CN108586515B - Synthesis method of trisilylamine - Google Patents
Synthesis method of trisilylamine Download PDFInfo
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- CN108586515B CN108586515B CN201810137101.1A CN201810137101A CN108586515B CN 108586515 B CN108586515 B CN 108586515B CN 201810137101 A CN201810137101 A CN 201810137101A CN 108586515 B CN108586515 B CN 108586515B
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- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004821 distillation Methods 0.000 claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000010926 purge Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims description 22
- 239000010935 stainless steel Substances 0.000 claims description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 239000004917 carbon fiber Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 claims description 7
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 7
- MLRYPOCSLBIUHY-ZHACJKMWSA-N (e)-dodec-2-en-1-ol Chemical compound CCCCCCCCC\C=C\CO MLRYPOCSLBIUHY-ZHACJKMWSA-N 0.000 claims description 7
- OTVPWGHMBHYUAX-UHFFFAOYSA-N [Fe].[CH]1C=CC=C1 Chemical compound [Fe].[CH]1C=CC=C1 OTVPWGHMBHYUAX-UHFFFAOYSA-N 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 5
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 claims description 5
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 5
- -1 5-chloro-8-quinolineacrylic acid Chemical compound 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910014329 N(SiH3)3 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- LNENVNGQOUBOIX-UHFFFAOYSA-N azidosilane Chemical class [SiH3]N=[N+]=[N-] LNENVNGQOUBOIX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/58—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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 System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a method for synthesizing trisilylamine, which is characterized by comprising the following steps: purging a catalytic distillation tower by using inert gas in advance, continuously adding monochlorosilane and ammonia into the catalytic distillation tower from a rectification section and a stripping section in a gaseous state for reaction respectively, wherein the molar ratio of the monochlorosilane to the ammonia is 1: 1.2-3, the space velocity of the monochlorosilane is 0.5-2/h, the reaction pressure is 0.2-1MPa, the reaction temperature of the distillation tower is 350-420 ℃, continuously leading out a reaction product at the bottom of the tower, separating NH4Cl, and obtaining high-purity trisilylamine by using a known impurity removal refining technology in the industry.
Description
Technical Field
The invention relates to a synthesis method of silylamine, in particular to a synthesis method of trisilylamine.
Background
The organoaminosilane precursors can be used in a variety of deposition processes including, but not limited to, atomic layer deposition ("ALD"), chemical vapor deposition ("CVD"), plasma enhanced chemical vapor deposition ("PECVD"), low pressure chemical vapor deposition ("LPCVD"), and atmospheric pressure chemical vapor deposition. Several classes of compounds are useful as precursors for silicon-containing films, such as, but not limited to, silicon oxide or silicon nitride films. Examples of such compounds suitable as precursors include silanes, chlorosilanes, polysilazanes, aminosilanes and azidosilanes. Inert carrier gases or diluents (such as, but not limited to, helium, hydrogen, nitrogen, etc.) are also used to deliver the precursors to the reaction chamber.
Trisilylamine can be according to the reaction formula:
3H3SiCl+4NH3→N(SiH3)3+3NH4Cl，
prepared from ammonia and monochlorosilane. A by-product of this reaction is ammonium chloride. The reaction of monochlorosilane and ammonia is a spontaneous exothermic reaction.
CN103974958B provides a process for the manufacture of trisilylamine,. a process for the preparation of trisilylamine in the liquid phase, the process comprising: charging monochlorosilane in liquid form as a solution in a solvent (H) which is inert to monochlorosilane, ammonia and trisilylamine and has a higher boiling point than TSA, into a reactor (1) in advance, and introducing ammonia (B) in the form of a solution in the solvent (H) into the reactor, carrying out the reaction in the reactor (1), then introducing the resulting product mixture from the reactor (1) into and through a filter unit (2) and separating solid ammonium chloride (C) from the product mixture, and introducing the filtrate from the filter unit (2) into a distillation column (3), in which distillation column (3) excess monochlorosilane (A') is distilled off at the top, condensed and mixed with the solvent to be conveyed in liquid form to the reactor (1), and gaseous substances (D) are discharged through the top of the distillation column (3), and the bottom product (E) is conveyed to a distillation column (4), in which distillation column (4) the product trisilylamine (G) is distilled off overhead and condensed, and the bottom product (F) is conveyed to a distillation column (5), in which distillation column (5) the solvent (H) is distilled off overhead, condensed and recycled to the reactor feed stream (A), (A'), (B) as solvent, and the high boilers are discharged via the bottom (I), wherein the solvent (H) is toluene.
