CN117185299B - Use of organometallic catalysts for the preparation of disilanes and process for the preparation of disilanes - Google Patents
Use of organometallic catalysts for the preparation of disilanes and process for the preparation of disilanes Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims description 7
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 150000003613 toluenes Chemical class 0.000 description 5
- 229910021338 magnesium silicide Inorganic materials 0.000 description 4
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YNBJMIXWGPOBGE-UHFFFAOYSA-N carbanide;cyclopenta-1,3-diene;titanium(4+) Chemical compound [CH3-].[CH3-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YNBJMIXWGPOBGE-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- RZUASTIKPBCXPU-UHFFFAOYSA-N ethene;platinum;triphenylphosphane Chemical compound [Pt].C=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RZUASTIKPBCXPU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 toluene (dehydrated toluene Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical compound CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 210000000608 photoreceptor cell Anatomy 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses an application of an organic metal catalyst in preparing disilane and a preparation method of disilane. The organometallic catalyst comprises Cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 ) The disilane is prepared by catalyzing monosilane with an organometallic catalyst. The invention adopts the organometallic catalyst as a new catalyst to prepare disilane, can effectively catalyze monosilane to synthesize disilane in one step, has mild reaction conditions and low raw material cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, relates to application of an organic metal catalyst in preparation of disilane and a preparation method of disilane, and particularly relates to application of the organic metal catalyst in preparation of disilane and a preparation method of disilane.
Background
Disilane is widely used as an important industrial specialty electron gas in applications such as solar cells, photoreceptor drums, amorphous silicon films, epitaxial growth, oxide films, nitride films, and chemical vapor deposition. At present, disilane is mainly synthesized by adopting a magnesium silicide method.
The reaction formula for synthesizing disilane by a magnesium silicide method is as follows: mg of 2 Si + HCl → Si 2 H 6 + MgCl 2 The reaction products are a mixture of monosilane, disilane, trisilane and butylsilane, and the monosilane is obtained after the final refining and separation of a plurality of products; the raw material magnesium silicide is obtained by reacting magnesium steam with silicon powder at the temperature of not lower than 500 ℃, and the process needs inert gas protection, so that the cost is high and the yield is low. Magnesium silicide may also react with ammonium chloride to produce ethyl acetateSilane, however, is the main product of silane, and disilane is very small in proportion, so that the method is not suitable for large-scale preparation of disilane. The monosilane is polymerized into higher silane after glow discharge, the higher silane is cooled and recycled by liquid nitrogen, and the monosilane and hydrogen are removed by adopting a low-temperature rectification method to obtain disilane, so that the process is complex and the monosilane is carried out under very low pressure, and the method has no practical value. It can be seen that the prior art preparation of disilane has the following drawbacks: (1) The reaction products are numerous, and disilane is obtained by later separation; (2) The reaction conditions are harsh, and the reaction can be carried out only under the conditions of very proper temperature, pressure, discharge frequency and voltage; (3) raw materials the cost is high. It is therefore an urgent need to provide a process for preparing disilanes that is gentle and economical in reaction conditions.
Disclosure of Invention
The invention mainly aims to provide an application of an organic metal catalyst in preparing disilane and a preparation method of disilane, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides the application of an organometallic catalyst in preparing disilane, wherein the organometallic catalyst comprises Cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 ) The disilane is prepared by catalyzing monosilane with an organometallic catalyst.
The embodiment of the invention also provides a preparation method of disilane, which comprises the following steps:
introducing monosilane and carrier gas into a catalyst system and reacting to obtain disilane;
wherein the catalyst system comprises an organometallic catalyst comprising Cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 )。
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the organic metal catalyst as a new catalyst to prepare disilane, can effectively catalyze monosilane reaction to form disilane;
(2) In the invention, monosilane is synthesized in one step by catalyzing monosilane by using an organometallic catalyst, the reaction condition is mild (the reaction is carried out at normal temperature and normal pressure), the cost of raw materials is low, and the method is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic diagram of an apparatus for catalyzing the reaction of monosilane to disilane in an exemplary embodiment of the present invention.
