Preparation method and preparation system for tris(dimethylamino)silane

Abstract

Disclosed in the present invention are a preparation method and preparation system for tris(dimethylamino)silane. The preparation method comprises: in the presence of a metal supported catalyst, reacting methylsilane with dimethylamine to prepare tris(dimethylamino)silane, the metal supported catalyst comprising metal nanoparticles and a catalyst support loaded with the metal nanoparticles. The present invention uses methylsilane and dimethylamine as raw materials to synthesize tris(dimethylamino)silane by means of a one-step reaction under the catalysis of the metal supported catalyst, wherein none of the raw materials and the catalyst causes chlorine pollution. In addition, the present invention uses three equivalents of dimethylamine gas and one equivalent of methylsilane to react, thereby preventing raw material waste.

Description

A preparation method and preparation system of tris(dimethylamino)silane

[0001] The present invention claims priority to Chinese patent application No. 2023114177307, filed with the Patent Office of China on October 30, 2023, entitled “A method and system for preparing tris(dimethylamino)silane”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The present invention belongs to the technical field of organic chemistry and relates to a preparation method and a preparation system of tri(dimethylamino)silane, and in particular to a preparation method and a preparation system of tri(dimethylamino)silane and use of a metal carrier catalyst in the preparation of tri(dimethylamino)silane. Background Art

[0003] Tris(dimethylamino)silane, also known as 3DMAS or TDMAS (CAS No. 15112-89-7), is a widely used organosilicon source. 3DMAS's strong stability and high vapor pressure make it an excellent vapor deposition precursor and a key raw material for depositing silicon oxynitride, carbonitride, nitride, and oxide thin films in atomic layer deposition.

[0004] In the synthesis method of 3DMAS, a direct reaction of trichlorosilane and dimethylamine gas is used. The reaction is rapid, but 6 equivalents of dimethylamine gas are required during the reaction, of which 3 equivalents of dimethylamine gas are used to react with trichlorosilane to form 3DMAS, and the other 3 equivalents of dimethylamine gas are wasted and need to combine with the acidic substances formed by the reaction to form by-products. The amount of this by-product is large and difficult to separate. The raw material trichlorosilane contains chlorine, so the product 3DMAS will be contaminated with chlorine, and when used by the client, hydrochloric acid will be formed, corroding products and equipment. 3DMAS can also be prepared by the reaction of trichlorosilane being substituted by tetrakis(dimethylamino)titanium. This reaction requires the use of an excess of trichlorosilane to react in a toluene solution. The reaction needs to be carried out at an extremely low temperature, and the toluene solution is toxic and requires later separation. In summary, the existing technology for preparing 3DMAS has the following defects: (1) the raw materials used (trichlorosilane and tetrakis(dimethylamino)titanium) are expensive and unstable in supply, and trichlorosilane contains chlorine, which will introduce chlorine impurities into the reaction system; (2) 6 equivalents of dimethylamine gas are used, of which 3 equivalents of dimethylamine gas combine with acidic substances in the reaction process to generate by-product waste, resulting in a waste of dimethylamine raw materials; (3) the by-products generated by the existing technology are solid waste, or a large amount of solvent is required, both of which need to be separated in the later stage. Therefore, it is an urgent problem to provide a method for preparing tris(dimethylamino)silane that is simple, low-cost, and free of chlorine pollution.

[0005] Summary of the Invention

[0006] The main purpose of the present invention is to provide a preparation method and preparation system of tris(dimethylamino)silane to overcome the deficiencies of the prior art.

[0007] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0008] An embodiment of the present invention provides a method for preparing tris(dimethylamino)silane, which comprises:

[0009] In the presence of a metal supported catalyst, monosilane is reacted with dimethylamine to produce tri(dimethylamino)silane;

[0010] Wherein, the metal support catalyst includes metal nanoparticles and a catalyst support loaded with the metal nanoparticles, the metal nanoparticles include any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, and the catalyst support includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

[0011] The embodiment of the present invention further provides a system for preparing tris(dimethylamino)silane, which is applied to the aforementioned method for preparing tris(dimethylamino)silane, and comprises:

[0012] a delivery unit for at least monosilane and dimethylamine;

[0013] A reaction unit, at least for reacting monosilane with dimethylamine;

[0014] The collecting unit is at least used for collecting tris(dimethylamino)silane.

