CN102343278A - Method for preparing heterogeneous catalyst used for epoxy cyclohexane and application thereof - Google Patents
Method for preparing heterogeneous catalyst used for epoxy cyclohexane and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a heterogeneous catalyst, and particularly relates to a preparation method of a heterogeneous catalyst used for epoxy cyclohexane and an application thereof. The catalyst takes SiO2-based mesopore molecular sieve as a carrier, the method comprises the following steps: forming a metal organic complex by organic metal salt and a complex in advance, then combing with an ionic liquid phase, highly dispersed and loaded on a tunnel surface of a porous SiO2 material by a grafting method. So that the catalyst has good catalysis performance in the application of cyclohexene on catalytic oxidation preparation of epoxy cyclohexane, in addition, the catalyst has the characteristics of controllable structure, good stability, easy separation, easy recovery and the like.
Description
Technical field:
The invention belongs to fine chemistry industry and catalyst preparation technical field, be specifically related to the preparation method that a kind of cyclohexene catalytic oxidation prepares the heterogeneous catalysis of 7-oxa-bicyclo[4.1.0.
Background technology:
7-oxa-bicyclo[4.1.0 is a kind of important fine chemical material and organic intermediate; Owing to have active epoxy radicals on its molecular structure; In industrial and agricultural production, can generate the chemical products of high added value with substance reaction such as ammonia, amine, phenol, alcohol and carboxylic acid, also be the very strong organic solvent of a kind of dissolubility simultaneously.Along with the exploitation successively of 7-oxa-bicyclo[4.1.0 purposes, in recent years its demand is also increased day by day.
With the cyclohexene is raw material, and preparing 7-oxa-bicyclo[4.1.0 through catalytic oxidation is present important a kind of process route.Can be divided into homogeneous phase method and heterogeneous method according to employed catalyst difference.Wherein the homogeneous phase method has the reaction condition gentleness, catalyst is active high; Characteristics such as epoxidation reaction is effective; But because mostly employed homogeneous catalyst is transistion metal compound; Cost an arm and a leg; And after reaction finishes, still be dissolved in the reaction system, cause catalyst separation and reclaim very difficulty.To these shortcomings; Thereby people are with immobilized heterogeneous (heterogeneous) catalyst of developing of these homogeneous catalysts; And prepare the solid catalyst that is insoluble to reaction system, overcome homogeneous catalyst and finished difficulty is separated and reclaimed in the back with reaction system drawback in reaction.Therefore this heterogeneous catalysis gets more and more people's extensive concerning.
The carrier of immobilized homogeneous catalyst has inorganic porous SiO usually
2, porous material such as aluminium oxide and organic polymer.Wherein, inorganic porous SiO
2It is one of the most frequently used carrier; Like titaniferous micro porous molecular sieves such as TS-1, Ti-Beta and Ti-MWW; In the catalysis cyclohexene prepares 7-oxa-bicyclo[4.1.0 reaction, show superior catalytic performance, but less duct size restrictions the extensive use of this type of catalyst.Subsequently, people adopt the bigger mesopore molecular sieve in aperture (M41S, SBA-15 and MSU-X etc.) as carrier, further preparing with multivalence attitude metal ion (Ti, Co, Mn and Fe etc.) are the heterogeneous catalysis in activated centre.Like people such as Corma (J.Chem.Soc.Chem.Commun.; 1994,147-148) adopt one-step method to prepare the Ti-MCM-41 catalyst, and Maschmeyer (Nature; 1995,378:159-162) wait the people to propose the mesoporous molecular sieve catalyst that grafting prepares titaniferous.These catalyst all show advantages of high catalytic activity in epoxidation reaction, (chemical journal .2003 61:202-207) has synthesized the Ti-SBA-15 catalyst through hydro-thermal method to domestic Zhao Dongyuan professor.But along with progressively going deep into of research, the co-ordination state that it is found that the very difficult control of these catalyst activated centre is so that have a strong impact on the catalytic performance of catalyst.In addition, the active component in these mesoporous molecular sieve catalysts (metal ion) comes off in course of reaction easily, causes the loss of noble metal.Simultaneously, metal ion is reunited under the certain reaction temperature easily, causes catalyst activity reduction.To these problems, we propose a kind of solid-loaded ionic-liquid catalyst that passes through in porous SiO
2The preparation method on duct surface, the formation homogeneous catalyst that at first the Ti activated centre of four-coordination combined with ionic liquid utilizes porous SiO
