CN108586515A - A kind of synthetic method of trimethylsilyl amine - Google Patents
A kind of synthetic method of trimethylsilyl amine Download PDFInfo
- Publication number
- CN108586515A CN108586515A CN201810137101.1A CN201810137101A CN108586515A CN 108586515 A CN108586515 A CN 108586515A CN 201810137101 A CN201810137101 A CN 201810137101A CN 108586515 A CN108586515 A CN 108586515A
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- CN
- China
- Prior art keywords
- parts
- tower
- chlorosilane
- trimethylsilyl amine
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- KOOADCGQJDGAGA-UHFFFAOYSA-N [amino(dimethyl)silyl]methane Chemical compound C[Si](C)(C)N KOOADCGQJDGAGA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- 238000004821 distillation Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000010926 purge Methods 0.000 claims abstract description 6
- 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 20
- 239000010935 stainless steel Substances 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 17
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- 239000004917 carbon fiber Substances 0.000 claims description 15
- SORXVYYPMXPIFD-UHFFFAOYSA-N iron palladium Chemical compound [Fe].[Pd] SORXVYYPMXPIFD-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- -1 polydimethylsiloxanes Polymers 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229940099367 lanolin alcohols Drugs 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000007380 fibre production Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- HJDKCHUESYFUMG-UHFFFAOYSA-N cycloocta-1,5-diene;nickel Chemical compound [Ni].C1CC=CCCC=C1 HJDKCHUESYFUMG-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 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 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910014329 N(SiH3)3 Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- IKXDEFIEGAVNOZ-UHFFFAOYSA-N [SiH4].[C] Chemical compound [SiH4].[C] IKXDEFIEGAVNOZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- LNENVNGQOUBOIX-UHFFFAOYSA-N azidosilane Chemical class [SiH3]N=[N+]=[N-] LNENVNGQOUBOIX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide 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
- 238000006884 silylation reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007740 vapor deposition 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 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 present invention provides a kind of synthetic methods of trimethylsilyl amine, it is characterised in that the preparation method includes the following steps：Inert gas purge catalytic distillation tower is used in advance, a chlorosilane and ammonia catalytic distillation tower is continuously added to from rectifying section and stripping section in a gaseous form simultaneously respectively to react, the molar ratio of one chlorosilane and ammonia is 1: 1.2 3, one chlorosilane air speed, 0.5 2/h, reaction pressure are 0.2 1MPa, and distillation column reaction temperature is 350 DEG C 420 DEG C, tower reactor reaction product is continuously drawn, NH4Cl is isolated, using removing impurities matter purification techniques known in the industry, obtains high-purity trimethylsilyl amine.
Description
Technical field
The present invention relates to a kind of synthetic method of silylation amine, especially a kind of synthetic method of trimethylsilyl amine.
Background technology
Organic amino silane precursor can be used for various depositing operations, including but not limited to atomic layer deposition (" ALD "), change
Learn vapor deposition (" CVD "), plasma enhanced chemical vapor deposition (" PECVD "), low-pressure chemical vapor deposition
(" LPCVD ") and aumospheric pressure cvd.A few class compounds can be used as silicon-containing film (such as, but not limited to, silica or
Silicon nitride film) precursor.The example for being suitable as these compounds of precursor includes silanes, chlorosilane class, poly- silicon nitrogen
Alkanes, amino silicone alkanes and azido silanes class.Inert carrier gas or diluent (such as, but not limited to, helium, hydrogen, nitrogen etc.) also use
In conveying in precursor to reative cell.
Trimethylsilyl amine can be according to reaction equation：
3H3SiCl+4NH3→N(SiH3)3+ 3NH4Cl,
It is prepared by ammonia and monochlorosilane.The by-product of the reaction is ammonium chloride.The reaction of monochlorosilane and ammonia is spontaneous
Exothermic reaction.
