CN103992343B - A kind of preparation method of dimethyl vinyl chlorosilane - Google Patents
A kind of preparation method of dimethyl vinyl chlorosilane Download PDFInfo
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- CN103992343B CN103992343B CN201410159449.2A CN201410159449A CN103992343B CN 103992343 B CN103992343 B CN 103992343B CN 201410159449 A CN201410159449 A CN 201410159449A CN 103992343 B CN103992343 B CN 103992343B
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- vinyldimethylethoxysilane
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Abstract
The invention discloses the preparation method of a kind of dimethyl vinyl chlorosilane, including: under conditions of catalyst exists, chloracetyl chloride and Vinyldimethylethoxysilane generation esterification, obtain described dimethyl vinyl chlorosilane.Preparation method of the present invention not only raw material is cheap and easy to get, and reaction condition is gentle, and product is prone to purification, and product yield and purity are the highest.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly relate to a kind of dimethyl vinyl chlorosilane
Preparation method.
Background technology
Dimethyl vinyl chlorosilane, has another name called Chlorodimethyl vinyl silanes, and molecular weight is 120.65,
No. CAS is 1719-58-0, and molecular formula is (CH3)2SiCH=CH2Cl(writes a Chinese character in simplified form Me2SiViCl), it is
The Functional silicones hydride compounds of a kind of excellent performance, utilizes the Si-CH=CH on silane molecule2
Unsaturated bond, can be used to synthesize other Functional silicones intermediate, also can be used as producing high performance silicon
Oil and the active termination agent of silastic material.At present, the dimethyl vinyl chlorosilane that document is reported
Synthetic method, mainly includes that Grignard, discrimination method, addition process and pyrocondensation are legal etc..
Document (Reactions of (Me3Si)3CSiMe2R compounds(R=CH=CH2,CH2CH
=CH2,C≡CPh,Ph,and CH2Ph)with electrophiles,Journal of Organometallic
Chemistry, 1985,291:25-33.) disclose a kind of Grignard and prepare Me2The method of SiViCl,
This method is mainly by dimethyldichlorosilane (Me2SiCl2) and vinyl magnesium bromide or vinylimidazolium chloride magnesium,
In the presence of tetrahydrofuran solvent, at room temperature reaction generates Me2SiViCl.Document (Reactivity of
silicon-hydrogen bonds in organosilanes,Zhurnal Obshchei Khimii,1982,
52 (11): 2565-2570.) dimethyl silicane hydroxide (Me is used2SiHCl) anti-with vinyl magnesium bromide
Dimethyl ethenyl hydrogen silane (Me should be generated2SiViH), Me2SiViH reacts raw again with thionyl chloride
Become Me2SiViCl。
The European patent document of Publication No. EP0461597 discloses a kind of discrimination method and prepares
Me2The method of SiViCl, this method uses tetramethyl divinyl siloxanes and Me2SiCl2For the most former
Material, selecting tri-n-butylamine organo-alkali compound is catalyst, then adds a certain amount of hydrochloric acid or minor amount of water,
Room temperature condition reacts 5 hours, Me in product2SiViCl may be up to more than 80%.Document
(Characteristics of hydrochlorination of vinylsilanes with several vinyl
Groups at the silicon atom, Zhurnal Obshchei Khimii, 1985,55 (6): 1345-1350.)
With dimethyl divinyl silane (Me2SiVi2) it is primary raw material, selection ferric chloride is catalyst,
Being passed through hydrogen chloride gas generation dismutation reaction in a kettle., product is mainly Me2SiViCl and
Me2SiCl2Mixture.
Document (Silyl and σ-silane ruthenium complexes:Chloride substituent
effects on the catalysed silylation of ethylene,Dalton Transactions,2010,
39 (36): 8492-8500.) one Me is disclosed2SiHCl and ethylene are by high pressure additive reaction system
Standby Me2The method of SiViCl, the solvent that this method is selected is toluene, joins without catalyst or selection ruthenium system
Mixture catalyst, reacts 166h, raw material Me under 5～20 atmospheric pressure2The conversion ratio of SiHCl reaches
100%, Me in product2SiViCl is 72:28 with the ratio of dimethyl ethyl silane.