CN106659999A provides a process for the preparation of trisilylamine in the liquid phase, wherein: (a) injecting at least Monochlorosilane (MCS) dissolved in a solvent (L) in liquid form into a reactor (1), wherein: the solvent relative to MCS, ammonia (NH)3) And TSA is inert, having a higher boiling point than TSA; stirring the solution and setting the temperature T of the solution to 10 ℃ or higher; and (b) in the reactionThe reaction is carried out in a vessel (1), wherein: excess NH will be stoichiometric with respect to the MCS3Introducing into a reactor (1) in which the temperature T is maintained, and then (c) depressurizing the reactor, setting the pressure to 0.5 bar absolute to 0.8 bar absolute; heating the reactor, leading the product mixture (TSA, L, NH)4Cl、DSA、NH3) Flows out of the top of the reactor (1) in gaseous form, flows through a distillation unit (2), and NH is separated by a vacuum unit (8)3The product mixture (TSA, L, NH) is condensed in a heat exchanger (7)4Cl, DSA), collecting the product mixture (TSA, L, NH) in a vessel (6)4Cl, DSA); then (d) filtering the product mixture with a filtration unit (3) to separate solid ammonium chloride (NH) from the product mixture4Cl), introducing the filtrate from the filtration unit (3) into a rectification column (4), wherein DSA and the mixture (TSA, L) are separated at the top of the column, DSA is separated at the top of the column, the mixture (TSA, L) is introduced into a rectification column (11), wherein TSA and the solvent (L) are separated at the top of the column, TSA is separated at the top of the column and the solvent is recycled, or introducing the filtrate from the filtration unit (3) into a batch-type rectification column (4), whereby DSA is separated at the top of the column first, TSA is separated at the top of the column and the solvent is recycled, and (e) introducing the bottom product mixture (L, NH)4Cl) from the reactor (1) flows through a filtration unit (5) in which solid ammonium chloride (NH) is separated4Cl) to obtain solvent (L) and collecting it in container (9), then (f) recycling 0-99% of this solvent, the unrecycled solvent being replaced by solvent (L).
Wo2012156191a1. process for the preparation of trisilylamine in the gas phase, wherein at least the starting materials ammonia and monohalosilane are introduced separately in gaseous form into a reactor, reacted with one another therein to form a product mixture comprising trisilylamine and the product mixture is withdrawn from the reactor after the reaction, characterized in that: the product mixture is withdrawn from the reactor as a gas mixture. The gaseous product mixture comprises trisilylamine, hydrogen halide and ammonia.
the prior patent and the prior art have the following defects: or a tubular reactor is adopted, so that the reaction efficiency is low and the operation difficulty is high; or a kettle type reactor is adopted, the reaction is difficult to control, and the carbon number distribution of the product is too wide; the defects of large bed resistance and the like can be caused, and the normal operation of the industrial device is influenced.
Disclosure of Invention
The object of the present invention is to provide an industrial solution for the preparation of trisilylamine from ammonia and monochlorohydrogen silane in the gas phase. This object is achieved by the method described below. An apparatus that can implement the method is also described below.
A method for synthesizing trisilylamine comprises the following steps:
1) the synthesis method of trisilylamine adopts a catalytic distillation tower, wherein the catalytic distillation tower consists of a rectifying section, a reaction section, a stripping section and a tower kettle which are sequentially connected from the top to the bottom, and is characterized by comprising the following steps: purging a catalytic distillation tower by using inert gas in advance, continuously adding monochlorosilane and ammonia into the catalytic distillation tower from a rectification section and a stripping section in a gaseous form for reaction respectively, wherein the molar ratio of the monochlorosilane to the ammonia is 1: 1.2-3, the space velocity of the monochlorosilane is 0.5-2/h, the reaction pressure is 0.2-1MPa, the reaction temperature of the distillation tower is 350-420 ℃, continuously leading out a reaction product at the bottom of the tower, separating NH4Cl, and obtaining high-purity trisilylamine by using a known impurity removal refining technology in the industry;
2) the reaction section is filled with stainless steel corrugated catalytic packing, and the preparation method comprises the following steps: adding 1-10 parts of iron-palladium-nickel carbon fiber into 100 parts of stainless steel corrugated filler gaps according to parts by weight, and then wrapping the stainless steel corrugated filler with glass fiber cloth to obtain a stainless steel corrugated catalytic filler;
3) the preparation method of the iron-palladium-nickel carbon fiber comprises the following steps:
according to the weight portion, 100 portions of polydimethylsilane is cracked under the protection of high-purity nitrogen at the temperature of 400-500 ℃ to prepare liquid polysilane, then 0.01-0.1 portion of cyclopentadienyl iron, 0.01-0.1 portion of dichloro (1, 5-cyclooctadiene) palladium, 0.01-0.1 portion of bis (1, 5-cyclooctadiene) nickel, 0.5-2 portions of azobisisoheptonitrile, 0.5-2 portions of trans-2-dodecenol, 0.01-0.1 portion of 5-chloro-8-quinolineacrylic acid are added for reaction for 10-40 hours, the product is dissolved by xylene, filtered and decompressed and distilled to prepare poly-iron-palladium-nickel-carbon silane, and the poly-iron-palladium-nickel-carbon silane is prepared by porous melt spinning and continuous firing at the temperature of 1800 ℃ under the protection of high-purity nitrogen, thus obtaining the iron-palladium-nickel carbon fiber.