[0015] The present invention also provides a method for preparing tris(dimethylamino)silane, which comprises:

[0016] Simultaneously introducing monosilane and dimethylamine into a reaction device, allowing the monosilane and dimethylamine to contact and react with a metal-supported catalyst in the reaction device, thereby producing tris(dimethylamino)silane;

[0017] Wherein, the metal support catalyst includes metal nanoparticles and a catalyst support loaded with the metal nanoparticles, the metal nanoparticles include any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, and the catalyst support includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

[0018] An embodiment of the present invention also provides a use of a metal-supported catalyst in catalyzing the reaction of monosilane and dimethylamine to prepare tri(dimethylamino)silane, wherein the metal-supported catalyst comprises metal nanoparticles and a catalyst carrier that loads the metal nanoparticles, wherein the metal nanoparticles comprise a combination of any one or more of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au, and the catalyst carrier comprises a combination of any one or more of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The present invention uses monosilane and dimethylamine as raw materials, and synthesizes tri(dimethylamino)silane in a single step under the catalysis of a metal-supported catalyst. Both the raw materials and the catalyst are free of chlorine pollution, and the market price is low and the supply is stable;

[0021] (2) The core of the present invention is the use of a metal-supported catalyst with high selectivity, where 3 equivalents of dimethylamine gas react with 1 equivalent of monosilane without causing waste of raw materials;

[0022] (3) In the present invention, dimethylamine and monosilane are reacted in one step to obtain the target product, without generating solid waste and without using solvent. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] FIG1 is a schematic diagram of a reaction apparatus for preparing tri(dimethylamino)silane in a typical embodiment of the present invention. DETAILED DESCRIPTION

[0025] In view of the defects of the existing technology, the inventors of this case have proposed the technical solution of the present invention after long-term research and extensive practice. It mainly uses metal-supported catalysts, raw materials silane and dimethylamine, to synthesize 3DMAS under gas phase conditions.

[0026] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0027] Specifically, as one aspect of the technical solution of the present invention, a method for preparing tris(dimethylamino)silane involves:

[0028] In the presence of a metal supported catalyst, monosilane is reacted with dimethylamine to produce tri(dimethylamino)silane;

[0029] Wherein, the metal support catalyst includes metal nanoparticles and a catalyst support loaded with the metal nanoparticles, the metal nanoparticles include any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, and the catalyst support includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

[0030] In some preferred embodiments, the metal nanoparticles include any one or more combinations of Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au, but are not limited thereto.

[0031] In some preferred embodiments, the content of metal nanoparticles in the metal supported catalyst is 0.5 to 5 wt%.

[0032] In some preferred embodiments, the average particle size of the metal nanoparticles is 0.5 nm to 10 nm.

[0033] For example, the average particle size of the metal nanoparticles is 0.5 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm or 10 nm.

[0034] In some preferred embodiments, the catalyst support has a porous structure, and the specific surface area of ​​the catalyst support is 10-300m 2 / g, pore size is 20nm-200nm.

[0035] In some preferred embodiments, the metal nanoparticles are supported on the surface and in the pores of the catalyst support.

[0036] In some preferred embodiments, the reaction temperature is 200-500°C.

[0037] In some preferred embodiments, the volume ratio of monosilane to dimethylamine is 1:3.

[0038] In the preparation method of tri(dimethylamino)silane provided in the present invention, silane gas and dimethylamine gas molecules are adsorbed on the surface of metal nanoparticles in the catalyst. The metal nanoparticles weaken the Si-H bond in silane and the NH bond in dimethylamine through electron transfer, thereby forming a Si-N structure.

[0039] Another aspect of an embodiment of the present invention further provides a system for preparing tris(dimethylamino)silane, which is applied to the aforementioned method for preparing tris(dimethylamino)silane, comprising:

[0040] a delivery unit for at least monosilane and dimethylamine;

[0041] A reaction unit, at least for reacting monosilane with dimethylamine;

[0042] The collecting unit is at least used for collecting tris(dimethylamino)silane.

