR1が炭素-炭素不飽和結合を有するアルコキシ基である場合、炭素-炭素不飽和結合を有するアルコキシ基のアルカリ金属アルコキシドをテトラヒドロフラン中で合成する工程と、アルカリ金属アルコキシドの溶媒を高沸点溶媒に置換する工程と、高沸点溶媒及び残余のテトラヒドロフランの混合溶媒中で、ハロゲン化シランとアルカリ金属アルコキシドとを反応させて、不飽和結合含有シラン化合物を合成する工程により混合物を得た後に、この混合物を蒸留する方法でも、不飽和結合含有シラン化合物を得ることができる。 When R 1 of the unsaturated bond-containing silane compound is an alkoxy group having a carbon-carbon unsaturated bond, a step of synthesizing an alkali metal alkoxy of an alkoxy group having a carbon-carbon unsaturated bond in tetrahydrofuran and an alkali. A step of substituting the solvent of the metal alkoxy with a high boiling point solvent and a step of reacting the halide silane with the alkali metal alkoxy in a mixed solvent of the high boiling point solvent and the residual tetrahydrofuran to synthesize an unsaturated bond-containing silane compound. An unsaturated bond-containing silane compound can also be obtained by a method of distilling the mixture after obtaining the mixture.
溶媒置換工程は特に限定されないが、高沸点溶媒を添加した後にテトラヒドロフランを減圧留去することが好ましい。溶媒置換後の高沸点溶媒とテトラヒドロフランの質量比は80:20~99:1程度である。この範囲内であれば、溶媒置換の効果を得つつ、簡単な操作で到達可能である。 The solvent replacement step is not particularly limited, but it is preferable to distill under reduced pressure after adding a high boiling point solvent. The mass ratio of the high boiling point solvent to tetrahydrofuran after the solvent substitution is about 80:20 to 99: 1. Within this range, it can be reached by a simple operation while obtaining the effect of solvent substitution.
この方法では、溶媒置換をすることで、蒸留で揮発させるテトラヒドロフランの量が減るため、蒸留に必要なエネルギーを減らすことができる。しかし、テトラヒドロフラン以外のグリニャール試薬の溶液は、安定でない場合が多いため、保管条件や反応条件の制御等が難しくなるという問題もある。 In this method, solvent substitution reduces the amount of tetrahydrofuran volatilized by distillation, so that the energy required for distillation can be reduced. However, since solutions of Grignard reagents other than tetrahydrofuran are often unstable, there is also a problem that it becomes difficult to control storage conditions and reaction conditions.
また、不飽和結合含有シラン化合物を合成した後の溶媒は、高沸点溶媒の濃度が高いため、蒸留で留去した高沸点溶媒を、グリニャール試薬の溶媒を置換する高沸点溶媒として再利用することができる。 Further, since the solvent after synthesizing the unsaturated bond-containing silane compound has a high concentration of the high boiling point solvent, the high boiling point solvent distilled off by distillation should be reused as a high boiling point solvent to replace the solvent of the Grinard reagent. Can be done.
以下、実施例により本発明を具体的に説明するが、本発明は係る実施例により限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to such Examples.
[実施例1-1:第3の方法]
フラスコにマグネシウム23.3g(0.96モル)、塩化ビニル66.3g(1.06モル)、テトラヒドロフラン750gを入れ、攪拌して、グリニャール試薬を合成した。その後、ジエチレングリコールジエチルエーテル650gを添加し、エバポレーターにて減圧濃縮し、溶媒置換を行った。溶媒置換後の混合溶媒中のテトラヒドロフランとジエチレングリコールジエチルエーテルの質量比は5:95であった。その後、冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、溶媒置換したグリニャール試薬を入れ、滴下漏斗を用いてトリクロロメチルシラン43.4g(0.29モル)、ジエチレングリコールジエチルエーテル75gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジエチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルメチルシラン4質量%とテトラヒドロフラン1質量%とジエチレングリコールジエチルエーテル95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルメチルシラン組成物22.5g(収率60%、GC純度96面積%)を得た。
[Example 1-1: Third method]
23.3 g (0.96 mol) of magnesium, 66.3 g (1.06 mol) of vinyl chloride and 750 g of tetrahydrofuran were placed in a flask and stirred to synthesize a Grignard reagent. Then, 650 g of diethylene glycol diethyl ether was added, and the mixture was concentrated under reduced pressure with an evaporator to replace the solvent. The mass ratio of tetrahydrofuran to diethylene glycol diethyl ether in the mixed solvent after the solvent substitution was 5:95. Then, put the solvent-substituted Grignard reagent in a three-necked flask equipped with a cooling condenser and a dropping funnel, and use the dropping funnel to add 43.4 g (0.29 mol) of trichloromethylsilane and 75 g of diethylene glycol diethyl ether over 6 hours. And added. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol diethyl ether. The liquid component was evaporated and condensed by evaporating the filtrate with an evaporator to remove the solid component, and a mixture containing 4% by mass of trivinylmethylsilane, 1% by mass of tetrahydrofuran and 95% by mass of diethylene glycol diethyl ether was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 125 ° C. at a reduced pressure of 10 kPa and distilled to obtain 22.5 g of a trivinylmethylsilane composition (yield 60%, GC purity 96). Area%) was obtained.
[実施例1-2:第1の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム80.7g(0.93モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてトリクロロメチルシラン61.3g(0.41モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液にジエチレングリコールジエチルエーテル500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルメチルシランとテトラヒドロフランとジエチレングリコールジエチルエーテルを含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度20kPaで100℃に加熱して蒸留してトリビニルメチルシラン組成物34.5g(収率65%、GC純度96面積%)を得た。
[Example 1-2: first method]
80.7 g (0.93 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran are placed in a three-necked flask equipped with a cooling condenser and a dropping funnel, and after stirring, 61.3 g (0.41 mol) of trichloromethylsilane is used using the dropping funnel. ), 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt is filtered, 500 g of diethylene glycol diethyl ether is added to the filtrate, and then the liquid component is evaporated and condensed with an evaporator to remove the solid component, and trivinylmethylsilane, tetrahydrofuran and diethylene glycol are removed. A mixture containing diethyl ether was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 100 ° C. at a reduced pressure of 20 kPa and distilled to obtain 34.5 g of a trivinylmethylsilane composition (yield 65%, GC purity 96). Area%) was obtained.