The impurity removal and purification techniques known in the art include distillation separation techniques, including multi-stage distillation and single-stage distillation.
The impurity removal and refining technology known in the industry comprises the processes of water washing, acid washing and alkali washing.
The impurity removal and purification techniques known in the art include adsorption, the adsorbent includes X-type molecular sieve, A-type molecular sieve, and activated carbon, and the adsorbent may be subjected to pretreatment such as acid treatment, heat treatment, and steam treatment before use.
The cyclopentadienyl iron, dichloro (1, 5-cyclooctadiene) palladium, bis (1, 5-cyclooctadiene) nickel, azobisisoheptonitrile, trans-2-dodecenol and 5-chloro-8-quinoline acrylic acid are all commercial products and comprise industrial products.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a catalytic distillation tower as a production device, takes gaseous monochlorosilane and ammonia as raw materials to carry out continuous catalytic distillation reaction, and stainless steel corrugated catalytic packing is filled in a reaction section of the catalytic distillation tower and is used as a catalyst. The product trisilylamine is continuously discharged from the tower bottom, and a trisilylamine product with higher purity can be obtained through the subsequent conventional refining procedure in the field.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, which are provided only for the purpose of illustration and are not intended to limit the scope of the present invention.
Example 1
A method for synthesizing trisilylamine, which comprises the following steps:
1) the synthesis method of trisilylamine adopts a catalytic distillation tower, wherein the catalytic distillation tower consists of a rectifying section, a reaction section, a stripping section and a tower kettle which are sequentially connected from the top to the bottom, and is characterized by comprising the following steps: purging a catalytic distillation tower by using inert gas in advance, continuously adding monochlorosilane and ammonia into the catalytic distillation tower from a rectification section and a stripping section in a gaseous form for reaction respectively, wherein the molar ratio of the monochlorosilane to the ammonia is 1: 1.8, the space velocity of the monochlorosilane is 1/h, the reaction pressure is 0.4MPa, the reaction temperature of the distillation tower is 370 ℃, continuously leading out a reaction product in a tower kettle, separating NH4Cl, and obtaining high-purity trisilylamine by using an impurity removal refining technology known in the industry;
2) the reaction section is filled with stainless steel corrugated catalytic packing, and the preparation method comprises the following steps: adding 2 parts of iron-palladium-nickel carbon fiber into 100 parts of stainless steel corrugated filler gaps according to parts by weight, and then wrapping the stainless steel corrugated filler with glass fiber cloth to obtain a stainless steel corrugated catalytic filler;
3) the preparation method of the iron-palladium-nickel carbon fiber comprises the following steps:
according to the weight portion, 100 portions of polydimethyl silane is cracked under the protection of high-purity nitrogen at 460 ℃ to prepare liquid polysilane, then 0.03 portion of cyclopentadienyl iron, 0.03 portion of dichloro (1, 5-cyclooctadiene) palladium, 0.05 portion of bis (1, 5-cyclooctadiene) nickel, 1 portion of azo-bis-iso-heptonitrile, 1 portion of trans-2-dodecenol and 0.05 portion of 5-chloro-8-quinoline acrylic acid are added, the reaction is carried out for 30 hours, the product is dissolved by xylene, filtered and decompressed and distilled to prepare the poly-iron-palladium-nickel-carbon silane. And (3) continuously sintering the carbon fiber at 1600 ℃ under the protection of high-purity nitrogen by porous melt spinning to obtain the Fe-Pd-Ni carbon fiber.
