Catalyst for synthesizing organosilane as well as preparation method and application thereof

Abstract

The invention provides a catalyst for synthesizing organosilane, a preparation method of the catalyst and a method for synthesizing organosilane by adopting the catalyst. The catalyst is a particle with a core-shell structure and is expressed as M / Fe3O4 (at) shell, metal M is selected from one of Pd, Pt, Ru, Rh and Ir, the core structure is Fe3O4 magnetic particles, and the shell structure is SiO2 or TiO2. According to the present invention, the catalyst has characteristics of easily available raw materials and high catalysis efficiency, can efficiently catalyze the reaction of silane and olefin to synthesize organosilane, and can be repeatedly utilized through simple magnetic separation after the reaction is completed so as to reduce the metal residue.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical industry and material synthesis, in particular to a catalyst for synthesizing organosilanes, a preparation method of the catalyst, and the use of the catalyst in synthesizing organosilanes. BACKGROUND

[0002] Organosilanes are the core basic raw materials of the organosilicon industry, and their product system covers key fields such as aerospace-grade high-temperature-resistant silicone resins, functional coating materials (such as glass surface hydrophobic treatment agents), semiconductor packaging dielectric materials, and organic-inorganic composite interface coupling agents. The current industrial production system mainly relies on the Rochow method. Although this process has the advantages of raw material economy and mass production, it still has obvious technical bottlenecks: ① Insufficient reaction selectivity leads to the coexistence of multiple products (such as methyltrichlorosilane and dimethyldichlorosilane), which requires high energy consumption for rectification separation; ② High temperature and high pressure reaction conditions (250-350℃) accelerate equipment corrosion, significantly increasing maintenance costs; ③ Poor adaptability of alkyl chain length, with short-chain methyl systems accounting for more than 90% of production capacity, and the synthesis efficiency of long-chain alkyl products decaying exponentially; ④ When the byproduct hydrogen chloride recovery system is imperfect, it can easily cause pipeline corrosion and acid gas emission problems. The Grignard reagent method is limited by double constraints: reagent synthesis requires strict temperature control (0-5℃) and inert gas protection, and the solvent system (such as tetrahydrofuran) has a risk of explosion, which significantly increases the cost of safety control in large-scale production, limiting its industrial application. Another synthesis method is the hydrosilylation reaction of olefins and silanes, which generally uses noble metals as catalysts. It is difficult to recover the catalyst in general production, and the cost of noble metal catalysts is high, which increases the production cost. In addition, the residue of noble metals can easily affect the application in the downstream material field.

[0003] The existing technology has the problems of high cost, low efficiency, and large pollution. Developing a new production process that is more efficient and more environmentally friendly is the key to industry upgrading. It is necessary to improve the performance of the catalyst, optimize the production process, and establish a recycling system to improve efficiency while reducing resource waste and environmental pollution. SUMMARY

[0004] In view of the problems existing in the prior art, the present application provides a catalyst for synthesizing organosilanes, a preparation method of the catalyst, and the use of the catalyst in synthesizing organosilanes. Compared with the existing method and existing catalyst, the cost is lower, the catalyst separation is easier, and the residue is less.

[0005] TECHNICAL SCHEME

[0006] According to one aspect of the present application, one object of the present application is to provide a catalyst for synthesizing organosilane, which is a particle having a core-shell structure, denoted as M / Fe3O4@shell, wherein the metal M is selected from one of Pd, Pt, Ru, Rh and Ir, wherein the core structure is a Fe3O4 magnetic particle, and the shell structure shell is SiO2 or TiO2.

[0007] Preferably, the mass ratio of the shell structure shell to the Fe3O4 magnetic particle is 1:10 to 1:1.

[0008] Preferably, the mass ratio of the metal M to the core-shell material is 1:10 to 1:200.

[0009] Preferably, the average particle size of the Fe3O4 magnetic particle is 10 to 80 nm.

[0010] Preferably, the average thickness of the shell structure shell is 2 to 30 nm.

[0011] Preferably, the metal M is enriched on the surface of the catalyst particle.

