WO2005103061A1 - Method of manufacturing an organoalkoxysilane having ester-functional groups - Google Patents
Method of manufacturing an organoalkoxysilane having ester-functional groups Download PDFInfo
- Publication number
- WO2005103061A1 WO2005103061A1 PCT/JP2005/008476 JP2005008476W WO2005103061A1 WO 2005103061 A1 WO2005103061 A1 WO 2005103061A1 JP 2005008476 W JP2005008476 W JP 2005008476W WO 2005103061 A1 WO2005103061 A1 WO 2005103061A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organoalkoxysilane
- group
- groups
- functional groups
- manufacturing
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- -1 alkali-metal salt Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 125000000962 organic group Chemical class 0.000 claims abstract description 15
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 28
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 9
- 229940114081 cinnamate Drugs 0.000 claims description 8
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 4
- HDHIIYSHHYSMPZ-UHFFFAOYSA-N 3-trimethoxysilylpropyl butanoate Chemical compound CCCC(=O)OCCC[Si](OC)(OC)OC HDHIIYSHHYSMPZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 4
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- HYFWOBSAALCFRS-UHFFFAOYSA-N 3-trimethoxysilylpropyl benzoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C1=CC=CC=C1 HYFWOBSAALCFRS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CIPGKMZNKNYCCP-UHFFFAOYSA-N 3-chloropropyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](CCCCl)(OCCOC)OCCOC CIPGKMZNKNYCCP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229940063559 methacrylic acid Drugs 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- WKPMPENCTLLSMD-UHFFFAOYSA-N (3-methoxysilyl-3-methylbutyl) acetate Chemical compound C(C)(=O)OCCC([SiH2]OC)(C)C WKPMPENCTLLSMD-UHFFFAOYSA-N 0.000 description 1
- DYGJHEURTSXSQK-UHFFFAOYSA-N (3-methoxysilyl-3-methylbutyl) benzoate Chemical compound C(C1=CC=CC=C1)(=O)OCCC([SiH2]OC)(C)C DYGJHEURTSXSQK-UHFFFAOYSA-N 0.000 description 1
- AHYPTIPUIGMRAA-UHFFFAOYSA-N (3-methoxysilyl-3-methylbutyl) butanoate Chemical compound C(CCC)(=O)OCCC([SiH2]OC)(C)C AHYPTIPUIGMRAA-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- RSWBWHPZXKLUEX-VOTSOKGWSA-N 2-Methylcinnamic Acid Chemical compound CC1=CC=CC=C1\C=C\C(O)=O RSWBWHPZXKLUEX-VOTSOKGWSA-N 0.000 description 1
- JMFBXUMHVSZUKY-UHFFFAOYSA-N 3-bromopropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCBr JMFBXUMHVSZUKY-UHFFFAOYSA-N 0.000 description 1
- GLISZRPOUBOZDL-UHFFFAOYSA-N 3-bromopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCBr GLISZRPOUBOZDL-UHFFFAOYSA-N 0.000 description 1
- XVNYMEVFHNKMIA-UHFFFAOYSA-N 3-bromopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCBr XVNYMEVFHNKMIA-UHFFFAOYSA-N 0.000 description 1
- NXSFUYQBFOLDBP-UHFFFAOYSA-N 3-bromopropyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](CCCBr)(OCCOC)OCCOC NXSFUYQBFOLDBP-UHFFFAOYSA-N 0.000 description 1
- OBEIFTRRQNVQEH-UHFFFAOYSA-N 3-dimethoxysilylbutyl acetate Chemical compound C(C)(=O)OCCC([SiH](OC)OC)C OBEIFTRRQNVQEH-UHFFFAOYSA-N 0.000 description 1
- OTLZHOVAKZJSCD-UHFFFAOYSA-N 3-dimethoxysilylbutyl benzoate Chemical compound C(C1=CC=CC=C1)(=O)OCCC([SiH](OC)OC)C OTLZHOVAKZJSCD-UHFFFAOYSA-N 0.000 description 1
- NRBWAHUUQVBSMH-UHFFFAOYSA-N 3-dimethoxysilylbutyl butanoate Chemical compound C(CCC)(=O)OCCC([SiH](OC)OC)C NRBWAHUUQVBSMH-UHFFFAOYSA-N 0.000 description 1
- QYSIFFONZZACGM-UHFFFAOYSA-N 3-dimethoxysilylheptyl acetate Chemical compound C(C)(=O)OCCC([SiH](OC)OC)CCCC QYSIFFONZZACGM-UHFFFAOYSA-N 0.000 description 1
- WKNZZVCKJQCYDI-UHFFFAOYSA-N 3-dimethoxysilylheptyl benzoate Chemical compound C(C1=CC=CC=C1)(=O)OCCC([SiH](OC)OC)CCCC WKNZZVCKJQCYDI-UHFFFAOYSA-N 0.000 description 1
- BLOYVYULNLEOFO-UHFFFAOYSA-N 3-dimethoxysilylheptyl butanoate Chemical compound C(CCC)(=O)OCCC([SiH](OC)OC)CCCC BLOYVYULNLEOFO-UHFFFAOYSA-N 0.000 description 1
- VWXZFDWVWMQRQR-UHFFFAOYSA-N 3-ethenylbenzoic acid Chemical class OC(=O)C1=CC=CC(C=C)=C1 VWXZFDWVWMQRQR-UHFFFAOYSA-N 0.000 description 1
- CVFSASRYPOODFZ-UHFFFAOYSA-N 3-silylpropyl acetate Chemical compound CC(=O)OCCC[SiH3] CVFSASRYPOODFZ-UHFFFAOYSA-N 0.000 description 1