[0043] In some preferred embodiments, the delivery unit includes a monosilane delivery unit and a dimethylamine delivery unit.

[0044] In some preferred embodiments, the reaction unit comprises a fixed bed reaction device, and a metal supported catalyst is disposed in the reaction unit.

[0045] Another aspect of the embodiments of the present invention further provides a method for preparing tris(dimethylamino)silane, which comprises:

[0046] Simultaneously introducing monosilane and dimethylamine into a reaction device, allowing the monosilane and dimethylamine to contact and react with a metal-supported catalyst in the reaction device, thereby producing tris(dimethylamino)silane;

[0047] Wherein, the metal support catalyst includes metal nanoparticles and a catalyst support loaded with the metal nanoparticles, the metal nanoparticles include any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, and the catalyst support includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

[0048] In some preferred embodiments, the metal nanoparticles include any one or more combinations of Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au, but are not limited thereto.

[0049] In some preferred embodiments, the content of metal nanoparticles in the metal supported catalyst is 0.5 to 5 wt%.

[0050] In some preferred embodiments, the average particle size of the metal nanoparticles is 0.5 nm to 10 nm.

[0051] In some preferred embodiments, the catalyst support has a porous structure, and the specific surface area of ​​the catalyst support is 10-300m 2 / g, pore size is 20nm-200nm.

[0052] In some preferred embodiments, the metal nanoparticles are supported on the surface and in the pores of the catalyst support.

[0053] In some preferred embodiments, the flow ratio of monosilane to dimethylamine fed into the reaction apparatus is 1:3, wherein the pressures of the two are the same, so the flow ratio is the molar ratio, that is:

[0054] Specifically, in the present invention, the flow ratio of monosilane to dimethylamine input into the reaction device is 15 sccm:45 sccm, or 10 sccm:30 sccm.

[0055] In some preferred embodiments, the raw material input into the reaction apparatus of the present invention may be in excess of monosilane.

[0056] In some preferred embodiments, the preparation method specifically includes: independently introducing monosilane and dimethylamine in the gas phase into a reaction device equipped with a metal support catalyst through a gas delivery pipeline and reacting them at 200-500° C. to obtain the tri(dimethylamino)silane.

[0057] Furthermore, the temperature of the gas delivery pipeline for delivering dimethylamine is 160-180°C.

[0058] Furthermore, the temperature of the gas pipeline for transporting dimethylamine mainly serves as a preheating temperature and can be close to the reaction temperature.

[0059] For example, the temperature of the gas delivery pipeline delivering dimethylamine may be 160°C, 165°C, 170°C, 175°C, or 180°C.

[0060] Furthermore, the reaction device includes a fixed bed reaction device.

[0061] Furthermore, the metal carrier catalyst is arranged in the middle of the reaction device, and the monosilane and dimethylamine are input from the top of the reaction device and then pass through the metal carrier catalyst; wherein, the metal carrier catalyst is fixed to the middle of the reaction device using quartz wool.

[0062] In some preferred embodiments, the preparation method further comprises: after the reaction is completed, condensing the obtained product by a condensation device.

[0063] In some more specific embodiments, the preparation method of tri(dimethylamino)silane can be carried out using the device schematic diagram shown in Figure 1. This method uses a metal-supported catalyst and raw materials monosilane and dimethylamine to synthesize tri(dimethylamino)silane (3DMAS) under gas phase conditions. Except for the monosilane delivery pipeline, all pipelines are heated to 160-180 degrees Celsius through a heating belt. The flow of monosilane and dimethylamine is controlled by a calibrated flow controller, and a one-way valve is separately installed in the delivery pipeline to ensure experimental safety. The fixed bed reactor material is a quartz tube, and the temperature range of the external heating furnace is 200 to 800 degrees Celsius. The metal-supported catalyst is fixed in the middle of the reactor by quartz wool to form a catalyst bed. The raw gas passes vertically through the catalyst bed from top to bottom. The post-reaction gas is adjusted by a six-way valve and is selected to enter a gas chromatograph (GC) for online reaction result analysis or enter a product collection tank in the condenser. The reaction tail gas needs to be treated through a combustion tower and a spray tower; the specific steps include:

[0064] Step 1: loading the metal supported catalyst into the fixed bed reactor 301;

[0065] Step 2: Set the gas pipeline, fixed bed reactor 301, gas chromatograph 401, product collection tank 501 and tail gas device to the conditions required for the experiment;

[0066] Step 3: Open the diaphragm valve 101 for monosilane and the diaphragm valve 201 for dimethylamine, and control the flow ratio of monosilane to dimethylamine to be 1:3 through the flowmeter 102 and the flowmeter 202 respectively; then mix and enter the fixed bed reactor 301 through the one-way valve 103 and the one-way valve 203 for reaction.

