CN102666554A - 甲硅烷和四烷氧基硅烷的制造方法 - Google Patents
甲硅烷和四烷氧基硅烷的制造方法 Download PDFInfo
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- CN102666554A CN102666554A CN2010800530351A CN201080053035A CN102666554A CN 102666554 A CN102666554 A CN 102666554A CN 2010800530351 A CN2010800530351 A CN 2010800530351A CN 201080053035 A CN201080053035 A CN 201080053035A CN 102666554 A CN102666554 A CN 102666554A
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- Prior art keywords
- formula
- catalyzer
- tetraalkoxysilane
- silicomethane
- general formula
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 65
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 229910052728 basic metal Inorganic materials 0.000 claims description 12
- 150000003818 basic metals Chemical class 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000011964 heteropoly acid Substances 0.000 abstract description 9
- 150000003839 salts Chemical group 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 229910052816 inorganic phosphate Inorganic materials 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 19
- 239000010936 titanium Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 150000002751 molybdenum Chemical class 0.000 description 3
- -1 monosubstituted ethoxy silane Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 150000003657 tungsten Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 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 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000001301 oxygen Substances 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
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IJRANYBINFUJGF-UHFFFAOYSA-N triazanium;trioxotungsten;phosphate Chemical compound [NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-]P([O-])([O-])=O IJRANYBINFUJGF-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- C07F7/025—Silicon compounds without C-silicon linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1813—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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Abstract