[実施例1-3:第2の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590g、ジエチレングリコールジエチルエーテル500gを入れ攪拌した後、滴下漏斗を用いてトリクロロメチルシラン61.3g(0.41モル)、ジエチレングリコールジエチルエーテル150gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジエチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルメチルシランとテトラヒドロフランとジエチレングリコールジエチルエーテルを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルメチルシラン組成物31.9g(収率60%、GC純度96面積%)を得た。
[Example 1-3: Second method]
109.4 g (1.26 mol) of vinyl chloride magnesium chloride, 590 g of tetrahydrofuran, and 500 g of diethylene glycol diethyl ether are placed in a three-necked flask equipped with a cooling condenser and a dropping funnel, stirred, and then trichloromethylsilane 61.3 g using a dropping funnel. (0.41 mol), 150 g of diethylene glycol diethyl ether was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol diethyl ether. The liquid component was evaporated and condensed in the filtrate with an evaporator to remove the solid component, and a mixture containing trivinylmethylsilane, tetrahydrofuran and diethylene glycol diethyl ether as main components was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 31.9 g (yield 60%, GC purity 96). Area%) was obtained.
[実施例1-4:第1の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてトリクロロメチルシラン61.3g(0.41モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液にメシチレン500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルメチルシランとテトラヒドロフランとメシチレンを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルメチルシラン組成物32.9g(収率62%、GC純度96面積%)を得た。
[Example 1-4: first method]
Put 109.4 g (1.26 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran in a three-necked flask equipped with a cooling condenser and a dropping funnel, and after stirring, 61.3 g (0.41 mol) of trichloromethylsilane using a dropping funnel. ), 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt is filtered, 500 g of mesitylene is added to the filtrate, and then the liquid component is evaporated and condensed by an evaporator to remove the solid component, and trivinylmethylsilane, tetrahydrofuran and mesitylene are mainly used. A mixture as an ingredient was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 32.9 g (yield 62%, GC purity 96). Area%) was obtained.
[実施例1-5:第3の方法]
フラスコにマグネシウム23.3g(0.96モル)、塩化ビニル66.3g(1.06モル)、テトラヒドロフラン750gを入れ、攪拌して、グリニャール試薬を合成した。その後、ジエチレングリコールジブチルエーテル650gを添加し、エバポレーターにて減圧濃縮し、溶媒置換を行った。溶媒置換後の混合溶媒中のテトラヒドロフランとジエチレングリコールジブチルエーテルの質量比は5:95であった。その後、冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、溶媒置換したグリニャール試薬を入れ、滴下漏斗を用いてトリクロロメチルシラン43.4g(0.29モル)、ジエチレングリコールジブチルエーテル75gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジブチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルメチルシラン4質量%とテトラヒドロフラン1質量%とジエチレングリコールジブチルエーテル95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルメチルシラン組成物20.4g(収率55%、GC純度97面積%)を得た。
[Example 1-5: Third method]
23.3 g (0.96 mol) of magnesium, 66.3 g (1.06 mol) of vinyl chloride and 750 g of tetrahydrofuran were placed in a flask and stirred to synthesize a Grignard reagent. Then, 650 g of diethylene glycol dibutyl ether was added, and the mixture was concentrated under reduced pressure with an evaporator to replace the solvent. The mass ratio of tetrahydrofuran to diethylene glycol dibutyl ether in the mixed solvent after solvent substitution was 5:95. Then, put the solvent-substituted Grignard reagent in a three-necked flask equipped with a cooling condenser and a dropping funnel, and use the dropping funnel to add 43.4 g (0.29 mol) of trichloromethylsilane and 75 g of diethylene glycol dibutyl ether over 6 hours. And added. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol dibutyl ether. The liquid component was evaporated and condensed by evaporating the filtrate with an evaporator to remove the solid component, and a mixture containing 4% by mass of trivinylmethylsilane, 1% by mass of tetrahydrofuran and 95% by mass of diethylene glycol dibutyl ether was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 125 ° C. at a reduced pressure of 10 kPa and distilled to obtain 20.4 g of a trivinylmethylsilane composition (yield 55%, GC purity 97). Area%) was obtained.
[比較例1-1]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてトリクロロメチルシラン61.3g(0.41モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルメチルシランとテトラヒドロフランを含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度20kPaで100℃に加熱して蒸留してトリビニルメチルシラン組成物47.0g(収率60%、GC純度65面積%)を得た。なお、空焚き防止のため、一部のトリビニルメチルシランを蒸留装置の釜に残した。
[Comparative Example 1-1]
In a three-necked flask equipped with a cooling condenser and a dropping funnel, 109.4 g (1.26 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran were placed and stirred, and then 61.3 g (0.41) of trichloromethylsilane using a dropping funnel. Mol), 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and the filtrate was evaporated and condensed with an evaporator to remove the solid component to obtain a mixture containing trivinylmethylsilane and tetrahydrofuran. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 100 ° C. at a reduced pressure of 20 kPa and distilled to obtain 47.0 g of a trivinylmethylsilane composition (yield 60%, GC purity 65). Area%) was obtained. A part of trivinylmethylsilane was left in the kettle of the distillation apparatus to prevent empty heating.