[0067] Step 4: During the reaction process, the six-way valve 302 remains in the product collection state and switches to the GC injection position during GC sampling. After the injection is completed, the six-way valve 302 is switched back to the product collection state. This step can realize the simultaneous online reaction result analysis and product collection.

[0068] Furthermore, the metal supported catalyst in the present invention is a metal nanoparticle supported catalyst, the metal nanoparticles in the metal nanoparticle supported catalyst include Pd, Pt, Au, Ni, Co, Ru, and bimetallic catalysts Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, the size of the metal nanoparticles is between 0.5 nanometers and 10 nanometers, and the catalyst support includes MgO, SiO2, TiO2, C, Al2O3, ZrO2 or CeO2.

[0069] Furthermore, in the present invention, monosilane and dimethylamine react at normal pressure and between 200 and 500 degrees Celsius.

[0070] Another aspect of an embodiment of the present invention also provides a use of a metal support catalyst in catalyzing the reaction of monosilane and dimethylamine to prepare tri(dimethylamino)silane, wherein the metal support catalyst includes metal nanoparticles and a catalyst support that loads the metal nanoparticles, the metal nanoparticles include any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au, and the catalyst support includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

[0071] In some preferred embodiments, the metal nanoparticles include any one or more combinations of bimetallic Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au, but are not limited thereto.

[0072] In some preferred embodiments, the content of metal nanoparticles in the metal supported catalyst is 0.5 to 5 wt%.

[0073] In some preferred embodiments, the average particle size of the metal nanoparticles is 0.5 nm to 10 nm.

[0074] In some preferred embodiments, the catalyst support has a porous structure, and the specific surface area of ​​the catalyst support is 10-300m 2 / g, pore size is 20nm-200nm.

[0075] In some preferred embodiments, the metal nanoparticles are supported on the surface and in the pores of the catalyst support.

[0076] In some preferred embodiments, the molar ratio of monosilane to dimethylamine is 1:3.

[0077] In some preferred embodiments, the temperature of the reaction of monosilane and dimethylamine is 200-500°C.

[0078] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments. This embodiment is implemented on the premise of the technical solution of the invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0079] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0080] In the following examples, the inventors of this case determined the peak position of pure 3DMAS in GC, and ultimately confirmed the successful preparation of 3DMAS based on the peak position of the product. At the same time, the obtained liquid product was distilled to obtain pure 3DMAS.

[0081] Example 1

[0082] 1. Preparation of metal supported catalyst Pt-Co / ZrO2:

[0083] (1) Add 5 g of powdered ZrO2 into a beaker, and then add Pt(NH3)4(NO3)2 and Co(NO3)2·6H2O solutions step by step. By calculation, the molar ratio of added Pt:Co is controlled at 1:1, and the Pt-Co content is controlled at 3.5 wt%. Continue stirring after addition until the added solution can be evenly infiltrated into the powdered ZrO2.

[0084] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0085] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0086] (4) After cooling, the powdered Pt-Co / ZrO2 was taken out and placed in a glove box for nitrogen protection.

[0087] 2. Preparation of 3DMAS:

[0088] (1) Weigh 1 g of a metal-supported catalyst, Pt-Co / ZrO2, with an average Pt-Co particle size of 5 nm and a Pt-Co content of 3.5 wt%, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0089] (2) Set the gas line temperature to 180°C, the reactor temperature to 350°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0090] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0091] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection mode every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 86.4% to 66.2%.

[0092] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 71.2%.

[0093] In this example, the successful preparation of 3DMAS was confirmed by comparing the peak position of the product in GC with that of pure 3DMAS.