2The hydroxyl that the surface is abundant is loaded into its high dispersive in the porous material through grafting.So not only help keeping homogeneous catalyst high activity and high selectivity characteristics; And can overcome the problem of reuniting and run off easily in the metal active center in course of reaction; It is few to have simultaneously catalyst amount again, is prone to separate with reaction system and characteristics such as recycling.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method and application thereof that is used to prepare the heterogeneous catalysis of 7-oxa-bicyclo[4.1.0
1, be used to prepare the preparation method of the heterogeneous catalysis of 7-oxa-bicyclo[4.1.0, it is characterized in that step is following:
(1) with porous SiO
2Material naturally cooled to room temperature in drier after 120-150 ℃ of dry 3-5 hour, and airtight preservation; With 1,3-dialkylimidazolium salt or Fixanol are dissolved in CHCl
3, again with the porous SiO of drying
2Material is placed in one, and after stirring 12-24h under 50-80 ℃, filters, and uses CHCl
3Wash, obtain the sample A of solid-loaded ionic-liquid after the drying;
(2) with organic metal salt at 80-120 ℃ of following vacuum drying 1-3h, be dissolved in the CHCl that contains complexing agent after under nitrogen protection, naturally cooling to room temperature then
3In the organic solvent, after stirring 5-8 hour under 50-80 ℃, obtain solution B;
Used organic metal salt be two luxuriant titaniums, ferrocene,, cuprocene, cobaltocene or two luxuriant manganese;
Used complexing agent is triethanolamine, triethylamine, tripropyl amine (TPA) or tripropanol amine;
(3) sample A is placed above-mentioned B solution, after stirring 5-8 hour under 50-80 ℃, mixture is filtered, use CHCl
3Washing placed 50-80 ℃ of following vacuum drying 3-5 hour then, after 400-600 ℃ of calcining 3-6 hour, obtained solid catalyst after naturally cooling to room temperature.
Wherein, the load capacity of metal ion is porous SiO
2The 0.5wt%-10wt% of carrier quality, ion liquid load capacity is porous SiO
2The 1w%t-50wt% of carrier quality.
Wherein, 1, the substituted alkyl chain length of 3-dialkylimidazolium or Fixanol is the alkyl chain of C1 to C8, the anion of salt is fluorine, chlorine, bromine, iodine, fluoboric acid root, fluorophosphoric acid root, trifluoracetic acid root or fluoroform acid group.
Wherein, porous SiO
2Material is MCM-41, MCM-48, SBA-15 or SBA-16.
Said Application of Catalyst is characterized in that: with CHCl
3Be solvent, cyclohexene is a raw material, and reaction temperature is 20-80 ℃, and the mass ratio of catalyst and cyclohexene is 0.01-0.3: 1, react that the cyclohexene conversion ratio is more than 70% after 6 hours, and epoxide ring hexene selectivity is more than 90%.
Prepare the 7-oxa-bicyclo[4.1.0 catalyst with present existing cyclohexene catalytic oxidation and compare, the present invention has following characteristics:
(1) this catalyst combines ionic liquid, metallo-organic complex and porous material, provides a kind of cyclohexene catalytic oxidation to prepare the method for 7-oxa-bicyclo[4.1.0 heterogeneous catalyst.
(2) co-ordination state of metal active constituent is controlled in this catalyst, has kept the characteristics such as high activity and high selectivity of homogeneous catalyst.
(3) ionic liquid is immobilized in porous SiO through the chemical bonding mode
2In the carrier duct, not only stoped the reunion of metal active constituent, and avoided utilizing again in the process problem such as loss easily in course of reaction and catalyst recovery.
(4) this catalyst is solid granular, helps separating with reaction system after reaction finishes and reclaiming.
The specific embodiment
Embodiment 1
Take by weighing 0.5g chlorination 1-methyl-3-(the 3-trimethoxy is silica-based) propyl imidazole in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the MCM-41 that 150 ℃ of dryings obtained after 3 hours in whipping process, and with this mixed system 80 ℃ of following reflux 12 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the MCM-41 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 20wt% of MCM-41 carrier quality.
0.03g be dissolved in the 5ml CHCl that contains the 1.7ml triethylamine two luxuriant titaniums 120 ℃ of following vacuum drying 1 hour, naturally cool to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 8 hours under 50 ℃, obtain solution B.
Take by weighing sample A and place solution B, 50 ℃ were stirred down after 8 hours, and mixture is filtered, and used CHCl
3Washing places 80 ℃ of following vacuum drying 3 hours then, after 600 ℃ of calcinings 3 hours, obtains the Ti/MCM-41 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion titanium is the 0.5wt% of MCM-41 carrier quality.