本发明涉及在具有基于无机磷酸盐或杂多酸盐结构的特定化学结构的催化剂的存在下,使通式(1)HnSi(OR)4-n(1)(式中,R表示碳原子数1~6的烷基,n为1~3的整数)所示的烷氧基硅烷在气相中进行歧化反应的甲硅烷和四烷氧基硅烷的制造方法。本发明的制造方法,与溶剂的分离容易,反应快,原料物质的转化率高。
Description
技术领域
本发明涉及通过烷氧基硅烷的歧化反应来制造甲硅烷和四烷氧基硅烷的方法。
背景技术
甲硅烷作为高纯度的挥发性硅材料是有用的,其广泛地用于制造太阳能电池、半导体、无定形硅感光材料、各种陶瓷材料。
关于甲硅烷的制造方法,迄今为止已知各种方法,已知使用硅化镁与酸或溴化铵的反应的方法、利用LiAlH4进行的氯化硅的还原法、四氟化硅的利用CaH2进行的还原法、利用烷氧基硅烷的歧化反应的方法。
上述的烷氧基硅烷的歧化反应中通常使用三烷氧基硅烷作为起始物质,按照下式来制造甲硅烷和四烷氧基硅烷。
4HSi(OR)3→SiH4+3Si(OR)4
与甲硅烷同样地,四烷氧基硅烷也是作为纯粹的硅前体材料有用的化学物质,所述硅前体材料用于生产用作光纤、光掩模、IC用密封材料的不同硅化合物。
使用三乙氧基硅烷和三甲氧基硅烷作为上述歧化反应的起始物质,如下式所示,四乙氧基硅烷和四甲氧基硅烷与甲硅烷一起被分别生产出来。
4HSi(OMe)3→SiH4+3Si(OMe)4
4HSi(OEt)3→SiH4+3Si(OEt)4
在进行上述反应时,作为歧化反应的催化剂,可以使用金属钠。然而,收率低,因此,该方法在实用上是没有用的。
在专利文献1(美国专利第4016188号说明书)中,记载了使用碱金属醇盐或碱金属硅酸盐作为催化剂的方法。然而,液相中的反应非常慢,反应时间超过10小时,不适于工业制造。
在专利文献2(日本特开2001-19418号公报)中,公开了一种甲硅烷和四烷氧基硅烷的制造方法,是使通式HnSi(OR)4-n[式中,n为1、2或3,R表示烷基或环烷基]所示的烷氧基硅烷歧化来制造甲硅烷和四烷氧基硅烷的方法,其包括以下工序:(i)使烷氧基硅烷在催化剂的存在下在溶剂中进行歧化反应来获得甲硅烷和四烷氧基硅烷的反应工序;(ii)从反应工序中取出含有催化剂和四烷氧基硅烷的溶剂的一部分的工序;(iii)通过蒸馏从取出的含有催化剂和四烷氧基硅烷的溶剂中分离出四烷氧基硅烷的一部分或全部量的工序。
然而,该方法也是溶液中的歧化反应,存在难以与溶剂分离这样的问题、以及反应速度不够高这样的问题。
在专利文献3(国际公开第2008/042445号小册子)中,记载了在担载于氧化铝的氟化钾(KF)催化剂上,将三甲氧基硅烷歧化来提供甲硅烷和四甲氧基硅烷的方法。该方法虽然不存在从反应产物中分离催化剂等这样的问题,但三甲氧基硅烷的转化率不够高。
专利文献1:美国专利第4016188号说明书
专利文献2:日本特开2001-19418号公报
专利文献3:国际公开第2008/042445号小册子
发明内容
发明所要解决的课题
本发明的目的是提供一种通过烷氧基硅烷的歧化反应来制造甲硅烷和四烷氧基硅烷的方法,其是用于解决上述那样的难以与溶剂分离、反应非常慢而不适于工业制造以及原料物质的转化率低这样的问题的方法。
用于解决课题的方法
本发明人为了解决上述现有技术的问题而进行了深入研究,结果发现通过在特定化学结构的催化剂的存在下,使下述通式(1)所示的烷氧基硅烷在气相中进行歧化反应,从而可以解决上述课题,
HnSi(OR)4-n (1)
(式中,R表示碳原子数1~6的烷基,n为1~3的整数。)
即,本发明涉及以下事项。
[1]一种甲硅烷和四烷氧基硅烷的制造方法,是在催化剂的存在下,使通式(1)所示的烷氧基硅烷在气相中进行歧化反应来制造甲硅烷和四烷氧基硅烷的方法,
HnSi(OR)4-n (1)
式中,R表示碳原子数1~6的烷基,n为1~3的整数,
所述制造方法的特征在于,使用选自下述通式(I)~(V)所示的化合物中的至少1种催化剂,
(MI 2O)z(MO2)(P2O5)x(H2O)y (I)
式中,M表示Zr、Ti、Sn或Si,MI表示氢原子、NH4或碱金属,x为0.5~4.5,y为0.15~6.5,z为0.15~3.5,
(MO2)(P2O5)x(H2O)y (II)
