CN101195634A - Method for synthesizing vinyl group containing chlorosilane - Google Patents
Method for synthesizing vinyl group containing chlorosilane Download PDFInfo
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- CN101195634A CN101195634A CNA200710168341XA CN200710168341A CN101195634A CN 101195634 A CN101195634 A CN 101195634A CN A200710168341X A CNA200710168341X A CN A200710168341XA CN 200710168341 A CN200710168341 A CN 200710168341A CN 101195634 A CN101195634 A CN 101195634A
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Abstract
The invention discloses a synthesis method of vinyl chlorosilane, which comprises A, using catalyst ether as solvent, using benzopyridine or carbazole as ligand to be reacted with chloroplatinic acid to produce platinum complex compound, B using a pump to feed solvent containing catalyst from the bottom of autoclave to the top of reaction tower, to be circulated in the tower and autoclave, C, arranging ceramic stuff in the reaction tower, continuously feeding gasified mixture of hydrogen chlorosilane and acetylene into the reaction tower, to be reacted with the catalyst at the surface of the stuff tower, continuously feeding materials and reacting, D, at 0.001-0.3MPa and 50-90DEG C, using platinum complex compound as catalyst, and using chlorohexane as solvent to synthesize vinyl chlorosilane. The invention has simple process and easy operation, while the vinyl chlorosilane selectivity is higher than 97.0%. The invention can eliminate vinyl recovery, with simple method, stable and controllable reaction.
Description
Technical field
The present invention relates to the Synthetic Organic Chemistry technical field, more specifically relate to a kind of method of synthesizing vinyl group containing chlorosilane.
Background technology
Adopt acetylene at present both at home and abroad mostly and contain silicon hydride chlorid catalysis addition technology synthesis of vinyl chlorosilane, but this method is more difficult to get an adduct of highly selective owing to there is the secondary adduct.The synthesis condition that how to suppress the secondary adduct has become the sector scientific worker's research object, as reaction pressure, temperature, solvent, catalyst activity, feed way and structure of reactor etc.
Petrov A is Akad Nauk USSR D.1zvest, Ottdel Khim Nauk, 1958:953 discloses a kind of Platinic chloride and Virahol of utilizing and has been catalyzer, acetylene and methyl dichloro hydrogen silane reaction under 0.9MPa, can obtain 81% methyl ethylene dichlorosilane, but acetylene high pressure operation down is abnormally dangerous, and selectivity is not high yet.
USP 4898961,1990, disclose a kind of method for preparing thiazolinyl silane, and it reacts by gaseous state alkynes is contacted in a very thin liquid medium that contains homogeneous catalyst of mobile with the silane containing hydrogen mixture, has suppressed the secondary adduct preferably.But the generation situation of other by product is explanation not, and transformation efficiency of raw material is not high, and reaction conditions is strict.
Marciniec B.Applied Organomet Chem, 1993,7:207 has reported that a kind of platinic compound of polymkeric substance load that utilizes is catalyzer, addition reaction by acetylene and trichlorosilane, prepared in reaction vinyl trichloro silane with the gas-solid phase, but catalyst levels is big, and is active low, easily inactivation.
Synthetic method/the Li Fengyi of vinyl chlorine-containing silane, Lan Zhili, Liu Wenming, University Of Nanchang // Chinese patent: CN1228435 discloses a kind of synthetic method of vinyl chlorine-containing silane, by in reaction system, adding the reactive behavior that polyvinyl siloxane keeps catalyzer, contain silicon hydride chlorid with the acetylene bubbling and make the reactant thorough mixing, the control reaction includes the amount of silicon hydride chlorid and product vinyl chlorine-containing silane, and the amount of water, alcohols and aminated compounds in the reaction system, make good catalyst activity and stable, the vinyl chlorine-containing silane selectivity is greater than 95%.But in system, add ethyl chlorine-containing silane in entry, alcohols and the amine afterreaction product, increase separating difficulty, influence product quality.Excessive greatly acetylene bubbling causes acetylene to reclaim difficulty.