- SDCQLLIBFJSYQI-UHFFFAOYSA-N 3-silylpropyl butanoate Chemical compound C(CCC)(=O)OCCC[SiH3] SDCQLLIBFJSYQI-UHFFFAOYSA-N 0.000 description 1
- ADBORBCPXCNQOI-UHFFFAOYSA-N 3-triethoxysilylpropyl acetate Chemical compound CCO[Si](OCC)(OCC)CCCOC(C)=O ADBORBCPXCNQOI-UHFFFAOYSA-N 0.000 description 1
- MDAXRQUXUUOQBR-UHFFFAOYSA-N 3-triethoxysilylpropyl benzoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C1=CC=CC=C1 MDAXRQUXUUOQBR-UHFFFAOYSA-N 0.000 description 1
- OCPCLBDBDMDYNY-UHFFFAOYSA-N 3-triethoxysilylpropyl butanoate Chemical compound CCCC(=O)OCCC[Si](OCC)(OCC)OCC OCPCLBDBDMDYNY-UHFFFAOYSA-N 0.000 description 1
- FZTPAOAMKBXNSH-UHFFFAOYSA-N 3-trimethoxysilylpropyl acetate Chemical compound CO[Si](OC)(OC)CCCOC(C)=O FZTPAOAMKBXNSH-UHFFFAOYSA-N 0.000 description 1
- CKEZAUDJDIPPIB-UHFFFAOYSA-N 4-chlorobutyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCCl CKEZAUDJDIPPIB-UHFFFAOYSA-N 0.000 description 1
- QIILEPOYRQQPRP-UHFFFAOYSA-N 4-chlorobutyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCCl QIILEPOYRQQPRP-UHFFFAOYSA-N 0.000 description 1
- YDSPKWVPKYHRDY-UHFFFAOYSA-N 4-chlorobutyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](CCCCCl)(OCCOC)OCCOC YDSPKWVPKYHRDY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- JWTWUOJKAFQVIY-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OCCC[SiH3] Chemical compound C(C1=CC=CC=C1)(=O)OCCC[SiH3] JWTWUOJKAFQVIY-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- ITIONVBQFUNVJV-UHFFFAOYSA-N Etomidoline Chemical compound C12=CC=CC=C2C(=O)N(CC)C1NC(C=C1)=CC=C1OCCN1CCCCC1 ITIONVBQFUNVJV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- SDBDMSZWUFJXGK-UHFFFAOYSA-N butyl-(3-chloropropyl)-dimethoxysilane Chemical compound CCCC[Si](OC)(OC)CCCCl SDBDMSZWUFJXGK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZCSLOBFDVTWIBL-UHFFFAOYSA-N chloromethyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)CCl ZCSLOBFDVTWIBL-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LPHLNZHFRMZONI-UHFFFAOYSA-N methyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[NH2+]C LPHLNZHFRMZONI-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940006198 sodium phenylacetate Drugs 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 1
- DXIHILNWDOYYCH-UHDJGPCESA-M sodium;(e)-3-phenylprop-2-enoate Chemical compound [Na+].[O-]C(=O)\C=C\C1=CC=CC=C1 DXIHILNWDOYYCH-UHDJGPCESA-M 0.000 description 1
- GOCYQQKRJUGVRU-SQQVDAMQSA-M sodium;(e)-but-2-enoate Chemical compound [Na+].C\C=C\C([O-])=O GOCYQQKRJUGVRU-SQQVDAMQSA-M 0.000 description 1
- SJRDNQOIQZOVQD-UHFFFAOYSA-M sodium;2,2-dimethylpropanoate Chemical compound [Na+].CC(C)(C)C([O-])=O SJRDNQOIQZOVQD-UHFFFAOYSA-M 0.000 description 1
- TWEGKFXBDXYJIU-UHFFFAOYSA-M sodium;2-methylpropanoate Chemical compound [Na+].CC(C)C([O-])=O TWEGKFXBDXYJIU-UHFFFAOYSA-M 0.000 description 1
- CHJJSYKJKKOTFO-UHFFFAOYSA-M sodium;but-3-enoate Chemical compound [Na+].[O-]C(=O)CC=C CHJJSYKJKKOTFO-UHFFFAOYSA-M 0.000 description 1
- HQIZDGAMCWYBKS-UHFFFAOYSA-M sodium;cyclopropanecarboxylate Chemical compound [Na+].[O-]C(=O)C1CC1 HQIZDGAMCWYBKS-UHFFFAOYSA-M 0.000 description 1
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MJRPMUINYAOXRW-UHFFFAOYSA-N tributylphosphane;hydrochloride Chemical compound [Cl-].CCCC[PH+](CCCC)CCCC MJRPMUINYAOXRW-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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Definitions
- the present invention relates to a novel method of manufacturing an organoalkoxysilane having ester-functional groups, the product being obtained easily and with a high yield.
- the method consists of conducting a reaction between an alkali-metal salt of a carboxylic acid and an organoalkoxysilane with halogen-substituted organic groups in the presence of a phase-transfer catalyst.
- Organoalkoxysilanes with acrylic-acid-ester-functional groups and/or methacrylic- acid-ester-functional groups are used as silane-coupling agents, raw materials for synthesis of acryl- and/or methacryl-modified silicone oils, or poiymerizable monomers for manufacturing acryl-type polymers that contain alkoxysilyl groups.