[0094] Example 2

[0095] 1. Preparation of metal supported catalyst Pt / CeO2:

[0096] (1) Add 5g of powdered CeO2 into a beaker, and then add Pt(NH3)4(NO3)2 solution. By calculation, the added amount of Pt content is controlled at 5wt%. Continue stirring after adding until the added solution can be evenly penetrated into the powdered CeO2.

[0097] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 3 hours.

[0098] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0099] (4) After cooling, the Pt / CeO2 powder was taken out and placed in a glove box for nitrogen protection.

[0100] 2. Preparation of 3DMAS:

[0101] (1) Weigh 500 mg of a Pt / CeO2 catalyst (Pt with an average particle size of 5 nm and a Pt content of 5 wt%) and mix it evenly with 3.5 g of quartz sand (the reaction is exothermic, and mixing with the quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0102] (2) Set the gas line temperature to 180 degrees Celsius, the reactor temperature to 250 degrees Celsius, set the GC to the detectable state, and add dry ice to the gas condensate collection tank.

[0103] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 10 sccm, and the flow rate of dimethylamine to 30 sccm.

[0104] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction lasted for a total of 24 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 74.8% to 45.2%.

[0105] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 60.1%.

[0106] A scanning transmission electron microscope image of the catalyst Pt / CeO2 used in this embodiment is shown in FIG1 , wherein the white particles are Pt nanoparticles.

[0107] Example 3

[0108] 1. Preparation of metal supported catalyst Pd-Fe / MgO:

[0109] (1) Place 10g of MgCO3 in a ceramic evaporating dish and place it in a horizontal tube oven with air flow at 20 cubic centimeters per minute and 700 degrees Celsius for 3 hours. After drying, remove the dish to obtain MgO as a catalyst carrier.

[0110] (2) Add 5g of powdered MgO into a beaker, and then add Pd(NO3)2 and Fe(NO3)3 solutions step by step. By calculation, the molar ratio of added Pd:Fe is controlled at 1:2, and the Pd-Fe content is controlled at 1wt%. Continue stirring after addition until the added solution can be evenly penetrated into the powdered MgO.

[0111] (3) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0112] (4) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0113] (5) After cooling, the Pd-Fe / MgO powder was taken out and placed in a glove box for nitrogen protection.

[0114] 2. Preparation of 3DMAS:

[0115] (1) Weigh 1 g of a metal-supported catalyst, Pd-Fe / MgO (Pt-Co / MgO), with an average Pd-Fe particle size of 3 nm and a Pd-Fe content of 1 wt %, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The evenly mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0116] (2) Set the gas line temperature to 160°C, the reactor temperature to 200°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0117] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0118] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 70.2% to 58.1%.

[0119] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 66.4%.

[0120] Example 4

[0121] 1. Preparation of metal supported catalyst Pt-Fe / SiO2:

[0122] (1) Add 5g of powdered SiO2 into a beaker, and then add Pt(NH3)4(NO3)2 and Fe(NO3)3 solutions step by step. By calculation, the molar ratio of added Pt:Fe is controlled at 1:3, and the Pt-Fe content is controlled at 2wt%. Continue stirring after adding until the added solution can penetrate into the powdered SiO2 very evenly.

[0123] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0124] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0125] (4) After cooling, the powdered Pt-Fe / SiO2 was taken out and placed in a glove box for nitrogen protection.

[0126] 2. Preparation of 3DMAS:

[0127] (1) Weigh 1 g of a metal-supported catalyst, Pt-Fe / SiO2, with an average Pt-Fe particle size of 3 nm and a Pt-Fe content of 2 wt%, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0128] (2) Set the gas line temperature to 170°C, the reactor temperature to 500°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0129] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0130] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 88.5% to 73.7%.

[0131] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 80.2%.

[0132] Example 5

[0133] 1. Preparation of metal supported catalyst Pd-Au / TiO2:

[0134] (1) Add 2 g of powdered TiO2 into a beaker, and then add Pd(NO3)2 and AuCl3 solutions step by step. By calculation, the molar ratio of added Pd:Au is controlled at 1:1, and the Pd-Au content is controlled at 5 wt%. Continue stirring after addition until the added solution can be evenly infiltrated into the powdered TiO2.