式中,M表示Zr、Ti、Sn或Si,x为0.5~4.5,y为0.15~6.5,
(MI 2O)z(MO2)(P2O5)x (III)
式中,M表示Zr、Ti、Sn或Si,MI表示氢原子、NH4或碱金属,x为0.5~4.5,z为0.15~3.5,
MI m[MII nMIII kOj] (IV)
式中,MI表示氢原子、NH4或碱金属,MII表示P(V)或As(V),MIII表示W(VI)或Mo(VI),n为1~3的整数,k为6、12、18或24,j为24、40或42,m为由式2j-5n-6k确定的整数,
MI m[MIV nMIII kOj] (V)
式中,MI表示氢原子、NH4或碱金属,MIV表示Si(IV)、Ge(IV)、Ti(IV)或Ce(IV),MIII表示W(VI)或Mo(VI),n为1~3的整数,k为6、12、18或24,j为24、40或42,m为由式2j-4n-6k确定的整数。
[2]根据上述[1]所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(I)中x为1、z为1的通式(Ia)所示的化合物,
(MI 2O)(MO2)(P2O5)(H2O)y (Ia)
式中,M和MI表示与上述[1]的记载相同的含义,y为0.25~4.0。
[3]根据上述[2]所述的甲硅烷和四烷氧基硅烷的制造方法,M为Zr或Ti。
[4]根据上述[1]所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(II)中M为Zr、x为1的通式(IIa)所示的化合物,
(ZrO2)(P2O5)(H2O)y (IIa)
式中,y为1.0~5.0。
[5]根据上述[4]所述的甲硅烷和四烷氧基硅烷的制造方法,y为1.3或3。
[6]根据上述[1]所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(III)中x为0.5、z为0.5的通式(IIIa)所示的化合物,
(MI 2O)0.5(MO2)(P2O5)0.5 (IIIa)
式中,M表示Zr或Ti,MI表示与上述[1]的记载相同的含义。
[7]根据上述[6]所述的甲硅烷和四烷氧基硅烷的制造方法,使用在通式(IIIa)中MI为K、M为Ti的下式所示的化合物,
(K2O)0.5(TiO2)(P2O5)0.5
[8]根据上述[1]所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(IV)中MII为P(V)、n为1的通式(IVa)所示的化合物,
MI m[PMIII kOj] (IVa)
式中,MI、MIII、k、j和m表示与上述[1]的记载相同的含义。
[9]根据上述[1]所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(V)中MIV为Si(IV)、n为1的通式(Va)所示的化合物,
MI m[SiMIII kOj] (Va)
式中,MI、MIII、k、j和m表示与上述[1]的记载相同的含义。
[10]根据上述[9]所述的甲硅烷和四烷氧基硅烷的制造方法,使用在通式(Va)中MI为K、MIII为W(VI)、k为12、j为40、m为4的下式所示的化合物,
K4[SiW12O40]。
发明的效果
本发明的方法是通过烷氧基硅烷的歧化来制造甲硅烷和四烷氧基硅烷的方法,通过使用特定化学结构的催化剂,在气相中进行反应,从而可以解决难以与溶剂分离这样的问题、反应非常慢这样的问题以及原料物质的转化率低这样的问题。
具体实施方式
以下,对本发明涉及的甲硅烷和四烷氧基硅烷的制造方法进行详细地说明。
本发明是甲硅烷和四烷氧基硅烷的制造方法,其特征在于,在特定化学结构的催化剂的存在下,使下述通式(1)所示的烷氧基硅烷在气相中进行歧化反应,
HnSi(OR)4-n (1)
(式中,R表示碳原子数1~6的烷基,n为1~3的整数。)
作为本发明的歧化反应的起始物质即通式(1)所示的烷氧基硅烷,可列举单烷氧基硅烷、二烷氧基硅烷或三烷氧基硅烷。R为碳原子数1~6的烷基,优选为碳原子数1~2的烷基。作为特别优选的烷氧基硅烷,可列举单甲氧基硅烷、二甲氧基硅烷、三甲氧基硅烷、单乙氧基硅烷、二乙氧基硅烷和三乙氧基硅烷。其中,最优选三甲氧基硅烷和三乙氧基硅烷。
用于本发明的方法的歧化催化剂是具有基于无机磷酸盐或杂多酸盐结构的化学结构的催化剂。
本发明的第一烷氧基硅烷的歧化催化剂选自具有以下化学结构的无机磷酸盐,
(MI 2O)z(MO2)(P2O5)x(H2O)y (I)
