CN1680397A - Synthesis of dimethyl silicane hydroxide - Google Patents
Synthesis of dimethyl silicane hydroxide Download PDFInfo
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- CN1680397A CN1680397A CN 200510049014 CN200510049014A CN1680397A CN 1680397 A CN1680397 A CN 1680397A CN 200510049014 CN200510049014 CN 200510049014 CN 200510049014 A CN200510049014 A CN 200510049014A CN 1680397 A CN1680397 A CN 1680397A
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Abstract
Synthesis of dimethyl hydrogen-chlorine silicane is carried out by taking methyl-hydrogen-dichloro-silicane and trimethyl chlorine silicane as materials, self-disproportionation reacting for methyl-hydrogen-dichloro-silicane in reactor (I) of fixed bed with solid carrier AlCl3 catalyst filling, synthesizing methyl dihydrochloride silicane, mixing the collected methyl dihydrochloride silicane with trimethyl chlorine silicane with mol ratio 0.5:1-1:1, re-distributing reacting in reactor (II) of fixed bed with solid carrier AlCl3 catalyst filling by liquid volume space velocity, and synthesizing dimethyl hydrogen-chlorine silicane at 250-400deg.C in reactor (I) and reactor ( II ), liquid space velocity of reactant in reactor (II) is 0.5-5.0h-1. Its advantages include low cost, simple production of catalyst, easy separation, and continuous production.
Description
Technical field
The present invention relates to extraordinary organosilane monomer synthetic technology research field, relate in particular to a kind of method of synthesization of dimethyl silicon hydride chlorid.
Background technology
[molecular formula is (CH to dimethyl silicane hydroxide
3)
2SiHCl] as a kind of chlorosilane of single functionality, normal temperature is colourless liquid down, 36 ℃ of boiling points, the relative density under 20 ℃ is 0.868, specific refractory power 1.383.Because its end group (CH
3)
2H is because of having reactive hydrogen, thereby aspect development and use, have an advantageous condition, utilize Si-H key wherein, can with the C=C addition on small molecules or the polymer, its Si-C key can link to each other with the silica chain again, and makes it become polysiloxane and organic polymer bonded bridging agent.In addition, dimethyl silicane hydroxide also can be used for preparing various carbon functional silanes or long chain alkyl silane and active silicone oil.Along with developing rapidly of organosilicon industry, the demand of dimethyl silicane hydroxide also constantly increases on the market, only depend on the dimethyl silicane hydroxide that obtains in the process of U.S. Pat 2380995 described direct method synthesizing methyl-chloro-silanes, can't satisfy the needs in market far away.Therefore, finding a kind of operational path of the silicon hydride chlorid of synthesization of dimethyl preferably, will be the outlet that solves this contradiction, also can promote further developing of organosilicon industry to a certain extent.
Chinese patent (application number) 93114760.3 discloses a kind of method for preparing dimethyl silicane hydroxide, this method is to react in proportion with methyl hydrogen dichlorosilane or methyl-monosilane in the presence of catalyzer with dimethyldichlorosilane(DMCS), it is amorphous or spherical that used catalyzer is, it is a kind of polymeric, any crosslinked organo-siloxane-ammonium compound, and this compound has a kind of basic structure that is similar to silicic acid.Shortcoming in the method for this disclosure of the Invention is that described Preparation of Catalyst is difficult and expensive.
It is raw material with the disilane by product that produces in industrial " direct method " synthesization of dimethyl dichlorosilane monomer production process that Chinese patent (application number) 95691153.X discloses a kind of, prepare the method for methyl hydrogen chlorosilane under the effect of catalyzer with hydrogen chloride gas generation scission reaction, this catalyzer mainly comprises: A) palladium (O) platinum (O) and B) be selected from tertiary amine, carboxylic acid amides, alkyl urea, tertiary phosphine, phosphamide, quaternary ammonium halide, the halid organic compound of quaternary phosphonium and composition thereof.The dimethylchlorosilane content of the method preparation of this disclosure of the Invention is less, is mainly methyl hydrogen dichlorosilane.
It is the main raw material method of prepared in reaction dimethyl silicane hydroxide in proportion with trimethylchlorosilane and methyl hydrogen dichlorosilane that Chinese patent 97195464.X and U.S. Pat P6245926 disclose a kind of, also need add straight chain or X 2-1401 silicone oil in this reactant feed, catalyst for reaction is an aluminum trichloride (anhydrous).The recycling difficulty of the lower and catalyzer of the yield of product dimethyl silicane hydroxide in this method.