[0012] According to another aspect of the present application, the present application provides a method for preparing the catalyst for synthesizing organosilane, which comprises the following steps:

[0013] 1. After mixing iron oleate with a solvent and oleic acid, heating to 320°C for 30 min, the product is washed with 3 times the mass of ethanol three times to obtain a nano-magnetic core (Fe3O4 nanoparticles).

[0014] 2. The nano-magnetic core prepared in step 1 is dispersed in a mixed solvent of ethanol and deionized water, concentrated ammonia is added, then an inert material precursor is added, stirred for 3-12 h, then washed with a mixed solution of ethanol and deionized water three times, and then the magnetic core-shell material is magnetically separated.

[0015] 3. The core-shell material prepared in step 2 above is dispersed in a solvent, an aqueous solution of a metal precursor is added to the above mixture, then a reducing agent is added under stirring, and stirred for 5 to 30 h, and then the catalyst is obtained after washing.

[0016] The solvent in step 1 is hexadecene, octadecene, eicosene, octyl ether, trioctylamine, etc.

[0017] The mass ratio of iron oleate to solvent in step 1 is 1:3 to 1:10.

[0018] The mass ratio of iron oleate to oleic acid in step 1 is 1:1 to 1:5.

[0019] In step 2, the mass ratio of the mixed solvent to the nanomagnetic core is 100:5 to 100:20.

[0020] The mass ratio of ethanol to water in step 2 is 1:1 to 5:1.

[0021] The concentrated ammonia water in step 2 is ammonia water with a mass percentage concentration of 25%.

[0022] The mass ratio of the concentrated ammonia water to the nanomagnetic core in step 2 is 1:1 to 1:5.

[0023] The inert material precursor in step 2 is one or more of tetraethyl orthosilicate and tetrabutyl titanate.

[0024] In step 2, the mass ratio of the inert material precursor to the nanomagnetic core is 1:10 to 1:1.

[0025] The solvent in step 3 is a mixture of ethanol and water.

[0026] The mass ratio of ethanol to water in step 3 is 1:1 to 5:1.

[0027] The metal precursor in step 3 is a chloride or nitrate of Pd, Pt, Ru, Rh, Ir, etc., such as one or more of palladium chloride, rhenium chloride, chloroplatinic acid and ruthenium chloride.

[0028] The mass percentage concentration of the aqueous solution of the metal precursor in step 3 is 5% to 20%.

[0029] The mass ratio of the metal precursor to the core-shell material in step 3 is 1:10 to 1:100.

[0030] The reducing agent in step 3 is selected from one or a mixture of formaldehyde, hydrazine hydrate, sodium borohydride, and sodium formate.

[0031] In step 3, the molar ratio of the reducing agent to the metal precursor is 5:1 to 20:1.

[0032] According to another aspect of the present invention, the present invention provides use of the catalyst for synthesizing organosilane in catalytic synthesis of organosilane.

[0033] According to another aspect of the present invention, the present invention provides a method for synthesizing organosilane using the above catalyst, wherein the method is selected from one of the following methods:

[0034] Method 1: Silane and olefin are mixed separately through a plunger pump through a mixer and then pumped into a continuous reactor. The mixture of olefin and catalyst is pumped into a continuous reactor through another plunger pump and further mixed with the mixture of silane and olefin. The mixture reacts under heating and then is stored in a storage tank after cooling. The catalyst and product are separated in a container with a strong magnet at the bottom.

[0035] or

[0036] Method 2: Add silane and olefin into a reactor, add a catalyst, stir the mixture, heat it and react, cool it after the reaction is completed to obtain the product, and separate the catalyst and product in a container with a strong magnet at the bottom.

[0037] The mixer in method 1 includes but is not limited to a static mixer, a jet mixer, a dynamic mixer, a centrifugal mixer, a continuous stirred tank, etc.

[0038] The continuous reactor described in method 1 is a microchannel continuous reactor, a dynamic tubular reactor, a loop reactor, a continuous stirred tank reactor, etc.

[0039] The silane in method 1 is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, isopropyldichlorosilane, dichlorodihydrosilane, dimethylsilane, diethylsilane, and dipropylsilane.

[0040] More preferably, the silane is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, dichlorodihydrosilane, and dimethylsilane.

[0041] The olefin in method 1 is selected from 1,3-butadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene.

[0042] More preferably, the olefin is selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, and 1,8-nonadiene.

