CN1656252A - 制造有机官能硅烷的电化学方法 - Google Patents
制造有机官能硅烷的电化学方法 Download PDFInfo
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- CN1656252A CN1656252A CNA038123339A CN03812333A CN1656252A CN 1656252 A CN1656252 A CN 1656252A CN A038123339 A CNA038123339 A CN A038123339A CN 03812333 A CN03812333 A CN 03812333A CN 1656252 A CN1656252 A CN 1656252A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 150000004756 silanes Chemical class 0.000 title abstract 3
- 238000002848 electrochemical method Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- -1 polyethylene Polymers 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 238000003487 electrochemical reaction Methods 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- RHQQHZQUAMFINJ-GKWSUJDHSA-N 1-[(3s,5s,8s,9s,10s,11s,13s,14s,17s)-3,11-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-hydroxyethanone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 RHQQHZQUAMFINJ-GKWSUJDHSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910016467 AlCl 4 Inorganic materials 0.000 claims description 2
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- UFHGABBBZRPRJV-UHFFFAOYSA-N Hydroxysanguinarine Chemical compound C12=CC=C3OCOC3=C2C(=O)N(C)C(C2=C3)=C1C=CC2=CC1=C3OCO1 UFHGABBBZRPRJV-UHFFFAOYSA-N 0.000 claims description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 22
- 125000003545 alkoxy group Chemical group 0.000 abstract 2
- 125000001475 halogen functional group Chemical group 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 12
- 238000002955 isolation Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HXLVDKGPVGFXTH-UHFFFAOYSA-N butyl(dimethyl)silane Chemical group CCCC[SiH](C)C HXLVDKGPVGFXTH-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 239000000460 chlorine Substances 0.000 description 3