Summary of the invention
The objective of the invention is to be to provide a kind of method of synthesizing vinyl group containing chlorosilane, method is easy, processing ease, the vinyl chlorine-containing silane selectivity is 97.0%, need not reclaim acetylene, and reacting balance is easily controlled, cost is low, the quality product percentage composition is greater than 99.0%, and the yield height has the remarkable economical effect.。
In order to realize above-mentioned task, the present invention adopts following technical measures:
A kind of synthetic method of vinyl chlorine-containing silane, it comprises the following steps:
A, the used catalyzer of the present invention are meant with ether and make solvent, dibenzopyridine or carbazole are made the complex compound of the platinum of ligand and Platinic chloride reaction generation, the ligand consumption is 2-20 a times of platinum molar weight, because this ligand is sterically hindered bigger, suppressed the formation of secondary adduct preferably, this complex compound is comparatively stable simultaneously, has slowed down in reaction process to be precipitated and inactivation by the silicon hydrogen reduction, has kept catalytic activity.
B, the said feeding manner of the present invention and reaction unit are to be transported to the reaction cat head with the solvent that pump will contain catalyzer from the reactor bottom, are allowed to condition at reaction tower still internal recycle.
In C, the reaction tower ceramic packing is housed, as ceramic waved plate or ceramic raschig rings, with the gasification after contain silicon hydride chlorid and the acetylene mixture is imported in the reaction tower continuously, allow itself and catalyzer in the packing tower surface reaction, the present invention adopts the continuously feeding reaction, and vinyl chlorosilane quality percentage composition is controlled at 45-55% in the system.
D, under 0.001-0.03Mpa pressure and the control of 50-90 ℃ of temperature, make catalyzer with platinum complex, do solvent synthesis of vinyl chlorosilane (keeping under the 0.001-0.03MPa reaction pressure, acetylene is 1: 1 mole with hydrogeneous chlorosilane feed ratio) with the chlorohexane mixture.Compare with Bubbling method, this reaction conditions has increased the gas-to-liquid contact area greatly, guarantee acetylene, contained silicon hydride chlorid and the abundant contact reacts of catalyzer, catalyst selectivity and production efficiency have been improved, and this technology had both guaranteed the excessive state of remaining of acetylene, had avoided containing simultaneously the recovery difficult problem of chlorosilane acetylene again.
The said concrete synthesizer of the present invention is to make reactor with 3000L enamel still kettle (distillation hole ￠ 500 or ￠ 400), on adorn 6 joint ￠ 500 * 1500 or 6 joint ￠ 400 * 1500 enamel towers joints are made reaction tower, each tower joint upper portion side wall has 1 acetylene and hydrogeneous chloro-silicane gaseous mixture body feed port ￠ 50, Ta Jienei ￠ 38 Raschig rings of packing into, the solvent that will contain catalyzer with the IMC50-32-160P magnetic drive pump are transported to the filler cat head at the bottom of the still kettle and are allowed to condition at reaction tower still internal recycle.The synthetic operation method is earlier will to add the 1000Kg chlorohexane in the reactor, be 5 * 10 in platinum catalyzer volumetric molar concentration
-5The Platinic chloride of M and 40-300g dibenzopyridine or 40-300g carbazole, use hydrogeneous chlorosilane vapourizing device of nitrogen replacement and reactive system again, after finishing, displacement starts recycle pump, and with system's heat temperature raising to 50-90 ℃, (reaction parameter is controlled to be that acetylene and the mol ratio that contains silicon hydride chlorid are 1, temperature of reaction is that 50-90 ℃, acetylene air input are 4-30m with entering the reaction tower reaction after hydrogeneous chlorosilane gas mixes through hydrogeneous chlorosilane vapourizing device with acetylene then
3/ h, reaction pressure are that 0.001-0.03MPa and reaction times are 8-24h), reaction changes rectifying still after finishing over to and carries out rectifying and obtain product (the quality product percentage composition is greater than 99.0%).