- organoalkoxysilanes were synthesized by subjecting carboxylic acid esters of unsaturated alcohols and hydrosilanes to hydrosilation in the presence of transition-metal catalysts.
- Japanese Unexamined Patent Application Publication (hereinafter referred to as "Kokai”) H9-208590 (equivalent to US5679821) discloses a method of obtaining an ester-functional alkoxysilane by subjecting an alkylallylester and hydroalkoxysilane to hydrosilation in the presence of a transition-metal catalyst.
- Publication 2001-512779 also discloses a method of obtaining an aromatic-carboxylic-acid-ester-functional trialkoxysilane by synthesizing an ester compound with unsaturated groups on terminals by subjecting an alcohol having alkenyl groups and a carboxylic acid having a phenyl groups to esterification in the presence of an acidic catalyst, and then subjecting the obtained compound to hydrosilation with an alkoxysilane in the presence of a platinum catalyst.
- a disadvantage of the above methods is the synthesis process that involves the use of either hydro alkoxysilanes that are difficult to handle, or unsaturated esters that are not always commercially available and therefore have to be synthesized in separate specially designed processes. Another problem is that the hydrosilation reaction has low positional selectivity, and therefore it is not always possible to obtain a product of high purity.
- Kokai 2002-249494 discloses a method of obtaining an ester-functional organoalkoxysilane without resorting to the hydrosilation reaction, but the above method utilizes acrylic- and/or methacrylic-acid as a starting material in the form of an alkali-metal salt, and, therefore, products that can be obtained by the aforementioned method are limited only to acrylic- and/or methacrylic-acid- ester-functional organoalkoxysilanes.
- the present invention provides a method of manufacturing an organoalkoxysilane that contains ester-functional groups and is represented by the following general formula: R 1 - COO - R 2 -Si (OR 3 ) n R 4 3 . n
- said method comprising the step of causing a reaction between (a) an alkali-metal salt of a carboxylic acid represented by the following general formula: R ⁇ OOM 1 ⁇ where R 1 is a substituted or unsubstituted Ci - C 15 univalent hydrocarbon group (except for a vinyl group and isopropenyl group), and M 1 is an alkali metal ⁇ and (b) an organoalkoxysilane that contains halogen-substituted organic groups and is represented by the following general formula: XR 2 Si (OR 3 ) n R 4 3 .
- n (where X is a halogen atom, R 2 is a Ci - C 6 alkylene group or alkylenoxyalkylene group, R 3 is an alkyl group or a C - C 4 alkoxyalkyl group, R 4 is a substituted or unsubstituted univalent Ci - C 15 hydrocarbon group, and «n» is an integer between 1 and 3) (c) in the presence of a phase-transfer catalyst.
- the present invention provides a method that allows efficient and economical production of a highly pure organoalkoxysilane that contains ester-functional groups and is suitable for use as a silane-coupling agent, a raw material for synthesis of modified silicone oils, or polymerizable monomers for the manufacture of silicon-containing polymers.
- An alkali-metal salt (a) of a carboxylic acid used in the method of the present invention is represented by the following general formula: R ⁇ OOM 1 (1), where R 1 designates substituted or unsubstituted univalent C ⁇ - C 15 hydrocarbon groups (except for vinyl and isopropenyl groups).
- Example of such groups are the following: _ C 1 5 alkyl groups; C 3 _ do cycloalkyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, or similar aryl groups; benzyl groups, phenethyl groups, or similar aralkyl groups; 1-propenyl groups, allyl groups, 2-phenylvinyl groups, or similar alkenyl groups, other than vinyl an isopropenyl groups. Most preferable are alkyl, cycloalkyl, aryl, aralkyl, and 2-phenylvinyl groups.
- alkali-metal salts of a carboxylic acid are the following: sodium acetate, sodium propionate, sodium crotonate, sodium cyclopropane carboxylate, sodium butyrate, sodium isobutyrate, sodium trimethylacetate, sodium vinylacetate, sodium salt of valeric acid, sodium salt of 2,4- hexadienoic acid, sodium salt of undecanoic acid, sodium salt of benzoic acid, sodium salt of rn-toluic acid, sodium salt of p-toluic acid, sodium phenylacetate, sodium salt of cinnamic acid, sodium salt of 3 -vinyl benzoic acid, sodium salt of 2-methyl cinnamic acid, or potassium equivalents of the aforementioned sodium salts.
- the aforementioned alkali-metal salts of carboxylic acids can be produced, e.g., by neutralizing a carboxylic acid with sodium or potassium hydroxide, or saponifying methyl carboxylates with sodium or potassium hydroxides.
- the alkali-metal salts of carboxylic acids can be supplied to the reaction in a solid form or in a liquid form as dispersions or solutions in appropriate solvents.
- the organoalkoxysilane (b) with halogen-substituted organic groups is represented by the following general formula: XR 2 Si (OR 3 ) honor R 4 3 .n where X is a halogen atom, e.g., a chlorine or bromine atom.
- R 2 is a - C 6 alkylene group or alkylenoxyalkylene group, such as a methylene group, ethylene group, methylmethylene group, propylene group, methylethylene group, butylene group, hexylene group, 1- mefhylpentylene group, 1,4-dimethylbutylene, or other alkylene groups; a methyleneoxypropylene group, methyleneoxypentylene group, or other alkylenoxyalkylene groups.
- R 3 is an alkyl group or a C 2 - C 4 alkoxyalkyl group.