[実施例2-1:第3の方法]
フラスコにマグネシウム16.3g(0.67モル)、塩化ビニル46.3g(0.74モル)、テトラヒドロフラン750gを入れ、攪拌して、グリニャール試薬を合成した。その後、ジエチレングリコールジエチルエーテル650gを添加し、エバポレーターにて減圧濃縮し、溶媒置換を行った。溶媒置換後の混合溶媒中のテトラヒドロフランとジエチレングリコールジエチルエーテルの質量比は5:95であった。その後、冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、溶媒置換したグリニャール試薬を入れ、滴下漏斗を用いてトリクロロフルオロシラン32.2g(0.21モル)、ジエチレングリコールジエチルエーテル75gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジエチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルフルオロシラン4質量%とテトラヒドロフラン1質量%とジエチレングリコールジエチルエーテル95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルフルオロシラン組成物14.0g(収率50%、GC純度96面積%)を得た。
[Example 2-1: Third method]
16.3 g (0.67 mol) of magnesium, 46.3 g (0.74 mol) of vinyl chloride and 750 g of tetrahydrofuran were placed in a flask and stirred to synthesize a Grignard reagent. Then, 650 g of diethylene glycol diethyl ether was added, and the mixture was concentrated under reduced pressure with an evaporator to replace the solvent. The mass ratio of tetrahydrofuran to diethylene glycol diethyl ether in the mixed solvent after the solvent substitution was 5:95. Then, put the solvent-substituted Grignard reagent in a three-necked flask equipped with a cooling condenser and a dropping funnel, and use the dropping funnel to add 32.2 g (0.21 mol) of trichlorofluorosilane and 75 g of diethylene glycol diethyl ether over 6 hours. And added. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol diethyl ether. The liquid component was evaporated and condensed by evaporating the filtrate with an evaporator to remove the solid component, and a mixture containing 4% by mass of trivinylfluorosilane, 1% by mass of tetrahydrofuran and 95% by mass of diethylene glycol diethyl ether was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 14.0 g (yield 50%, GC purity 96). Area%) was obtained.
[実施例2-2:第1の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム80.7g(0.93モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてトリクロロフルオロシラン46g(0.30モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液にジエチレングリコールジエチルエーテル500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルフルオロシランとテトラヒドロフランとジエチレングリコールジエチルエーテルを含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度20kPaで100℃に加熱して蒸留してトリビニルフルオロシラン組成物24.5g(収率60%、GC純度94面積%)を得た。
[Example 2-2: first method]
80.7 g (0.93 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran were placed in a three-necked flask equipped with a cooling condenser and a dropping funnel, and after stirring, 46 g (0.30 mol) of trichlorofluorosilane (0.30 mol) using a dropping funnel. 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt is filtered, 500 g of diethylene glycol diethyl ether is added to the filtrate, and then the liquid component is evaporated and condensed by an evaporator to remove the solid component, and trivinylfluorosilane, tetrahydrofuran and diethylene glycol are removed. A mixture containing diethyl ether was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 100 ° C. at a reduced pressure of 20 kPa and distilled to obtain 24.5 g of a trivinylfluorosilane composition (yield 60%, GC purity 94). Area%) was obtained.
[実施例2-3:第2の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム80.7g(0.93モル)、テトラヒドロフラン590g、ジエチレングリコールジエチルエーテル500gを入れ攪拌した後、滴下漏斗を用いてトリクロロフルオロシラン46g(0.30モル)、ジエチレングリコールジエチルエーテル150gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジエチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルフルオロシランとテトラヒドロフランとジエチレングリコールジエチルエーテルを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルフルオロシラン組成物22.5g(収率55%、GC純度94面積%)を得た。
[Example 2-3: Second method]
80.7 g (0.93 mol) of vinyl chloride magnesium chloride, 590 g of tetrahydrofuran, and 500 g of diethylene glycol diethyl ether are placed in a three-necked flask equipped with a cooling condenser and a dropping funnel and stirred, and then 46 g (0) of trichlorofluorosilane using a dropping funnel. .30 mol), 150 g of diethylene glycol diethyl ether was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol diethyl ether. The liquid component was evaporated and condensed in the filtrate with an evaporator to remove the solid component, and a mixture containing trivinylfluorosilane, tetrahydrofuran and diethylene glycol diethyl ether as main components was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 125 ° C. at a reduced pressure of 10 kPa and distilled to 22.5 g of a trivinylfluorosilane composition (yield 55%, GC purity 94). Area%) was obtained.
[実施例2-4:第1の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム80.7g(0.93モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてトリクロロフルオロシラン46g(0.30モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液にメシチレン500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルフルオロシランとテトラヒドロフランとメシチレンを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルフルオロシラン組成物24.8g(収率60%、GC純度93面積%)を得た。
[Example 2-4: first method]
80.7 g (0.93 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran were placed in a three-necked flask equipped with a cooling condenser and a dropping funnel, and after stirring, 46 g (0.30 mol) of trichlorofluorosilane (0.30 mol) using a dropping funnel. 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt is filtered, 500 g of mesitylene is added to the filtrate, and then the liquid component is evaporated and condensed with an evaporator to remove the solid component, and trivinylfluorosilane, tetrahydrofuran and mesitylene are mainly used. A mixture as an ingredient was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 125 ° C. at a reduced pressure of 10 kPa and distilled to obtain 24.8 g of a trivinylfluorosilane composition (yield 60%, GC purity 93). Area%) was obtained.