Detailed Description
In view of the drawbacks of the prior art, the present inventors have long studied and practiced in a large number, and have proposed the technical solution of the present invention, which is mainly to use a suitable organometallic catalyst, namely: cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 ) Disilane is formed by a catalytic monosilane one-step reaction.
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In particular, as one aspect of the present invention, it relates to the use of an organometallic catalyst comprising Cp in the preparation of disilane 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 ) The disilane is silicon carbide catalyzed by an organometallic catalystAn alkane.
Specifically, the Cp is 2 Ti(CH 3 ) 2 Is dimethyl titanocene (Petasis reagent); the (Ph) 3 P) 2 Pt(C 2 H 4 ) Is ethylene bis (triphenylphosphine) platinum.
In some preferred embodiments, the organometallic catalyst comprises (Ph 3 P) 2 Pt(C 2 H 4 )。
In some preferred embodiments, the Cp 2 Ti(CH 3 ) 2 Is mainly prepared by the reaction of titanocene chloride and methyl magnesium chloride.
Another aspect of the embodiment of the present invention also provides a method for preparing disilane, which includes:
monosilane and carrier gas are introduced into the catalyst system and reacted, preparing disilane;
wherein the catalyst system comprises an organometallic catalyst comprising Cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 )。
In some preferred embodiments, the preparation method specifically comprises:
mixing an organometallic catalyst with a solvent to form the catalyst system, and placing the catalyst system in a batch reaction device;
simultaneously introducing monosilane and carrier gas into the catalyst system, and stirring at room temperature for reaction to obtain disilane; wherein the stirring speed is 100-400 rpm.
Further, the stirring rate was 200rpm.
Further, the preparation method further comprises the following steps: before monosilane and carrier gas are introduced into the catalyst system, nitrogen substitution treatment is performed on the batch reaction device.
In some preferred embodiments, the flow ratio of monosilane to carrier gas is 1:5 to 1:10.
In some preferred embodiments, the molar ratio of organometallic catalyst to solvent is 0.0005: 1-0.01: 1.
in some preferred embodiments, the solvent includes one or more of toluene (dehydrated toluene), tetrahydrofuran (dehydrated tetrahydrofuran), and is not limited thereto.
In some preferred embodiments, the carrier gas includes any one or a combination of more of nitrogen, helium, argon, and the like, and is not limited thereto.
In some preferred embodiments, the organometallic catalyst comprises (Ph 3 P) 2 Pt(C 2 H 4 )。
In some preferred embodiments, the Cp 2 Ti(CH 3 ) 2 The preparation method of (2) comprises the following steps: slowly dripping titanocene chloride into methyl magnesium chloride, reacting, separating liquid, washing, drying, filtering, and distilling to obtain Cp-containing solution 2 Ti(CH 3 ) 2 Is a solution of (a) and (b).
Further, the reaction temperature of the titanocene chloride and the methyl magnesium chloride is-20-0 ℃ and the time is 30min.
In some more specific embodiments, the Cp 2 Ti(CH 3 ) 2 The preparation method of (2) comprises the following steps:
42 g of titanocene chloride and 500 ml of dehydrated toluene were charged into a 1500 ml three-necked flask (equipped with a stirrer, thermometer and dropping funnel) under nitrogen atmosphere. The three-necked flask was cooled to-10 ℃ with stirring by a cold and hot integrated machine. 130 ml of methyl magnesium chloride (3 mol/L, tetrahydrofuran solvent) was charged into a dropping funnel, and slowly dropping the mixture into the flask within 1 hour, and controlling the temperature of the reaction solution to be about 0 ℃. After the addition was completed, stirring was continued for 30min.