- the following are examples of the alkyl group: a methyl group, propyl group, butyl group, pentyl group, isopropyl group, isobutyl group, cyclopentyl group, and cyclohexyl group.
- the aforementioned alkoxyalkyl group can be exemplified by a methoxyethyl group, methoxypropyl group, and methoxybutyl group. Of these, most preferable are a methyl group, ethyl group, and methoxyethyl group.
- R 4 is a substituted or unsubstituted univalent Ci - 5 hydrocarbon group, such as a methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, cyclopentyl group, cyclohexyl group, or a similar alkyl group; a phenyl group, tolyl group, xylyl group, naphthyl group, or a similar aryl group; a vinyl group, allyl group, butenyl group, pentene group, hexenyl group, or a similar alkenyl group; and benzyl group, phenethyl group, or a similar aralkyl group.
- the aforementioned groups can be substituted by alkoxy groups, alkoxycarbonyl groups, acyl groups, cyano groups, etc. Most preferable are methyl groups. In the above formula, «n» is an integer between 1 and 3.
- the aforementioned organoalkoxysilane with halogen-substituted organic groups may be represented by a chloromethyldimethylmethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -chloropropyltriethoxysilane, ⁇ - chloropropyl-tris- (methoxyethoxy) silane, ⁇ - chloropropylmethyldimethoxysilane, ⁇ -chloropropylbutyldimethoxysilane, ⁇ -chlorobutyltrimethoxysilane, ⁇ -chlorobutylmethyldimethoxysilane, ⁇ -chlorobutyl-tris-(methoxyethoxy) silane, ⁇ -bromopropyltrimethoxysilane, ⁇ -bromopropyltriethoxysilane, ⁇ -bromopropyl-tris- (methoxyethoxy)
- ⁇ -chloropropyltrimethoxysilane ⁇ -chloropropyltriethoxysilane, ⁇ - chloropropyl-tris-(methoxyethoxy) silane, and ⁇ -chloropropylmethyldimethoxysilane, especially, ⁇ -chloropropyltrimethoxysilane and ⁇ -chloropropylmethyldimethoxysilane.
- Phase-transfer catalyst (c) may be comprised of a conventional one used in the art.
- Preferable phase-transfer catalysts are the following: tributylammom ' um bromide, octylmethylammonium chloride, or similar quaternary ammonium salts; tributylphosphonium chloride, or similar quaternary phosphonium salts; triethylamine, or similar tertiary amines; crown ethers; 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,4-diazabicyclo [2.2.2] octane, and 1,5-diazabicyclo [4.3.0]-nona-5-ene, or similar cyclically-structured tertiary amines.
- DBU 1,8-diazabicyclo [5.4.0] undeca-7-ene
- 1,4- diazabicyclo [2.2.2] octane 1,4- diazabicyclo [2.2.2] octane
- 1,5-diazabicyclo [4.3.0]-nona-5-ene especially 1,8- diazabicyclo [5.4.0] undeca-7-ene (hereinafter referred to as DBU) that is readily available.
- phase-transfer catalyst (c) should be used in an amount of 0.0001 to 0.2 mole, preferably 0.001 to 0.05 mole for each 1 mole of the organoalkoxysilane with halogen-substituted organic groups (component (b)).
- reaction temperature within the range of 30 to 180°C, preferably within the range of 100 to 160°C. Duration of the reaction will depend on the type of the alkali-metal salt of a carboxylic acid (component (a)), the amount of the phase-transfer catalyst (c), the reaction temperature, and other factors of the reaction, but in general the reaction may last from 10 hours to 10 min.
- the method of the invention can be carried out without participation of a solvent.
- a solvent inert to the catalyst and starting material such as benzene, toluene, xylene, or a similar aromatic solvent, as well as methanol, ethanol or another alcohol-type solvent, or dimethylformamide, can be used.
- the organoalkoxysilane (b) with halogen-substituted organic groups has high hydrolyzability, introduction of water into the reaction system may decrease the yield of the product. Therefore, it is recommended to use the alkali-metal salt (a) of a carboxylic acid in a sufficiently dry state. Drying of component (a) may be carried out by heating in vacuum, or by azeotropic dehydration, h case component (b) has low hydrolyzability, component (a) may be used in an aqueous solution.
- reaction inhibitors such as methoxyphenol and 2,6-di-t-butyl-4-methylphenol; phenothiazine; amino-type compounds or sulfur-containing compounds.
- a sufficiently pure final product is obtained by removing salts of by-products by filtering, centrifugal separation, water treatment, or by any other suitable method. If necessary, further purification can be carried out by distillation or another method.
- the organoalkoxysilane with ester-functional groups obtained by the above- described method is represented by the following general formula: R 1 - COO - R 2 -Si (OR 3 ) n R 4 3- n , where R 1 , R 2 , R 3 , R 4 , and «n» are the same as defined above.
- a 1000 ml four-neck flask equipped with a refluxing condenser, stirrer, and thermometer was filled with 145.38 g (1.65 mole) of butyric acid, and then 185.14 g (1.65 mole) of a 48% aqueous solution of potassium hydroxide was added dropwise.
- the obtained mixture was combined with 300 g of toluene and subjected to azeotropic dehydration.
- the contents were combined with 298.1 g (1.5 mole) of ⁇ -chloropropyltrimethoxysilane, and 1.14 g (0.0075 mole) of DBU as a phase-transfer catalyst, and the mixture was stirred for 2 hours at 130°C.