[0043] The total reaction molar ratio of silane to olefin in method 1 is 1:2 to 1:10, preferably 1:2-1:8.

[0044] The mass ratio of the catalyst to the olefin in method 1 is 1:10000 to 1:100, preferably 1:10000 to 1:500.

[0045] The molar ratio of silane to olefin in the mixing device of method 1 is 1:1-1:8, preferably 1:1-1:4.

[0046] The reaction temperature in method 1 is 40-150° C. and the pressure is 0.1-2.0 MPa, preferably 50-120° C. and 0.1-1.0 MPa.

[0047] The reaction time in the continuous reactor in method 1 is 5s-20min, preferably 10s-10min, and more preferably 30s-5min.

[0048] The silane in method 2 is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, isopropyldichlorosilane, dichlorodihydrosilane, dimethylsilane, diethylsilane, and dipropylsilane.

[0049] More preferably, the silane is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, dichlorodihydrosilane, and dimethylsilane.

[0050] The olefin in the second method is selected from 1,3-butadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene.

[0051] More preferably, the olefin is selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, and 1,8-nonadiene.

[0052] The molar ratio of the silane to the olefin in the second method is 1:2 to 1:10, preferably 1:2 to 1:8.

[0053] The mass ratio of the catalyst to the olefin in the second method is 1:10000 to 1:100, preferably 1:10000 to 1:500.

[0054] The reaction temperature in the reaction apparatus in method 2 is 40-150° C. and the pressure is 0.1-2.0 MPa, preferably 50-120° C. and 0.1-1.0 MPa.

[0055] The reaction time in the reaction apparatus in method 2 is 10-180 min, preferably 10-80 min, more preferably 10-60 min.

[0056] Beneficial effects

[0057] The catalyst provided by the present invention has readily available raw materials and high catalytic efficiency, can efficiently catalyze the reaction of silane and olefin to synthesize organosilane, and can be reused after simple magnetic separation after the reaction is completed, thereby reducing metal residue. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0059] Figure 1 The SEM (a) and TEM (b) images of the core-shell material obtained in step 2 of Example 1 and the TEM image of the catalyst (c) obtained in step 3 show that the particles are evenly distributed.

[0060] Figure 2 The XRD pattern of the core-shell material obtained in step 2 and the catalyst obtained in step 3 in Example 1 shows that the phase of iron in the obtained material is ferroferric oxide, and no XRD diffraction peaks appear due to the uniform distribution of the shell material and the metal particles.

[0061] Figure 3 The following is the NMR spectrum of the product obtained in Example 1. DETAILED DESCRIPTION

[0062] The present invention will be described in detail below. Before describing, it should be understood that the terms used in this specification and the appended claims should not be interpreted as limited to the general meaning and dictionary meaning, but should be interpreted according to the meaning and concept corresponding to the technical aspects of the present invention on the basis of the principle that allows the inventor to appropriately define the terms for the best interpretation. Therefore, the descriptions presented here are merely preferred examples for illustrative purposes and are not intended to limit the scope of the present invention. It should be understood that other equivalents or improvements can be obtained therefrom without departing from the spirit and scope of the present invention.

[0063] As used herein, the terms "comprises," "includes," "has," "contains" or any other similar terms are open conjunctions that are intended to cover non-exclusive inclusions. For example, a composition or article containing multiple elements is not limited to the elements listed herein, but may also include other elements that are not explicitly listed but are generally inherent to the composition or article. In addition, unless expressly stated to the contrary, the term "or" refers to an inclusive "or" rather than an exclusive "or." For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist). In addition, as used herein, the terms "comprises," "includes," "has," and "contains" should be interpreted as specifically disclosed and simultaneously cover closed or semi-closed conjunctions such as "consisting of" and "consisting essentially of."

[0064] Throughout this document, all features or conditions defined as numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered to encompass and specifically disclose all possible subranges and individual values ​​within those ranges, particularly integer values. For example, a description of a range "1 to 8" should be considered to specifically disclose all possible subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so forth, particularly those defined by all integer values, and should be considered to specifically disclose individual values ​​within those ranges such as 1, 2, 3, 4, 5, 6, 7, and 8. Unless otherwise indicated, the foregoing interpretation applies to all of the present disclosure, regardless of whether the ranges are comprehensive or not.