[実施例2-5:第3の方法]
フラスコにマグネシウム16.3g(0.67モル)、塩化ビニル46.3g(0.74モル)、テトラヒドロフラン750gを入れ、攪拌して、グリニャール試薬を合成した。その後、ジエチレングリコールジブチルエーテル650gを添加し、エバポレーターにて減圧濃縮し、溶媒置換を行った。溶媒置換後の混合溶媒中のテトラヒドロフランとジエチレングリコールジブチルエーテルの質量比は5:95であった。その後、冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、溶媒置換したグリニャール試薬を入れ、滴下漏斗を用いてトリクロロフルオロシラン32.2g(0.21モル)、ジエチレングリコールジブチルエーテル75gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジブチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルフルオロシラン4質量%とテトラヒドロフラン1質量%とジエチレングリコールジブチルエーテル95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリビニルフルオロシラン組成物12.8g(収率45%、GC純度95面積%)を得た。
[Example 2-5: Third method]
16.3 g (0.67 mol) of magnesium, 46.3 g (0.74 mol) of vinyl chloride and 750 g of tetrahydrofuran were placed in a flask and stirred to synthesize a Grignard reagent. Then, 650 g of diethylene glycol dibutyl ether was added, and the mixture was concentrated under reduced pressure with an evaporator to replace the solvent. The mass ratio of tetrahydrofuran to diethylene glycol dibutyl ether in the mixed solvent after solvent substitution was 5:95. Then, put the solvent-substituted Grignard reagent in a three-necked flask equipped with a cooling condenser and a dropping funnel, and use the dropping funnel to add 32.2 g (0.21 mol) of trichlorofluorosilane and 75 g of diethylene glycol dibutyl ether over 6 hours. And added. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol dibutyl ether. The liquid component was evaporated and condensed by evaporating the filtrate with an evaporator to remove the solid component, and a mixture containing 4% by mass of trivinylfluorosilane, 1% by mass of tetrahydrofuran and 95% by mass of diethylene glycol dibutyl ether was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 12.8 g (yield 45%, GC purity 95). Area%) was obtained.
[比較例2-1]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、塩化ビニルマグネシウム80.7g(0.93モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてトリクロロフルオロシラン46g(0.30モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリビニルフルオロシランとテトラヒドロフランを含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度20kPaで100℃に加熱して蒸留してトリビニルフルオロシラン組成物33.0g(収率54%、GC純度63面積%)を得た。なお、空焚き防止のため、一部のトリビニルフルオロシランを蒸留装置の釜に残した。
[Comparative Example 2-1]
80.7 g (0.93 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran are placed in a three-necked flask equipped with a cooling condenser and a dropping funnel, and after stirring, 46 g (0.30 mol) of trichlorofluorosilane is used using a dropping funnel. , 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and the filtrate was evaporated and condensed with an evaporator to remove the solid component to obtain a mixture containing trivinylfluorosilane and tetrahydrofuran. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 100 ° C. at a reduced pressure of 20 kPa to 33.0 g (yield 54%, GC purity 63). Area%) was obtained. A part of trivinylfluorosilane was left in the kettle of the distillation apparatus to prevent empty heating.
[実施例3-1:第3の方法]
フラスコにマグネシウム24.3g(1.00モル)、塩化ビニル67.9g(1.09モル)、テトラヒドロフラン750gを入れ、攪拌して、グリニャール試薬を合成した。その後、ジエチレングリコールジエチルエーテル650gを添加し、エバポレーターにて減圧濃縮し、溶媒置換を行った。溶媒置換後の混合溶媒中のテトラヒドロフランとジエチレングリコールジエチルエーテルの質量比は5:95であった。その後、冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、溶媒置換したグリニャール試薬を入れ、滴下漏斗を用いてテトラクロロシラン36.2g(0.21モル)、ジエチレングリコールジエチルエーテル75gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジエチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、テトラビニルシラン4質量%とテトラヒドロフラン1質量%とジエチレングリコールジエチルエーテル95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してテトラビニルシラン組成物20.8g(収率72%、GC純度99面積%)を得た。
[Example 3-1: Third method]
24.3 g (1.00 mol) of magnesium, 67.9 g (1.09 mol) of vinyl chloride and 750 g of tetrahydrofuran were placed in a flask and stirred to synthesize a Grignard reagent. Then, 650 g of diethylene glycol diethyl ether was added, and the mixture was concentrated under reduced pressure with an evaporator to replace the solvent. The mass ratio of tetrahydrofuran to diethylene glycol diethyl ether in the mixed solvent after the solvent substitution was 5:95. Then, put the solvent-substituted Grignard reagent in a three-necked flask equipped with a cooling condenser and a dropping funnel, and use the dropping funnel to add 36.2 g (0.21 mol) of tetrachlorosilane and 75 g of diethylene glycol diethyl ether over 6 hours. Added. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol diethyl ether. The liquid component was evaporated and condensed in the filtrate with an evaporator to remove the solid component, and a mixture containing 4% by mass of tetravinylsilane, 1% by mass of tetrahydrofuran and 95% by mass of diethylene glycol diethyl ether was obtained. Initially, this mixture is heated to 40 ° C. at a reduced pressure of 30 kPa, and at the final stage, it is heated to 125 ° C. at a reduced pressure of 10 kPa and distilled to obtain 20.8 g of a tetravinylsilane composition (yield 72%, GC purity 99 area%). ) Was obtained.
[実施例3-2:第1の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてテトラクロロシラン51g(0.30モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液にジエチレングリコールジエチルエーテル500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、テトラビニルシランとテトラヒドロフランとジエチレングリコールジエチルエーテルを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してテトラビニルシラン組成物23.9g(収率68%、GC純度95面積%)を得た。
[Example 3-2: first method]
Put 109.4 g (1.26 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran in a three-necked flask equipped with a cooling condenser and a dropping funnel, stir, and then use a dropping funnel to put 51 g (0.30 mol) of tetrachlorosilane and tetrahydrofuran. 200 g was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt is filtered, 500 g of diethylene glycol diethyl ether is added to the filtrate, and then the liquid component is evaporated and condensed by an evaporator to remove the solid component, and tetravinylsilane, tetrahydrofuran and diethylene glycol diethyl ether are removed. Was obtained as a main component. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 23.9 g (yield 68%, GC purity 95 area%). ) Was obtained.