[0135] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0136] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0137] (4) After cooling, the Pd-Au / TiO2 powder was taken out and placed in a glove box for nitrogen protection.

[0138] 2. Preparation of 3DMAS:

[0139] (1) Weigh 1 g of a metal-supported catalyst, Pd-Au / TiO2, with an average Pd-Au particle size of 6 nm and a Pd-Au content of 5 wt%, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The evenly mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0140] (2) Set the gas line temperature to 170°C, the reactor temperature to 500°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0141] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0142] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 78.9% to 61.4%.

[0143] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 69.3%.

[0144] Example 6

[0145] 1. Preparation of metal supported catalyst Pt-Au / Al2O3:

[0146] (1) Add 5 g of powdered Al2O3 into a beaker, and then add Pt(NH3)4(NO3)2 and AuCl3 solutions step by step. By calculation, the molar ratio of added Pt:Au is controlled at 1:1, and the content of Pt-Au is controlled at 0.5 wt%. Continue stirring after addition until the added solution can be evenly infiltrated into the powdered Al2O3.

[0147] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0148] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0149] (4) After cooling, the Pt-Au / Al2O3 powder was taken out and placed in a glove box for nitrogen protection.

[0150] 2. Preparation of 3DMAS:

[0151] (1) Weigh 1 g of a metal-supported catalyst, Pt-Au / Al2O3, with an average Pt-Au particle size of 0.6 nm and a Pt-Au content of 0.5 wt%, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The evenly mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0152] (2) Set the gas line temperature to 170°C, the reactor temperature to 500°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0153] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0154] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 83.1% to 63.8%.

[0155] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 72.5%.

[0156] Example 7

[0157] 1. Preparation of metal supported catalyst Ni / C:

[0158] (1) Add 2g of carbon powder to a beaker, and then add Ni(acac)2(H2O)2 solution. By calculation, the Ni content is controlled at 5wt%. Continue stirring after adding until the added solution can be evenly penetrated into the carbon powder.

[0159] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 3 hours.

[0160] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0161] (4) After cooling, the Ni / C powder is taken out and placed in a glove box for nitrogen protection.

[0162] 2. Preparation of 3DMAS:

[0163] (1) Weigh 500 mg of Ni / C catalyst (with an average Ni particle size of 5 nm and a Ni content of 5 wt%) and mix it evenly with 3.5 g of quartz sand (the reaction is exothermic, and mixing with the quartz sand facilitates heat transfer). The evenly mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0164] (2) Set the gas line temperature to 180 degrees Celsius, the reactor temperature to 250 degrees Celsius, set the GC to the detectable state, and add dry ice to the gas condensate collection tank.

[0165] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 10 sccm, and the flow rate of dimethylamine to 30 sccm.

[0166] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection mode every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction lasted for a total of 24 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 70.4% to 56.3%.

[0167] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 61.5%.

[0168] Example 8

[0169] 1. Preparation of metal supported catalyst Pt / ZrO2:

[0170] (1) Add 2g ZrO2 into a beaker, and then add Pt(NH3)4(NO3)2 solution. By calculation, the added amount of Pt content is controlled at 3.5wt%. Continue stirring after adding until the added solution can be evenly penetrated into the carbon powder.

[0171] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0172] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0173] (4) After cooling, the Pt / ZrO2 powder was taken out and placed in a glove box for nitrogen protection.

[0174] 2. Preparation of 3DMAS:

[0175] (1) Weigh 1 g of a Pt / ZrO2 catalyst (Pt with an average particle size of 5 nm and a Pt content of 3.5 wt%) and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0176] (2) Set the gas line temperature to 180°C, the reactor temperature to 350°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0177] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0178] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection mode every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 70.3% to 53.6%.

[0179] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 60.4%.

[0180] Example 9

[0181] 1. Preparation of metal supported catalyst Co / ZrO2:

[0182] (1) Add 2g ZrO2 into a beaker, and then add Co(NO3)2·6H2O solution. By calculation, the content of Co added is controlled at 3.5wt%. Continue stirring after adding until the added solution can be evenly penetrated into the carbon powder.