CN103974958B provides the manufacturing method of trimethylsilyl amine, and prepares trimethylsilyl amine in the liquid phase
Method, the method includes：Monochlorosilane is previously charged into reactor (1) with the liquid form of the solution in solvent (H)
In, wherein the solvent is inert for monochlorosilane, ammonia and trimethylsilyl amine and with boiling point than TSA high,
The reactor is imported with the solution form in solvent (H) with by ammonia (B), is reacted in reactor (1), then in the future
The products therefrom mixture of autoreactor (1) imports and passes through filter unit (2), and is isolated from the product mixtures
The filtrate of solid ammonium chloride (C) and inherent filtration in future device unit (2) imports destilling tower (3), will be excessive in destilling tower (3)
Monochlorosilane (A'), which is distilled out by tower top, condenses and mixed with the solvent, is delivered as a liquid to reactor (1), and
Gaseous matter (D) is discharged by the tower top of destilling tower (3), and bottom product (E) is transported to destilling tower (4), in destilling tower
(4) the product trimethylsilyl amine (G) is distilled out and condensed by tower top in, and bottom product (F) is transported to distillation
Tower (5), solvent (H) by tower top distilled out, condenses and is recovered in destilling tower (5) reactor feed stream (A), (A'),
(B) it is used as solvent, and high boiling substance is discharged by bottom of tower (I), wherein the solvent (H) is toluene.
CN106659999A provides the method for preparing trimethylsilyl amine in the liquid phase, wherein：(a) it will at least be dissolved in
A chlorosilane (MCS) in solvent (L) is injected with liquid in reactor (1), wherein：The solvent is relative to MCS, ammonia (NH3)
It is inert with TSA, there is the boiling point than TSA high；Agitating solution, and the temperature T of solution is set as 10 DEG C or higher；And
(b) it is reacted in reactor (1), wherein：By the NH relative to MCS stoichiometric excess3It is introduced into reactor (1),
Middle holding temperature T, then (c) reactor is depressurized, it is 0.5 bar of absolute pressure to 0.8 bar of absolute pressure to set pressure；Heating is anti-
Answer device, guiding product mixtures (TSA, L, NH4Cl、DSA、NH3) in a gaseous form outflow reactor (1) tower top, to flow through distillation single
First (2) detach NH through vacuum unit (8)3, condensed product mixture (TSA, L, NH in heat exchanger (7)4Cl, DSA), in container
(6) product mixtures (TSA, L, NH are collected in4Cl、DSA)；Then (d) uses filter element (3) filtration product mixture, from production
Object mixture detaches solid ammonium chloride (NH4Cl), filter liquor is imported into rectifying column (4) from filter element (3), wherein in tower top point
From DSA and mixture (TSA, L), DSA is isolated in tower top, mixture (TSA, L) is introduced into rectifying column (11), wherein in tower top
TSA and solvent (L) are detached, isolates TSA in tower top, and solvent is recycled, or filter liquor is introduced from filter element (3)
Intermittent fractionation tower (4) first isolates DSA from tower top as a result, then isolates TSA from tower top, and solvent is recycled, with
And (e) guide bottom product mixture (L, NH4Cl filter element (5)) is flowed through from reactor (1), detaches solid chlorine wherein
Ammonium (NH4Cl), obtain solvent (L) and collect in container (9), then (f) recycles the solvent of 0-99%, does not recycle
Solvent by solvent (L) substitute.
WO2012156191A1. the method for preparing trimethylsilyl amine in the gas phase, wherein at least starting material ammonia and one
Halogen silyl is imported into reactor in a gaseous form respectively, reacts to each other to be formed comprising trimethylsilyl amine wherein
Product mixtures simultaneously export the product mixtures from reactor after reacting, it is characterised in that：The product mixtures
It is exported from reactor in the form of admixture of gas.The gaseous product mixture include trimethylsilyl amine, hydrogen halides and
Ammonia.
Existing patent and technical literature, there is shortcoming：Or tubular reactor is used, reaction efficiency is low, and operation is difficult
Degree is big；Or tank reactor is used, reaction is difficult to control, and product carbon number distribution is wide；The shortcomings of bed resistance being caused big, shadow
Ring the normal operation to commercial plant.
Invention content
It is an object of the present invention to provide a kind of industry preparing trimethylsilyl amine by ammonia and a chlorine hydrogen silicon in the gas phase to solve
Certainly scheme.This target is realized by methods as described below.A kind of equipment that implementing this method is also described below.