Example 2
A method for synthesizing trisilylamine comprises the following steps:
1) the synthesis method of trisilylamine adopts a catalytic distillation tower, wherein the catalytic distillation tower consists of a rectifying section, a reaction section, a stripping section and a tower kettle which are sequentially connected from the top to the bottom, and is characterized by comprising the following steps: purging a catalytic distillation tower by using inert gas in advance, continuously adding monochlorosilane and ammonia into the catalytic distillation tower from a rectification section and a stripping section in a gaseous form for reaction respectively, wherein the molar ratio of the monochlorosilane to the ammonia is 1: 1.2, the space velocity of the monochlorosilane is 0.5/h, the reaction pressure is 0.2MPa, the reaction temperature of the distillation tower is 350 ℃, continuously leading out a reaction product at the bottom of the tower, separating NH4Cl, and obtaining high-purity trisilylamine by using an impurity removal refining technology known in the industry;
2) the reaction section is filled with stainless steel corrugated catalytic packing, and the preparation method comprises the following steps: adding 1 part of iron-palladium-nickel carbon fiber into 100 parts of stainless steel corrugated filler gaps according to parts by weight, and then wrapping the stainless steel corrugated filler with glass fiber cloth to obtain a stainless steel corrugated catalytic filler;
3) the preparation method of the iron-palladium-nickel carbon fiber comprises the following steps:
according to the weight portion, 100 portions of polydimethyl silane is cracked under the protection of high-purity nitrogen at 400 ℃ to prepare liquid polysilane, then 0.01 portion of cyclopentadienyl iron, 0.01 portion of dichloro (1, 5-cyclooctadiene) palladium, 0.01 portion of bis (1, 5-cyclooctadiene) nickel, 0.5 portion of azo-bis-iso-heptonitrile, 0.5 portion of trans-2-dodecenol and 0.01 portion of 5-chloro-8-quinoline acrylic acid are added for reaction for 10 hours, and the product is dissolved by dimethylbenzene, filtered and decompressed and distilled to prepare the poly-iron-palladium-nickel-carbon silane. And (3) continuously sintering the carbon fiber at 1000 ℃ under the protection of high-purity nitrogen by porous melt spinning to obtain the Fe-Pd-Ni carbon fiber.
Example 3
A method for synthesizing trisilylamine comprises the following steps:
1) the synthesis method of trisilylamine adopts a catalytic distillation tower, wherein the catalytic distillation tower consists of a rectifying section, a reaction section, a stripping section and a tower kettle which are sequentially connected from the top to the bottom, and is characterized by comprising the following steps: purging a catalytic distillation tower by using inert gas in advance, continuously adding monochlorosilane and ammonia into the catalytic distillation tower from a rectification section and a stripping section in a gaseous form for reaction respectively, wherein the molar ratio of the monochlorosilane to the ammonia is 1: 3, the space velocity of the monochlorosilane is 2/h, the reaction pressure is 1MPa, the reaction temperature of the distillation tower is 420 ℃, continuously leading out a reaction product at the bottom of the tower, separating NH4Cl, and obtaining high-purity trisilylamine by using a known impurity removal refining technology in the industry;
2) the reaction section is filled with stainless steel corrugated catalytic packing, and the preparation method comprises the following steps: adding 10 parts of iron-palladium-nickel carbon fiber into 100 parts of stainless steel corrugated filler gaps according to parts by weight, and then wrapping the stainless steel corrugated filler with glass fiber cloth to obtain a stainless steel corrugated catalytic filler;
3) the preparation method of the iron-palladium-nickel carbon fiber comprises the following steps:
according to the weight portion, 100 portions of polydimethylsilane is cracked under the protection of high-purity nitrogen at 500 ℃ to prepare liquid polysilane, then 0.1 portion of cyclopentadienyl iron, 0.1 portion of dichloro (1, 5-cyclooctadiene) palladium, 0.1 portion of bis (1, 5-cyclooctadiene) nickel, 2 portions of azo-bis-iso-heptonitrile, 2 portions of trans-2-dodecenol and 0.1 portion of 5-chloro-8-quinoline acrylic acid are added, the reaction is carried out for 40 hours, the product is dissolved by xylene, filtered and distilled under reduced pressure to prepare poly-iron-palladium-nickel-carbon silane, and the poly-iron-palladium-nickel-carbon silane is continuously sintered at 1800 ℃ under the protection of high-purity nitrogen through porous melt spinning to prepare the iron-palladium-nickel carbon fiber.
Comparative example 1
The same procedure as in example 1 was repeated except that cyclopentadienyl iron was not added.
Comparative example 2
Dichloro (1, 5-cyclooctadiene) palladium was not added, but otherwise the procedure was as in example 1.
Comparative example 3
Bis (1, 5-cyclooctadiene) nickel was not added, but the procedure was as in example 1.
Comparative example 4
Trans-2-dodecenol is not added, as in example 1.