- the obtained product was separated by adding 450 g of water and purified by evaporating an organic layer via distillation in vacuum. It was confirmed by a gas chromatography analysis that the final product was comprised of 311.7 g (1.25 moles) of trimethoxysilylpropyl butyrate. A yield of separation was relatively high and was 83%.
- a 1000 ml four-neck flask equipped with a refluxing cooler, stirrer, and thermometer was filled with 68.45 g (0.46 mole) of cinnamic acid and 150 g of water, and then 51.43 g (0.44 mole) of a 48% aqueous solution of potassium hydroxide was added dropwise.
- the obtained mixture was subjected to azeotropic dehydration with 150 g of toluene.
- the contents were combined with 79.49 g (0.40 5 mole) of ⁇ -chloropropyltrimethoxysilane, 50 g of xylene, and 0.30 g (0.002 mole) of DBU, as a phase-transfer catalyst, and the mixture was stirred for 6 hours at 120°C.
- the obtained reaction product was separated by adding 120 g of water and purified by evaporating an organic layer via distillation in vacuum. It was confirmed by a gas chromatography analysis that the final product was comprised of 79.72 g (0.26 mole) of trimethoxysilylpropyl cinnamate. A yield of separation was 64%.
- Comparative Example 1 A test was carried at the same conditions as in Practical Example 1, with the exception that DBU was not added. Only a trace amount of the trimethoxysilylpropyl butyrate present in the mixture obtained after completion was detected by gas chromatography.
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Abstract
A method of manufacturing an organoalkoxysilane that contains ester-functional groups comprising the step of causing a reaction between (a) an alkali-metal salt of a carboxylic acid and (b) an organoalkoxysilane that contains halogen-substituted organic groups (c) in the presence of a phase-transfer catalyst.
Description
METHOD OF MANUFACTURING AN ORGANOALKOXYSILANE HAVING ESTER-FUNCTIONAL GROUPS
Technical Field [0001 ] The present invention relates to a novel method of manufacturing an organoalkoxysilane having ester-functional groups, the product being obtained easily and with a high yield. The method consists of conducting a reaction between an alkali-metal salt of a carboxylic acid and an organoalkoxysilane with halogen-substituted organic groups in the presence of a phase-transfer catalyst.
Background Art [0002] Organoalkoxysilanes with acrylic-acid-ester-functional groups and/or methacrylic- acid-ester-functional groups are used as silane-coupling agents, raw materials for synthesis of acryl- and/or methacryl-modified silicone oils, or poiymerizable monomers for manufacturing acryl-type polymers that contain alkoxysilyl groups. Heretofore, such organoalkoxysilanes were synthesized by subjecting carboxylic acid esters of unsaturated alcohols and hydrosilanes to hydrosilation in the presence of transition-metal catalysts. Japanese Unexamined Patent Application Publication (hereinafter referred to as "Kokai") H9-208590 (equivalent to US5679821) discloses a method of obtaining an ester-functional alkoxysilane by subjecting an alkylallylester and hydroalkoxysilane to hydrosilation in the presence of a transition-metal catalyst.
[0003] Although with regard to a different compound, Japanese Official Patent
Publication 2001-512779 (equivalent to EP 1007604) also discloses a method of obtaining an aromatic-carboxylic-acid-ester-functional trialkoxysilane by synthesizing an ester compound with unsaturated groups on terminals by subjecting an alcohol having alkenyl groups and a carboxylic acid having a phenyl groups to esterification in the presence of an acidic catalyst, and then subjecting the obtained compound to hydrosilation with an alkoxysilane in the presence of a platinum catalyst.
[0004] A disadvantage of the above methods is the synthesis process that involves the use of either hydro alkoxysilanes that are difficult to handle, or unsaturated esters that are not always commercially available and therefore have to be synthesized in separate specially designed processes. Another problem is that the hydrosilation reaction has low positional selectivity, and therefore it is not always possible to obtain a product of high purity.
[0005] On the other hand, Kokai 2002-249494 (equivalent to EP1234830) discloses a method of obtaining an ester-functional organoalkoxysilane without resorting to the hydrosilation reaction, but the above method utilizes acrylic- and/or methacrylic-acid as a starting material in the form of an alkali-metal salt, and, therefore, products that can be obtained by the aforementioned method are limited only to acrylic- and/or methacrylic-acid- ester-functional organoalkoxysilanes. Furthermore, since the process involves addition of a polymerization inhibitor, such as phenothiazine required for inhibiting polymerization during the reaction, this may be an obstacle for processes in which a acrylic- and/or methacrylic- acid-ester-functional organoalkoxysilane, that constitutes a product, has to participate in vinyl polymerization.
Disclosure of Invention [0006] Based on the results of a detailed study, the author has found that a desired organoalkoxysilane with ester-functional groups can be efficiently produced by causing an alkali-metal salt of a carboxylic acid other than acrylic and/or methacrylic acid to participate in a reaction with a halogenated alkylalkoxysilane in the presence of a phase-transfer catalyst without the use of polymerization inhibitors. Thus the author arrived at the present invention. It is an object of the present invention to provide a method that allows easy high- yield production of an organoalkoxysilane with carboxylic-acid-ester-functional groups without the use of polymerization inhibitors.