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OHGZTTYNJFNQFU-UHFFFAOYSA-N 4-dimethylsilyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C([SiH](C)C)C=C1 OHGZTTYNJFNQFU-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- RTYNSTRFACIKRL-UHFFFAOYSA-N chloro-(4-methoxyphenyl)-dimethylsilane Chemical compound COC1=CC=C([Si](C)(C)Cl)C=C1 RTYNSTRFACIKRL-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- FCKFHVFZPCZMDQ-UHFFFAOYSA-N hexyl(dimethyl)silane Chemical compound CCCCCC[SiH](C)C FCKFHVFZPCZMDQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMCZAFXJZGCLQH-UHFFFAOYSA-N (4-methoxyphenyl)-dimethylsilane Chemical compound COC1=CC=C([SiH](C)C)C=C1 SMCZAFXJZGCLQH-UHFFFAOYSA-N 0.000 description 1
- COSWCAGTKRUTQV-UHFFFAOYSA-N 1,1,3-trimethylurea Chemical compound CNC(=O)N(C)C COSWCAGTKRUTQV-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- SQTLUXJWUCHKMT-UHFFFAOYSA-N 4-bromo-n,n-diphenylaniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 SQTLUXJWUCHKMT-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- YCIPQJTZJGUXND-UHFFFAOYSA-N Aglaia odorata Alkaloid Natural products C1=CC(OC)=CC=C1C1(C(C=2C(=O)N3CCCC3=NC=22)C=3C=CC=CC=3)C2(O)C2=C(OC)C=C(OC)C=C2O1 YCIPQJTZJGUXND-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- C07F7/0896—Compounds with a Si-H linkage
-
- 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
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明涉及制备通式(1)有机官能硅烷的方法。其中,利用未分开的电解槽,使通式(2)的硅烷与通式R1-Y的化合物进行电化学反应,条件是相对于每摩尔X络合剂最多为0.1摩尔。R1、R2、R3、R4、X和Y的含义如权利要求1中所定义。
Description
技术领域
本发明涉及利用牺牲阳极制备有机官能硅烷的电化学方法。
背景技术
Shono等(Chem.Letters 1985,463-466)宣称可以在分开的电解槽内借助于惰性阳极,在有三甲基氯硅烷存在的情况下通过用电化学方法还原苄基卤和烯丙基卤以较高的产率制备对应的苄基硅烷(例如:PhCH2SiMe3)及烯丙基硅烷。
此外,例如,Von Biran,Bordeau等(J.Chim.Phys.,1996,93,591-600,Organometallics,2001,20(10),1910-1917)描述了在有HMPA等络合剂存在的情况下,利用牺牲阳极通过电化学方法制备有机官能硅烷。
Von Bordeau,Biran等(Organometallics,2001,20(10),1910-1917)同样描述了利用硅烷二甲基二氯硅烷(硅烷M2)通过电化学方法制备取代的芳族卤化物。相对于传统方法,电化学制备法的优点在于Si-C键形成的高选择性。相比之下,在传统化学方法中该Si-C键通过与必须事先借助丁基锂或镁生成的有机金属亲核体进行偶联反应而生成。然而,仅在不但具有络合剂如HMPA及导电盐(四丁基溴化铵)存在,而且另外利用镍催化剂(二氯二吡啶镍)及2,2’-联吡啶作为辅催化剂的条件下实施电解,Biran等才成功地制成甲硅烷化的芳族化合物,例如对-甲氧基苯基二甲基氯硅烷(见下列反应方程式)。