Document (Thermal condensation of hydrosilanes with chloroethylenes.I.
Reaction of1,2-dichloroethylene with hydrosilanes,Zhurnal Obshchei Khimii,
1981,51 (8): 1829-1834.) disclose one thermal condensation method and prepare Me2The method of SiViCl,
This method is with Me2SiHCl and vinyl chloride are primary raw material, in tank reactor or pipeline reactor,
Me is generated 300～600 DEG C of pyrocondensation reactions2SiViCl。
Patent CN103113399A discloses a kind of method preparing dimethyl vinyl chlorosilane, should
Method is first dimethyl silicane hydroxide, chloroplatinic acid composition catalyst and solvent to be mixed, and is mixed
Liquid；Then being passed through in mixed liquor with the form of bubbling by acetylene and carry out hydrosilylation, reaction completes
After, the dimethyl vinyl chlorosilane described in isolated and purified acquisition.
But existing preparation Me2All there is certain defect in the method for SiViCl, as a large amount of in used in reaction
Solvent, reaction raw materials silane source difficulty, reaction need High Temperature High Pressure, separate carry from mix products
Pure target product more difficulties etc., these not only cause technological operation dangerous, and production cost is relatively
Height, limits the industrial applications of these methods.
Summary of the invention
The invention provides the preparation method of a kind of dimethyl vinyl chlorosilane, solve existing method
Severe reaction conditions, the problem that product is difficult to separate.
A kind of preparation method of dimethyl vinyl chlorosilane, including:
Under conditions of catalyst exists, chloracetyl chloride and Vinyldimethylethoxysilane generation ester
Change reaction, obtain described dimethyl vinyl chlorosilane.
Equation is as follows:
Me2ViSiOEt+ClCH2COCl→Me2ViSiCl+ClCH2COEt
Me2SiViOEt refers to Vinyldimethylethoxysilane, Me2SiViCl refers to dimethyl ethenyl
Chlorosilane, wherein Vi represents vinyl, and OEt represents ethyoxyl.
Described catalyst is carbonate, preferably in sodium bicarbonate, sodium carbonate, magnesium carbonate and zinc carbonate
At least one.
Preferably, the mass ratio 100:0.1～5 of described chloracetyl chloride and catalyst, more elects 100 as:
1～3.
Carry out for avoiding moisture to affect reaction, it is preferred that described Vinyldimethylethoxysilane warp
Dried, can use molecular sieve drying to remove water.
Preferably, described Vinyldimethylethoxysilane is 0.5～1.2 with the mol ratio of chloracetyl chloride:
1, more preferably 0.6～1.0:1.
Preferably, the temperature of described esterification is 0 DEG C～90 DEG C, more preferably 10 DEG C～50 DEG C.
Preferably, the time of described esterification is 1～6 hour, more preferably 2～4 hours.
The most abundant for reaction, described esterification is: first mixed with catalyst by chloracetyl chloride, so
After Vinyldimethylethoxysilane is added drop-wise in mixed liquor, drip complete follow-up continuation of insurance temperature anti-
Should, until having reacted.
Described preparation method also includes the isolated and purified process of product, and described isolation and purification method can be normal
Pressure rectification or air-distillation.
Compared with prior art, the invention have the benefit that
Preparation method of the present invention not only raw material is cheap and easy to get, and reaction condition is gentle, and product is prone to purification,
And product yield and purity are the highest.
Detailed description of the invention
Embodiment 1
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:1 mass ratio add chloracetyl chloride, sodium bicarbonate catalyst；Stirring
After Jun Yun, the Vinyldimethylethoxysilane (mol ratio with chloracetyl chloride that then will process
For 0.7:1) it is added drop-wise in reaction vessel, continue on stirring by reactant liquor mix homogeneously, control esterification
Reaction temperature is 20 DEG C.After Vinyldimethylethoxysilane drips, continue insulation reaction
3 hours；Use gas chromatogram that reactant liquor in course of reaction is carried out dynamic tracking mensuration.Reaction terminates
Rear employing distillation mode carries out separating-purifying to crude product, obtains product dimethyl vinyl chlorosilane
Actual recovery is 80.1%.