Embodiment 2
Take by weighing 0.05g fluoboric acid 1-butyl-3-(the 3-trimethoxy is silica-based) propyl imidazole in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the MCM-48 that 120 ℃ of dryings obtained after 5 hours in whipping process, and with this mixed system 50 ℃ of following reflux 24 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the MCM-48 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 1wt% of MCM-48 carrier quality.
0.6g be dissolved in the 5ml CHCl that contains the 30ml triethanolamine ferrocene 80 ℃ of following vacuum drying 3 hours, naturally cools to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 5 hours under 80 ℃, obtain solution B.
Take by weighing sample A and place solution B, 80 ℃ were stirred down after 5 hours, and mixture is filtered, and used CHCl
3Washing places 50 ℃ of following vacuum drying 5 hours then, after 400 ℃ of calcinings 6 hours, obtains the Fe/MCM-48 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion iron is the 10wt% of MCM-48 carrier quality.
Embodiment 3
Take by weighing 0.7g and fluoridize 1-butyl-3-(the 3-trimethoxy is silica-based) propyl imidazole in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the SBA-15 that 130 ℃ of dryings obtained after 4 hours in whipping process, and with this mixed system 60 ℃ of following reflux 20 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the SBA-15 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 50wt% of SBA-15 carrier quality.
0.3g be dissolved in the 5ml CHCl that contains the 20ml tripropyl amine (TPA) ferrocene 100 ℃ of following vacuum drying 2 hours, naturally cools to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 7 hours under 60 ℃, obtain solution B.
Take by weighing sample A and place solution B, 60 ℃ were stirred down after 7 hours, and mixture is filtered, and used CHCl
3Washing places 60 ℃ of following vacuum drying 4 hours then, after 500 ℃ of calcinings 5 hours, obtains the Fe/SBA-15 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion iron is the 4wt% of SBA-15 carrier quality.
Embodiment 4
Take by weighing 0.5g trifluoracetic acid 1-octyl group-3-(the 3-trimethoxy is silica-based) propyl imidazole in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the SBA-15 that 150 ℃ of dryings obtained after 3 hours in whipping process, and with this mixed system 80 ℃ of following reflux 12 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the SBA-15 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 25wt% of SBA-15 carrier quality.
0.2g be dissolved in the 5ml CHCl that contains the 15ml tripropanol amine ferrocene 100 ℃ of following vacuum drying 2 hours, naturally cools to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 5 hours under 80 ℃, obtain solution B.
Take by weighing sample A and place solution B, 80 ℃ were stirred down after 5 hours, and mixture is filtered, and used CHCl
3Washing places 80 ℃ of following vacuum drying 3 hours then, after 600 ℃ of calcinings 3 hours, obtains the Fe/SBA-15 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion iron is the 2wt% of SBA-15 carrier quality.
Embodiment 5
Take by weighing 0.5g and fluoridize 1-methyl-3-(the 3-trimethoxy is silica-based) propyl group pyridine in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the SBA-16 that 120 ℃ of dryings obtained after 5 hours in whipping process, and with this mixed system 60 ℃ of following reflux 20 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the SBA-16 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 30wt% of SBA-16 carrier quality.
0.1g be dissolved in the 5ml CHCl that contains the 10ml triethylamine cobaltocene 80 ℃ of following vacuum drying 3 hours, naturally cools to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 5 hours under 80 ℃, obtain solution B.
Take by weighing sample A and place solution B, 50 ℃ were stirred down after 8 hours, and mixture is filtered, and used CHCl
3Washing places 80 ℃ of following vacuum drying 3 hours then, after 500 ℃ of calcinings 5 hours, obtains the Co/SBA-16 solid catalyst after naturally cooling to room temperature.The load capacity of ion cobalt is the 1wt% of SBA-16 carrier quality.
Embodiment 6
Take by weighing 0.5g trifluoro formic acid 1-butyl-3-(the 3-trimethoxy is silica-based) propyl imidazole in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the MCM-41 that 120 ℃ of dryings obtained after 5 hours in whipping process, and with this mixed system 50 ℃ of following reflux 24 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the MCM-41 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 20wt% of MCM-41 carrier quality.
0.03g be dissolved in the 5ml CHCl that contains the 3ml tripropanol amine two luxuriant manganese 100 ℃ of following vacuum drying 2 hours, naturally cool to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 8 hours under 50 ℃, obtain solution B.
