CN1041521C - 从硅烷中去除含氢硅烷的方法 - Google Patents
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- CN1041521C CN1041521C CN93120581A CN93120581A CN1041521C CN 1041521 C CN1041521 C CN 1041521C CN 93120581 A CN93120581 A CN 93120581A CN 93120581 A CN93120581 A CN 93120581A CN 1041521 C CN1041521 C CN 1041521C
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 150000004756 silanes Chemical class 0.000 title abstract description 7
- 239000001257 hydrogen Substances 0.000 title description 3
- 229910052739 hydrogen Inorganic materials 0.000 title description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 7
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052737 gold Inorganic materials 0.000 abstract description 6
- 239000010931 gold Substances 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 11
- -1 alkyl chlorosilane Chemical compound 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
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- 239000002184 metal Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 3
- JZALIDSFNICAQX-UHFFFAOYSA-N dichloro-methyl-trimethylsilylsilane Chemical compound C[Si](C)(C)[Si](C)(Cl)Cl JZALIDSFNICAQX-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 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
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- MVKRJEALUDVITB-UHFFFAOYSA-N [SiH4].C(C)Cl Chemical compound [SiH4].C(C)Cl MVKRJEALUDVITB-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/123—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-halogen linkages
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
-
- 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
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种从具有通式I的硅烷及其混合物中去除含有直接与硅键合的氢原子的硅烷的方法，RxCl3-xSi-[SiRyCl2-y]n-A (I)其中R代表具有1-18个碳原子的、无乙烯双键的、可任意被卤素取代的烃残基，A代表氯原子或残基R，X为0，1，2或3，Y为0，1或2，n为0或1。所述的含有直接与硅键合的氢原子的硅烷与氯化氢在作为催化剂的银或金的存在下反应从而获得相应的氯硅烷。
Description
本发明涉及一种从烃-硅烷，烃-卤代硅烷和卤代硅烷中去除含有直接与硅键合的氢原子的硅烷的方法。
在由硅和氯代甲烷直接合成甲基氯硅烷的过程，除了具有通式MeaSiCl4-a的硅烷(其中a为0至4中的一个值，Me在此及下面均代表甲基)外，还有少量的乙基氯硅烷，各种氢化硅烷，尤其是MebHSiCl3-b(其中b为0至2中的一个值)，以及乙基二氯硅烷EtHSiCl2形成，该合成反应在250至300℃，使用铜催化剂的条件下进行。所述的直接合成反应特别公开于W.No.11，Chemistryand Technology of Silicones，Academic Press，Inc.，Orlando，Florida，1968，Chapter 2.2。