[0065] If a quantity or other value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that all ranges consisting of any upper limit or preferred value of the range and any lower limit or preferred value of the range have been specifically disclosed herein, regardless of whether these ranges are disclosed separately. In addition, when a numerical range is mentioned herein, unless otherwise specified, the range should include its endpoints and all integers and fractions within the range.

[0066] In this document, numerical values ​​should be understood to have the accuracy of the number of significant digits of the numerical value, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0067] In the catalyst preparation method according to the present invention, the solvent in step 1 is selected from hexadecene, octadecene, eicosene, octyl ether, trioctylamine, and the like. Because this step needs to be performed at a relatively high temperature, it is necessary to perform it in a solvent with a high boiling point. The above-mentioned solvents used in the present invention have the dual functions of high boiling point, low polarity, stability, and high temperature resistance, making them the optimal solvents for performing this step. If the molecular chain of the organic solvent is too short, the boiling point is not high, which is not conducive to the performance of this step.

[0068] Meanwhile, in the preparation method of the catalyst according to the present invention, oleic acid is used as one of the reactants in step 1. Here, oleic acid can be used as a ligand to cover the surface of iron oleate, thereby improving its thermal stability and making the decomposition process more controllable.

[0069] In addition, unless otherwise specified, the reagents and solvents disclosed below were purchased from Sinopharm Chemical Reagent Co., Ltd., XRD was measured using a D8 Advance (Bruker, Germany) X-ray diffractometer (XRD), TEM was measured on a Hitachi H-7650 transmission electron microscope, and SEM was measured on a Hitachi S-4800 scanning electron microscope.

[0070] The products were analyzed using gas chromatography (GC). Qualitative analysis of low-boiling-point products was performed by GC-MS and comparison with the GC retention times of standards, confirming that the raw material involved in the reaction was methyl methacrylate. Low-boiling-point substances were quantitatively determined using a Shimadzu GC2020 gas chromatograph, and quantitative analysis was performed by comparing retention times and peak areas with those of standards.

[0071] The following examples are merely examples of embodiments of the present invention and do not constitute any limitation thereto. Those skilled in the art will appreciate that modifications without departing from the spirit and scope of the present invention fall within the scope of protection of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are commercially available products.

[0072] Example 1

[0073] 1) Add 360 g of iron oleate complex, 2 L of octadecene, and 57 g of oleic acid to a four-necked flask, rapidly heat to 320°C, react for 3 h, then stop heating. After cooling to room temperature, add 500 ml of ethanol for precipitation, and magnetically separate. Wash three times to obtain Fe3O4 nanoparticles.

[0074] 2) Take 10g of Fe3O4 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (80mL of ethanol + 20mL of deionized water), add 5mL of concentrated ammonia (28wt%), and then add 1mL of tetraethyl orthosilicate. After continuing to stir for 6h, wash three times with a mixed solution of ethanol and deionized water, and magnetic separation is used to obtain Fe3O4@SiO2 nanoparticles.

[0075] 3) Take 10g of Fe3O4@SiO2 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (50mL of ethanol + 50mL of deionized water), add 50mL of 0.1M H2PtCl6 solution, and then continue to add 2% sodium borohydride solution dropwise. After stirring for 2h, wash it three times with a mixed solution of ethanol and deionized water, and magnetic separation is performed to obtain Pt / Fe3O4@SiO2 catalyst.

[0076] Figure 1 The SEM (a) and TEM (b) images of the core-shell material obtained in step 2 of Example 1 and the TEM image of the catalyst (c) obtained in step 3 are shown in the figure. The photos show that the particles are evenly distributed.

[0077] Figure 2 The XRD diagram of the core-shell material obtained in step 2 and the catalyst obtained in step 3 of Example 1 is shown in the figure, which shows that the phase of iron in the obtained material is ferroferric oxide, and no XRD diffraction peaks appear due to the uniform distribution of the shell material and the metal particles.