Take by weighing sample A and place solution B, 60 ℃ were stirred down after 7 hours, and mixture is filtered, and used CHCl
3Washing places 60 ℃ of following vacuum drying 4 hours then, after 400 ℃ of calcinings 6 hours, obtains the Mn/MCM-41 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion manganese is the 0.5wt% of MCM-41 carrier quality.
Embodiment 7
Take by weighing 0.5g bromination 1-methyl-3-(the 3-trimethoxy is silica-based) propyl group pyridine in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the MCM-41 that 150 ℃ of dryings obtained after 3 hours in whipping process, and with this mixed system 80 ℃ of following reflux 12 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the MCM-41 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 15wt% of MCM-41 carrier quality.
0.5g be dissolved in the 5ml CHCl that contains the 35ml tripropyl amine (TPA) cobaltocene 100 ℃ of following vacuum drying 2 hours, naturally cools to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 5 hours under 80 ℃, obtain solution B.
Take by weighing sample A and place solution B, 60 ℃ were stirred down after 7 hours, and mixture is filtered, and used CHCl
3Washing places 80 ℃ of following vacuum drying 3 hours then, after 600 ℃ of calcinings 3 hours, obtains the Co/MCM-41 solid catalyst after naturally cooling to room temperature.The load capacity of ion cobalt is the 10wt% of MCM-41 carrier quality.
Embodiment 8
Take by weighing 0.06g iodate 1-methyl-3-(the 3-trimethoxy is silica-based) propyl group pyridine in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the MCM-48 that 130 ℃ of dryings obtained after 4 hours in whipping process, and with this mixed system 70 ℃ of following reflux 16 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the MCM-48 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 1wt% of MCM-48 carrier quality.
0.2g be dissolved in the 5ml CHCl that contains the 10ml tripropanol amine cobaltocene 110 ℃ of following vacuum drying 1.5 hours, naturally cools to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 6 hours under 70 ℃, obtain solution B.
Take by weighing sample A and place solution B, 70 ℃ were stirred down after 6 hours, and mixture is filtered, and used CHCl
3Washing places 80 ℃ of following vacuum drying 3 hours then, after 400 ℃ of calcinings 3 hours, obtains the Co/MCM-48 solid catalyst after naturally cooling to room temperature.The load capacity of ion cobalt is the 2wt% of MCM-48 carrier quality.
Embodiment 9
Take by weighing 0.8g fluorophosphoric acid 1-methyl-3-(the 3-trimethoxy is silica-based) propyl group pyridine in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the SBA-16 that 130 ℃ of dryings obtained after 4 hours in whipping process, and with this mixed system 70 ℃ of following reflux 16 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the SBA-16 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 50wt% of SBA-16 carrier quality.
0.1g be dissolved in the 5ml CHCl that contains the 10ml tripropyl amine (TPA) two luxuriant manganese 120 ℃ of following vacuum drying 1 hour, naturally cool to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 6 hours under 70 ℃, obtain solution B.
Take by weighing sample A and place solution B, 70 ℃ were stirred down after 6 hours, and mixture is filtered, and used CHCl
3Washing places 50 ℃ of following vacuum drying 5 hours then, after 600 ℃ of calcinings 3 hours, obtains the Mn/SBA-16 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion manganese is the 1wt% of SBA-16 carrier quality.
Embodiment 10
Take by weighing 0.8g and fluoridize 1-octyl group-3-(the 3-trimethoxy is silica-based) propyl group pyridine in flask, add 10ml CHCl
3Organic solvent adds 1.0g and is placed in one through the MCM-41 that 150 ℃ of dryings obtained after 3 hours in whipping process, and with this mixed system 80 ℃ of following reflux 12 hours; Reaction finishes the back filters, and uses CHCl
3Wash, promptly get the MCM-41 (sample A) of solid-loaded ionic-liquid after the drying.Ion liquid load capacity is the 40wt% of MCM-41 carrier quality.
0.03g be dissolved in the 5ml CHCl that contains the 2.5ml triethanolamine two luxuriant titaniums 120 ℃ of following vacuum drying 1 hour, naturally cool to room temperature then under nitrogen protection after
3In the organic solvent, after stirring 8 hours under 50 ℃, obtain solution B.
Take by weighing sample A and place solution B, 50 ℃ were stirred down after 8 hours, and mixture is filtered, and used CHCl
3Washing places 80 ℃ of following vacuum drying 3 hours then, after 400 ℃ of calcinings 6 hours, obtains the Ti/MCM-41 solid catalyst after naturally cooling to room temperature.The load capacity of metal ion titanium is the 0.5wt% of MCM-41 carrier quality.