(式中,M表示Zr、Ti、Sn或Si,MI表示氢原子、NH4或碱金属,x为0.5~4.5,y为0.15~6.5,z为0.15~3.5。)
存在若干种调制上述磷酸盐催化剂组合物的方法。一般的方法是通过公知的适当步骤在水溶液中在低温形成选自Zr、Ti、Sn和Si中的金属的氧化物的溶胶的方法。例如,有将醇盐水解的方法、将选自Zr、Ti、Sn和Si中的金属的氧化物MO2的沉淀物利用磷酸或碱进行解胶的方法。所得的溶胶可以通过磷酸溶液来稳定化,接着通过加热或碱处理来沉积。此外,可以对相应的盐或氧化物的混合物实施一直以来已知的高温热处理。作为其它方法,可以使用冷冻化学法,其包含水溶液中的催化剂核的调制、催化剂的低温升华以及稳定化。
在上述通式(I)所示的催化剂中,优选x为1、z为1的通式(Ia)所示的化合物,特别优选M为Zr或Ti的化合物。
(MI 2O)(MO2)(P2O5)(H2O)y (Ia)
(式中,M和MI表示与上述相同含义,y为0.25~4.0。)
该组催化剂表示1价的阳离子与选自Zr、Ti、Sn和Si中的金属的混合磷酸盐。作为该盐的例子,有K2Ti(PO4)2(H2O)0.3即(K2O)(TiO2)(P2O5)(H2O)0.3。其可以通过将摩尔比为1:2的TiO2和KH2PO4与15质量%的水的混合物进行通常的高温退火而以半水合物的形式来调制。加热时,一边使水分慢慢地放出,一边使温度上升至400℃。
本发明的第二烷氧基硅烷的歧化催化剂选自具有以下化学结构的无机磷酸盐,
(MO2)(P2O5)x(H2O)y (II)
(式中,M表示Zr、Ti、Sn或Si,x为0.5~4.5,y为0.15~6.5。)
上述通式(II)所示的催化剂中,优选M为Zr、x为1的通式(IIa)所示的化合物。
(ZrO2)(P2O5)(H2O)y (IIa)
(式中,y为1.0~5.0。)
通式(IIa)所示的化合物作为Zr(HPO4)2·nH2O所示的磷酸锆盐是已知的。其中,特别优选y为1.3的式(ZrO2)(P2O5)(H2O)1.3以及y为3的式(ZrO2)(P2O5)(H2O)3所示的化合物。这些化合物也可以记为Zr(HPO4)2·0.3H2O、Zr(HPO4)2·2H2O。
本发明的第三烷氧基硅烷的歧化催化剂选自具有以下化学结构的无机磷酸盐,
(MI 2O)z(MO2)(P2O5)x (III)
(式中,M表示Zr、Ti、Sn或Si,MI表示氢原子、NH4或碱金属,x为0.5~4.5,z为0.15~3.5。)
在上述通式(III)所示的催化剂中,优选x为0.5、z为0.5的通式(IIIa)所示的化合物。
(MI 2O)0.5(MO2)(P2O5)0.5 (IIIa)
(式中,M表示Zr或Ti,MI表示与上述相同含义)。
通式(IIIa)所示的化合物也可以记为MI(MO)PO4。其中,特别优选MI为K、M为Ti的式(K2O)0.5(TiO2)(P2O5)0.5即K(TiO)PO4。
可以通过若干种适当方法来调制该催化剂。制造例如下所述。
(a)调制胶体性溶液(由钛四醇盐或氯氧化物得到的TiO2前体)。
(b)接着,将溶胶溶液与磷酸和碳酸钾的稀释水溶液混合。
(c)将混合而得的K(TiO)PO4胶体溶液涂布在γ-氧化铝载体上,在500~550℃进行热处理。通过分析涂层部分,可以确认K(TiO)PO4的生成。
本发明的第四烷氧基硅烷的歧化催化剂选自具有以下化学结构的化合物,
MI m[MII nMIII kOj] (IV)
(式中,MI表示氢原子、NH4或碱金属,MII表示P(V)或As(V),MIII表示W(VI)或Mo(VI),n为1~3的整数,k为6、12、18或24,j为24、40或42,m为由式2j-5n-6k确定的整数。)
该组催化剂为阴离子性复合化合物。即为,在内部的配位区域在形成复合体的元素MII的周围具有6价的配体的杂多酸。该催化剂表示具有1价的阳离子的杂多酸或其盐,包含5价的磷和砷作为形成复合体的元素,在内部的配位区域具有钼盐或钨盐作为阴离子配体。
在上述式(IV)所示的催化剂中,优选MII为P(V)、n为1的通式(IVa)所示的化合物。
MI m[PMIII kOj] (IVa)
(式中,MI、MIII、k、j和m表示与上述相同含义。)
作为该类型的催化剂的例子,可列举K3[PMo12O40]、H7[PMo12O42]、H3[PMo12O40]、H7[PW12O42]。
本发明的第五烷氧基硅烷的歧化催化剂选自具有以下化学结构的化合物。
MI m[MIV nMIII kOj] (V)