[0078] 1g of the catalyst prepared in the present embodiment was added to 300mL1,5-hexadiene and stirred for standby use. In a microchannel reactor (liquid holding volume of 54ml), the above-mentioned 1,5-hexadiene catalyst mixture and methyldichlorosilane were pumped in respectively, and the reaction was carried out at 60°C. The feed rates of the two reactants were 5.6mL / min (1,5-hexadiene) and 1.7mL / min (methyldichlorosilane), and the residence time was 7.4min. After the material reached a stable state, the reaction product was collected. The yield of product 5-hexenylmethyldichlorosilane was 94%. After the mixture was poured into a beaker, a strong magnet was used to magnetically separate the catalyst and recover the recovered 5-hexenylmethyldichlorosilane, and the yield was 92% of 5-hexenylmethyldichlorosilane used continuously for 5 times. Figure 3 This is the NMR spectrum of the product obtained in this example.

[0079] Example 2

[0080] 1) Add 360 g of iron oleate complex, 2 L of octadecene, and 57 g of oleic acid to a four-necked flask, rapidly heat to 320°C, react for 3 h, then stop heating. After cooling to room temperature, add 500 ml of ethanol for precipitation, and magnetically separate. Wash three times to obtain Fe3O4 nanoparticles.

[0081] 2) Take 10g of Fe3O4 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (80mL of ethanol + 20mL of deionized water), add 5mL of concentrated ammonia (28wt%), and then add 1.5mL of tetrabutyl titanate. After continuing to stir for 6h, wash the mixture three times with a mixed solution of ethanol and deionized water, and magnetic separation is used to obtain Fe3O4@TiO2 nanoparticles.

[0082] 3) Take 10g of Fe3O4@TiO2 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (50mL of ethanol + 50mL of deionized water), add 50mL of 0.1M H2PtCl6 solution, and then continue to add 2% sodium borohydride solution dropwise. After stirring for 2h, wash it three times with a mixed solution of ethanol and deionized water, and magnetic separation is performed to obtain Pt / Fe3O4@TiO2 catalyst.

[0083] 30 L of 1,7-octadiene was added to a 100 L reactor, followed by 5 kg of dichlorosilane and 5 g of the catalyst. After mixing thoroughly, the mixture was heated to 80°C for 6 hours before cooling. Gas chromatography revealed a 93% yield of di(7-octenyl)dichlorosilane. The mixture was poured into a beaker, and the catalyst was magnetically separated and recovered using a strong magnet. After five consecutive uses, the yield of di(7-octenyl)dichlorosilane was 90%.

[0084] Example 3

[0085] 1) Add 360 g of iron oleate complex, 2 L of octadecene, and 57 g of oleic acid to a four-necked flask, rapidly heat to 320°C, react for 3 h, then stop heating. After cooling to room temperature, add 500 ml of ethanol for precipitation, and magnetically separate. Wash three times to obtain Fe3O4 nanoparticles.

[0086] 2) Take 10g of Fe3O4 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (80mL of ethanol + 20mL of deionized water), add 5mL of concentrated ammonia (28wt%), and then add 1.5mL of tetrabutyl titanate. After continuing to stir for 6h, wash the mixture three times with a mixed solution of ethanol and deionized water, and magnetic separation is used to obtain Fe3O4@TiO2 nanoparticles.

[0087] 3) Take 10g of Fe3O4@TiO2 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (50mL of ethanol + 50mL of deionized water), add 50mL of 0.1M HAuCl4 solution, and then add 2% sodium borohydride solution dropwise. After stirring for 2h, wash the mixture three times with a mixed solution of ethanol and deionized water, and magnetic separation is performed to obtain the Au / Fe3O4@TiO2 catalyst.

[0088] 1g of the catalyst in the embodiment was added to 300mL of 1,5-hexadiene and stirred for use. The above-mentioned 1,5-hexadiene catalyst mixture and methyldichlorosilane were pumped into a microchannel reactor (liquid holding volume of 54ml) and reacted at 60°C. The feed rates of the two reactants were 5.6mL / min (1,5-hexadiene) and 1.7mL / min (methyldichlorosilane), respectively, and the residence time was 7.4min. After the material reached a steady state, the reaction product was collected. The yield of the product 5-hexenylmethyldichlorosilane was 94%. After the mixture was poured into a beaker, a strong magnet was used to magnetically separate the catalyst and recover it. The yield of 5-hexenylmethyldichlorosilane was 92% after five consecutive uses.