Catalytic performance is investigated:
Be furnished with at 50ml and successively add 10ml CHCl in the three-neck flask of reflux condensate device
3, 10mmol cyclohexene, 10mmol TBHP, 5mmol 1,3, (mass ratio of catalyst and cyclohexene is 0.01-0.3: 1) for 5-trimethylbenzene (internal standard compound) and above-mentioned catalyst.At N
2Under the atmosphere, magnetic agitation, 60 ℃ of constant temperature oil baths react that the cyclohexene conversion ratio is all more than 70% after 6 hours, and epoxide ring hexene selectivity is all more than 90%.
Claims (5)
1. be used to prepare the preparation method of the heterogeneous catalysis of 7-oxa-bicyclo[4.1.0, it is characterized in that step is following:
(1) with porous SiO
2Material naturally cooled to room temperature in drier after 120-150 ℃ of dry 3-5 hour, and airtight preservation; With 1,3-dialkylimidazolium salt or Fixanol are dissolved in CHCl
3, again with the porous SiO of drying
2Material is placed in one, and after stirring 12-24h under 50-80 ℃, filters, and uses CHCl
3Wash, obtain the sample A of solid-loaded ionic-liquid after the drying;
(2) with organic metal salt at 80-120 ℃ of following vacuum drying 1-3h, be dissolved in the CHCl that contains complexing agent after under nitrogen protection, naturally cooling to room temperature then
3In the organic solvent, after stirring 5-8 hour under 50-80 ℃, obtain solution B;
Used organic metal salt be two luxuriant titaniums, ferrocene,, cuprocene, cobaltocene or two luxuriant manganese;
Used complexing agent is triethanolamine, triethylamine, tripropyl amine (TPA) or tripropanol amine;
(3) sample A is placed above-mentioned B solution, after stirring 5-8 hour under 50-80 ℃, mixture is filtered, use CHCl
3Washing placed 50-80 ℃ of following vacuum drying 3-5 hour then, after 400-600 ℃ of calcining 3-6 hour, obtained solid catalyst after naturally cooling to room temperature.
2. catalyst according to claim 1, the load capacity that it is characterized in that metal ion is porous SiO
2The 0.5wt%-10wt% of carrier quality, ion liquid load capacity is porous SiO
2The 1w%t-50wt% of carrier quality.
3. catalyst according to claim 1; It is characterized in that 1; The substituted alkyl chain length of 3-dialkylimidazolium or Fixanol is the alkyl chain of C1 to C8, and the anion of salt is fluorine, chlorine, bromine, iodine, fluoboric acid root, fluorophosphoric acid root, trifluoracetic acid root or fluoroform acid group.
4. catalyst according to claim 1 is characterized in that: porous SiO
2Material is MCM-41, MCM-48, SBA-15 or SBA-16.
5. Application of Catalyst according to claim 1 is characterized in that: with CHCl
3Be solvent, cyclohexene is a raw material, and reaction temperature is 20-80 ℃, and the mass ratio of catalyst and cyclohexene is 0.01-0.3: 1, react that the cyclohexene conversion ratio is more than 70% after 6 hours, and epoxide ring hexene selectivity is more than 90%.
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| CN104907074A (en) * | 2014-03-13 | 2015-09-16 | 中国石油化工股份有限公司 | Ester hydrogenation catalyst, preparation method and ester hydrogenation reaction method |
| CN104907074B (en) * | 2014-03-13 | 2017-12-22 | 中国石油化工股份有限公司 | Ester through hydrogenation catalyst and preparation method thereof and the method for ester through hydrogenation reaction |
| CN105435809A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A hydrogenation catalyst, a preparing method thereof, applications of the hydrogenation catalyst and a hydrogenation reaction method |
| CN105435809B (en) * | 2014-08-27 | 2018-03-20 | 中国石油化工股份有限公司 | The method of hydrogenation catalyst and its preparation method and application and hydrogenation reaction |
| CN112007634A (en) * | 2019-05-28 | 2020-12-01 | 新特能源股份有限公司 | Novel catalyst for vinyl trichlorosilane, preparation method thereof and method for preparing vinyl trichlorosilane through catalysis of novel catalyst |
| CN112007634B (en) * | 2019-05-28 | 2023-08-29 | 新特能源股份有限公司 | Novel vinyl trichlorosilane catalyst, preparation method thereof and method for preparing vinyl trichlorosilane by catalysis of novel vinyl trichlorosilane catalyst |
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Application publication date: 20120208 |