在上述式(V)中,MI表示氢原子、NH4或碱金属,MIV表示Si(IV)、Ge(IV)、Ti(IV)或Ce(IV),MIII表示W(VI)或Mo(VI)。n为1~3的整数,k为6、12、18或24,j为24、40或42,m为由式(2j-4n-6k)确定的整数。
该组催化剂也与杂多酸或其盐有关。该催化剂包含作为4价的金属的Si(IV)、Ge(IV)、Ti(IV)或Ce(IV)作为形成复合体的元素。
在上述式(V)所示的催化剂中,优选MIV为Si(IV)、n为1的通式(Va)所示的化合物。
MI m[SiMIII kOj] (Va)
(式中,MI、MIII、k、j和m表示与上述相同含义。)
作为该类型的催化剂的例子,可列举Na8[TiMo6O24]、K4[SiW12O40],其中,特别优选K4[SiW12O40]。
上述通式(IV)或(V)所示的催化剂可以采用作为各杂多酸或其盐的制造方法已知的适当方法来调制。
典型的方法是在酸性水溶液中,使钼盐或钨盐与磷酸进行反应,接着进行干燥的方法。将钼盐的情况下的反应示于下式。
H3PO4+12Na2MoO4+12H2SO4
→H3[PMo12O40]+12Na2SO4+12H2O
然后,通过部分的水分蒸发、无机载体的浸渍、加热处理来获得目标的催化剂。通过使用从以下2种方法中选择的方法来调制相应的杂多酸盐。
(i)采用金属氢氧化物或碳酸盐对杂多酸慢慢地处理,
(ii)使用阳离子交换法对被担载的杂多酸的表面进行中和。
关于本发明的催化剂的结构,大部分作为固体被使用。它们能够以固体的粒状物的形态、或在氧化铝、二氧化钛、二氧化硅、碳和其它类型的惰性无机载体上担载有催化剂的形态这两种形态来使用。
作为其它的催化剂调制方法的具体例,有本发明的催化剂对离子交换树脂的表面的沉积。作为对于调制本发明的担载催化剂有用的离子交换树脂,可列举不具有磷酸基的交联型阳离子交换树脂。
如果这样获得的催化剂以相对于起始物质的烷氧基硅烷100质量份为至少0.02质量份的量来使用,则在本发明目的下是有效果的。这些催化剂通常在0.02~50质量份、优选在0.1~20质量份的范围内使用。
歧化反应可以以间歇式和连续流通式这两种方式来实施。作为起始原料使用的烷氧基硅烷和催化剂的化学反应性不高,因此,可以对装置的材料没有特别限制地实施工艺。
因此,由于可以使用各种不同类型的反应器,因此可以说是适合工业制造方法的催化剂系统。
优选歧化反应在加热下并且在大气压下进行反应。优选的温度取决于所使用的起始物质的烷氧基硅烷,但通常在100~200℃的范围内。
歧化反应可以在反应压力为0.2~10大气压的范围内进行,由于不显著依赖于压力,因此优选在大气压下实施工艺。然而可知,反应产物的甲硅烷一旦与空气接触,就会立即燃烧。因此,为了防止包含甲硅烷的反应介质与空气氧气接触而引起的燃烧,优选在氮气或氩气那样的惰性气体气氛中进行反应。
通过反应而生成的甲硅烷具有-111.9℃的沸点,从反应器中取出后以气体状被捕集。在间歇式的情况下,四烷氧基硅烷残留在反应器内。在使用流通式反应器的情况下,四烷氧基硅烷和未反应的三烷氧基硅烷通过反应器,四烷氧基硅烷被凝结,三烷氧基硅烷返回到催化反应器中。本发明所使用的催化剂在起始物质和反应产物这两者中是不溶性的,可以在长期运转期间中使用。
实施例
以下,通过实施例进一步详细地说明本发明,但本发明不限于这些实施例。
比较例1:
将氟化钾和干燥甲醇(1:13~20质量份)的溶液通过在减压下使溶剂慢慢地蒸发来进行氟化钾的再结晶,接着一边升温一边干燥,从而调制活性型的氟化钾。
不仅优选纯化所使用的甲醇为纯度超过99.9%的美国药典试验适用(A.C.S.),而且优选利用干燥氮气气氛。在使甲醇蒸发的阶段,优选25~35℃的温度。
接下来的真空下的干燥应当在至少5~6小时的期间,在75~120℃的范围内进行。
担载氟化钾的氧化铝如下调制。将粒径0.3~1.0mm的中性氧化铝30g和上述那样通过再结晶调制而成的氟化钾20g与200ml去离子水混合。一边微弱地脱气,一边使溶剂在50~60℃蒸发,将残留的产物一边脱气一边干燥3小时。
接下来,使用该产物作为三甲氧基硅烷歧化反应的催化剂来调制甲硅烷和四烷氧基硅烷的工艺如下实施。向具备电炉的Pyrex(注册商标)玻璃制反应管中填充1.0g的担载氟化钾的氧化铝,加热至120℃。将蒸发出的三甲氧基硅烷(流速3.5ml/分钟)和氦气(流速35ml/分钟)的混合物在预热器中加热至120℃,接着供给至反应管,在120℃实施歧化反应。每隔20分钟通过气相色谱(GC)对从反应管出来的气体状反应混合物进行分析。
