CN1228435A - Synthesis method of vinyl chlorine-containing silane - Google Patents
Synthesis method of vinyl chlorine-containing silane Download PDFInfo
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- CN1228435A CN1228435A CN 98105072 CN98105072A CN1228435A CN 1228435 A CN1228435 A CN 1228435A CN 98105072 CN98105072 CN 98105072 CN 98105072 A CN98105072 A CN 98105072A CN 1228435 A CN1228435 A CN 1228435A
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Abstract
The synthesis method of vinyl cotaining chloro silicane is characterized by adding polyvinyl siloxane in the reaction system to keep the reaction activity of the catalyst, using acetylene to bubble the hydrogen containing chloro silicane and sufficiently mix the reactants, controlling the quantities of hydrogen containing chloro silicane and product vinyl cotaining chloro silicane in the reaction, and controlling the quantities of H2O, alcohols compound and amines compound in the reaction system so as to make the catalyst possess good and stable activity. The vinyl chloro silicane selectivity is greater than 95%, secondary additive product content is less than 3%, and R4-n-1 SiCln+1 content is less than 3%. Its method is simple and condition is mild.
Description
The invention provides a kind of method of utilizing silicon hydrogen additive process highly selective synthesizing vinyl group containing chlorosilane, belong to the field of chemical synthesis.
Vinyl chlorine-containing silane is the important monomer of organosilicon industry, and wherein the methyl ethylene dichlorosilane is a requisite raw material during vinylsiloxane rubber is produced, and vinyl trichloro silane is important silane coupling agent.Both at home and abroad at present catalyzing addition reaction of silicon with hydrogen synthesizing vinyl group containing chlorosilanes that adopt acetylene and contain silicon hydride chlorid more, this method has the reaction conditions gentleness, characteristics such as reactive behavior is good, but because the secondary addition reaction is serious, more difficult highly selective obtains the adduct vinyl chlorine-containing silane one time, has a certain amount of by product R in the product simultaneously
4-n-1SiCl
N+1(n=1,2,3; R is the alkyl that is less than 4 C).In addition, in this type of addition reaction of silicon with hydrogen, platinum compound or complex compound catalyst (as chloroplatinic acid catalyst, Karstedt catalyzer) commonly used though have the high advantage of reactive behavior, are easy to inactivation in reaction process.
Petrov A D.lzvest Akad Nauk USSR, Ottdel Khim Nauk, 1958:953 discloses a kind of Platinic chloride/Virahol that utilizes and has been catalyzer, acetylene and dimethyl dichlorosilane (DMCS) reaction under 9 normal atmosphere, can obtain 81% methyl ethylene dichlorosilane, but the acetylene high top pressure operation has danger, and selectivity still shows not high.
Marciniec B.Applied Organomet Chem, 1993,7:207 has reported and has a kind ofly utilized polymer supported platinic compound to be catalyzer, addition reaction of silicon with hydrogen by acetylene and trichlorosilane, reaction method synthesis of vinyl trichlorosilane with the gas-solid phase, but catalyst levels is big, and is active low, easily inactivation.
USP4898961,1990, a kind of method for preparing thiazolinyl silane is disclosed, it contacts by the liquid medium that contains homogeneous catalyst that gasiform alkynes and silane containing hydrogen mixture and mobile is very thin reacts, suppressed the secondary adduct preferably, but the generation situation of other by products is explanation not, and transformation efficiency of raw material is not high, and reaction conditions is strict.
USP5041595,1991, disclose a kind of method of synthesis of high purity vinyl alkoxy silane, suppressed the generation of by product tetraalkoxysilane preferably, do not related to the synthetic of vinyl chlorine-containing silane by the content of chlorion and alkylamine in the control reaction raw materials.
In order to keep the activity of Platinic chloride catalyst series, USP4578497,1986, disclosing a kind of oxygen-containing gas that utilizes makes platinum catalyst keep method with regeneration activity, USP5359113,1994, disclose a kind of utilization and in reaction process, constantly added the active method that organo-peroxide keeps silicon hydrogen addition catalyst.But because the combustion range of acetylene and air is 3-80%, and organo-peroxide can oxidation acetylene, therefore utilizes aforesaid method to keep acetylene and the activity that contains the silicon hydrogen addition catalyst of silicon hydride chlorid is infeasible.