[0089] Example 4

[0090] 1) Add 360 g of iron oleate complex, 2 L of octadecene, and 57 g of oleic acid to a four-necked flask, rapidly heat to 320°C, react for 3 h, then stop heating. After cooling to room temperature, add 500 ml of ethanol for precipitation, and magnetically separate. Wash three times to obtain Fe3O4 nanoparticles.

[0091] 2) Take 10g Fe3O4 nanoparticles, stirring and dispersing in 100 mL of a mixed solution of ethanol and deionized water (80 mL of ethanol + 20 mL of deionized water), after adding 5 mL of concentrated ammonia water (28 wt%), adding 1.5 mL of tetraethyl orthosilicate, continuing to stir for 6 h, washing with a mixed solution of ethanol and deionized water three times, and magnetically separating to obtain Fe3O4@SiO2 nanoparticles.

[0092] 3) Take 10g Fe3O4@SiO2 nanoparticles, stirring and dispersing in 100 mL of a mixed solution of ethanol and deionized water (50 mL of ethanol + 50 mL of deionized water), after adding 50 mL of 0.1M PdCl2 solution, continuing to add 2% sodium borohydride solution dropwise, continuing to stir for 2 h, washing with a mixed solution of ethanol and deionized water three times, and magnetically separating to obtain Pd / Fe3O4@SiO2 catalyst.

[0093] In 300 mL of 1,7-octadiene, 1 g of the catalyst in the example was added and stirred uniformly for standby. In the microchannel reactor (liquid holding volume of 54 ml), the above-mentioned 1,7-octadiene catalyst mixture was pumped in, and dichlorodihydrogen silicon was introduced into the reactor through a mass flow controller, and the reaction was carried out at 90°C, the feeding speed of the two reaction materials was 5.6 mL / min (1,7-octadiene) and 1.0 g / min (dichlorodihydrogen silicon) respectively, and the residence time was 9.6 min. When the material reached a stable state, the reaction product was collected, and the yield of the product bis(7-octenyl) dichlorosilane was 96%. After the mixture was poured into a beaker and the catalyst was magnetically separated and recovered, the yield of bis(7-octenyl) dichlorosilane was 95% for continuous use for 5 times.

[0094] Example 5

[0095] 1) In a four-necked flask, 360 g of iron oleate complex, 2 L of octadecene and 57 g of oleic acid were added, and the temperature was quickly raised to 320°C and reacted for 3 h, then the heating was stopped, and after the temperature was lowered to room temperature, 500 ml of ethanol was added for precipitation, and the Fe3O4 magnetic nanoparticles were magnetically separated and washed three times.

[0096] 2) Take 10g Fe3O4 nanoparticles, stirring and dispersing in 100 mL of a mixed solution of ethanol and deionized water (80 mL of ethanol + 20 mL of deionized water), after adding 5 mL of concentrated ammonia water (28 wt%), adding 1.5 mL of tetraethyl orthosilicate, continuing to stir for 6 h, washing with a mixed solution of ethanol and deionized water three times, and magnetically separating to obtain Fe3O4@SiO2 nanoparticles.

[0097] 3) Take 10g of Fe3O4@SiO2 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (50mL of ethanol + 50mL of deionized water), add 50mL of 0.1M RuCl3 solution, and then add 2% sodium borohydride solution dropwise. After stirring for 2h, wash the mixture three times with a mixed solution of ethanol and deionized water, and magnetic separation is performed to obtain the Ru / Fe3O4@SiO2 catalyst.

[0098] 30 L of 1,7-octadiene was added to a 100 L reactor, followed by 3 kg of dimethylsilane and 5 g of the catalyst under stirring. After mixing thoroughly, the mixture was heated to 80°C and held for 6 hours before cooling. Gas chromatography revealed a 93% yield of di(7-octenyl)dimethylsilane. The mixture was poured into a beaker, and the catalyst was magnetically separated and recovered using a strong magnet. After five consecutive uses, the yield of di(7-octenyl)dimethylsilane was 90%.

[0099] Example 6

[0100] 1) Add 360 g of iron oleate complex, 2 L of octadecene, and 57 g of oleic acid to a four-necked flask, rapidly heat to 320°C, react for 3 h, then stop heating. After cooling to room temperature, add 500 ml of ethanol for precipitation, and magnetically separate. Wash three times to obtain Fe3O4 nanoparticles.