反应开始10分钟后,未反应的三甲氧基硅烷、生成的甲硅烷和四甲氧基硅烷的比例在反应产物中实质上是一定的。二甲氧基硅烷和单甲氧基硅烷在经过最初的1小时后的反应中检测不到。
进行了5小时流通反应之后的分析显示以下结果。
即,三甲氧基硅烷的转化率为63%,相对于被供给的三甲氧基硅烷的甲硅烷的收率为63%(即,相对于转化了的三甲氧基硅烷的甲硅烷的收率为100%),相对于被供给的三甲氧基硅烷的四甲氧基硅烷的收率为63%(即,相对于转化了的三甲氧基硅烷的四甲氧基硅烷的收率为100%)。采用GC也未检测出任何副产物。
实施例1:
将水合后的二氧化锆的溶胶以原子比P/Zr=2.0用1.0M/L的H3PO4溶液进行处理,在105℃干燥直至质量恒定。所得的颗粒状的产物为直径0.8~1.6mm的球状,比表面积为35m2/g。通过X射线试验,显示产物为无定形。通过化学分析,该产物具有在上述通式(II)中x为1、y为3的化学结构。即,所得的产物的化学结构相当于式:(ZrO2)(P2O5)(H2O)3。其也可以记为Zr(HPO4)2·2H2O。将该产物在填充至试验用单元(cell)中之后、供给三甲氧基硅烷之前,在氦气流通下在130℃预加热1小时。使用该产物作为三甲氧基硅烷歧化反应的催化剂,与比较例1同样地评价其催化活性。将结果示于表1中。
实施例2~9:
通过下述方法来调制实施例2~9的催化剂。
实施例2的催化剂:将实施例1的催化剂采用氯化钠溶液进行处理,进行离子交换,然后进行洗涤和干燥。
实施例3的催化剂:将实施例1的催化剂采用碳酸钾K2CO3溶液进行滴定处理,然后进行洗涤和干燥。
实施例4的催化剂:将氧化钛TiO2与磷酸二氢钾KH2PO4的15质量%水溶液以氧化钛TiO2:磷酸二氢钾KH2PO4=1:2的摩尔比进行混合,缓慢地加热干燥直至水分消失。
实施例5的催化剂:将氧化钛TiO2采用磷酸H3PO4溶液和碳酸钾K2CO3溶液进行处理,将生成的K(TiO)PO4溶胶涂布在氧化铝(γ-Al2O3)上。
实施例6的催化剂:担载在碳粒子上的磷钨酸,
实施例7的催化剂:担载在碳粒子上的磷钼酸钠,
实施例8的催化剂:磷钨酸铵粉末与氧化铝颗粒的混合物,
实施例9的催化剂:硅钨酸钾粉末与氧化铝颗粒的混合物。
使用上述催化剂作为三甲氧基硅烷歧化反应的催化剂,评价其催化活性。
三甲氧基硅烷的歧化反应和产物的分析采用与比较例1同样的方法来实施。将全部的催化剂在装入试验用单元中之后、在供给三甲氧基硅烷之前,在氦气流通下在表1所记载的温度预加热1小时。将结果示于表1中。
在实施例1和实施例2中,最初的1~1.5小时期间的反应产物显示生成与2~3%的甲醇等当量的二甲基硅烷醇。经过该期间之后,分析结果显示作为反应产物仅为甲硅烷和四甲氧基硅烷。
对于实施例3~8的实验,GC分析未显示除了甲硅烷和四甲氧基硅烷以外的产物。因此,关于转化了的三甲氧基硅烷,工艺的选择率为100%。未能在反应混合物中发现醇、六甲氧基二硅氧烷的二聚体那样的其它反应产物。
所使用的全部的催化剂不溶于起始物质和反应产物。
在反应期间,未观察到催化剂的质量减少。在5小时的反应期间,也未观察到催化活性的降低。
由表1所示的结果可知,本发明的催化剂的效率高。
这些反应可以使用流通式的形态,该形态容易适用于以连续的工业规模来制造甲硅烷和四烷氧基硅烷。另外,四烷氧基硅烷可以作为液体回收,甲硅烷可以作为气体回收,因此两者的分离容易。
表1
实施例10~15:
使用表2所示的催化剂和烷氧基硅烷,与比较例1同样地进行歧化反应和产物的分析。
关于选择率,以摩尔%计算四烷氧基硅烷相对于单烷氧基硅烷、二烷氧基硅烷、三烷氧基硅烷和四烷氧基硅烷的合计量的比例。在反应产物中未检测出醇或硅氧烷二聚体那样的其它杂质。将结果示于表2中。
表2
由表2可知,进行了试验的本发明的催化剂的效率高。另外,如果延长气体状的反应混合物与反应器中的催化剂的接触时间,则可以使转化率提高。
Claims (10)
1.一种甲硅烷和四烷氧基硅烷的制造方法,是在催化剂的存在下,使通式(1)所示的烷氧基硅烷在气相中进行歧化反应来制造甲硅烷和四烷氧基硅烷的方法,
HnSi(OR)4-n (1)
式中,R表示碳原子数1~6的烷基,n为1~3的整数,
所述制造方法的特征在于,使用选自下述通式(I)~(V)所示的化合物中的至少1种催化剂,
(MI 2O)z(MO2)(P2O5)x(H2O)y (I)
式中,M表示Zr、Ti、Sn或Si,MI表示氢原子、NH4或碱金属,x为0.5~4.5,y为0.15~6.5,z为0.15~3.5,
(MO2)(P2O5)x(H2O)y (II)