120 ml of ammonium chloride (6 wt% aqueous solution) was added to a 2000 ml three-necked flask (equipped with a stirrer, thermometer and dropping funnel) under nitrogen atmosphere. The three-necked flask was cooled to 0℃with stirring by a cold and hot machine. The reaction-completed liquid in a 1500 ml flask was slowly added to the ammonium chloride solution for half an hour, and the temperature was controlled within 5 ℃. After all addition, the mixture was transferred to a separating funnel, the aqueous phase was removed, the organic phase was washed three times with cold water, once with saturated brine, dried over 50 g of sodium sulfate to remove water and filtered, and the solution was distilled under reduced pressure until the mass of the solution was about 160g (distilled temperature 30 ℃ C.) and the resultant solution was directly used as a catalyst for the synthesis of disilane.
The invention adopts an organometallic catalyst to form disilane by catalyzing monosilane to react in one step, and byproducts comprise hydrogen and Si n H 2n+2 （n≥3）。
In some more specific embodiments, the disilane preparation method includes:
step one: loading a catalyst (containing a solvent) into a batch reactor;
step two: setting GC and tail gas equipment to the conditions required for the experiment;
step three: the monosilane and nitrogen gas path valves are opened, adjusting the flow ratio of monosilane to nitrogen;
step four: in the reaction process, manual GC sampling is performed through a three-way valve.
Specifically, a schematic diagram of a reaction device adopted by disilane is shown in fig. 1, disilane is synthesized in one step by using raw monosilane through an organometallic catalyst, the flow of monosilane and diluent gas nitrogen is controlled by a calibrated flow controller, and a one-way valve is independently arranged on a conveying pipeline to ensure experimental safety; the reactor uses intermittent type formula stainless steel reation kettle, and reaction gas lets in catalyst solution system through inserting the bottom tube, and gaseous phase product is discharged through non-bottom tube and is passed through Gas Chromatograph (GC) or tail gas, and liquid phase product remains in reation kettle, and reaction tail gas does not collect, directly handles through burning tower and spray column, specifically includes: monosilane and diluent gas nitrogen are respectively passed through a diaphragm valve 101 and a diaphragm valve 201, the flow rates are controlled by a flowmeter 102 and a flowmeter 103, then respectively passed through a one-way valve 103 and a one-way valve 203, mixed and fed into a batch reactor 301 for reaction, and then the products are controlled by a three-way valve 302 to enter a gas chromatograph 401 or to be subjected to tail gas collection.
The technical scheme of the invention is further described in detail below with reference to a plurality of preferred embodiments, the embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals. Ethylene bis (triphenylphosphine) platinum (Ph) employed in the present invention 3 P) 2 Pt(C 2 H 4 ) Purchased from Sigma-Aldrich.
Wherein Cp is 2 Ti(CH 3 ) 2 The preparation method of (2) is from the literature: payack, J.F., hughes, D.L., cai, D, ian F, cottrell, I.F., verhoeven, T.R. org., synth 2002, 79, 19 DOI 10.15227/orgsyn.079.0019, cp in the examples below 2 Ti(CH 3 ) 2 The method specifically comprises the following steps:
120 ml of ammonium chloride (6% aqueous solution) was added to a 2000 ml three-necked flask (equipped with a stirrer, thermometer and dropping funnel) under nitrogen atmosphere. The three-necked flask was cooled to 0℃with stirring by a cold and hot machine. The reaction-completed liquid in a 1500 ml flask was slowly added to the ammonium chloride solution for half an hour, and the temperature was controlled within 5 ℃. After all addition, the mixture was transferred to a separating funnel, the aqueous phase was removed, the organic phase was washed three times with cold water, once with saturated brine, dried over 50 g of sodium sulfate to remove water and filtered, and the solution was distilled under reduced pressure until the mass of the solution was about 160g (distilled temperature 30 ℃), and the obtained solution was used as a catalyst directly for the synthesis of disilane, designated as catalyst 1.
Example 1
(1) In a glove box with nitrogen protection, 10 ml of catalyst 1 solution and 50 ml of dehydrated toluene were added to a 250 ml stainless steel batch reactor, and the valves of the bottom tube and the non-bottom tube on the reactor were closed.
(2) The stainless steel reaction kettle is connected with a reaction pipeline to perform nitrogen replacement, so that no water or oxygen exists in the pipeline.