[0101] 2) Take 10g of Fe3O4 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (80mL of ethanol + 20mL of deionized water), add 5mL of concentrated ammonia (28wt%), and then add 1.5mL of tetraethyl orthosilicate. After continuing to stir for 6h, wash three times with a mixed solution of ethanol and deionized water, and magnetic separation is used to obtain Fe3O4@SiO2 nanoparticles.

[0102] 3) Take 10g of Fe3O4@SiO2 nanoparticles, stir and disperse them in a mixed solution of 100mL of ethanol and deionized water (50mL of ethanol + 50mL of deionized water), add 50mL of 0.1M H2PtCl6 solution, and then continue to add 5% formaldehyde solution dropwise. After stirring for 2h, wash it three times with a mixed solution of ethanol and deionized water, and magnetic separation is performed to obtain Pt / Fe3O4@SiO2 catalyst.

[0103] A 100-L reactor was charged with 30 L of 1,5-hexadiene and stirred with 2.6 kg of dimethylsilane. Then, 5 g of the above-mentioned catalyst was added with stirring. After mixing thoroughly, the mixture was heated to 80°C and held for 6 hours. The temperature was then lowered. Gas chromatography revealed a 93% yield of di(5-hexenyl)dimethylsilane. The mixture was poured into a beaker and the catalyst was magnetically separated and recovered using a strong magnet. After five consecutive uses, the yield of di(5-hexenyl)dimethylsilane was 90%.

[0104] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A catalyst for synthesizing organosilanes, the catalyst being particles having a core-shell structure, expressed as M / Fe3O4@shell, wherein the metal M is selected from one of Pd, Pt, Ru, Rh and Ir, wherein the core structure is Fe3O4 magnetic particles, and the shell structure is SiO2 or TiO2.

2. The catalyst according to claim 1, characterized in that Preferably, the mass ratio of the shell structure to the Fe3O4 magnetic particles is 1:10 to 1:1; Preferably, the mass ratio of the metal M to the core-shell material is 1:10 to 1:200; Preferably, the average particle size of the Fe3O4 magnetic particles is 10 to 80 nm; Preferably, the average thickness of the shell structure is 2 to 30 nm; Preferably, the metal M is enriched on the surface of the catalyst particles.

3. The method for preparing the catalyst according to claim 1 or 2, comprising the steps of: 1) mixing iron oleate with a solvent and oleic acid, heating the mixture to 320° C. and reacting the mixture for 30 min, and washing the mixture three times with ethanol of a mass equal to 3 times the mass of the mixture to obtain nanomagnetic cores (Fe 3 O 4 nanoparticles); 2) dispersing the nanomagnetic core prepared in step 1 in a mixed solvent of ethanol and deionized water, adding concentrated ammonia and then the inert material precursor, stirring for 3-12 hours, and then washing three times with a mixed solution of ethanol and deionized water, and then magnetically separating the magnetically separable core-shell material; 3) The core-shell material prepared in step 2 is dispersed in a solvent, an aqueous solution of a metal precursor is added to the mixture, a reducing agent is added under stirring, and the reaction is stirred for 5 to 30 hours, followed by washing to obtain a catalyst.

4. The preparation method according to claim 3, characterized in that Preferably, the solvent in step 1 is hexadecene, octadecene, eicosene, octyl ether, trioctylamine, etc.; Preferably, in step 1, the mass ratio of iron oleate to solvent is 1:3 to 1:10; Preferably, in step 1, the mass ratio of iron oleate to oleic acid is 1:1 to 1:

5.

5. The preparation method according to claim 3, characterized in that Preferably, in step 2, the mass ratio of the mixed solvent to the nanomagnetic core is 100:5 to 100:20; Preferably, the mass ratio of ethanol to water in step 2 is 1:1 to 5:1; Preferably, the concentrated ammonia water in step 2 is ammonia water with a mass percentage concentration of 25%; Preferably, the mass ratio of the concentrated ammonia water to the nanomagnetic core in step 2 is 1:1 to 1:5; Preferably, the inert material precursor in step 2 is one or more of tetraethyl orthosilicate and tetrabutyl titanate; Preferably, in step 2, the mass ratio of the inert material precursor to the nanomagnetic core is 1:10 to 1:

1.