[実施例3-3:第2の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590g、ジエチレングリコールジエチルエーテル500gを入れ攪拌した後、滴下漏斗を用いてテトラクロロシラン51g(0.30モル)、ジエチレングリコールジエチルエーテル150gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジエチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、テトラビニルシランとテトラヒドロフランとジエチレングリコールジエチルエーテルを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してテトラビニルシラン組成物28.9g(収率70%、GC純度99面積%)を得た。
[Example 3-3: Second method]
In a three-necked flask equipped with a cooling condenser and a dropping funnel, 109.4 g (1.26 mol) of vinyl chloride magnesium chloride, 590 g of tetrahydrofuran, and 500 g of diethylene glycol diethyl ether were placed and stirred, and then 51 g of tetrachlorosilane (0. 30 mol), 150 g of diethylene glycol diethyl ether was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol diethyl ether. The liquid component was evaporated and condensed in the filtrate with an evaporator to remove the solid component, and a mixture containing tetravinylsilane, tetrahydrofuran and diethylene glycol diethyl ether as main components was obtained. This mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 28.9 g (yield 70%, GC purity 99 area%). ) Was obtained.
[実施例3-4:第1の方法]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてテトラクロロシラン51g(0.30モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液にメシチレン500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、テトラビニルシランとテトラヒドロフランとメシチレンを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してテトラビニルシラン組成物29.2g(収率70%、GC純度98面積%)を得た。
[Example 3-4: First method]
Put 109.4 g (1.26 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran in a three-necked flask equipped with a cooling condenser and a dropping funnel, stir, and then use a dropping funnel to put 51 g (0.30 mol) of tetrachlorosilane and tetrahydrofuran. 200 g was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt is filtered, 500 g of mesitylene is added to the filtrate, and then the liquid component is evaporated and condensed by an evaporator to remove the solid component, and the main components are tetravinylsilane, tetrahydrofuran and mesityrene. The mixture was obtained. This mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 29.2 g (yield 70%, GC purity 98 area%). ) Was obtained.
[実施例3-5:第3の方法]
フラスコにマグネシウム24.3g(1.00モル)、塩化ビニル67.9g(1.09モル)、テトラヒドロフラン750gを入れ、攪拌して、グリニャール試薬を合成した。その後、ジエチレングリコールジブチルエーテル650gを添加し、エバポレーターにて減圧濃縮し、溶媒置換を行った。溶媒置換後の混合溶媒中のテトラヒドロフランとジエチレングリコールジブチルエーテルの質量比は5:95であった。その後、冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、溶媒置換したグリニャール試薬を入れ、滴下漏斗を用いてテトラクロロシラン36.2g(0.21モル)、ジエチレングリコールジブチルエーテル75gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、この塩を100gのジエチレングリコールジブチルエーテルで洗浄した。濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、テトラビニルシラン4質量%とテトラヒドロフラン1質量%とジエチレングリコールジブチルエーテル95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してテトラビニルシラン組成物17.7g(収率60%、GC純度97面積%)を得た。
[Example 3-5: Third method]
24.3 g (1.00 mol) of magnesium, 67.9 g (1.09 mol) of vinyl chloride and 750 g of tetrahydrofuran were placed in a flask and stirred to synthesize a Grignard reagent. Then, 650 g of diethylene glycol dibutyl ether was added, and the mixture was concentrated under reduced pressure with an evaporator to replace the solvent. The mass ratio of tetrahydrofuran to diethylene glycol dibutyl ether in the mixed solvent after solvent substitution was 5:95. Then, put the solvent-substituted Grignard reagent in a three-necked flask equipped with a cooling condenser and a dropping funnel, and use the dropping funnel to add 36.2 g (0.21 mol) of tetrachlorosilane and 75 g of diethylene glycol dibutyl ether over 6 hours. Added. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and this salt was washed with 100 g of diethylene glycol dibutyl ether. The liquid component was evaporated and condensed in the filtrate with an evaporator to remove the solid component, and a mixture containing 4% by mass of tetravinylsilane, 1% by mass of tetrahydrofuran and 95% by mass of diethylene glycol dibutyl ether was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 17.7 g (yield 60%, GC purity 97 area%). ) Was obtained.
[比較例3-1]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、塩化ビニルマグネシウム109.4g(1.26モル)、テトラヒドロフラン590gを入れ攪拌した後、滴下漏斗を用いてテトラクロロシラン51g(0.30モル)、テトラヒドロフラン200gを6時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化マグネシウム塩を濾過し、濾液をエバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、テトラビニルシラン5質量%とテトラヒドロフラン95質量%を含む混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してテトラビニルシラン組成物39.5g(収率58%、GC純度60面積%)を得た。なお、空焚き防止のため、一部のテトラビニルシランを蒸留装置の釜に残した。
[Comparative Example 3-1]
In a three-necked flask equipped with a cooling condenser and a dropping funnel, 109.4 g (1.26 mol) of vinyl chloride magnesium and 590 g of tetrahydrofuran were placed and stirred, and then 51 g (0.30 mol) of tetrachlorosilane was used using a dropping funnel. 200 g of tetrahydrofuran was added over 6 hours. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced magnesium chloride salt was filtered, and the filtrate was evaporated and condensed with an evaporator to remove the solid component to obtain a mixture containing 5% by mass of tetravinylsilane and 95% by mass of tetrahydrofuran. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 39.5 g (yield 58%, GC purity 60 area%). ) Was obtained. In addition, in order to prevent empty heating, some tetravinylsilane was left in the kettle of the distillation apparatus.