直接合成反应最希望获得的目标产物是Me2SiCl2，该产物可以通过水解作用和缩聚作用转化为具有不同官能团和结构的硅氧烷聚合物。
大多数硅氧烷聚合物的一个基本质量特征是在聚合物骨架中的三官能团(trifunctional)杂质的含量是尽可能最低的。所采用的Me2SiCl2的可能的三官能团杂质之一是EtHSiCl2。
因为Me2SiCl2的沸点(70-71℃)与EtHSiCl2的沸点(74-76℃)仅差4℃，所以为了特别的用途而在所需要的纯化中得到Me2SiCl2，需要很高的蒸馏代价(effort)，如高回流比，实际上的大量的理论塔板数，高能源需求和降低了的时空产率(space/time yield)。
EP-A423948披露了一种从有机硅烷混合物中去除含有直接与硅键合的氢原子的硅烷(H-硅烷)的方法，该方法通过将有机硅烷混合物与氯化氢气体在适合的催化剂的存在下反应从而得到相应的烷基氯硅烷，所述的催化剂选自元素周期表中的副族VIII，也就是说Pd，Pt，Rh，Ru，Ni，Os，Ir及其化合物。采取这种措施可增大所期望的有机硅烷与杂质间的沸点差，因此蒸馏可以在显著降低了的代价下进行。
这种已知方法的缺点是除了镍以外所有用作催化剂的金属都相当的贵；如果用镍作催化剂，需要相应高的催化剂浓度，但由此获得的转化却是低的；并且在某些情况下金属太敏感易引起催化剂中毒。
本发明涉及一种从具有通式I
RxCl3-xSi-[SiRyCl2-y]n-A (I)的硅烷及其混合物中去除含有直接与硅键合的氢原子的硅烷的方法，其中R代表具有1-18个碳原子的、无乙烯双键的、可任意被卤素取代的烃残基，A代表氯原子或残基R，x为0，1，2或3，y为0，1或2，n为0或1。在该方法中所述的含有直接与硅键合的氢原子的硅烷与氯化氢在作为催化剂的银或金的存在下反应从而获得相应的氯硅烷。
根据本发明的方法H-硅烷实际上能完全被转变成高沸点的氢硅烷，其中氯原子被键合在原先氢原子被键合的位置上。例如，四氯硅烷由三氯硅烷制备，乙基三氯硅烷由乙基二氯硅烷制备，以及二甲基二氯硅烷由二甲基氯硅烷制备。如不希望在产品混合物中存在这些氯硅烷，则通过蒸馏即可很容易将它们除去。
所述的反应在以固体形式存在的催化剂的作用下可非常快速地进行，因而该反应是异相催化的。所以所述的催化剂可以在蒸馏柱中或直通式反应器(flow-through reactor)中使用。
银与到目前为止所用的金属Pd，Pt，Rh，Os及Ir相比要便宜得多，而且用银比用Ni作催化剂更能加快反应速度。
因为在元素的电位序中金具有非常高的正电位，所以它对中毒现象及并非所需的、与烷基氯硅烷或氯化氢的反应具有较大的抗性，因此与到目前为止所用的金属Pd，Pt，Rh，Ru，Os，Ni和Ir相比金具有较长的使用寿命。
银与金的合金也可以应用于本发明的方法中。
所述的催化剂优选以细分散的形式应用，在这种情况下催化剂优选吸附于载体上。吸附有银和金的载体也可以被采用。
载体的例子有活性炭，木炭及无机氧化物，如二氧化硅，氧化铝(III)，硅酸盐，二氧化钛和二氧化锆，以及碳化物，如碳化硅；优选的例子是木炭，活性炭及二氧化硅。
细分散的金属吸附于载体之上的这类催化剂可以在载体的存在下通过金属化合物的还原而制备。
载体上的金属浓度，以催化剂的总重量计优选为0.8-5％(重量)；然而较高或较低的浓度也是可行的。
在通式I中烃残基R的例子为烷基残基，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，季戊基和叔戊基；己基残基，如正己基；庚基残基，如正庚基；辛基残基，如正辛基和异辛基，如2，2，4-三甲基戊基；壬基残基，如正壬基；癸基残基，如正癸基；十二烷基残基，如正十二烷基；十八烷基残基，如正十八烷基；环烷基残基，如环戊基，环己基，环庚基和甲基环己基；芳基残基，如苯基，萘基，蒽基和菲基；烷芳基残基，如邻、间、对-甲苯基，二甲苯基和乙基苯基；以及芳烷基残基，如苄基和α-，β-苯乙基。
被卤素取代的残基R的例子为卤代烷基残基，如3，3，3-三氟-正丙基，2，2，2，2’，2’，2’-六氟异丙基，七氟异丙基，以及卤代芳基残基，如邻、间、对-氯苯基。
优选的残基R是那些被未取代的烃基残基，尤其是那些具有1-8个碳原子的烃基，特别是甲基，乙基，甲苯基和苯基。
n优选为0。
任何需要的H-硅烷均可由本发明的方法去除。例如所述的H-硅烷具有通式II。
R′zSiH4-2 (II)其中R′表示任意被卤素取代的、具有1-18个碳原子的烃基残基，并且z为0至3中的一个值。
残基R′的例子可为上述R的例子和烷烯基残基，如乙烯基和烯丙基。
优选要去除的H-硅烷的例子是硅烷、氯硅烷、二氯硅烷、三氯硅烷、甲基硅烷、甲基氯硅烷、甲基二氯硅烷、二甲基氯硅烷和乙基二氯硅烷。
本发明的方法特别适用于纯化从直接合成甲基氯硅烷，尤其是含有EtHSiCl2的二甲基二氯硅烷反应得到的以及其它由直接合成而形成的副产物中得到的粗产物和预纯化的产物。所述的直接合成的副产物已被揭示于，例如W.No.11，Chemistry and Technology ofSilicones，Academic Press，Inc.，Orlando，Florida，1968，Chapter 2.2，以及A.Hunyar，Chemie der Silikone[硅氧烷化学]，VerlagTechnik，Berlin 1952，pages 92 to 94中。