(3) The reaction is carried out at normal temperature and normal pressure, valves of a bottom inserting pipe and a non-bottom inserting pipe on the reaction kettle are opened, gas path valves of monosilane and diluted nitrogen are opened, the flow of monosilane is set to be 5sccm, the flow of nitrogen is set to be 45sccm, reaction gas enters through the bottom inserting pipe, and the stirring of the reaction kettle is set to be 200 revolutions per minute.
(4) The reaction time was 6 hours total and the disilane yield was 44.7% as calculated by GC results.
In this example, successful preparation of disilane was detected by the peak position of the disilane standard in gas chromatography.
Example 2
(1) In a glove box under nitrogen, 0.5g (Ph 3 P) 2 Pt(C 2 H 4 ) And 60 ml of dehydrated toluene is added into the 250 ml stainless steel batch reactor, and valves of a bottom inserting pipe and a non-bottom inserting pipe on the reactor are closed.
(2) The stainless steel reaction kettle is connected with a reaction pipeline to perform nitrogen replacement, so that no water or oxygen exists in the pipeline.
(3) The reaction is carried out at normal temperature and normal pressure, valves of a bottom inserting pipe and a non-bottom inserting pipe on the reaction kettle are opened, gas path valves of monosilane and diluted nitrogen are opened, the flow of monosilane is set to be 5sccm, the flow of nitrogen is set to be 45sccm, reaction gas enters through the bottom inserting pipe, and the stirring of the reaction kettle is set to be 200 revolutions per minute.
(4) The reaction time was 3 hours in total, and the disilane yield was 51.1% as calculated by GC results.
Example 3
(1) In a glove box with nitrogen protection, 10 ml of catalyst 1 solution and 50 ml of dehydrated toluene were added to a 250 ml stainless steel batch reactor, and the valves of the bottom tube and the non-bottom tube on the reactor were closed.
(2) The stainless steel reaction kettle is connected with a reaction pipeline to perform nitrogen replacement, so that no water or oxygen exists in the pipeline.
(3) The reaction is carried out at normal temperature and normal pressure, valves of a bottom inserting pipe and a non-bottom inserting pipe on the reaction kettle are opened, gas path valves of monosilane and diluted nitrogen are opened, the flow of monosilane is set to be 1sccm, the flow of nitrogen is set to be 5sccm, reaction gas enters through the bottom inserting pipe, and the stirring of the reaction kettle is set to be 300 revolutions per minute.
(4) The reaction time was 6 hours in total, and the disilane yield was 63.9% as calculated by GC results.
Example 4
(1) In a glove box under nitrogen, 1g (Ph 3 P) 2 Pt(C 2 H 4 ) And 100 ml of dehydrated toluene is added into the 250 ml stainless steel batch reactor, and valves of a bottom inserting pipe and a non-bottom inserting pipe on the reactor are closed.
(2) The stainless steel reaction kettle is connected with a reaction pipeline to perform nitrogen replacement, so that no water or oxygen exists in the pipeline.
(3) The reaction is carried out at normal temperature and normal pressure, valves of a bottom inserting pipe and a non-bottom inserting pipe on the reaction kettle are opened, gas path valves of monosilane and diluted nitrogen are opened, the flow of monosilane is set to be 2sccm, the flow of nitrogen is set to be 10sccm, reaction gas enters through the bottom inserting pipe, and the stirring of the reaction kettle is set to be 400 revolutions per minute.
(4) The reaction time was 1 hour in total, and the disilane yield was 70.8% as calculated by GC results.
Example 5
(1) In a glove box under nitrogen, 1g (Ph 3 P) 2 Pt(C 2 H 4 ) And 100 ml of dehydrated tetrahydrofuran is added into a 250 ml stainless steel batch reaction kettle, and valves of a bottom inserting pipe and a non-bottom inserting pipe on the reaction kettle are closed.
(2) The stainless steel reaction kettle is connected with a reaction pipeline to perform nitrogen replacement, so that no water or oxygen exists in the pipeline.