Embodiment 2
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:3 mass ratio add chloracetyl chloride, sodium carbonate catalyst；Stirring is all
After even, the Vinyldimethylethoxysilane (amount with the material of chloracetyl chloride that then will process
Ratio is 0.65:1) it is added drop-wise in reaction vessel, continue on stirring by reactant liquor mix homogeneously, control
Esterification reaction temperature processed is 40 DEG C.After Vinyldimethylethoxysilane drips, continue to protect
Temperature reaction 2.5 hours；Use gas chromatogram that reactant liquor in course of reaction is carried out dynamic tracking mensuration.
Reaction uses distillation mode that crude product is carried out separating-purifying after terminating, and obtains product dimethyl vinyl
The actual recovery of chlorosilane is 91.7%.
Embodiment 3
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:1 mass ratio add chloracetyl chloride, catalyst, wherein sodium carbonate with
The mass ratio of sodium bicarbonate is 1:1；After stirring, the dimethyl ethenyl second that then will process
TMOS (being 0.8:1 with the mol ratio of chloracetyl chloride) is added drop-wise in reaction vessel, continues on and stirs
Mixing reactant liquor mix homogeneously, controlling esterification reaction temperature is 35 DEG C.When dimethylvinylsiloxy base oxethyl
After silane dropping, continue insulation reaction 4 hours；Gas chromatogram is used to react in course of reaction
Liquid carries out dynamic tracking mensuration.Reaction uses distillation mode that crude product is carried out separating-purifying after terminating,
The actual recovery obtaining product dimethyl vinyl chlorosilane is 93.4%.
Embodiment 4
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:2 mass ratio add chloracetyl chloride, magnesium carbonate catalyst；Stirring is all
After even, then by the Vinyldimethylethoxysilane processed (with the mol ratio of chloracetyl chloride it is
0.85:1) it is added drop-wise in reaction vessel, continues on stirring by reactant liquor mix homogeneously, control esterification
Reaction temperature is 30 DEG C.After Vinyldimethylethoxysilane drips, continue insulation reaction
4 hours；Use gas chromatogram that reactant liquor in course of reaction is carried out dynamic tracking mensuration.Reaction terminates
Rear employing distillation mode carries out separating-purifying to crude product, obtains product dimethyl vinyl chlorosilane
Actual recovery is 85.7%.
Embodiment 5
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:3 mass ratio add chloracetyl chloride, magnesium carbonate catalyst；Stirring is all
After even, then by the Vinyldimethylethoxysilane processed (with the mol ratio of chloracetyl chloride it is
0.75:1) it is added drop-wise in reaction vessel, continues on stirring by reactant liquor mix homogeneously, control esterification
Reaction temperature is 20 DEG C.After Vinyldimethylethoxysilane drips, continue insulation reaction
3 hours；Use gas chromatogram that reactant liquor in course of reaction is carried out dynamic tracking mensuration.Reaction terminates
Rear employing distillation mode carries out separating-purifying to crude product, obtains product dimethyl vinyl chlorosilane
Actual recovery is 84.8%.
Embodiment 6
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:4 mass ratio add chloracetyl chloride, catalyst, wherein zinc carbonate with
The mass ratio of magnesium carbonate is 1:1；；After stirring, the dimethyl ethenyl ethoxy that then will process
Base silane (being 0.9:1 with the mol ratio of chloracetyl chloride) is added drop-wise in reaction vessel, continues on stirring
By reactant liquor mix homogeneously, controlling esterification reaction temperature is 15 DEG C.When dimethylvinylsiloxy base oxethyl silicon
After alkane dropping, continue insulation reaction 2 hours；Use gas chromatogram to reactant liquor in course of reaction
Carry out dynamic tracking mensuration.Reaction uses distillation mode that crude product is carried out separating-purifying after terminating,
Actual recovery to product dimethyl vinyl chlorosilane is 82.1%.