It is the main raw material method of prepared in reaction dimethyl silicane hydroxide in proportion with trimethylchlorosilane and methyl hydrogen dichlorosilane that U.S. Pat P6077967 discloses a kind of, and used catalyzer also is an aluminum trichloride (anhydrous).In reactant, add (C
6H
5)
2Si (OC
2H
5)
2Or MeSi (OC
2H
5)
3During two kinds of materials, can improve the content of dimethyl silicane hydroxide in the product.
U.S. Pat P4181673 discloses that a kind of to be lower than 40 ℃ of mixtures with the boiling point that produces in industrial " direct method " synthesization of dimethyl dichlorosilane monomer production process be raw material, with a spot of H
2PtCl
6Making catalyzer, heat fractionation in the atmospheric tower of 85 blocks of theoretical trays, is under 50 the condition, can obtain the dimethyl silicane hydroxide that purity is 97wt% in reflux ratio, and the rate of recovery can reach 79 ~ 85wt%.
Summary of the invention
The objective of the invention is to overcome the method that the shortcoming that has technology now provides a kind of synthesization of dimethyl silicon hydride chlorid.
It is to be raw material with methyl hydrogen dichlorosilane and trimethylchlorosilane, makes methyl hydrogen dichlorosilane be filled with immobilized AlCl earlier
3Pass through self disproportionation reaction synthesizing methyl two silicon hydride chlorid in the fixed-bed reactor of catalyzer (I); Then with methyl two silicon hydride chlorid collected and trimethylchlorosilane with 0.5: 1 ~ 1: 1 mixed in molar ratio well the back with certain liquid volume air speed by being filled with immobilized AlCl
3Redistribution reaction synthesization of dimethyl silicon hydride chlorid takes place in the fixed-bed reactor of catalyzer (II); Reactor (I) and temperature (II) are 250 ~ 400 ℃, and the liquid volume air speed of reactant is 0.5 ~ 5.0h in the reactor (II)
-1
The present invention can come the synthesization of dimethyl silicon hydride chlorid at lower cost.In the method, because this reaction belongs to gas and solid heterogeneous reaction, the simple and product of Preparation of catalysts process is easy to separate with catalyzer, can be used for serialization and produces.
Description of drawings
Fig. 1 is the process flow diagram of the method for synthesization of dimethyl silicon hydride chlorid.
Embodiment
The method detailed process of synthesization of dimethyl silicon hydride chlorid is as follows: by an adjustable volume pump methyl hydrogen dichlorosilane is squeezed into certain input speed from storage tank and be filled with immobilized AlCl
3The fixed-bed reactor of catalyst agent (I) upper end, reactor (I) adopts stainless steel 316L material to make, its internal diameter is 20mm, long 800mm, adopt three sections heating of open-type Reaktionsofen temperature control, its bottom axial centre is inserted with the stainless steel thermocouple sheath of a 3mm, in order to the temperature of assaying reaction device bed different positions.Methyl hydrogen dichlorosilane is 250～400 ℃ in the disproportionation temperature of reactor (I), preferred temperature of reaction is 280～320 ℃, the reactor outlet product separates by condenser, methyl two silicon hydride chlorid of gained are collected in the low temperature storage tank, help improving the yield of dimethyl silicane hydroxide in the disproportionation products in this process in lower liquid volume air speed and preferred range.
Methyl two silicon hydride chlorid collected and trimethylchlorosilane mixed according to the certain molar ratio example put into storage tank, by another adjustable volume pump this mixture is squeezed into certain liquid volume air speed from storage tank (temperature is controlled at about 0 ℃) and filled immobilized AlCl
3The fixed-bed reactor of catalyzer (II) upper end, the same reactor of manufactured materials, size and temperature control method (I) of reactor (II), reactor (II) temperature is 250～400 ℃, preferred temperature of reaction is 280～320 ℃; The mol ratio of methyl two silicon hydride chlorid and trimethylchlorosilane is 0.5: 1～1: 1; Preferred mol ratio is 0.8: 1～1: 1; The liquid volume air speed is 0.5～5.0h
-1, preferred liquid volume air speed is 1.5～3.0h
-1Wherein the liquid volume air speed is defined as the ratio of the bed volume of the volumetric rate of liquid starting material charging and catalysts, and unit is h
-1The reactor outlet product is collected in the thick product receptor by freezing, and reaction finishes back sampling from the product receptor and adopts vapor-phase chromatography to carry out quantitative analysis.