此外,为了以可接受的产率得到所需的产品,必须大幅过量使用硅烷。迄今为止,在该条件下仅可成功使用溴化物作为反应物。
发明内容
本发明提供一种用以制造化学通式(I)所示的有机官能硅烷的方法。
其中,利用未分开的电解槽使化学通式(2)所示的硅烷
与化学通式(3)所示的化合物进行电化学反应
R1-Y (3),
其中,
R1是化学通式(4)所示的基,
R6R7R8C (4),
R6、R7及R8,单独地或共同地为单体、低聚物、或聚合物基,R2及R3,单独地或共同地为任选地被取代的C1-C30烃基,其中一个或更多个非相邻亚甲基单元可由-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、-CO-NR5-、-NH-或-N-C1-C20烃基替代,且其中一个或更多个非相邻次甲基单元可由-N=、-N=N-或-P=基替代,
R4是氢或任选地取代的C1-C30烃基,其中一个或更多个非相邻亚甲基单元可由-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、-CO-NR5-、-NH-或-N-C1-C20烃基替代,且其中一个或更多个非相邻次甲基单元可由-N=、-N=N-或-P=基替代,
X及Y选自Br、Cl、I、OR5及
R5是C1-C10烷基,
条件是相对于每摩尔X,至多有0.1摩尔络合剂存在。
该方法适于量少的情况下,且无需添加络合剂如有害健康的HMPA(六甲替磷酰三胺)或DMPU(N,N’-二甲基亚丙基脲),而且无需催化剂或辅催化剂即可实施。因此可以简单有效的方式制得化学通式(I)所示的硅烷。
此外,该方法的适用范围极广,即可使用带有多种不同的取代基的芳族及脂肪族卤化物(从而不仅限于溴化物)。该反应依照化学计量进行(无需任何过量的硅烷),该方法以极高的选择性进行,即,即使有也仅可检出极少量的副产品,且所形成的化学通式(1)所示的有机硅烷可以良好至优异的产率(通常为70至90%)得以分离。
具体实施方式
单体R6、R7及R8基优选是氢、氰基或任选被取代的C1-C30烃基,其中一个或更多个非相邻亚甲基单元可由-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、-CO-NR5-、-NH-或-N-C1-C20烃基替代,且其中一个或更多个非相邻次甲基单元可由-N=、-N=N-或-P=基替代,并且其中一个或更多个非相邻的碳原子可被硅原子替代。
适当的取代基是例如卤素,特别是氟、氯、溴及碘,氰基、氨基。
特别优选的单体R6、R7及R8基是C1-C20芳基及C1-C20烷基,其中不相邻的亚甲基单元可由-O-基替代,且不相邻的碳原子可由硅原子替代。
低聚物及聚合物R6、R7及R8基是例如聚合物、合成低聚物及聚合物如聚氯乙烯、聚乙烯、聚丙烯、聚乙酸乙烯酯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚丙烯腈、聚偏1,1-二氯乙烯(PVC)、聚氟乙烯、聚偏1,1-二氟乙烯、聚偏氰乙烯(polyvinylidene cyanide)、聚丁二烯、聚异戊二烯、聚醚、聚酯、聚酰胺、聚酰亚胺、聚硅氧烷、聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯酰胺、聚乙二醇及其衍生物等,包含共聚物如苯乙烯-丙烯酸酯共聚物、乙酸乙烯酯-丙烯酸酯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯三元共聚物(EPDM)、乙丙橡胶(EPM)、聚丁二烯(BR)、聚-异丁烯-异戊二烯(丁基橡胶,JJR)、聚异戊二烯(IR)及丁苯橡胶(SBR)。
低聚物及聚合物R6、R7及R8基是例如天然低聚物及聚合物,如纤维素、淀粉、酪蛋白及天然树胶,以及半合成低聚物及聚合物如纤维素衍生物,例如甲基纤维素、羟甲基纤维素及羧甲基纤维素。
化学通式(1)及(2)中的符号包含R2、R3及R4基直接或经由氧原子与硅原子键结的可能性。
烃基R2、R3及R4的实例是烷基,如甲基、乙基、正-丙基、异丙基、正-丁基、异丁基、叔-丁基、正-戊基、异戊基、新戊基或叔-戊基,己基如正-己基,庚基如正-庚基,辛基如正-辛基及异辛基如2,2,4-三甲基戊基,壬基如正-壬基,癸基如正-癸基,十二烷基如正-十二烷基,十八基如正-十八基;烯基如乙烯基及烯丙基;环烷基如环戊基、环己基、环庚基及甲基环己基;芳基如苯基、萘基及蒽基及菲基;烷芳基如邻-、间-、对-甲苯基、二甲苯基及乙基苯基;芳烷基如苄基、α-及β-苯乙基。优选的R2、R3及R4基为C1-C6烷基,特别优选甲基及乙基或苯基。
使用化学通式(2)及(3)所示的化合物的混合物或组合物也是适宜的。