The said solvent of the present invention is chlorohexane, ethylcyclohexane, toluene, dimethylbenzene, chlorobenzene, dichlorobenzene, or a kind of in the chlorohexane.
The present invention has reacting balance in the confined reaction system, need not reclaim the acetylene of chlorine-containing silane, has significantly reduced environmental pollution and equipment corrosion, and facility investment is few and the during-operation service expense is low.Catalyzer is stable and selectivity is good, and the vinyl chlorosilane selectivity is greater than 97.0%, and the secondary adduct is less than 2.0%, METHYL TRICHLORO SILANE or silicon tetrachloride and ethyl chloride silane are less than 1.0%, good product quality (content is greater than 99.0%) and yield height, cost is low, has favorable economic benefit.
Embodiment
Embodiment 1:
A kind of method of synthesizing vinyl group containing chlorosilane, the steps include: that A, catalyzer are that ether is done the complex compound that solvent, dibenzopyridine or carbazole are made the platinum of ligand and Platinic chloride reaction generation, the ligand consumption is 2 or 4 or 7 or 10 or 15 or 17 or 20 times of platinum molar weight, and described solvent is a kind of in chlorohexane, ethylcyclohexane, toluene, dimethylbenzene, chlorobenzene, the dichlorobenzene solvent.B, the solvent that will contain catalyzer with pump are transported to the reaction cat head from the reactor bottom, are allowed to condition at reaction tower still internal recycle.Reaction unit is to make reactor with 3000L enamel still kettle (distillation hole ￠ 500), on adorn 6 joint ￠ 500 * 1500 enamel towers joints and make reaction tower, each tower joint upper portion side wall has 1 acetylene and hydrogeneous chloro-silicane gaseous mixture body feed port, Ta Jienei ￠ 38 Raschig rings of packing into, the solvent that will contain catalyzer with the IMC50-32-160P magnetic drive pump are transported to the filler cat head at the bottom of the still kettle and are allowed to condition at reaction tower still internal recycle.In C, the reaction tower ceramic packing is housed, pottery waved plate or ceramic raschig rings, with the gasification after contain silicon hydride chlorid and the acetylene mixture is imported in the reaction tower continuously, allow itself and catalyzer in the packing tower surface reaction, the continuously feeding reaction, vinyl chlorosilane quality percentage composition is controlled at 45 or 47 or 49 or 51 or 53 or 55% in the system.D, be controlled under 50 or 55 or 60 or 66 or 70 or 75 or 80 or 85 or 90 ℃, make catalyzer, do solvent synthesis of vinyl chlorosilane with the chlorohexane mixture with the platinum complex at the 0.001-0.03Mpa pressure and temperature.Its concrete operation method is earlier will to add the 1000Kg chlorohexane in the reactor, be 5 * 10 in platinum catalyzer volumetric molar concentration
-5The Platinic chloride of M and 100g dibenzopyridine or 150g carbazole, use nitrogen replacement dimethyl dichlorosilane (DMCS) vaporizer and reactive system again, after finishing, displacement starts recycle pump, and with system's heat temperature raising to 70 ℃, (mol ratio that reaction parameter is controlled to be acetylene and dimethyl dichlorosilane (DMCS) is 1, temperature of reaction is that 70 ℃, acetylene air input are 15m with entering the reaction tower reaction after dimethyl dichlorosilane (DMCS) gas mixes through the dimethyl dichlorosilane (DMCS) vaporizer with acetylene then
3/ h, reaction pressure are that 0.001-0.03MPa and reaction times are 15h), reaction changes rectifying still after finishing over to and carries out rectifying and obtain product (product content is 99.5%).The selectivity of methyl ethylene dichlorosilane is 97.6%, and METHYL TRICHLORO SILANE is 0.8%, and the secondary adduct is 1.6%.