H-硅烷的浓度通常为100至500ppm，然而待纯化的、由甲基氯硅烷合成的产物也可以含有较高或较低浓度的H-硅烷。
本发明的方法优选在50-150℃的温度及环境压力下进行。然而，也可采用较高或较低的温度和压力。
本发明所采用的催化剂可以在液相或气相中使用。
由于化学计量的原因，为了完全去除H-硅烷，每个氢原子必须使用至少一个氯化氢分子。氯化氢气体优选以超化学计量的量使用，因为使用这种手段可以使保留时间减少并使转化度增大。
本发明的方法可以间断、半连续或完全连续的方式进行，优选采用完全连续的工艺进行。
在所述的连续的工艺中，H-硅烷的保留时间在一优选的实施例中为0.5-30秒，这依赖于H-硅烷的起始浓度。然而，较长或较短的保留时间也是可以选择的。
在下述实施例中：
a)所有的量均以重量计；
b)所有的压力均为0.1MPa(绝对)；
c)所有的温度均为20℃，
除非在每一情况下另有说明。
此外，使用了下述缩略语：
Me：甲基残基
Et：乙基残基
催化剂的制备
将35g用硝酸纯化干燥过的碎片状活性炭-Conterbon BA from Lurgi，Frankfurt-与5g硝酸银混合，将140ml蒸馏水和1ml醋酸与所述的混合物一齐加热至70℃，然后向其中加入3ml甲醛溶液(浓度为37％)，同时加以搅拌。将被包覆了的活性炭从液相中分离出去并用蒸馏水洗涤，然后在120℃的温度下用油泵真空干燥10小时。活性炭上银的含量约为1.8％(重量)。
将30g用硝酸纯化并干燥的碎片状活性炭-Conterbon BA from Lurgi，Frankfurt-与2.5g四氯金酸混合，将300m1蒸馏水和8ml浓盐酸与所述的混合物一齐加热至80℃然后向其中加入8ml甲醛溶液(浓度为37％)，同时搅拌。将被包覆了的活性炭从液相中分离出去并用蒸馏水洗涤，然后在120℃的温度下用油泵真空干燥10小时。活性炭上的金含量约为0.23％。
实施例1和2(根据本发明)以及
实施例3(未根据本发明)
首先将110g Me2SiCl2和520ppm的EtHSiCl2的混合物引入一三颈烧瓶中，该烧瓶装配有滴液漏斗，进气管和一个装有蒸馏头的镜式玻璃柱(a mirrored-glasscolumn)并且处于氩气氛状态。将A克的催化剂引入所述的镜式玻璃柱。
将烧瓶中的硅烷加热至70℃，同时搅拌，并将氯化氢以4l/hr.的速度通入混合物中。蒸发的硅烷和氯化氢气体流经所述的玻璃柱，浓缩于蒸馏头中并被分出去。Me2SiCl2/EtHSiCl2(520ppm)以馏份从系统中被去除的速度计量加入烧瓶中。
在B分钟的运行时间后，将反应中断，并用GC分析馏份。
在所述的反应时间后馏份的量为C ml(质量流Dml/hr.)；这与催化剂上的气态Me2SiCl2的约E秒的保留时间相对应。馏份中EtHSiCl2的浓度为F ppm。
表I
| 实施例 | 催化剂 | A(g) | B(分钟) | C(ml) | D(ml/h | E(s) | F(ppm) |
| 1 | 金/活性炭(0.23％)*) | 17 | 125 | 250 | 120 | 2.6 | 35 |
| 2 | 银/活性炭(1.8％)*) | 22 | 155 | 350 | 135 | 3.5 | 25 |
| 3 | 活性炭*) | 17 | 193 | 610 | 190 | 1.7 | 120 |
*)见催化剂的制备
实施例4(根据本发明)
试验用的装置及程序如实施例1所述，改变之处在于所采用的硅烷具有如下组成(重量％)：
60％的四甲基二氯二硅烷
34％的甲基二氯硅烷
6％残余物(各种甲基氯-单-和二硅烷)
用20g银/活性炭作为催化剂，烧瓶的温度增高至150℃，质量流减少到50ml/hr.，保留时间增至12秒。所得到的馏份具有如下组成：
30％四甲基二氯二硅烷
57％甲基三氯硅烷
4％甲基二氯硅烷(以HCl计的转化度：94％)
四甲基二氯二硅烷在反应烧瓶中浓缩了；而甲基二氯硅烷仅以痕量存在。
Claims (4)
1、一种从具有通式I的硅烷及其混合物中去除含有直接与硅键合的氢原子的硅烷的方法，RxCl3-xSi-[SiRyC12-y]n-A
(I)其中R代表具有1-18个碳原子的、无乙烯双键的、可任意被卤素取代的烃残基，A代表氯原子或残基R，X为0，1，2或3，y为0，1或2，n为0或1，其中所述的含有与硅键合的氢原子的硅烷与氯化氢在作为催化剂的银或金的存在下反应从而获得相应的氯硅烷。
2、如权利要求1所述的方法，其特征在于所述的催化剂以在细分散的形式吸附在载体上。
3、如权利要求1或2所述的方法，其特征在于从由甲基氯硅烷合成过程中得到的产物混合物中去除含有直接与硅键合的氢原子的硅烷。
4、如权利要求1、2或3所述的方法，其特征在于被去除的是EtSiHCl2。
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| DE4241696A DE4241696A1 (de) | 1992-12-10 | 1992-12-10 | Verfahren zur Entfernung von wasserstoffhaltigen Silanen aus Silanen |