在该方法中相对于每摩尔X,络合剂含量优选为至多0.01摩尔,特别优选不含络合剂。络合剂是例如六甲替磷酰三胺(HMPA)、N,N’-二甲基亚丙基脲或四氢-1,3-二甲基-2(1H)-嘧啶酮(pyrimidinone)(DMPH)、三(3,6-二氧杂庚基)胺(TDA-1)、四甲基脲(TMU)。
阳极可由具有足够的导电性且在所选反应条件下呈化学惰性的所有材料组成。优选采用牺牲阳极作为阳极。该牺牲阳极含有在加工中溶解形成阳离子的金属或合金。优选的金属是镁、铁、钛、锌、铝、铜、锡,特别优选镁。
对电极(阴极)可同样由具有足够的导电性且在所选反应条件下呈化学惰性的所有材料组成。优选为石墨或惰性金属如金、银、铂、铼、钌、铑、锇、铱及钯,或具有相当惰性的其他金属或合金例如不锈钢。
在反应开始时为了使反应混合物达到足够的电导率,优选加入导电盐。所用导电盐为不与反应组分反应的惰性盐或其混合物。
导电盐的实例是如化学通式M+Y-所示的盐类,其中M是例如Mg、Li、Na、NBu4、NMe4、NEt4,而Y是例如ClO4、Cl、Br、I、NO3、BF4、AsF6、BPh4、PF6、AlCl4、CF3SO3及SCN,其中Bu、Me、Et及Ph分别是丁基、甲基、乙基及苯基。合适的电解质的实例包括四乙基四氟硼酸铵及四丁基四氟硼酸铵。特别优选的导电盐是MgCl2及LiCl。
该方法优选在溶剂中实施。可用的溶剂是不与化学通式(1)至(3)所示的化合物反应且其本身仅在较化学通式(2)所示的化合物更大的负电位下被还原的所有质子惰性溶剂。适当的溶剂是所用化合物在操作时的浓度及温度的条件下至少部分可溶于其中的任何溶剂。在一特定具体实施例中,所用的化学通式(2)及(3)所示的化合物本身可用作溶剂。其实例是二甲基二氯硅烷。
适当的溶剂的实例是醚类,如四氢呋喃、1,2-二甲氧基乙烷、1,3-二氧戊环、二(2-甲氧基乙基)醚、二氧六环、乙腈、γ-丁内酯、硝基甲烷、液体SO2、三(二氧杂-3,6-庚基)胺、三甲基脲、二甲基甲酰胺、二甲亚砜及这些溶剂的混合物。
该溶剂优选为无水的。特别优选为四氢呋喃。
化学通式(3)所示的化合物在溶剂中的浓度优选为0.05至5mol/l,特别优选为0.1至2mol/l。
以1摩尔化学通式(3)所示的化合物为基准,化学通式(2)所示的化合物的用量优选为0.8至1.5摩尔,特别优选为0.9至1.2摩尔。
该方法可通过任何通常的方法,利用具有阴极及牺牲阳极的电解槽实施。该电解槽可以是分开式或非分开式电解槽,但优选为非分开式电解槽,因为其构造最简单。该方法优选在惰性气体环境中进行,优选的惰性气体是氮气、氩气或氦气。为控制电位或电流强度,该电解槽最好配以恒电位仪或恒流仪(恒定电流)。反应的实施可控制或不控制电压。
以化学通式(3)所示的化合物为基准,电荷Q的量优选为1.1至5F/mol,特别优选为1.5至3F/mol。
该方法优选在超声波作用下实施。
实施该方法的温度优选为5℃至50℃,特别优选为10至30℃。
上述分子式中所有上述的化学符号均是各自独立界定。在所有分子式中,硅原子均是四价。
除另有说明外,下列实施例中所有数量及百分比均是基于重量,所有压力均是0.10MPa(绝对),且所有温度均是20℃。
该反应是在保护气气氛(氩、氮)中实施,所用的所有溶剂均无水且所用的反应物都是高纯度的。
电解装置:
使用未分开的电解槽用于电解,其中,由高纯度镁制成的棒状牺牲阳极(直径8mm)置于中央,直径4cm的圆筒状不锈钢薄片组成的阴极置于阳极周围。电解是在电流恒定的情况下进行,阴极上的电流密度不超过0.5mA/cm2。在整个电解过程中该电解槽置于超声波浴中进行超声处理,该超声波浴用水冷却,以使温度不超过室温(20℃)太多。
实施例1:(对-甲氧基苯基)二甲基硅烷的制备
将1.2g(28.3mmol)无水氯化锂溶解于50毫升无水THF内并将其移至经保护气冲洗的干燥的电解槽内。添加5.00g(35.1mmol)对-氯代茴香醚及3.32g(35.1mmol)氯二甲基硅烷之后,在15mA(电流密度i=0.4mA/cm2)的恒定电流下实施电解。在总体反应时间138小时之后(注:此对应于电荷Q的量为2.2F/mol),停止电解。
分离净化(Workup):在减压条件下移去四氢呋喃后,使剩余的残渣与75毫升饱和的氯化铵水溶液混合,随后每次用50毫升正-戊烷萃取共三次。合并有机相并用硫酸钠干燥。移去正-戊烷后,制得4.95g预期产品(对-甲氧基苯基)二甲基硅烷(产率:理论值的85%)。
实施例2:(对-甲氧基苯基)二甲基硅烷的制备