[実施例4-1]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、18wt%ナトリウムアセチリド―テトラヒドロフラン懸濁液85.3g(0.32モル)、テトラヒドロフラン100gを入れ攪拌した後、滴下漏斗を用いてトリクロロメチルシラン15g(0.10モル)、テトラヒドロフラン15gを1時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化ナトリウム塩を濾過で除去し、濾液にジエチレングリコールジエチルエーテル500gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリエチニルメチルシランとテトラヒドロフランとジエンチレングリコールジエチルエーテルを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリエチニルメチルシラン組成物8.5g(収率70%、GC純度97面積%)を得た。
[Example 4-1]
85.3 g (0.32 mol) of 18 wt% sodium acetylide-tetrahydrofuran suspension and 100 g of tetrahydrofuran are placed in a three-necked flask equipped with a cooling condenser and a dropping funnel, stirred, and then trichloromethylsilane 15 g using a dropping funnel. (0.10 mol), 15 g of tetrahydrofuran was added over 1 hour. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced sodium chloride salt is removed by filtration, 500 g of diethylene glycol diethyl ether is added to the filtrate, and then the liquid component is evaporated and condensed with an evaporator to remove the solid component, and triethynylmethylsilane and tetrahydrofuran are removed. And a mixture containing dientylene glycol diethyl ether as a main component was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 8.5 g (yield 70%, GC purity 97). Area%) was obtained.
[比較例4-1]
冷却コンデンサーおよび滴下漏斗を備えた3つ口フラスコに、18wt%ナトリウムアセチリド―テトラヒドロフラン懸濁液 85.3g(0.32モル)、テトラヒドロフラン100gを入れ、滴下漏斗を用いてトリクロロメチルシラン15g(0.1モル)、テトラヒドロフラン15gを1時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化ナトリウム塩を濾過で除去した、濾液として得られた混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度20kPaで100℃に加熱して蒸留しトリエチニルメチルシラン組成物10.9g(収率60%、GC純度65面積%)を得た。なお、空焚き防止のため、一部のトリエチニルメチルシランを蒸留装置の釜に残した。
[Comparative Example 4-1]
In a three-necked flask equipped with a cooling condenser and a dropping funnel, 85.3 g (0.32 mol) of 18 wt% sodium acetylide-tetrahydrofuran suspension and 100 g of tetrahydrofuran were placed, and 15 g of trichloromethylsilane (0. 1 mol), 15 g of tetrahydrofuran was added over 1 hour. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced sodium chloride salt was removed by filtration, and the mixture obtained as a filtrate was initially heated to 40 ° C. at a reduced pressure of 30 kPa and finally heated to 100 ° C. at a reduced pressure of 20 kPa for distillation. 10.9 g of a triethynylmethylsilane composition (yield 60%, GC purity 65 area%) was obtained. A part of triethynylmethylsilane was left in the kettle of the distillation apparatus to prevent empty heating.
[実施例5-1]
フラスコにプロパルギルアルコール 6.7g(0.12モル)、水素化ナトリウム2.9g(0.12モル)、テトラヒドロフラン70gを添加した。その後、滴下漏斗を用いてトリクロロメチルシラン6.0g(0.04モル)、テトラヒドロフラン10gを1時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化ナトリウム塩を濾過で除去し、濾液にジエチレングリコールジブチルエーテル200gを添加した後、エバポレーターにて液体成分を蒸発・凝縮させて固形成分を除去して、トリ(2―プロピニルオキシ)メチルシランとテトラヒドロフランとジエンチレングリコールジブチルエーテルを主成分とする混合物を得た。この混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで125℃に加熱して蒸留してトリ(2―プロピニルオキシ)メチルシラン組成物6.0g(収率70%、GC純度97面積%)を得た。
[Example 5-1]
To the flask was added 6.7 g (0.12 mol) of propargyl alcohol, 2.9 g (0.12 mol) of sodium hydride and 70 g of tetrahydrofuran. Then, using a dropping funnel, 6.0 g (0.04 mol) of trichloromethylsilane and 10 g of tetrahydrofuran were added over 1 hour. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced sodium chloride salt is removed by filtration, 200 g of diethylene glycol dibutyl ether is added to the filtrate, and then the liquid component is evaporated and condensed with an evaporator to remove the solid component to remove tri (2-propynyloxy). ) A mixture containing methylsilane, tetrahydrofuran and dientylene glycol dibutyl ether as main components was obtained. The mixture is initially heated to 40 ° C. at a reduced pressure of 30 kPa and distilled to 125 ° C. at a reduced pressure of 10 kPa to 6.0 g of a tri (2-propynyloxy) methylsilane composition (yield 70%). , GC purity 97 area%) was obtained.
[比較例5-1]
フラスコにプロパルギルアルコール 6.7g(0.12モル)、水素化ナトリウム2.9g(0.12モル)、テトラヒドロフラン70gを添加した。その後、滴下漏斗を用いてトリクロロメチルシラン6.0g(0.04モル)、テトラヒドロフラン10gを1時間かけて添加した。滴下後、室温で1時間攪拌を続けた。
反応後、副生成する塩化ナトリウム塩を濾過で除去した。濾液として得られた混合物を初期には減圧度30kPaで40℃に加熱し、終期には減圧度10kPaで110℃に加熱して蒸留しトリ(2―プロピニルオキシ)メチルシラン組成物6.9g(収率50%、GC純度60面積%)を得た。なお、空焚き防止のため、一部のトリ(2―プロピニルオキシ)メチルシランを蒸留装置の釜に残した。
[Comparative Example 5-1]
To the flask was added 6.7 g (0.12 mol) of propargyl alcohol, 2.9 g (0.12 mol) of sodium hydride and 70 g of tetrahydrofuran. Then, using a dropping funnel, 6.0 g (0.04 mol) of trichloromethylsilane and 10 g of tetrahydrofuran were added over 1 hour. After the dropping, stirring was continued for 1 hour at room temperature.
After the reaction, the by-produced sodium chloride salt was removed by filtration. The mixture obtained as a filtrate is initially heated to 40 ° C. at a reduced pressure of 30 kPa, and finally heated to 110 ° C. at a reduced pressure of 10 kPa and distilled to 6.9 g of a tri (2-propynyloxy) methylsilane composition (yield). A rate of 50% and a GC purity of 60 area%) were obtained. A part of tri (2-propynyloxy) methylsilane was left in the kettle of the distillation apparatus to prevent empty heating.