[0183] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, the oven temperature is set to 300 degrees Celsius, and the drying is maintained for 2 hours.

[0184] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0185] (4) After cooling, the powdered Co / ZrO2 was taken out and placed in a glove box for nitrogen protection.

[0186] 2. Preparation of 3DMAS:

[0187] (1) Weigh 1 g of a Co / ZrO2 catalyst (the average particle size of Co in the Co / ZrO2 is 5 nm, and the Co content is 3.5 wt%) and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0188] (2) Set the gas line temperature to 180°C, the reactor temperature to 350°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0189] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0190] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 60.4% to 47.3%.

[0191] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 54.6%.

[0192] Comparative Example 1

[0193] The method is the same as that of Example 1, except that the metal support catalyst Pt-Co / ZrO2 is missing in the quartz tube reactor, and detection shows that no 3DMAS can be generated.

[0194] Comparative Example 2

[0195] 1. Preparation of metal supported catalyst Pt-Co / ZrO2:

[0196] (1) Add 5 g of powdered ZrO2 into a beaker, and then add Pt(NH3)4(NO3)2 and Co(NO3)2·6H2O solutions step by step. By calculation, the molar ratio of added Pt:Co is controlled at 1:1, and the Pt-Co content is controlled at 3.5 wt%. Continue stirring after addition until the added solution can be evenly infiltrated into the powdered ZrO2.

[0197] (2) Stop stirring, pour the wet powder into a ceramic evaporating dish, and place it in a horizontal tube oven with air flow. The air flow rate is set to 20 cubic centimeters per minute, and the oven temperature is set to 800 degrees Celsius (at this temperature, the nanoparticles will agglomerate and the particle size will increase). Keep drying for 2 hours.

[0198] (3) In the same tube furnace, the air introduced was replaced with 3.5% H2 / Ar gas, the flow rate and temperature were kept unchanged, and the conditions were maintained for 30 minutes.

[0199] (4) After cooling, the powdered Pt-Co / ZrO2 was taken out and placed in a glove box for nitrogen protection.

[0200] 2. Preparation of 3DMAS:

[0201] (1) Weigh 1 g of a metal-supported catalyst, Pt-Co / ZrO2, with an average Pt-Co particle size of 15 nm and a Pt-Co content of 3.5 wt%, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0202] (2) Set the gas line temperature to 180°C, the reactor temperature to 350°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0203] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0204] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 46.2% to 29.3%.

[0205] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 34.2%.

[0206] Comparative Example 3

[0207] (1) Weigh 1 g of a metal-supported catalyst, Pt-Co / ZrO2, with an average Pt-Co particle size of 0.1 nm and a Pt-Co content of 0.5 wt%, and mix it evenly with 3 g of quartz sand (the reaction is exothermic, and mixing with the mixed quartz sand facilitates heat transfer). The mixed catalyst is secured to the center of a quartz tube reactor using quartz wool.

[0208] (2) Set the gas line temperature to 180°C, the reactor temperature to 350°C, set the GC to detectable status, and add dry ice to the gas condensate collection tank;

[0209] (3) After the equipment reaches the specified temperature, open the monosilane and dimethylamine gas valves, set the flow rate of monosilane to 15 sccm, and the flow rate of dimethylamine to 45 sccm.

[0210] (4) During the reaction, the six-way valve remained in the product collection mode and was switched to the GC injection position every 20 minutes. After 10 seconds of injection, the six-way valve was switched back to the product collection mode. The reaction time was 13 hours. GC results showed that the 3DMAS content in the product mixture gradually decreased from 32.6% to 19.4%.

[0211] (5) After the reaction was completed, the liquid level meter showed that 2 / 3 of the liquid product had been collected in the collection tank. Samples were taken for GC detection, and the content of 3DMAS in the liquid product was 24.5%.