依照与实施例1类似的方式,使10.00g(53.5mmol)4-溴代茴香醚与化学计量量5.06g(53.5mmol)的氯二甲基硅烷进行电化学反应。经48小时电解及与实施例1类似的分离净化之后,得到预期产品对-甲氧基苯基二甲基硅烷,产率为85%。
实施例3:[4-(N,N-二甲基氨基)苯基]-二甲基硅烷的合成
依照与实施例1类似的方式,自5.00g(25.0mmol)4-溴-N,N-二甲基苯胺开始,以2.36g(25mmol)氯二甲基硅烷实施电化学反应。经98小时电解(电荷Q的量=2.2F/mol)及与实施例1类似的分离净化之后,制得3.12g[4-(N,N-二甲基氨基)苯基]-二甲基硅烷;其对应于产率理论值的70%。
实施例4:[4-(二甲基甲硅烷基)苯氧基]-叔丁基二甲基硅烷的制备
与实施例1类似,使7.50g(26.1mmol)的(4-溴代苯氧基)-叔丁基二甲基硅烷与2.47g(26.1mmol)的氯二甲基硅烷进行电化学反应。在总体反应时间138小时(电荷Q的量=2.2F/mol)及与实施例1类似的分离净化之后,制得6.40g的[4-(二甲基甲硅烷基)-苯氧基]-叔丁基二甲基硅烷。其对应于产率理论值的90%。
实施例5:正-戊基二甲基硅烷的制备
依照与实施例1类似的方式,自4.00g(37.5mmol)的1-氯戊烷及3.55g(37.5mmol)的氯二甲基硅烷开始,电解147小时(电荷Q的量=2.2F/mol)及进行与实施例1类似的分离净化之后,制得总计4.15g预期产品(正-戊基二甲基硅烷)。此对应于85%的产率。
实施例6:正-己基二甲基硅烷的制备
类似于实施例1,自5.00g(30.3mmol)的己基溴及化学计量量2.86g(30.3mmol)的氯二甲基硅烷开始,电解22小时及进行与实施例1类似的分离净化之后,制得总计2.90g产品正-己基二甲基硅烷。此对应的产率为理论值的66%。
实施例7:(对-甲氧基苯基)甲氧基二甲基硅烷的合成
类似于实施例1,使5.00g(35.1mmol)的对氯代茴香醚与4.22g(35.1mmol)的二甲氧基二甲基硅烷相互进行电化学反应。电解共138小时(电荷Q的量=2.2F/mol)及进行与实施例1类似的分离净化之后,制得5.50g产品对-甲氧基苯基-甲氧基二甲基硅烷(产率:理论值的80%)。
实施例8:(对-甲氧基苯基)甲氧基二甲基硅烷的合成
与实施例1类似,自5.00g(26.7mmol)的对-溴代茴香醚及化学计量量3.20g(26.7mmol)的二甲氧基二甲基硅烷开始,电解24小时并进行与实施例1相同的分离净化之后,制得2.72g预期产品(理论产率的52%)。
实施例9:[4-(甲氧基二甲基甲硅烷基)-苯氧基]-叔丁基二甲基甲硅烷的制备
依照类似于实施例1的方式,将7.50g(26.1mmol)的(4-溴代苯氧基)-叔丁基二甲基硅烷与化学计量量的二甲氧基二甲基硅烷(3.14g(26.1mmol))进行电解。电解1 03小时(Q=2.2F/mol)并进行与实施例1类似的分离净化之后,制得4.60g预期产品[4-(甲氧基二甲基甲硅烷基)苯氧基]-叔丁基二甲基硅烷。此对应于理论产率的60%。
实施例10:(N,N-二乙基氨基)-对-甲氧基苯基二甲基硅烷的合成
类似于实施例1,使2.80g(1 5.1mmol)的对-溴代茴香醚与化学计量量2.50g(15.1mmol)的(N,N-二乙基氨基)二甲基氯硅烷发生电化学反应。24小时之后,终止电解。进行与实施例1类似的分离净化后,制得1.62g预期产品(N,N-二乙基氨基)-对-甲氧基苯基二甲基硅烷(理论产率的45%)。
实施例11:(3-丁烯基)甲氧基二甲基硅烷的合成
与实施例1的方式类似,使4.00g(29.6mmol)的4-溴-1-丁烯与3.56g(29.6mmol)的二甲氧基二甲基硅烷进行电化学反应。电解116小时(电荷Q的量=2.2F/mol)并进行类似于实施例1的分离净化之后,制得3.50g预期产品(3-丁烯基)甲氧基二甲基硅烷。产率为83%。
实施例12:聚[(二甲基甲硅烷基)亚甲基-co-乙烯基氯的制备
类似于实施例1,自1.00g(16mmolCl)的聚氯乙烯及1.51g(16mmol)的氯二甲基硅烷开始,在15mA恒定电流下进行电解。电解共63小时(电荷Q的量=2.2F/mol)后,终止电解。在减压下除去部分溶剂,将反应溶液浓缩至一半体积。随后,在剧烈搅拌的情况下,将该浓缩的溶液徐徐滴入250毫升甲醇内。在该过程中,所形成的聚合物沉淀出来。每次用150毫升甲醇清洗该沉淀的聚合物共三次,最终减压干燥至恒重。
实施例13:正-戊基二甲基硅烷的合成
依照类似实施例5的方式,但使用钛阳极取代镁阳极,在同样的条件下,将4.00g(37.5mmol)的1-氯戊烷及3.55g(37.5mmol)的氯二甲基硅烷进行电解,历时总计8天。利用GC-MS进行分析,除反应物之外,在粗产品内检出预期产品(组成:55%正-戊基二甲基硅烷目标产物,45%的1-氯戊烷反应物)。