実施例・比較例における、蒸留条件、蒸留後の組成物について、表1にまとめた。蒸留後の組成物中のビニルシラン化合物の純度、テトラヒドロフランと高沸点溶媒の含有量は、ガスクロマトグラフィーにより分析して得られた面積%である。なお、本系では、ガスクロマトグラフィーで測定した面積%が、質量%と近い数値となるため、上記の面積%は、質量%と読み替えることができる。なお、表中のTHFはテトラヒドロフランを、DGDEはジエチレングリコールジエチルエーテルを、DGDBはジエチレングリコールジブチルエーテルを意味する。 Table 1 summarizes the distillation conditions and the composition after distillation in Examples and Comparative Examples. The purity of the vinylsilane compound in the composition after distillation and the content of tetrahydrofuran and the high boiling point solvent are the area% obtained by analysis by gas chromatography. In this system, the area% measured by gas chromatography is a value close to the mass%, so the above area% can be read as the mass%. In the table, THF means tetrahydrofuran, DGDE means diethylene glycol diethyl ether, and DGDB means diethylene glycol dibutyl ether.
実施例1-1~1-5では、比較例1-1に比べて、高純度のトリビニルメチルシラン組成物を得ることができた。また、実施例1-1~1-5では、比較例1-1に比べて、純度だけでなく収率も向上している。同様に実施例2-1~2-5では、比較例2-1に比べて高純度のトリビニルフルオロシラン組成物を収率良く得ることができ、実施例3-1~3-5では、比較例3-1に比べて高純度のテトラビニルシラン組成物を収率良く得ることができた。また、実施例4-1では、比較例4-1に比べて高純度のトリエチニルメチルシランを収率良く得ることができ、実施例5-1では、比較例5-1に比べて高純度のトリ(2-プロピニルオキシ)メチルシランを収率良く得ることができた。 In Examples 1-1 to 1-5, a high-purity trivinylmethylsilane composition could be obtained as compared with Comparative Example 1-1. Further, in Examples 1-1 to 1-5, not only the purity but also the yield is improved as compared with Comparative Example 1-1. Similarly, in Examples 2-1 to 2-5, a high-purity trivinylfluorosilane composition can be obtained in a higher yield than in Comparative Example 2-1. In Examples 3-1 to 3-5, similarly, a high-purity trivinylfluorosilane composition can be obtained. A high-purity tetravinylsilane composition could be obtained in a higher yield than that of Comparative Example 3-1. Further, in Example 4-1 it was possible to obtain high-purity triethynylmethylsilane in a higher yield than in Comparative Example 4-1 and in Example 5-1 it was possible to obtain higher purity than in Comparative Example 5-1. (2-Propinyloxy) methylsilane could be obtained in good yield.
Claims (16)
前記高沸点溶媒が、炭化水素系溶媒であり、
精製工程を非水系で行う、不飽和結合含有シラン化合物の精製方法。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕 Distillation is performed on a mixture of at least one unsaturated bond-containing silane compound represented by the following general formula (1), tetrahydrofuran, the unsaturated bond-containing silane compound, and a high-boiling solvent having a boiling point higher than that of tetrahydrofuran. A method for purifying an unsaturated bond-containing silane compound, which comprises performing.
The high boiling point solvent is a hydrocarbon solvent.
A method for purifying an unsaturated bond-containing silane compound in which the purification step is performed in a non-aqueous system .
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
前記高沸点溶媒が、1,3,5-トリメチルベンゼンであることを特徴とする請求項1に記載の不飽和結合含有シラン化合物の精製方法。 The silane compound is at least one selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, triethynylmethylsilane and tri (2-propynyloxy) methylsilane.
The method for purifying an unsaturated bond-containing silane compound according to claim 1, wherein the high boiling point solvent is 1,3,5 -trimethylbenzene.
合成後の混合物に対し、前記不飽和結合含有シラン化合物及びテトラヒドロフランより沸点の高い高沸点溶媒を加える工程と、
得られた混合物を蒸留する工程と、
を含むことを特徴とする不飽和結合含有シラン化合物の製造方法であって、
前記高沸点溶媒が、炭化水素系溶媒であり、
精製工程を非水系で行う、不飽和結合含有シラン化合物の製造方法。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕 A step of synthesizing at least one unsaturated bond-containing silane compound represented by the following general formula (1) in tetrahydrofuran,
A step of adding the unsaturated bond-containing silane compound and a high boiling point solvent having a boiling point higher than that of tetrahydrofuran to the mixture after synthesis.
The step of distilling the obtained mixture and
A method for producing an unsaturated bond-containing silane compound, which comprises.
The high boiling point solvent is a hydrocarbon solvent.
A method for producing an unsaturated bond-containing silane compound, wherein the purification step is performed in a non-aqueous system .
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
合成後の混合物を蒸留する工程と、
を含むことを特徴とする不飽和結合含有シラン化合物の製造方法であって、
前記高沸点溶媒が、炭化水素系溶媒であり、
精製工程を非水系で行う、不飽和結合含有シラン化合物の製造方法。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕 A step of synthesizing at least one unsaturated bond-containing silane compound represented by the following general formula (1) in a mixed solvent of tetrahydrofuran, the unsaturated bond-containing silane compound and a high boiling solvent having a boiling point higher than that of tetrahydrofuran. ,
The process of distilling the post-synthesis mixture and
A method for producing an unsaturated bond-containing silane compound, which comprises.
The high boiling point solvent is a hydrocarbon solvent.
A method for producing an unsaturated bond-containing silane compound, wherein the purification step is performed in a non-aqueous system .
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
前記高沸点溶媒が、1,3,5-トリメチルベンゼンであることを特徴とする請求項10または11に記載のシラン化合物の製造方法。 The unsaturated bond-containing silane compound is at least one selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, triethynylmethylsilane and tri (2-propynyloxy) methylsilane.
The method for producing a silane compound according to claim 10 or 11 , wherein the high boiling point solvent is 1,3,5 -trimethylbenzene.