A kind of synthetic method of trimethylsilyl amine, includes the following steps：
1）A kind of synthetic method of trimethylsilyl amine, is prepared, the catalytic distillation tower is from tower top to tower using catalytic distillation tower
Bottom is made of sequentially connected rectifying section, conversion zone, stripping section and tower reactor, it is characterised in that the preparation method includes following
Step：Use inert gas purge catalytic distillation tower in advance, respectively simultaneously by a chlorosilane and ammonia in a gaseous form from rectifying section with
Stripping section is continuously added to catalytic distillation tower and is reacted, and the molar ratio of a chlorosilane and ammonia is 1: 1.2-3, and a chlorosilane is empty
Fast 0.5-2/h, reaction pressure 0.2-1MPa, distillation column reaction temperature are 350 DEG C -420 DEG C, and tower reactor reaction product is continuously drawn
Go out, isolate NH4Cl, using removing impurities matter purification techniques known in the industry, obtains high-purity trimethylsilyl amine；
2）The conversion zone filling is equipped with stainless steel ripple catalytic filler, and preparation method is：By weight, 100 parts of stainless steel waves
1-10 parts of iron palladium nickel carbon fibers are added in line filler gap, and stainless steel ripple packing is wrapped up with glass fabric then, is obtained
Stainless steel ripple catalytic filler；
3）The iron palladium nickel carbon fiber production method is：
By weight, for 100 parts of polydimethylsiloxanes at 400-500 DEG C, liquid polysilane is made in the lower cracking of high pure nitrogen protection,
Add 0.01-0.1 parts of cyclopentadienyl group iron, 0.01-0.1 parts dichloro (1,5- cyclo-octadiene) palladium, 0.01-0.1 parts
Bis- (1,5- cyclo-octadiene) nickel, 0.5-2 parts of azobisisoheptonitrile, 0.5-2 parts of trans- 2- lanolin alcohols, 0.01-0.1 parts
The chloro- 8- quinoline acrylic acid of 5-, react 10-40 hour, product xylene soluble, filtering, the obtained Polyferric Sulfate palladium nickel of vacuum distillation
Carbon silane, through porous melt spinning, high pure nitrogen protects lower 1000-1800 DEG C of continuous burnt, and iron palladium nickel carbon fiber is made.
The removing impurities matter purification techniques known in the industry, including rectifying isolation technics, including multistage rectification and single-stage essence
It evaporates.
The removing impurities matter purification techniques known in the industry, including be washing, pickling, alkali washing process.
The removing impurities matter purification techniques known in the industry, including absorption, the adsorbent includes X-type molecular sieve, A types
Molecular sieve, activated carbon, adsorbent can be handled using preceding by pretreatment, such as acid, heat treatment and steam treatment.
The cyclopentadienyl group iron, dichloro (1,5- cyclo-octadiene) palladium, bis- (1,5- cyclo-octadiene) nickel, two different heptan of azo
Nitrile, trans- 2- lanolin alcohols, the chloro- 8- quinoline acrylic acid of 5-, is commercial product, including technical grade product.
Compared with prior art, the invention has the advantages that：
For the present invention using catalytic distillation tower as process units, a chlorosilane and ammonia are raw material in a gaseous form, are continuously urged
Change distillation reaction, the conversion zone of catalytic distillation tower loads stainless steel ripple catalytic filler, which uses as catalyst.Product
Trimethylsilyl amine is continuously discharged by tower reactor, and the front three silicon of higher purity can be obtained through subsequent this field regular refiner process
Alkyl amine product.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is furture elucidated, but these embodiments are only used for explaining the present invention, without
It is for limiting the scope of the invention.
Embodiment 1
A kind of synthetic method of trimethylsilyl amine, includes the following steps：
1）A kind of synthetic method of trimethylsilyl amine, is prepared, the catalytic distillation tower is from tower top to tower using catalytic distillation tower
Bottom is made of sequentially connected rectifying section, conversion zone, stripping section and tower reactor, it is characterised in that the preparation method includes following
Step：Use inert gas purge catalytic distillation tower in advance, respectively simultaneously by a chlorosilane and ammonia in a gaseous form from rectifying section with
Stripping section is continuously added to catalytic distillation tower and is reacted, and the molar ratio of a chlorosilane and ammonia is 1: 1.8, a chlorosilane air speed
1/h, reaction pressure 0.4MPa, distillation column reaction temperature are 370 DEG C, and tower reactor reaction product is continuously drawn, is isolated
NH4Cl obtains high-purity trimethylsilyl amine using removing impurities matter purification techniques known in the industry；
2）The conversion zone filling is equipped with stainless steel ripple catalytic filler, and preparation method is：By weight, 100 parts of stainless steel waves
2 parts of iron palladium nickel carbon fibers are added in line filler gap, and stainless steel ripple packing is wrapped up with glass fabric then, is obtained stainless
Steel ripple catalytic filler；
3）The iron palladium nickel carbon fiber production method is：
By weight, for 100 parts of polydimethylsiloxanes at 460 DEG C, liquid polysilane is made in the lower cracking of high pure nitrogen protection, then adds
Enter 0.03 part of cyclopentadienyl group iron, 0.03 part dichloro (1,5- cyclo-octadiene) palladium, 0.05 part of bis- (1,5- cyclo-octadiene)
Nickel, 1 part of azobisisoheptonitrile, 1 part of trans- 2- lanolin alcohols, 0.05 part of the chloro- 8- quinoline acrylic acid of 5-, reaction 30 are small
When, product xylene soluble, filtering is evaporated under reduced pressure and Polyferric Sulfate palladium nickel carbon silane is made.Through porous melt spinning, high pure nitrogen
Under protection, iron palladium nickel carbon fiber is made in 1600 DEG C of continuous burnts.