[0007] The present invention provides a method of manufacturing an organoalkoxysilane that contains ester-functional groups and is represented by the following general formula: R1 - COO - R2 -Si (OR3)n R4 3.n
(where R1, R2, R3, R4, and «n» are the same as defined below), said method comprising the step of causing a reaction between
(a) an alkali-metal salt of a carboxylic acid represented by the following general formula: R^OOM1 {where R1 is a substituted or unsubstituted Ci - C15 univalent hydrocarbon group (except for a vinyl group and isopropenyl group), and M1 is an alkali metal} and (b) an organoalkoxysilane that contains halogen-substituted organic groups and is represented by the following general formula: XR2Si (OR3)n R4 3.n (where X is a halogen atom, R2 is a Ci - C6 alkylene group or alkylenoxyalkylene group, R3 is an alkyl group or a C - C4 alkoxyalkyl group, R4 is a substituted or unsubstituted univalent Ci - C15 hydrocarbon group, and «n» is an integer between 1 and 3) (c) in the presence of a phase-transfer catalyst.
Best Mode for Carrying Out the invention [0008] The present invention provides a method that allows efficient and economical production of a highly pure organoalkoxysilane that contains ester-functional groups and is suitable for use as a silane-coupling agent, a raw material for synthesis of modified silicone oils, or polymerizable monomers for the manufacture of silicon-containing polymers.
[0009] An alkali-metal salt (a) of a carboxylic acid used in the method of the present invention is represented by the following general formula: R^OOM1 (1), where R1 designates substituted or unsubstituted univalent C\ - C15 hydrocarbon groups (except for vinyl and isopropenyl groups). Example of such groups are the following: _ C15 alkyl groups; C3 _ do cycloalkyl groups; phenyl groups, tolyl groups, xylyl groups, naphthyl groups, or similar aryl groups; benzyl groups, phenethyl groups, or similar aralkyl groups; 1-propenyl groups, allyl groups, 2-phenylvinyl groups, or similar alkenyl groups, other than vinyl an isopropenyl groups. Most preferable are alkyl, cycloalkyl, aryl, aralkyl, and 2-phenylvinyl groups. The aforementioned groups can be substituted by alkoxy groups, alkoxycarbonyl groups, acyl groups, cyano groups, etc. In the above formula, M designates an alkali metal, preferably, sodium or potassium. Preferable alkali-metal salts of a carboxylic acid are the following: sodium acetate, sodium propionate, sodium crotonate, sodium cyclopropane carboxylate, sodium butyrate, sodium isobutyrate, sodium
trimethylacetate, sodium vinylacetate, sodium salt of valeric acid, sodium salt of 2,4- hexadienoic acid, sodium salt of undecanoic acid, sodium salt of benzoic acid, sodium salt of rn-toluic acid, sodium salt of p-toluic acid, sodium phenylacetate, sodium salt of cinnamic acid, sodium salt of 3 -vinyl benzoic acid, sodium salt of 2-methyl cinnamic acid, or potassium equivalents of the aforementioned sodium salts.
[0010] The aforementioned alkali-metal salts of carboxylic acids can be produced, e.g., by neutralizing a carboxylic acid with sodium or potassium hydroxide, or saponifying methyl carboxylates with sodium or potassium hydroxides. The alkali-metal salts of carboxylic acids can be supplied to the reaction in a solid form or in a liquid form as dispersions or solutions in appropriate solvents.
[0011] The organoalkoxysilane (b) with halogen-substituted organic groups is represented by the following general formula: XR2Si (OR3)„ R4 3.n where X is a halogen atom, e.g., a chlorine or bromine atom. R2 is a - C6 alkylene group or alkylenoxyalkylene group, such as a methylene group, ethylene group, methylmethylene group, propylene group, methylethylene group, butylene group, hexylene group, 1- mefhylpentylene group, 1,4-dimethylbutylene, or other alkylene groups; a methyleneoxypropylene group, methyleneoxypentylene group, or other alkylenoxyalkylene groups. Of these, preferable are a methylene group, propylene group, butylene group, methyleneoxypropylene group, methyleneoxypentylene group, especially propylene group. R3 is an alkyl group or a C2 - C4 alkoxyalkyl group. The following are examples of the alkyl group: a methyl group, propyl group, butyl group, pentyl group, isopropyl group, isobutyl group, cyclopentyl group, and cyclohexyl group. The aforementioned alkoxyalkyl group can be exemplified by a methoxyethyl group, methoxypropyl group, and methoxybutyl group. Of these, most preferable are a methyl group, ethyl group, and methoxyethyl group. R4 is a substituted or unsubstituted univalent Ci - 5 hydrocarbon group, such as a methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, cyclopentyl group, cyclohexyl group, or a similar alkyl group; a phenyl group, tolyl group, xylyl group, naphthyl group, or a similar aryl group; a vinyl group, allyl group, butenyl group, pentene group, hexenyl group, or a similar alkenyl group; and benzyl group, phenethyl group, or a similar aralkyl group. The aforementioned groups can be substituted by alkoxy groups,
alkoxycarbonyl groups, acyl groups, cyano groups, etc. Most preferable are methyl groups. In the above formula, «n» is an integer between 1 and 3.
[0012] The aforementioned organoalkoxysilane with halogen-substituted organic groups may be represented by a chloromethyldimethylmethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ- chloropropyl-tris- (methoxyethoxy) silane, γ- chloropropylmethyldimethoxysilane, γ-chloropropylbutyldimethoxysilane, δ-chlorobutyltrimethoxysilane, δ-chlorobutylmethyldimethoxysilane, δ-chlorobutyl-tris-(methoxyethoxy) silane, γ-bromopropyltrimethoxysilane, γ-bromopropyltriethoxysilane, γ-bromopropyl-tris- (methoxyethoxy) silane, and γ-bromopropylmethyldimethoxysilane. Of these, most preferable are γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ- chloropropyl-tris-(methoxyethoxy) silane, and γ-chloropropylmethyldimethoxysilane, especially, γ-chloropropyltrimethoxysilane and γ-chloropropylmethyldimethoxysilane.