テトラヒドロフラン中で炭素-炭素不飽和結合を有するグリニャール試薬、アルカリ金属アセチリド又はアルカリ金属アルコキシドを合成する工程と、
前記グリニャール試薬、アルカリ金属アセチリド又はアルカリ金属アルコキシドの溶媒を、前記不飽和結合含有シラン化合物及びテトラヒドロフランより沸点の高い高沸点溶媒に置換する工程と、
前記高沸点溶媒及び残余のテトラヒドロフランの混合溶媒中で、シラノール基若しくは加水分解性基を有するシラン化合物と前記グリニャール試薬と、又は、ハロゲン化シランとアルカリ金属アセチリド若しくはアルカリ金属アルコキシドとを反応させて、前記不飽和結合含有シラン化合物を合成する工程と、
合成後の混合物を蒸留する工程と、
を含むことを特徴とする不飽和結合含有シラン化合物の製造方法であって、
前記高沸点溶媒が、炭化水素系溶媒であり、
精製工程を非水系で行う、不飽和結合含有シラン化合物の製造方法。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕 A method for producing at least one unsaturated bond-containing silane compound represented by the following general formula (1).
A step of synthesizing a Grignard reagent, an alkali metal acetylide or an alkali metal alkoxide having a carbon-carbon unsaturated bond in tetrahydrofuran, and
A step of substituting the solvent of the Grignard reagent, the alkali metal acetylide or the alkali metal alkoxide with the unsaturated bond-containing silane compound and a high boiling point solvent having a boiling point higher than that of tetrahydrofuran.
In the mixed solvent of the high boiling point solvent and the residual tetrahydrofuran, the silane compound having a silanol group or a hydrolyzable group is reacted with the Grignard reagent, or the halogenated silane is reacted with an alkali metal acetylide or an alkali metal alkoxide. The step of synthesizing the unsaturated bond-containing silane compound and
The process of distilling the post-synthesis mixture and
A method for producing an unsaturated bond-containing silane compound, which comprises.
The high boiling point solvent is a hydrocarbon solvent.
A method for producing an unsaturated bond-containing silane compound, wherein the purification step is performed in a non-aqueous system .
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
前記不飽和結合含有シラン化合物がトリビニルメチルシラン、トリビニルフルオロシラン、テトラビニルシラン、トリエチニルメチルシラン及びトリ(2-プロピニルオキシ)メチルシランからなる群から選ばれるいずれか一種以上であり、
前記高沸点溶媒が1,3,5-トリメチルベンゼンであることを特徴とする請求項13に記載の不飽和結合含有シラン化合物の製造方法。 The silane compound or halogenated silane having a hydrolyzable group is any one or more of the group consisting of any one or more selected from the group consisting of trichloromethylsilane, trichlorofluorosilane and tetrachlorosilane.
The unsaturated bond-containing silane compound is at least one selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, triethynylmethylsilane and tri (2-propynyloxy) methylsilane.
The method for producing an unsaturated bond-containing silane compound according to claim 13 , wherein the high boiling point solvent is 1,3,5 -trimethylbenzene.
前記組成物中の前記不飽和結合含有シラン化合物の含有量が90質量%以上であり、
前記組成物中のテトラヒドロフラン及び前記高沸点溶媒の含有量はそれぞれ1質量ppm以上であり、
前記組成物中のテトラヒドロフラン及び前記高沸点溶媒の合計の含有量が10質量%以下であり、
前記高沸点溶媒が、1,3,5-トリメチルベンゼン、1,2,4-トリメチルベンゼン、ジエチルベンゼン、ブチルベンゼン、1,3,5-トリエチルベンゼン及びジイソプロピルベンゼンからなる群から選ばれるいずれか一種以上であることを特徴とする不飽和結合含有シラン化合物の組成物。
Si(R1)x(R2)4-x (1)
〔一般式(1)中、R1はそれぞれ互いに独立して、炭素-炭素不飽和結合を有する基を表す。R2はそれぞれ互いに独立して、フッ素基、炭素数が1以上10以下の直鎖又は分岐状のアルキル基から選択され、前記アルキル基はフッ素原子及び/又は酸素原子を有していてもよい。xは2以上4以下の整数である。〕 A composition comprising at least one unsaturated bond-containing silane compound represented by the following general formula (1), tetrahydrofuran, the unsaturated bond-containing silane compound, and a high-boiling solvent having a boiling point higher than that of tetrahydrofuran.
The content of the unsaturated bond-containing silane compound in the composition is 90% by mass or more, and the content is 90% by mass or more.
The contents of tetrahydrofuran and the high boiling point solvent in the composition are 1 mass ppm or more, respectively.
The total content of the tetrahydrofuran and the high boiling point solvent in the composition is 10% by mass or less, and the content is 10% by mass or less.
One or more of the high boiling point solvents selected from the group consisting of 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, diethylbenzene, butylbenzene, 1,3,5-triethylbenzene and diisopropylbenzene. A composition of an unsaturated bond-containing silane compound.
Si (R 1 ) x (R 2 ) 4-x (1)
[In the general formula (1), R 1 represents a group having a carbon-carbon unsaturated bond independently of each other. R 2 is independently selected from a fluorine group and a linear or branched alkyl group having 1 or more and 10 or less carbon atoms, and the alkyl group may have a fluorine atom and / or an oxygen atom. .. x is an integer of 2 or more and 4 or less. ]
前記高沸点溶媒が1,3,5-トリメチルベンゼンであることを特徴とする請求項15に記載の不飽和結合含有シラン化合物の組成物。 The unsaturated bond-containing silane compound is at least one selected from the group consisting of trivinylmethylsilane, trivinylfluorosilane, tetravinylsilane, triethynylmethylsilane and tri (2-propynyloxy) methylsilane.
The composition of the unsaturated bond-containing silane compound according to claim 15 , wherein the high boiling point solvent is 1,3,5 -trimethylbenzene.
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