Embodiment 2
A kind of synthetic method of trimethylsilyl amine, includes the following steps：
1）A kind of synthetic method of trimethylsilyl amine, is prepared, the catalytic distillation tower is from tower top to tower using catalytic distillation tower
Bottom is made of sequentially connected rectifying section, conversion zone, stripping section and tower reactor, it is characterised in that the preparation method includes following
Step：Use inert gas purge catalytic distillation tower in advance, respectively simultaneously by a chlorosilane and ammonia in a gaseous form from rectifying section with
Stripping section is continuously added to catalytic distillation tower and is reacted, and the molar ratio of a chlorosilane and ammonia is 1: 1.2, and a chlorosilane is empty
Fast 0.5/h, reaction pressure 0.2MPa, distillation column reaction temperature are 350 DEG C, and tower reactor reaction product is continuously drawn, is isolated
NH4Cl obtains high-purity trimethylsilyl amine using removing impurities matter purification techniques known in the industry；
2）The conversion zone filling is equipped with stainless steel ripple catalytic filler, and preparation method is：By weight, 100 parts of stainless steel waves
1 part of iron palladium nickel carbon fiber is added in line filler gap, and stainless steel ripple packing is wrapped up with glass fabric then, is obtained stainless
Steel ripple catalytic filler；
3）The iron palladium nickel carbon fiber production method is：
By weight, for 100 parts of polydimethylsiloxanes at 400 DEG C, liquid polysilane is made in the lower cracking of high pure nitrogen protection, then adds
Enter 0.01 part of cyclopentadienyl group iron, 0.01 part dichloro (1,5- cyclo-octadiene) palladium, 0.01 part of bis- (1,5- cyclo-octadiene)
Nickel, 0.5 part of azobisisoheptonitrile, 0.5 part of trans- 2- lanolin alcohols, 0.01 part of the chloro- 8- quinoline acrylic acid of 5-, reaction
10 hours, product xylene soluble, filtering was evaporated under reduced pressure and Polyferric Sulfate palladium nickel carbon silane is made.It is high-purity through porous melt spinning
Under nitrogen protection, iron palladium nickel carbon fiber is made in 1000 DEG C of continuous burnts.
Embodiment 3
A kind of synthetic method of trimethylsilyl amine, includes the following steps：
1）A kind of synthetic method of trimethylsilyl amine, is prepared, the catalytic distillation tower is from tower top to tower using catalytic distillation tower
Bottom is made of sequentially connected rectifying section, conversion zone, stripping section and tower reactor, it is characterised in that the preparation method includes following
Step：Use inert gas purge catalytic distillation tower in advance, respectively simultaneously by a chlorosilane and ammonia in a gaseous form from rectifying section with
Stripping section is continuously added to catalytic distillation tower and is reacted, and the molar ratio of a chlorosilane and ammonia is 1: 3, a chlorosilane air speed
2/h, reaction pressure 1MPa, distillation column reaction temperature are 420 DEG C, and tower reactor reaction product is continuously drawn, NH4Cl is isolated,
Using removing impurities matter purification techniques known in the industry, high-purity trimethylsilyl amine is obtained；
2）The conversion zone filling is equipped with stainless steel ripple catalytic filler, and preparation method is：By weight, 100 parts of stainless steel waves
10 parts of iron palladium nickel carbon fibers are added in line filler gap, and stainless steel ripple packing is wrapped up with glass fabric then, is obtained not
Become rusty steel ripple catalytic filler；
3）The iron palladium nickel carbon fiber production method is：
By weight, for 100 parts of polydimethylsiloxanes at 500 DEG C, liquid polysilane is made in the lower cracking of high pure nitrogen protection, then adds
Enter 0.1 part of cyclopentadienyl group iron, 0.1 part dichloro (1,5- cyclo-octadiene) palladium, 0.1 part of bis- (1,5- cyclo-octadiene) nickel, 2
The azobisisoheptonitrile of part, 2 parts of trans- 2- lanolin alcohols, 0.1 part of the chloro- 8- quinoline acrylic acid of 5- react 40 hours, production
Product xylene soluble, filtering are evaporated under reduced pressure and Polyferric Sulfate palladium nickel carbon silane are made, through porous melt spinning, high pure nitrogen protection
Under, iron palladium nickel carbon fiber is made in 1800 DEG C of continuous burnts.