Embodiment 2: reaction unit is to make reactor with 3000L enamel still kettle (distillation hole ￠ 400), on adorn 6 joint ￠ 400 * 1500 enamel towers joints and make reaction tower, each tower joint upper portion side wall has 1 acetylene and hydrogeneous chloro-silicane gaseous mixture body feed port, Ta Jienei ￠ 38 Raschig rings of packing into, the solvent that will contain catalyzer with the IMC50-32-160P magnetic drive pump are transported to the filler cat head at the bottom of the still kettle and are allowed to condition at reaction tower still internal recycle.Working method is earlier will to add the 1000Kg chlorohexane in the reactor, be 5 * 10 in platinum catalyzer volumetric molar concentration
-5The Platinic chloride of M and 120g dibenzopyridine or 200g carbazole, use nitrogen replacement trichlorosilane alkane vaporizer and reactive system again, after finishing, displacement starts recycle pump, and with system's heat temperature raising to 80 ℃, (mol ratio that reaction parameter is controlled to be acetylene and trichlorosilane alkane is 1, temperature of reaction is that 80 ℃, acetylene air input are 10m with entering the reaction tower reaction after trichlorosilane alkane gas mixes through trichlorosilane alkane vaporizer with acetylene then
3/ h, reaction pressure are that 0.001-0.03MPa and reaction times are 17h), reaction changes rectifying still after finishing over to and carries out rectifying and obtain product (product content is 99.2%).The selectivity of vinyl trichloro silane is 97.2%, and tetrachloro silicane is 0.8%, and the secondary adduct is 2.0%.(its concrete steps are identical with embodiment 1.)
Embodiment 3: reaction unit is to make reactor with 3000L enamel still kettle (distillation hole ￠ 500), on adorn 6 joint ￠ 500 * 1500 enamel towers joints and make reaction tower, each tower joint upper portion side wall has 1 acetylene and hydrogeneous chloro-silicane gaseous mixture body feed port, Ta Jienei ￠ 38 Raschig rings of packing into, the solvent that will contain catalyzer with the IMC50-32-160P magnetic drive pump are transported to the filler cat head at the bottom of the still kettle and are allowed to condition at reaction tower still internal recycle.Working method is earlier will to add the 1000Kg chlorohexane in the reactor, be 5 * 10 in platinum catalyzer volumetric molar concentration
-5The Platinic chloride of M and 120g dibenzopyridine or 200g carbazole, use nitrogen replacement trichlorosilane alkane vaporizer and reactive system again, after finishing, displacement starts recycle pump, and with system's heat temperature raising to 80 ℃, (mol ratio that reaction parameter is controlled to be acetylene and trichlorosilane alkane is 1, temperature of reaction is that 80 ℃, acetylene air input are 15m with entering the reaction tower reaction after trichlorosilane alkane gas mixes through trichlorosilane alkane vaporizer with acetylene then
3/ h, reaction pressure are that 0.001-0.03MPa and reaction times are 15h), reaction changes rectifying still after finishing over to and carries out rectifying and obtain product (product content is 99.4%).The selectivity of vinyl trichloro silane is 97.5%, and tetrachloro silicane is 0.7%, and the secondary adduct is 1.8%.(its concrete steps are identical with embodiment 1.)
The scope of the invention is not restricted to the described embodiments, and described embodiment only is used for illustrating a method of the present invention, and the embodiment of any equal effect within the scope of the present invention.In fact, according to description above, except that the invention described above embodiment, the various improvement that the present invention is carried out are conspicuous for those skilled in the art.Described improvement is in the protection domain of claims of the present invention.All patents and document that the present invention mentions are quoted reference in the present invention as proof.