Be filled in the immobilized AlCl in the fixed-bed reactor among the present invention
3The activity of such catalysts component is AlCl
3, carrier is a gac, the solvent of employing is a dehydrated alcohol; Catalyzer adopts the preparation of dipping evaporation calcination method, and its process is as follows: with active component A lCl
3Separate wiring solution-forming in solvent, AlCl
3With the proportioning of solvent be 10%～60%, add AlCl more successively
3Ethanolic soln, carrier, temperature of reaction are 20～90 ℃, and the reaction times is 2～8h, and reaction finishes after filtration, washs, and get solid matter at 100～200 ℃ of down dry 2～10h, calcine 2～10h, AlCl down at 400～600 ℃ then
3With the mass ratio of carrier be 20%～80%, the physical and chemical performance of prepared catalyzer is as shown in table 1.
The physical and chemical performance of table 1 catalyzer
| Profile | Strip |
| Size/mm charge capacity/% specific surface area/m 2·g -1Specific pore volume/mlg -1Bulk density/gml -1 | ????0.5～1.0 ????76.9 ????1285 ????0.75 ????0.87 |
To help to understand the present invention by following embodiment, but can not limit content of the present invention, be described in detail, no longer give unnecessary details in following examples about the preparation method of methyl two silicon hydride chlorid.
Embodiment 1
Methyl hydrogen dichlorosilane is being filled with immobilized AlCl
3By self disproportionation reaction synthesizing methyl two silicon hydride chlorid, reactor (I) temperature is 300 ℃ in the fixed-bed reactor of catalyzer (I), and the liquid volume air speed of methyl hydrogen dichlorosilane is 1.5h
-1, reactor (I) outlet product goes out methyl two silicon hydride chlorid by subzero fractionation; Then that methyl two silicon hydride chlorid and the trimethylchlorosilane collected is well back with 1.5h with 0.8: 1 mixed in molar ratio
-1The liquid volume air speed by being filled with immobilized AlCl
3Redistribution reaction synthesization of dimethyl silicon hydride chlorid takes place in the fixed-bed reactor of catalyzer (II), and reactor (II) temperature is 280 ℃; Finish reaction after reaction-ure feeding finishes, collect product and adopt vapor-phase chromatography to carry out quantitative analysis.Wherein trimethylchlorosilane 21.9%, methyl two silicon hydride chlorid 18.4%, dimethyl silicane hydroxide 59.3%.
Embodiment 2
Methyl hydrogen dichlorosilane is being filled with immobilized AlCl
3By self disproportionation reaction synthesizing methyl two silicon hydride chlorid, reactor (I) temperature is 300 ℃ in the fixed-bed reactor of catalyzer (I), and the liquid volume air speed of methyl hydrogen dichlorosilane is 1.5h
-1, reactor (I) outlet product goes out methyl two silicon hydride chlorid by subzero fractionation; Then that methyl two silicon hydride chlorid and the trimethylchlorosilane collected is well back with 3.0h with 1: 1 mixed in molar ratio
-1The liquid volume air speed by being filled with immobilized AlCl
3Redistribution reaction synthesization of dimethyl silicon hydride chlorid takes place in the fixed-bed reactor of catalyzer (II), and reactor (II) temperature is 280 ℃; Finish reaction after reaction-ure feeding finishes, collect product and adopt vapor-phase chromatography to carry out quantitative analysis.Wherein trimethylchlorosilane 41.9%, methyl two silicon hydride chlorid 17.7%, dimethyl silicane hydroxide 39.8%.
Embodiment 3
Methyl hydrogen dichlorosilane is being filled with immobilized AlCl
3By self disproportionation reaction synthesizing methyl two silicon hydride chlorid, reactor (I) temperature is 300 ℃ in the fixed-bed reactor of catalyzer (I), and the liquid volume air speed of methyl hydrogen dichlorosilane is 1.5h
-1, reactor (I) outlet product goes out methyl two silicon hydride chlorid by subzero fractionation; Then that methyl two silicon hydride chlorid and the trimethylchlorosilane collected is well back with 1.5h with 0.8: 1 mixed in molar ratio
-1The liquid volume air speed by being filled with immobilized AlCl
3Redistribution reaction synthesization of dimethyl silicon hydride chlorid takes place in the fixed-bed reactor of catalyzer (II), and reactor (II) temperature is 320 ℃, finishes reaction after reaction-ure feeding finishes, and collects product and adopts vapor-phase chromatography to carry out quantitative analysis.Wherein trimethylchlorosilane 16.3%, methyl two silicon hydride chlorid 12.9%, dimethyl silicane hydroxide 70.5%.