| DEP4241696.5 | 1992-12-10 |
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| CN1041521C true CN1041521C (zh) | 1999-01-06 |
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| US5401872A (en) * | 1994-03-07 | 1995-03-28 | Hemlock Semiconductor | Treatment of vent gas to remove hydrogen chloride |
| US5493042A (en) * | 1995-06-15 | 1996-02-20 | Dow Corning Corporation | Process for removing silanes from by-product stream |
| DE10244996A1 (de) * | 2002-09-26 | 2004-04-01 | Basf Ag | Katalysator für die katalytische Chlorwasserstoff-Oxidation |
| DE102007030949A1 (de) * | 2007-07-04 | 2009-01-08 | Wacker Chemie Ag | Verfahren zur Umwandlung von Si-H-Verbindungen in Si-Halogen-Verbindungen |
| DE102007030948A1 (de) * | 2007-07-04 | 2009-01-08 | Wacker Chemie Ag | Verfahren zur Umwandlung von Si-H-Verbindungen in Si-Halogen-Verbindungen |
| CN110669066B (zh) * | 2019-10-15 | 2022-04-19 | 徐州医科大学 | 一种二硅烷及其制备方法 |
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| DE1201348B (de) * | 1964-03-03 | 1965-09-23 | Wacker Chemie Gmbh | Verfahren zur Beseitigung von stoerenden Verunreinigungen in Organochlorsilanen |
| FR1442035A (fr) * | 1964-07-31 | 1966-06-10 | Gen Electric | Procédés d'obtention d'organohalosilane |
| US3646092A (en) * | 1969-05-20 | 1972-02-29 | Inst Silikon & Fluorkarbonchem | Process for the recovery of trimethylfluorosilane from a mixture of silicontetrachloride trimethylchlorosilane and hydrocarbons boiling at the same range |
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1992
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| US4985579A (en) * | 1989-10-16 | 1991-01-15 | Dow Corning Corporation | Removal of hydrogen-containing silanes from organosilane mixtures |
| EP0423948A2 (en) * | 1989-10-16 | 1991-04-24 | Dow Corning Corporation | Removal of hydrogen-containing silanes from organosilane mixtures |
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| US5302736A (en) | 1994-04-12 |
| EP0601578A1 (de) | 1994-06-15 |
| CN1092777A (zh) | 1994-09-28 |
| DE4241696A1 (de) | 1994-06-16 |
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| ES2070651T3 (es) | 1995-06-01 |
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