(3) The reaction is carried out at normal temperature and normal pressure, valves of a bottom inserting pipe and a non-bottom inserting pipe on the reaction kettle are opened, gas path valves of monosilane and diluted nitrogen are opened, the flow of monosilane is set to be 5sccm, the flow of argon is set to be 50sccm, reaction gas enters through the bottom inserting pipe, and the stirring of the reaction kettle is set to be 100 revolutions per minute.
(4) The reaction time was 1 hour in total, and the disilane yield was 65% as calculated by GC results.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.
Claims (12)
1. Use of an organometallic catalyst for the preparation of disilane, characterized in that: the organometallic catalyst is selected from Cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 ) The disilane is prepared by catalyzing monosilane at room temperature and pressure by an organometallic catalyst.
2. Use according to claim 1, characterized in that: the organometallic catalyst is selected from (Ph 3 P) 2 Pt(C 2 H 4 ) The method comprises the steps of carrying out a first treatment on the surface of the The Cp is 2 Ti(CH 3 ) 2 Is mainly prepared by the reaction of titanocene chloride and methyl magnesium chloride.
3. A method for preparing disilane, comprising:
mixing an organic metal catalyst and a solvent to form a catalyst system, placing the catalyst system in a batch reaction device, and then simultaneously introducing monosilane and carrier gas into the catalyst system and stirring the monosilane and the carrier gas at room temperature for reaction to prepare disilane;
wherein the catalyst system comprises an organometallic catalyst selected from Cp 2 Ti(CH 3 ) 2 And/or (Ph) 3 P) 2 Pt(C 2 H 4 )。
4. A method of preparation according to claim 3, characterized in that: the stirring speed is 100-400 rpm.
5. A method of preparing as claimed in claim 3, further comprising: before monosilane and carrier gas are introduced into the catalyst system, nitrogen substitution treatment is performed on the batch reaction device.
6. A method of preparation according to claim 3, characterized in that: the flow ratio of monosilane to carrier gas is 1:5-1:10.
7. A method of preparation according to claim 3, characterized in that: the molar ratio of organometallic catalyst to solvent was 0.0005: 1-0.01: 1.
8. a method of preparation according to claim 3, characterized in that: the solvent is selected from toluene and/or tetrahydrofuran.
9. A method of preparation according to claim 3, characterized in that: the carrier gas is selected from any one or a combination of more of nitrogen, helium and argon.
10. A method of preparation according to claim 3, characterized in that: the organometallic catalyst is selected from (Ph 3 P) 2 Pt(C 2 H 4 )。
11. The process of claim 3, wherein the Cp is 2 Ti(CH 3 ) 2 The preparation method of (2) comprises the following steps: slowly dripping titanocene chloride into methyl magnesium chloride, reacting, separating liquid, washing, drying, filtering, and distilling to obtain Cp-containing solution 2 Ti(CH 3 ) 2 Is a solution of (a) and (b).
12. The method of manufacturing according to claim 11, wherein: the reaction temperature of the titanocene chloride and the methyl magnesium chloride is-20-0 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2230926A1 (en) * | 1995-09-07 | 1997-03-13 | Merck & Co., Inc. | A process for the preparation of dimethyl titanocene |
| CN105120999A (en) * | 2013-04-24 | 2015-12-02 | 赢创德固赛有限公司 | Process and apparatus for preparation of polysilanes |
| CN115477305A (en) * | 2022-10-19 | 2022-12-16 | 浙江中宁硅业有限公司 | Disilane and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2230926A1 (en) * | 1995-09-07 | 1997-03-13 | Merck & Co., Inc. | A process for the preparation of dimethyl titanocene |
| CN105120999A (en) * | 2013-04-24 | 2015-12-02 | 赢创德固赛有限公司 | Process and apparatus for preparation of polysilanes |
| CN115477305A (en) * | 2022-10-19 | 2022-12-16 | 浙江中宁硅业有限公司 | Disilane and preparation method thereof |
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