式中,M表示Zr、Ti、Sn或Si,x为0.5~4.5,y为0.15~6.5,
(MI 2O)z(MO2)(P2O5)x (III)
式中,M表示Zr、Ti、Sn或Si,MI表示氢原子、NH4或碱金属,x为0.5~4.5,z为0.15~3.5,
MI m[MII nMIII kOj] (IV)
式中,MI表示氢原子、NH4或碱金属,MII表示P(V)或As(V),MIII表示W(VI)或Mo(VI),n为1~3的整数,k为6、12、18或24,j为24、40或42,m为由式2j-5n-6k确定的整数,
MI m[MIV nMIII kOj] (V)
式中,MI表示氢原子、NH4或碱金属,MIV表示Si(IV)、Ge(IV)、Ti(IV)或Ce(IV),MIII表示W(VI)或Mo(VI),n为1~3的整数,k为6、12、18或24,j为24、40或42,m为由式2j-4n-6k确定的整数。
2.根据权利要求1所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(I)中x为1、z为1的通式(Ia)所示的化合物,
(MI 2O)(MO2)(P2O5)(H2O)y (Ia)
式中,M和MI表示与权利要求1的记载相同的含义,y为0.25~4.0。
3.根据权利要求2所述的甲硅烷和四烷氧基硅烷的制造方法,M为Zr或Ti。
4.根据权利要求1所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(II)中M为Zr、x为1的通式(IIa)所示的化合物,
(ZrO2)(P2O5)(H2O)y (IIa)
式中,y为1.0~5.0。
5.根据权利要求4所述的甲硅烷和四烷氧基硅烷的制造方法,y为1.3或3。
6.根据权利要求1所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(III)中x为0.5、z为0.5的通式(IIIa)所示的化合物,
(MI 2O)0.5(MO2)(P2O5)0.5 (IIIa)
式中,M表示Zr或Ti,MI表示与权利要求1的记载相同的含义。
7.根据权利要求6所述的甲硅烷和四烷氧基硅烷的制造方法,使用在通式(IIIa)中MI为K、M为Ti的下式所示的化合物,
(K2O)0.5(TiO2)(P2O5)0.5
8.根据权利要求1所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(IV)中MII为P(V)、n为1的通式(IVa)所示的化合物,
MI m[PMIII kOj] (IVa)
式中,MI、MIII、k、j和m表示与权利要求1的记载相同的含义。
9.根据权利要求1所述的甲硅烷和四烷氧基硅烷的制造方法,作为催化剂,使用在通式(V)中MIV为Si(IV)、n为1的通式(Va)所示的化合物,
MI m[SiMIII kOj] (Va)
式中,MI、MIII、k、j和m表示与权利要求1的记载相同的含义。
10.根据权利要求9所述的甲硅烷和四烷氧基硅烷的制造方法,使用在通式(Va)中MI为K、MIII为W(VI)、k为12、j为40、m为4的下式所示的化合物,
K4[SiW12O40]。
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US9045503B2 (en) | 2015-06-02 |
US9233987B2 (en) | 2016-01-12 |
CN102666554B (zh) | 2014-11-05 |
KR20120032544A (ko) | 2012-04-05 |
WO2011065359A1 (ja) | 2011-06-03 |
US20150232486A1 (en) | 2015-08-20 |
TWI444330B (zh) | 2014-07-11 |
TW201132588A (en) | 2011-10-01 |
KR101344356B1 (ko) | 2014-01-22 |
KR20130123466A (ko) | 2013-11-12 |
US20120226064A1 (en) | 2012-09-06 |
JPWO2011065359A1 (ja) | 2013-04-11 |
JP5647620B2 (ja) | 2015-01-07 |
KR101381189B1 (ko) | 2014-04-04 |
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