The objective of the invention is to select rational feed process, optimize reaction conditions, H in the control reaction system by keeping silicon hydrogen addition catalyst activity
2The amount of O, alcohols and aminated compounds suppresses secondary affixture and R dramatically
4-n-1SiCl
N+1Generation, a kind of method of highly selective synthesizing vinyl group containing chlorosilane is provided.
The said silicon hydrogen of the present invention addition catalyst is meant platinum compound or complex compound catalyst (as chloroplatinic acid catalyst, Karstedt catalyzer).The present invention adds polyvinyl siloxane in reaction system, liquid-state oligomers, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, pentamethyl-five vinyl D5s and poly-(two-vinyl) siloxanes etc. as poly-ethylene methacrylic radical siloxane, vinyl by polyvinyl siloxane is to the mating reaction of platinum, to slow down catalyzer precipitation and inactivation keeps the reactive behavior of this type of catalyzer gradually in reaction process.The protective material consumption is 8-40 a times of catalyzer molar weight, and more suitable amount is 8-20 times.
The consumption of the said silicon hydrogen of the present invention addition catalyst is taken at generally that concentration is 1-200 * 10 in the initial reaction system
-5M gets final product.
The present invention is the mode that contains silicon hydride chlorid by the acetylene bubbling, makes acetylene and contain silicon hydride chlorid and mixed fully to improve the selectivity of vinyl chlorosilane, to suppress the generation of secondary affixture.Acetylene is generally got 1.2-20 with the mole proportioning that contains silicon hydride chlorid, and more suitable scope is 1.5-3.0.
Acetylene and the input speed that contains the silicon hydride chlorid gaseous mixture are by solvent load in the reactor and catalytic amount and temperature of reaction decision among the present invention, total principle is to make that the acetylene molar weight is greater than hydrogeneous chlorosilane mol in the reaction zone, and the dawn makes the amount that contains silicon hydride chlorid in the reaction zone be advisable less than 5%.The ratio of generally getting acetylene and material input speed (ml/min) that contains silicon hydride chlorid and solvent volume (ml) is 0.1-8/min.
The present invention takes continuously feeding, and the intermittent reaction mode is reacted, and the molar weight of vinyl chlorine-containing silane product in the reaction zone is controlled at less than 70%, and scope preferably is less than 50%.
The used solvent of the present invention is inert solvents such as hexanaphthene, benzene, toluene, trichloroethane, dimethylbenzene, trimethylbenzene, dichlorobenzene, chlorobenzene.The suitable solvent is dimethylbenzene, chlorobenzene and dichlorobenzene.
The said addition reaction of silicon with hydrogen of the present invention is to carry out under normal pressure.Temperature of reaction system is generally got 40-120 ℃.
The present invention is by the H in the control reaction system
2The content of O, alcohols and aminated compounds reduces by product R
4-n-1SiCl
N+1Produce.
The present invention has following characteristics: 1, good catalyst activity and more stable can recycle more than four times; 2, vinyl chlorine-containing silane selectivity＞95%; 3, secondary adduct content＜3%, R
4-n-1SiCl
N+1Content＜3%; 4, synthetic method is simple, the reaction conditions gentleness, and equipment requirements is simple.
The present invention will be further described by following examples.
Embodiment 1: be equipped with at 100ml and add 30ml toluene in the there-necked flask of reflux condensate device, volumetric molar concentration is 10 * 10
-4The M chloroplatinic acid catalyst, tetramethyl-tetrem thiazolinyl cyclopolysiloxane 2ml, acetylene gas is behind process voltage stabilizing and current stabilization, enter in the bubbler that dimethyl dichlorosilane (DMCS) is housed, the gaseous mixture bubbling of acetylene that comes out in the bubbler and dimethyl dichlorosilane (DMCS) enters in the there-necked flask, and the proportioning of acetylene and dimethyl dichlorosilane (DMCS) is 1.5,60 ℃ of temperature of reaction, acetylene bubbling speed is 50ml/min, reaction 4h.Recording the dimethyl dichlorosilane (DMCS) transformation efficiency is 100%, and the selectivity of methyl ethylene dichlorosilane is 95.17%, and METHYL TRICHLORO SILANE is 2.85%, and the secondary affixture is 1.79%.