[0013] Phase-transfer catalyst (c) may be comprised of a conventional one used in the art. Preferable phase-transfer catalysts are the following: tributylammom'um bromide, octylmethylammonium chloride, or similar quaternary ammonium salts; tributylphosphonium chloride, or similar quaternary phosphonium salts; triethylamine, or similar tertiary amines; crown ethers; 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,4-diazabicyclo [2.2.2] octane, and 1,5-diazabicyclo [4.3.0]-nona-5-ene, or similar cyclically-structured tertiary amines. Of these, most preferable are 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,4- diazabicyclo [2.2.2] octane, and 1,5-diazabicyclo [4.3.0]-nona-5-ene, especially 1,8- diazabicyclo [5.4.0] undeca-7-ene (hereinafter referred to as DBU) that is readily available.
[0014] It is recommended to add components (a) and (b) to the reaction in such a proportion that the alkali-metal salt of a carboxylic acid (component (a)) be used in an amount of 0.1 to 2.0 moles, preferably 0.5 to 1.5 moles, for each 1.0 mole of the organoalkoxysilane with halogen-substituted organic groups (component (b)). Phase-transfer catalyst (c) should be used in an amount of 0.0001 to 0.2 mole, preferably 0.001 to 0.05 mole for each 1 mole of the organoalkoxysilane with halogen-substituted organic groups (component (b)). It is preferable to have a reaction temperature within the range of 30 to 180°C, preferably
within the range of 100 to 160°C. Duration of the reaction will depend on the type of the alkali-metal salt of a carboxylic acid (component (a)), the amount of the phase-transfer catalyst (c), the reaction temperature, and other factors of the reaction, but in general the reaction may last from 10 hours to 10 min.
[0015] If the organoalkoxysilane (b) with halogen-substituted organic groups incorporates the functions of a reaction substrate and solvent, the method of the invention can be carried out without participation of a solvent. Otherwise, a solvent inert to the catalyst and starting material, such as benzene, toluene, xylene, or a similar aromatic solvent, as well as methanol, ethanol or another alcohol-type solvent, or dimethylformamide, can be used.
[0016] If the organoalkoxysilane (b) with halogen-substituted organic groups has high hydrolyzability, introduction of water into the reaction system may decrease the yield of the product. Therefore, it is recommended to use the alkali-metal salt (a) of a carboxylic acid in a sufficiently dry state. Drying of component (a) may be carried out by heating in vacuum, or by azeotropic dehydration, h case component (b) has low hydrolyzability, component (a) may be used in an aqueous solution.
[0017] There is no need in using a polymerization inhibitor in the reaction conducted by the method of the invention. If necessary, however, the following reaction inhibitors can be used: phenol compounds such as methoxyphenol and 2,6-di-t-butyl-4-methylphenol; phenothiazine; amino-type compounds or sulfur-containing compounds.
[0018] Upon completion of the reaction by the method of the invention, a sufficiently pure final product is obtained by removing salts of by-products by filtering, centrifugal separation, water treatment, or by any other suitable method. If necessary, further purification can be carried out by distillation or another method.
[0019] The organoalkoxysilane with ester-functional groups obtained by the above- described method is represented by the following general formula: R1 - COO - R2 -Si (OR3)n R43-n, where R1, R2, R3, R4, and «n» are the same as defined above. The following are examples of the compounds that can be represented by the above formula:
dimethylmethoxysilylpropyl acetate, methyldimethoxysilylpropyl acetate, trimethoxysilylpropyl acetate, triethoxysilylpropyl acetate, tris-(methoxyethoxy) silylpropyl acetate, butyldimethoxysilylpropyl acetate; dimethylmethoxysilylpropyl butyrate, methyldimethoxysilylpropyl butyrate, trimethoxysilylpropyl butyrate, triethoxysilylpropyl butyrate, tris-(methoxyethoxy) silylpropyl butyrate, butyldimethoxysilylpropyl butyrate; dimethylmethoxysilylpropyl cinnamate, methyldimethoxysilylpropyl cinnamate, trimethoxysilylpropyl cinnamate, triethoxysilylpropyl cinnamate, tris-(methoxyethoxy) silylpropyl cinnamate, butyldimethoxysilylpropyl cinnamate; dimethylmethoxysilylpropyl benzoate, methyldimethoxysilylpropyl benzoate, trimethoxysilylpropyl benzoate, triethoxysilylpropyl benzoate, tris-(methoxyethoxy) silylpropyl benzoate, and butyldimethoxysilylpropyl benzoate.
Examples [0020] The invention will be further described more specifically with reference to practical examples. However, these examples should not be construed as limiting the scope of the invention.
[0021] Practical Example 1
A 1000 ml four-neck flask equipped with a refluxing condenser, stirrer, and thermometer was filled with 145.38 g (1.65 mole) of butyric acid, and then 185.14 g (1.65 mole) of a 48% aqueous solution of potassium hydroxide was added dropwise. The obtained mixture was combined with 300 g of toluene and subjected to azeotropic dehydration. The contents were combined with 298.1 g (1.5 mole) of γ-chloropropyltrimethoxysilane, and 1.14 g (0.0075 mole) of DBU as a phase-transfer catalyst, and the mixture was stirred for 2 hours at 130°C. The obtained product was separated by adding 450 g of water and purified by evaporating an organic layer via distillation in vacuum. It was confirmed by a gas chromatography analysis that the final product was comprised of 311.7 g (1.25 moles) of trimethoxysilylpropyl butyrate. A yield of separation was relatively high and was 83%.