6. The preparation method according to claim 3, characterized in that Preferably, the solvent in step 3 is a mixture of ethanol and water; Preferably, the mass ratio of ethanol to water in step 3 is 1:1 to 5:1; Preferably, the metal precursor in step 3 is a chloride or nitrate of Pd, Pt, Ru, Rh, Ir, etc., such as one or more of palladium chloride, rhenium chloride, chloroplatinic acid, and ruthenium chloride; Preferably, the mass percentage concentration of the aqueous solution of the metal precursor in step 3 is 5% to 20%; Preferably, in step 3, the mass ratio of the metal precursor to the core-shell material is 1:10 to 1:100; Preferably, the reducing agent in step 3 is selected from one or a mixture of formaldehyde, hydrazine hydrate, sodium borohydride, and sodium formate; Preferably, in step 3, the molar ratio of the reducing agent to the metal precursor is 5:1 to 20:

1.

7. Use of the catalyst according to claim 1 or 2 in the catalytic synthesis of organosilane.

8. A method for synthesizing organosilane using the catalyst according to claim 1 or 2, wherein the method is selected from one of the following methods: Method 1: Silane and olefin are mixed separately through a plunger pump through a mixer and then pumped into a continuous reactor. The mixture of olefin and catalyst is pumped into a continuous reactor through another plunger pump and further mixed with the mixture of silane and olefin. The mixture reacts under heating and then is cooled and stored in a storage tank. The catalyst and product are separated in a container with a strong magnet at the bottom. or Method 2: Add silane and olefin into a reactor, add a catalyst, stir the mixture, heat it and react, cool it after the reaction is completed to obtain the product, and separate the catalyst and product in a container with a strong magnet at the bottom.

9. The method according to claim 8, characterized in that The mixer in method 1 includes but is not limited to a static mixer, a jet mixer, a dynamic mixer, a centrifugal mixer, a continuous stirred tank, etc.; The continuous reactor in method 1 is a microchannel continuous reactor, a dynamic tubular reactor, a loop reactor, a continuous stirred tank reactor, etc.; The silane in method 1 is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, isopropyldichlorosilane, dichlorodihydrosilane, dimethylsilane, diethylsilane, and dipropylsilane; More preferably, the silane is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, dichlorodihydrosilane, and dimethylsilane; The olefin in method 1 is selected from 1,3-butadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene; More preferably, the olefin is selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, and 1,8-nonadiene; The total reaction molar ratio of silane to olefin in method 1 is 1:2 to 1:10, preferably 1:2-1:8; The mass ratio of the catalyst to the olefin in method 1 is 1:10000 to 1:100, preferably 1:10000 to 1:500; The molar ratio of silane to olefin in the mixing device of method 1 is 1:1-1:8, preferably 1:1-1:4; The reaction temperature in method 1 is 40-150°C and the pressure is 0.1-2.0 MPa, preferably 50-120°C and 0.1-1.0 MPa; The reaction time in the continuous reactor in method 1 is 5s-20min, preferably 10s-10min, and more preferably 30s-5min.

10. The method according to claim 8, characterized in that The silane in method 2 is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane, isopropyldichlorosilane, dichlorodihydrosilane, dimethylsilane, diethylsilane, and dipropylsilane; More preferably, the silane is selected from methyldichlorosilane, ethyldichlorosilane, propyldichlorosilane, dichlorodihydrosilane, and dimethylsilane; The olefin in method 2 is selected from 1,3-butadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene; More preferably, the olefin is selected from 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, and 1,8-nonadiene; The molar ratio of the silane to the olefin in the second method is 1:2 to 1:10, preferably 1:2 to 1:8; The mass ratio of the catalyst to the olefin in method 2 is 1:10000 to 1:100, preferably 1:10000 to 1:500; The reaction temperature in the reaction apparatus of method 2 is 40-150°C and the pressure is 0.1-2.0 MPa, preferably 50-120°C and 0.1-1.0 MPa; The reaction time in the reaction apparatus in method 2 is 10-180 min, preferably 10-80 min, more preferably 10-60 min.

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