Comparative example 1
Cyclopentadienyl group iron is added without, the other the same as in Example 1.
Comparative example 2
Dichloro (1,5- cyclo-octadiene) palladium is added without, the other the same as in Example 1.
Comparative example 3
Bis- (1,5- cyclo-octadiene) nickel are added without, the other the same as in Example 1.
Comparative example 4
Trans- 2- lanolin alcohols are added without, the other the same as in Example 1.
Comparative example 5
The chloro- 8- quinoline acrylic acid of 5- is added without, the other the same as in Example 1.
Comparative example 6
Without using stainless steel ripple catalytic filler, the other the same as in Example 1.
Table 1：The yield % for the test specimen trimethylsilyl amine that different process is made.
Claims (3)
1. a kind of synthetic method of trimethylsilyl amine, it is characterised in that：It is prepared using catalytic distillation tower, the catalytic distillation tower
It is formed from tower top to bottom of tower by sequentially connected rectifying section, conversion zone, stripping section and tower reactor, it is characterised in that the preparation side
Method includes the following steps：Inert gas purge catalytic distillation tower is used in advance, respectively while by a chlorosilane and ammonia in a gaseous form
Catalytic distillation tower being continuously added to from rectifying section and stripping section to be reacted, the molar ratio of a chlorosilane and ammonia is 1: 1.2-3,
One chlorosilane air speed 0.5-2/h, reaction pressure 0.2-1MPa, distillation column reaction temperature is 350 DEG C -420 DEG C, and tower reactor is reacted
Product is continuously drawn, and NH4Cl is isolated, and using removing impurities matter purification techniques known in the industry, obtains high-purity trimethylsilyl
Amine；
The conversion zone filling is equipped with stainless steel ripple catalytic filler, and preparation method is：By weight, 100 parts of stainless steel ripples
1-10 parts of iron palladium nickel carbon fibers are added in filler gap, and stainless steel ripple packing is wrapped up with glass fabric then, is obtained not
Become rusty steel ripple catalytic filler；
The iron palladium nickel carbon fiber production method is：
By weight, for 100 parts of polydimethylsiloxanes at 400-500 DEG C, liquid polysilane is made in the lower cracking of high pure nitrogen protection, then
0.01-0.1 parts of cyclopentadienyl group iron, 0.01-0.1 parts dichloro (1,5- cyclo-octadiene) palladium, 0.01-0.1 parts of pair is added
(1,5- cyclo-octadiene) nickel, 0.5-2 parts of azobisisoheptonitrile, 0.5-2 parts of trans- 2- lanolin alcohols, 0.01-0.1 parts
The chloro- 8- quinoline acrylic acid of 5- reacts 10-40 hours, product xylene soluble, and filtering is evaporated under reduced pressure and Polyferric Sulfate palladium nickel carbon is made
Silane, through porous melt spinning, high pure nitrogen protects lower 1000-1800 DEG C of continuous burnt, and iron palladium nickel carbon fiber is made.
2. a kind of synthetic method of trimethylsilyl amine described in claim 1, it is characterised in that：Described is known in the industry de-
Impurity purification techniques, including rectifying isolation technics, including multistage rectification and single-stage rectifying.
3. a kind of synthetic method of trimethylsilyl amine described in claim 1, it is characterised in that：Described is known in the industry de-
Impurity purification techniques, including washing, pickling, alkali washing process.
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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 |
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