Embodiment 2: be equipped with at 1000ml and add 500ml toluene in the there-necked flask of reflux condensate device, volumetric molar concentration is 2 * 10
-4The M chloroplatinic acid catalyst, poly-ethylene methacrylic radical siloxane 5ml, acetylene gas is behind process voltage stabilizing and current stabilization, enter in the bubbler that dimethyl dichlorosilane (DMCS) is housed, the gaseous mixture bubbling of acetylene that comes out in the bubbler and dimethyl dichlorosilane (DMCS) enters in the there-necked flask, and the proportioning of acetylene and dimethyl dichlorosilane (DMCS) is 2.0,70 ℃ of temperature of reaction, acetylene bubbling speed is 210ml/min, reaction 4h.Recording the dimethyl dichlorosilane (DMCS) transformation efficiency is 100%, and the selectivity of methyl ethylene dichlorosilane is 96.43%, and METHYL TRICHLORO SILANE is 1.86%, and the secondary affixture is 1.59%.
Embodiment 3: be equipped with at 100ml and add 30ml toluene in the there-necked flask of reflux condensate device, volumetric molar concentration is 1 * 10
-4The M chloroplatinic acid catalyst, eight vinyl cyclotetrasiloxane 2ml, acetylene gas is behind process voltage stabilizing and current stabilization, enter in the bubbler that trichlorosilane is housed, the gaseous mixture bubbling of acetylene that comes out in the bubbler and trichlorosilane enters in the there-necked flask, and the proportioning of acetylene and trichlorosilane is 1.5,80 ℃ of temperature of reaction, acetylene bubbling speed is 60ml/min, reaction 4h.Recording the trichlorosilane transformation efficiency is 100%, and the selectivity of vinyl trichloro silane is 95.94%, silicon tetrachloride 1.97%.The secondary affixture is 1.56%.
Claims (4)
1, a kind of under normal pressure, 40-120 ℃ temperature, make catalyzer with platinum compound or complex compound, inert solvent is made the method for reaction solvent synthesizing vinyl group containing chlorosilane, it is characterized in that in reaction system, adding 8-40 times of polyvinyl siloxane of catalyzer molar weight, contain silicon hydride chlorid with the acetylene bubbling, its mole proportioning is 1.2-20, and make the reaction include silicon hydride chlorid amount less than 5%, the amount of product vinyl chlorine-containing silane is less than 70%.
2, method according to claim 1, its will levy be the add-on of polyvinyl siloxane be the catalyzer molar weight 8-20 doubly.
3, method according to claim 1 is characterized in that acetylene and the mole proportioning that contains silicon hydride chlorid are 1.5-3.0.
4, method according to claim 1 is characterized in that making the amount of vinyl chlorine-containing silane in the reaction zone less than 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98105072A CN1074416C (en) | 1998-03-07 | 1998-03-07 | Synthesis method of vinyl chlorine-containing silane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98105072A CN1074416C (en) | 1998-03-07 | 1998-03-07 | Synthesis method of vinyl chlorine-containing silane |
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| Publication Number | Publication Date |
|---|---|
| CN1228435A true CN1228435A (en) | 1999-09-15 |
| CN1074416C CN1074416C (en) | 2001-11-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98105072A Expired - Fee Related CN1074416C (en) | 1998-03-07 | 1998-03-07 | Synthesis method of vinyl chlorine-containing silane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974027A (en) * | 2010-10-08 | 2011-02-16 | 威海新元化工有限公司 | Synthetic method of vinyl organosilicon tricyclic body |
| CN101012237B (en) * | 2007-01-29 | 2011-05-04 | 南昌大学 | Synthesis method of vinyl alkoxy silane |
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898961A (en) * | 1989-07-17 | 1990-02-06 | Dow Corning Corporation | Method for preparing alkenylsilanes |
-
1998
- 1998-03-07 CN CN98105072A patent/CN1074416C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012237B (en) * | 2007-01-29 | 2011-05-04 | 南昌大学 | Synthesis method of vinyl alkoxy silane |
| CN101974027A (en) * | 2010-10-08 | 2011-02-16 | 威海新元化工有限公司 | Synthetic method of vinyl organosilicon tricyclic body |
| CN101974027B (en) * | 2010-10-08 | 2014-07-30 | 威海新元化工有限公司 | Synthetic method of vinyl organosilicon tricyclic body |
| 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 |
| 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 |
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| CN1074416C (en) | 2001-11-07 |
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