Claims (2)
1. the method for a synthesizing vinyl group containing chlorosilane the steps include:
A, catalyzer are that ether is made solvent, and dibenzopyridine or carbazole are made the complex compound of ligand and Platinic chloride reaction generation platinum, and the ligand consumption is 2-20 a times of platinum molar weight;
B, the solvent that will contain catalyzer with pump are transported to the reaction cat head from the reactor bottom, at reaction tower still internal recycle;
C, in reaction tower, adorn ceramic packing, pottery waved plate or ceramic raschig rings, import hydrogeneous chlorine silicon and acetylene mixture after the gasification in the reaction tower continuously, allow itself and catalyzer in the packing tower surface reaction, the continuously feeding reaction, vinyl chlorosilane quality percentage composition is controlled at 45-55% in the system;
D, under 0.001-0.03Mpa pressure and the control of 50-90 ℃ of temperature, make catalyzer with platinum complex, do solvent synthesis of vinyl chlorosilane with chlorohexane;
Described solvent is a kind of in chlorine hexane, ethylcyclohexane, toluene, dimethylbenzene, chlorobenzene, the dichlorobenzene solvent.
2. the method for a kind of synthesizing vinyl group containing chlorosilane according to claim 1, it is characterized in that: acetylene is 1: 1 mole with hydrogeneous chlorosilane feed ratio.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183701A (en) * | 2011-12-30 | 2013-07-03 | 浙江新安化工集团股份有限公司 | Chlorosilane-containing ethylene preparation method |
| CN103570756A (en) * | 2012-08-07 | 2014-02-12 | 山东万达有机硅新材料有限公司 | Method for preparing vinyl trichlorosilane compound |
| 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 |
| CN112028922A (en) * | 2019-06-04 | 2020-12-04 | 江西蓝星星火有机硅有限公司 | Method for preparing vinyl chlorosilane by acetylene method |
| CN114394991A (en) * | 2022-01-27 | 2022-04-26 | 浙江锦华新材料股份有限公司 | Method for catalytically synthesizing vinyl trichlorosilane |
| CN114409694A (en) * | 2022-03-11 | 2022-04-29 | 新疆晶硕新材料有限公司 | Method and device for preparing vinyl trichlorosilane |
-
2007
- 2007-11-14 CN CN200710168341XA patent/CN101195634B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183701A (en) * | 2011-12-30 | 2013-07-03 | 浙江新安化工集团股份有限公司 | Chlorosilane-containing ethylene preparation method |
| CN103183701B (en) * | 2011-12-30 | 2016-02-03 | 浙江新安化工集团股份有限公司 | The preparation method of vinyl chlorine-containing silane |
| CN103570756A (en) * | 2012-08-07 | 2014-02-12 | 山东万达有机硅新材料有限公司 | Method for preparing vinyl trichlorosilane compound |
| 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 |
| CN112028922A (en) * | 2019-06-04 | 2020-12-04 | 江西蓝星星火有机硅有限公司 | Method for preparing vinyl chlorosilane by acetylene method |
| CN112028922B (en) * | 2019-06-04 | 2023-08-04 | 江西蓝星星火有机硅有限公司 | Method for preparing vinyl chlorosilane by acetylene method |
| CN114394991A (en) * | 2022-01-27 | 2022-04-26 | 浙江锦华新材料股份有限公司 | Method for catalytically synthesizing vinyl trichlorosilane |
| CN114409694A (en) * | 2022-03-11 | 2022-04-29 | 新疆晶硕新材料有限公司 | Method and device for preparing vinyl trichlorosilane |
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| CN101195634B (en) | 2010-10-06 |
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Denomination of invention: Method for synthesizing vinyl group containing chlorosilane Effective date of registration: 20120323 Granted publication date: 20101006 Pledgee: Bank of Communications Ltd Wuhan East Lake New Technology Development Zone sub branch Pledgor: Organic Silicon New Material Co., Ltd., Wuhan Univ., Hubei Registration number: 2012990000106 |
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Effective date of registration: 20131113 Address after: 430072 Hubei city of Wuhan province Wuchang Wuhan University LUOJIASHAN Maple Garden Patentee after: Organic Silicon New Material Co., Ltd., Wuhan Univ., Hubei Patentee after: Zhejiang Kaihua Synthetic Materials Co., Ltd. Address before: 430072 Hubei city of Wuhan province Wuchang Wuhan University LUOJIASHAN Maple Garden Patentee before: Organic Silicon New Material Co., Ltd., Wuhan Univ., Hubei |
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