Comparative example 5
5-chloro-8-quinolineacrylic acid was not added, as was the case with example 1.
Comparative example 6
The procedure of example 1 was repeated except that the stainless steel corrugated catalyst packing was not used.
Table 1: test samples made by different processes were in% trisilylamine yield.
Claims (4)
1. A method for synthesizing trisilylamine is characterized in that: by catalytic distillationThe method comprises the following steps of preparing a tower, wherein the catalytic distillation tower consists of a rectifying section, a reaction section, a stripping section and a tower kettle which are sequentially connected from the top to the bottom of the tower, and is characterized in that the synthesis method comprises the following steps: purging a catalytic distillation tower with inert gas in advance, continuously adding monochlorosilane and ammonia from a rectification section and a stripping section into the catalytic distillation tower for reaction in a gaseous form, wherein the molar ratio of the monochlorosilane to the ammonia is 1: 1.2-3, the space velocity of the monochlorosilane is 0.5-2/h, the reaction pressure is 0.2-1MPa, the reaction temperature of the distillation tower is 350-420 ℃, continuously extracting a reaction product in a tower kettle, and separating NH4Cl, and then refining to obtain trisilylamine;
the reaction section is filled with stainless steel corrugated catalytic packing, and the preparation method comprises the following steps: adding 1-10 parts of iron-palladium-nickel carbon fiber into 100 parts of stainless steel corrugated filler gaps according to parts by weight, and then wrapping the stainless steel corrugated filler with glass fiber cloth to obtain a stainless steel corrugated catalytic filler;
the preparation method of the iron-palladium-nickel carbon fiber comprises the following steps:
according to the weight portion, 100 portions of polydimethylsilane is cracked under the protection of high-purity nitrogen at the temperature of 400-500 ℃ to prepare liquid polysilane, then 0.01-0.1 portion of cyclopentadienyl iron, 0.01-0.1 portion of dichloro (1, 5-cyclooctadiene) palladium, 0.01-0.1 portion of bis (1, 5-cyclooctadiene) nickel, 0.5-2 portions of azobisisoheptonitrile, 0.5-2 portions of trans-2-dodecenol, 0.01-0.1 portion of 5-chloro-8-quinolineacrylic acid are added for reaction for 10-40 hours, the product is dissolved by xylene, filtered and decompressed and distilled to prepare poly-iron-palladium-nickel-carbon silane, and the poly-iron-palladium-nickel-carbon silane is prepared by porous melt spinning and continuous firing at the temperature of 1800 ℃ under the protection of high-purity nitrogen, thus obtaining the iron-palladium-nickel carbon fiber.
2. A method of synthesizing trisilylamine according to claim 1, wherein: the refining technology is adsorption, and the adsorbent is selected from X-type molecular sieve, A-type molecular sieve and active carbon.
3. A method of synthesizing trisilylamine according to claim 2, wherein: the adsorbent is pre-treated prior to use.
4. A method of synthesizing trisilylamine according to claim 3, wherein: the pretreatment is selected from acid treatment or heat treatment.
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| CN102458643A (en) * | 2009-06-04 | 2012-05-16 | 伏太斯有限责任公司 | Apparatus and method for the production of trisilylamine |
| CN103608287A (en) * | 2011-05-17 | 2014-02-26 | 赢创德固赛有限公司 | Method for producing trisilylamine in the gas phase |
| CN104909371A (en) * | 2015-07-14 | 2015-09-16 | 黄国强 | Device and method of purifying silane by complexation and rectification |
| CN204873856U (en) * | 2015-07-14 | 2015-12-16 | 天津市净纯科技有限公司 | Device of trichlorosilane disproportionation rectification production silane |
| CN106659999A (en) * | 2014-03-14 | 2017-05-10 | 赢创德固赛有限公司 | Method for producing pure trisilylamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102458643A (en) * | 2009-06-04 | 2012-05-16 | 伏太斯有限责任公司 | Apparatus and method for the production of trisilylamine |
| CN103608287A (en) * | 2011-05-17 | 2014-02-26 | 赢创德固赛有限公司 | Method for producing trisilylamine in the gas phase |
| CN106659999A (en) * | 2014-03-14 | 2017-05-10 | 赢创德固赛有限公司 | Method for producing pure trisilylamine |
| CN104909371A (en) * | 2015-07-14 | 2015-09-16 | 黄国强 | Device and method of purifying silane by complexation and rectification |
| CN204873856U (en) * | 2015-07-14 | 2015-12-16 | 天津市净纯科技有限公司 | Device of trichlorosilane disproportionation rectification production silane |
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