[0212] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0213] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical variations made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing tri(dimethylamino)silane, characterized in that: include: In the presence of a metal supported catalyst, monosilane is reacted with dimethylamine to obtain tri(dimethylamino)silane; Among them, the metal carrier catalyst includes metal nanoparticles and a catalyst carrier loading the metal nanoparticles, the metal nanoparticles include any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, and the catalyst carrier includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

2. The preparation method according to claim 1, characterized in that: The metal nanoparticles include any one or more combinations of Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au; and / or, the content of metal nanoparticles in the metal carrier catalyst is 0.5 to 5 wt%; and / or, the average particle size of the metal nanoparticles is 0.5 nm to 10 nm; And / or, the catalyst carrier has a porous structure, and the specific surface area of ​​the catalyst carrier is 10-300m 2 / g, pore size is 20nm-200nm; And / or, the metal nanoparticles are loaded on the surface of the catalyst carrier and in the pores contained therein.

3. The preparation method according to claim 1, characterized in that: The reaction temperature is 200-500° C.; and / or the volume ratio of monosilane to dimethylamine is 1:

3.

4. A system for preparing tris(dimethylamino)silane, which is applied to the method for preparing tris(dimethylamino)silane according to any one of claims 1 to 3, characterized in that: include: a delivery unit for at least monosilane and dimethylamine; A reaction unit, at least for reacting monosilane with dimethylamine; The collecting unit is at least used for collecting tri(dimethylamino)silane.

5. The preparation system according to claim 4, characterized in that: The delivery unit includes a monosilane delivery unit and a dimethylamine delivery unit; And / or, the reaction unit comprises a fixed bed reaction device, and a metal carrier catalyst is arranged in the reaction unit.

6. A method for preparing tri(dimethylamino)silane, characterized in that: include: Simultaneously introducing monosilane and dimethylamine into a reaction device, so that the monosilane and dimethylamine contact and react with a metal carrier catalyst in the reaction device, thereby preparing tri(dimethylamino)silane; The metal carrier catalyst includes metal nanoparticles and a catalyst carrier loaded with the metal nanoparticles, and the metal nanoparticles include Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au The catalyst carrier includes any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, and CeO2.

7. The preparation method according to claim 6, characterized in that: The metal nanoparticles include any one or more combinations of Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au; and / or, the content of metal nanoparticles in the metal carrier catalyst is 0.5 to 5 wt%; and / or, the average particle size of the metal nanoparticles is 0.5 nm to 10 nm; And / or, the catalyst carrier has a porous structure, and the specific surface area of ​​the catalyst carrier is 10-300m 2 / g, pore size is 20nm-200nm.

8. The preparation method according to claim 6, characterized in that: The flow ratio of the monosilane to dimethylamine input into the reaction device is 1:3; And / or, the preparation method specifically comprises: independently and simultaneously introducing monosilane and dimethylamine in a gas phase into a reaction device provided with a metal carrier catalyst through a gas delivery pipeline and reacting at 200-500° C. to obtain the tri(dimethylamino)silane; wherein the temperature of the gas delivery pipeline for delivering dimethylamine is 160-180° C.; And / or, the reaction device comprises a fixed bed reaction device; And / or, the metal carrier catalyst is arranged in the middle of the reaction device, and the monosilane and dimethylamine are input from the top of the reaction device and then pass through the metal carrier catalyst; wherein the metal carrier catalyst is fixed in the middle of the reaction device by quartz wool; And / or, the preparation method further comprises: after the reaction is completed, condensing the obtained product by a condensation device.

9. A use of a metal carrier catalyst in catalyzing the reaction of monosilane and dimethylamine to prepare tri(dimethylamino)silane, the metal carrier catalyst comprising metal nanoparticles and a catalyst carrier supporting the metal nanoparticles, the metal nanoparticles comprising any one or more combinations of Pd, Pt, Au, Ni, Co, Ru, Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, Pt-Au, the catalyst carrier comprising any one or more combinations of MgO, SiO2, TiO2, C, Al2O3, ZrO2, CeO2.

10. The use according to claim 9, characterized in that: The metal nanoparticles include any one or more combinations of Pd-Fe, Pt-Fe, Pt-Co, Pd-Au, and Pt-Au; and / or, the content of metal nanoparticles in the metal carrier catalyst is 0.5 to 5 wt%; and / or, the average particle size of the metal nanoparticles is 0.5 nm to 10 nm; And / or, the catalyst carrier has a porous structure, and the specific surface area of ​​the catalyst carrier is 10-300m 2 / g, pore size is 20nm-200nm.

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