[0022] Practical Example 2
A 1000 ml four-neck flask equipped with a refluxing cooler, stirrer, and thermometer was filled with 68.45 g (0.46 mole) of cinnamic acid and 150 g of water, and then 51.43 g (0.44 mole) of a 48% aqueous solution of potassium hydroxide was added dropwise. The obtained
mixture was subjected to azeotropic dehydration with 150 g of toluene. The contents were combined with 79.49 g (0.40 5 mole) of γ-chloropropyltrimethoxysilane, 50 g of xylene, and 0.30 g (0.002 mole) of DBU, as a phase-transfer catalyst, and the mixture was stirred for 6 hours at 120°C. The obtained reaction product was separated by adding 120 g of water and purified by evaporating an organic layer via distillation in vacuum. It was confirmed by a gas chromatography analysis that the final product was comprised of 79.72 g (0.26 mole) of trimethoxysilylpropyl cinnamate. A yield of separation was 64%.
[0023] Practical Example 3 A 1000 ml four-neck flask equipped with a refluxing cooler, stirrer, and thermometer was filled with 151.31 g (1.05 mole) of sodium benzoate, 100 g of toluene, 198.72 g (1.00 mole) of γ-chloropropyltrimethoxysilane, and 0.76 g (0.05 mole) of DBU, as a phase-transfer catalyst, and the mixture was stirred for 3 hours at 120°C. The obtained reaction product was separated by adding 240 g of water and purified by evaporating an organic layer via distillation in vacuum. It was confirmed by a gas chromatography analysis that the final product was comprised of 227.59 g (0.80 mole) of trimethoxysilylpropyl benzoate. A yield of separation was relatively high and equal to 80%.
[0024] Comparative Example 1 A test was carried at the same conditions as in Practical Example 1, with the exception that DBU was not added. Only a trace amount of the trimethoxysilylpropyl butyrate present in the mixture obtained after completion was detected by gas chromatography.
Claims
1. A method of manufacturing an organoalkoxysilane that contains ester-functional groups and is represented by the following general formula: R1 - COO - R2 -Si (OR3)n R43-n (where R1, R2, R3, R4, and «n» are the same as defined below), said method comprising the step of causing a reaction between (a) an alkali-metal salt of a carboxylic acid represented by the following general formula: R^OOM1 {where R1 is a substituted or unsubstituted Ci - C15 univalent hydrocarbon group (except for a vinyl group and isopropenyl group), and M1 is an alkali metal} and (b) an organoalkoxysilane that contains halogen-substituted organic groups and is represented by the following general formula: XR2Si (OR3)n R4 3.n (where X is a halogen atom, R2 is a 
- C6 alkylene group or alkylenoxyalkylene group, R3 is an alkyl group or a C2 - C4 alkoxyalkyl group, R4 is a substituted or unsubstituted Ci - Cι5 univalent hydrocarbon group, and «n» is an integer between 1 and 3) (c) in the presence of a phase-transfer catalyst.
2. The method of Claim 1 for manufacturing an organoalkoxysilane that contains ester- functional groups, wherein said phase-transfer catalyst (c) is a tertiary-amine compound with a cyclic structure selected from the group that consists of 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,4-diazabicyclo [2.2.2] octane, and 1,5-diazabicyclo [4.3.0]-nona-5-ene.
3. The method of Claim 1 for manufacturing an organoalkoxysilane that contains ester- functional groups, wherein said (b) organoalkoxysilane that contains halogen-substituted organic groups and (c) a phase-transfer catalyst are used in a mole ratio within the range of (1:0.001) to (1:0.20).
4. The method of Claims 1 or 2 for manufacturing an organoalkoxysilane that contains ester-functional groups, wherein said (a) alkali-metal salt of a carboxylic acid is a sodium salt of a carboxylic acid or a potassium salt of carboxylic acid.
5. The method of Claims 1 or 2 for manufacturing an organoalkoxysilane that contains ester-functional groups, wherein said (b) organoalkoxysilane that contains halogen- substituted organic groups is an organoalkoxysilane that contains chlorine-substituted organic groups or an organoalkoxysilane that contains bromine-substituted organic groups.
6. The method of Claims 1 or 2 for manufacturing an organoalkoxysilane that contains ester-functional groups, wherein said organoalkoxysilane that contains halogen- substituted organic groups is γ-chloropropyltrimethoxysilane, γ- chloropropyltriethoxysilane, γ-chlόropropyl-tris-(methoxyethoxy) silane or γ- chloropropyl methyldimethoxysilane.
7. The method of Claims 1 or 2 for manufacturing an organoalkoxysilane that contains ester-functional groups, wherein said organoalkoxysilane that contains ester-functional groups is trimethoxysilylpropyl butyrate, trimethoxysilylpropyl cinnamate or trimethoxysilylpropyl benzoate.
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| JP2004-131530 | 2004-04-27 | ||
| JP2004131530A JP2005314246A (en) | 2004-04-27 | 2004-04-27 | Method for producing ester functional group-containing organoalkoxysilane |
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| WO2010125123A1 (en) | 2009-04-30 | 2010-11-04 | Dow Corning Corporation | Elastomer compositions modified by silanes |
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