Embodiment 4
Methyl hydrogen dichlorosilane is being filled with immobilized AlCl
3By self disproportionation reaction synthesizing methyl two silicon hydride chlorid, reactor (I) temperature is 300 ℃ in the fixed-bed reactor of catalyzer (I), and the liquid volume air speed of methyl hydrogen dichlorosilane is 1.5h
-1, reactor (I) outlet product goes out methyl two silicon hydride chlorid by subzero fractionation; Then that methyl two silicon hydride chlorid and the trimethylchlorosilane collected is well back with 3.0h with 1: 1 mixed in molar ratio
-1The liquid volume air speed by being filled with immobilized AlCl
3Redistribution reaction synthesization of dimethyl silicon hydride chlorid takes place in the fixed-bed reactor of catalyzer (II), and reactor (II) temperature is 320 ℃, finishes reaction after reaction-ure feeding finishes, and collects product and adopts vapor-phase chromatography to carry out quantitative analysis.Wherein trimethylchlorosilane 32.4%, methyl two silicon hydride chlorid 13.5%, dimethyl silicane hydroxide 56.1%.
Claims (1)
1. the method for a synthesization of dimethyl silicon hydride chlorid is characterized in that, is raw material with methyl hydrogen dichlorosilane and trimethylchlorosilane, makes methyl hydrogen dichlorosilane be filled with immobilized AlCl earlier
3Pass through self disproportionation reaction synthesizing methyl two silicon hydride chlorid in the fixed-bed reactor of catalyzer (I); Then with methyl two silicon hydride chlorid collected and trimethylchlorosilane with 0.5: 1 ~ 1: 1 mixed in molar ratio well the back with certain liquid volume air speed by being filled with immobilized AlCl
3Redistribution reaction synthesization of dimethyl silicon hydride chlorid takes place in the fixed-bed reactor of catalyzer (II); Reactor (I) and temperature (II) are 250 ~ 400 ℃, and the liquid volume air speed of reactant is 0.5 ~ 5.0h in the reactor (II)
-1
Priority Applications (1)
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|---|---|---|---|
| CNB2005100490143A CN1300151C (en) | 2005-02-01 | 2005-02-01 | Synthesis of dimethyl silicane hydroxide |
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|---|---|---|---|
| CNB2005100490143A CN1300151C (en) | 2005-02-01 | 2005-02-01 | Synthesis of dimethyl silicane hydroxide |
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| CN1300151C CN1300151C (en) | 2007-02-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104936965A (en) * | 2013-01-17 | 2015-09-23 | 瓦克化学股份公司 | Method for producing alkyl chlorosilanes by way of rearrangement reactions |
| CN106632447A (en) * | 2016-10-28 | 2017-05-10 | 嘉兴学院 | Preparation method of dimethyl hydrogen chlorosilane |
| CN113480567A (en) * | 2021-08-20 | 2021-10-08 | 唐山偶联硅业有限公司 | Method for preparing dimethyl hydrogen chlorosilane by homogeneous disproportionation reaction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4240730A1 (en) * | 1992-12-03 | 1994-06-09 | Wacker Chemie Gmbh | Process for the preparation of dimethylchlorosilane |
-
2005
- 2005-02-01 CN CNB2005100490143A patent/CN1300151C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104936965A (en) * | 2013-01-17 | 2015-09-23 | 瓦克化学股份公司 | Method for producing alkyl chlorosilanes by way of rearrangement reactions |
| CN104936965B (en) * | 2013-01-17 | 2017-10-31 | 瓦克化学股份公司 | A kind of method that alkylchlorosilane is prepared by rearrangement reaction |
| CN106632447A (en) * | 2016-10-28 | 2017-05-10 | 嘉兴学院 | Preparation method of dimethyl hydrogen chlorosilane |
| CN113480567A (en) * | 2021-08-20 | 2021-10-08 | 唐山偶联硅业有限公司 | Method for preparing dimethyl hydrogen chlorosilane by homogeneous disproportionation reaction |
| CN113480567B (en) * | 2021-08-20 | 2022-11-22 | 唐山偶联硅业有限公司 | Method for preparing dimethyl hydrogen chlorosilane by homogeneous disproportionation reaction |
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Assignee: Quzhou Ruilijie Chemical Industry Co.,Ltd. Assignor: Zhejiang University Contract record no.: 2010330001130 Denomination of invention: Synthesis of dimethyl silicane hydroxide Granted publication date: 20070214 License type: Exclusive License Open date: 20051012 Record date: 20100618 |
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