比较例:对-甲氧基苯基二甲基氯硅烷的合成(见Biran,Bordeau等,Organometallics 2001,20(10),1910-1917)
在装有圆柱形铝或镁棒(直径1cm)作为牺牲阳极、同心不锈钢栅(或碳)作为阴极(表面积:1.0±0.2dm2)的未分开电解槽中(100ml),在氮气气氛下实施反应如下:
施加0.1A的恒定电流(电流密度:0.1±0.05A/dm2)并将无水THF(20毫升)、HMPA(6毫升)及硅烷(40至60毫升)相继加入干燥的电解槽内。将反应溶液除气并预电解(通过形成相应电化学惰性的硅氧烷移除残留的微量水)后,添加0.45g(1.2mmol)的NiBr2(bpy)镍催化剂及过量的2,2’-联吡啶辅催化剂(0.78g,5mmol)。进行电解(i=0.1A)直至电荷达到理论量。经类似于上述实施例的分离净化后,制得预期产品对-甲氧基苯基二甲基氯硅烷。产率为86%。无催化剂且无辅催化剂时,转化率为8至13%,催化剂为98%。
Claims (8)
1.一种用以制造化学通式(I)所示的有机官能硅烷的方法,
其中,利用未分开的电解槽使化学通式(2)所示的硅烷
与化学通式(3)所示的化合物进行电化学反应,
R1-Y (3)
其中,
R1是化学通式(4)所示的基,
R6R7R8C (4),
R6、R7及R8单独地或共同地为单体、低聚物、或聚合物基,R2及R3单独地或共同地为任选被取代的C1-C30烃基,其中一个或更多个非相邻亚甲基单元可由-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、-CO-NR5-、-NH-或-N-C1-C20烃基替代,且其中一个或更多个非相邻次甲基单元可由-N=、-N=N-或-P=基替代,
R4是氢或任选被取代的C1-C30烃基,其中一个或更多个非相邻亚甲基单元可由-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、-CO-NR5-、-NH-或-N-C1-C20烃基替代,且其中一个或更多个非相邻次甲基单元可由-N=、-N=N-或-P=基替代,
X及Y选自Br、Cl、I、OR5及
R5是C1-C10烷基,条件是相对于每摩尔X,至多有0.1摩尔络合剂存在。
2.如权利要求1所述的方法,其中单体R6、R7及R8基选自氢、氰基或任选被取代的C1-C30烃基,其中一个或更多个非相邻亚甲基单元可由-O-、-CO-、-COO-、-OCO-、或-OCOO-、-S-、-CO-NR5-、-NH-或-N-C1-C20烃基替代,且其中一个或更多个非相邻次甲基单元可由-N=、-N=N-或-P=基替代,并且其中一个或更多个非相邻的碳原子可被硅原子替代。
3.如权利要求1所述的方法,其中低聚物及聚合物R6、R7及R8基选自聚氯乙烯、聚乙烯、聚丙烯、聚乙酸乙烯酯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚丙烯腈、聚偏1,1-二氯乙烯(PVC)、聚氟乙烯、聚偏1,1-二氟乙烯、聚偏氰乙烯、聚丁二烯、聚异戊二烯、聚醚、聚酯、聚酰胺、聚酰亚胺、聚硅氧烷、聚乙烯醇、聚乙烯吡咯烷酮、聚丙烯酰胺、聚乙二醇及其衍生物,包含共聚物如苯乙烯-丙烯酸酯共聚物、乙酸乙烯酯-丙烯酸酯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯三元共聚物(EPDM)、乙丙橡胶(EPM)、聚丁二烯(BR)、聚-异丁烯-异戊二烯(丁基橡胶,JJR)、聚异戊二烯(IR)及丁苯橡胶(SBR)。
4.如权利要求1-3之一所述的方法,其中所述阳极是牺牲阳极,且包括选自镁、铁、钛、锌、铝、铜及锡的金属或金属的合金。
5.如权利要求1-4之一所述的方法,其中加入的导电盐如化学通式M+Y-所示,其中M是Mg、Li、Na、NBu4、NMe4、NEt4,而Y是ClO4、Cl、Br、I、NO3、BF4、AsF6、BPh4、PF6、AlCl4、CF3SO3及SCN,其中Bu、Me、Et及Ph分别是丁基、甲基、乙基及苯基。
6.如权利要求1-5之一所述的方法,其中存在质子惰性溶剂,该质子惰性溶剂不与化学通式(1)至(3)所示的化合物反应且其本身仅在较化学通式(2)所示的化合物更大的负电位下被还原。
7.如权利要求1-6所述的方法,其中以1摩尔化学通式(3)所述的化合物为基准,化学通式(2)所示的化合物的用量是0.8至1.5摩尔。
8.如权利要求1-7所述的方法,其在超声波作用下实施。
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DE10223939A DE10223939A1 (de) | 2002-05-29 | 2002-05-29 | Elektrochemisches Verfahren zur Herstellung von organofunktionellen Silanen |
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WO (1) | WO2003100134A1 (zh) |
Cited By (4)
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CN103328691A (zh) * | 2010-07-29 | 2013-09-25 | 液体光有限公司 | 杂环催化电化学过程 |
CN103924259A (zh) * | 2014-04-22 | 2014-07-16 | 浙江合盛硅业有限公司 | 一种室温制备聚二烷基硅氧烷混合环体的方法 |
CN103952716A (zh) * | 2014-05-16 | 2014-07-30 | 罗凯 | 一种电解合成硅氧烷的方法 |
CN104072533A (zh) * | 2014-06-10 | 2014-10-01 | 中国科学院广州能源研究所 | 一类含低聚氧化乙烯单元的硅腈类化合物及其制备方法、在锂电池中的应用 |
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DE102004029258A1 (de) * | 2004-06-17 | 2006-01-12 | Consortium für elektrochemische Industrie GmbH | Verfahren zur elektrochemischen Knüpfung von Silicium-Kohlenstoff- und Silicium-Wasserstoff-Bindungen unter Verwendung einer Wasserstoff-Elektrode |
CN113403636B (zh) * | 2021-05-26 | 2022-09-13 | 新疆大学 | 一种α,β-二氯苯亚砜类化合物的合成方法 |
WO2023222245A1 (de) | 2022-05-20 | 2023-11-23 | Wacker Chemie Ag | Verfahren zur herstellung von organosiliciumverbindungen |
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GB8917725D0 (en) * | 1989-08-03 | 1989-09-20 | Dow Corning | Electrochemical synthesis of organosilicon compounds |
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CN103328691A (zh) * | 2010-07-29 | 2013-09-25 | 液体光有限公司 | 杂环催化电化学过程 |
CN103924259A (zh) * | 2014-04-22 | 2014-07-16 | 浙江合盛硅业有限公司 | 一种室温制备聚二烷基硅氧烷混合环体的方法 |
CN103952716A (zh) * | 2014-05-16 | 2014-07-30 | 罗凯 | 一种电解合成硅氧烷的方法 |
CN104072533A (zh) * | 2014-06-10 | 2014-10-01 | 中国科学院广州能源研究所 | 一类含低聚氧化乙烯单元的硅腈类化合物及其制备方法、在锂电池中的应用 |
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EP1507898A1 (de) | 2005-02-23 |
WO2003100134A1 (de) | 2003-12-04 |
JP2005527706A (ja) | 2005-09-15 |
DE10223939A1 (de) | 2003-12-24 |
US20050234255A1 (en) | 2005-10-20 |
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