Embodiment 7
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:2 mass ratio add chloracetyl chloride, zinc carbonate catalyst；Stirring is all
After even, then by the Vinyldimethylethoxysilane processed (with the mol ratio of chloracetyl chloride it is
0.7:1) it is added drop-wise in reaction vessel, continues on stirring and reactant liquor mix homogeneously, control are esterified anti-
Answering temperature is 25 DEG C.After Vinyldimethylethoxysilane drips, continue insulation reaction
3.5 hour；Use gas chromatogram that reactant liquor in course of reaction is carried out dynamic tracking mensuration.Reaction knot
Use distillation mode that crude product is carried out separating-purifying after bundle, obtain product dimethyl vinyl chlorosilane
Actual recovery be 87.6%.
Embodiment 8
Vinyldimethylethoxysilane (molecular weight: 130.26 boiling points: 93-99 DEG C) is first used
Molecular sieve drying, is carried out except water processes；Then equipped with thermometer, spherical condensation tube, nitrogen protection
Reaction vessel in press 100:1 mass ratio add chloracetyl chloride, zinc carbonate catalyst；Stirring is all
After even, then by the Vinyldimethylethoxysilane processed (with the mol ratio of chloracetyl chloride it is
0.8:1) it is added drop-wise in reaction vessel, continues on stirring and reactant liquor mix homogeneously, control are esterified anti-
Answering temperature is 25 DEG C.After Vinyldimethylethoxysilane drips, continue insulation reaction 3
Hour；Use gas chromatogram that reactant liquor in course of reaction is carried out dynamic tracking mensuration.After reaction terminates
Use distillation mode that crude product is carried out separating-purifying, obtain the reality of product dimethyl vinyl chlorosilane
Border yield is 83.7%.
Claims (1)
1. a preparation method for dimethyl vinyl chlorosilane, including:
By Vinyldimethylethoxysilane first by molecular sieve drying, carry out except water processes；Then exist
Add by the mass ratio of 100:1 equipped with in the reaction vessel that thermometer, spherical condensation tube, nitrogen are protected
Enter chloracetyl chloride, catalyst；After stirring, the dimethylvinylsiloxy base oxethyl that then will process
Silane is added drop-wise in reaction vessel, continues on stirring by reactant liquor mix homogeneously, control esterification
Temperature is 35 DEG C, after Vinyldimethylethoxysilane drips, continues insulation reaction 4
Hour；Reaction uses distillation mode that crude product is carried out separating-purifying after terminating；
Wherein, catalyst be mass ratio be the mixture of sodium carbonate and the sodium bicarbonate of 1:1, dimethyl
Ethenylethoxy silicon is 0.8:1 with the mol ratio of chloracetyl chloride.
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| CN201410159449.2A CN103992343B (en) | 2014-04-21 | 2014-04-21 | A kind of preparation method of dimethyl vinyl chlorosilane |
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| CN109867692A (en) * | 2017-12-01 | 2019-06-11 | 中昊晨光化工研究院有限公司 | A kind of preparation method of tetramethyl divinyl disilazane |
| CN111620902A (en) * | 2020-06-08 | 2020-09-04 | 无锡晶睿光电新材料有限公司 | Preparation method of unsaturated organic silazane |
| CN114634524B (en) * | 2020-12-16 | 2023-12-26 | 江西贝特利新材料有限公司 | Preparation method and application of dimethylvinylchlorosilane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136064A (en) * | 1991-02-15 | 1992-08-04 | Dow Corning Corporation | Olefinic and acetylenic azasilacyclopentanes |
| CN103113399A (en) * | 2013-03-08 | 2013-05-22 | 嘉兴学院 | Method for preparing dimethyl vinyl chlorosilane |
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2014
- 2014-04-21 CN CN201410159449.2A patent/CN103992343B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136064A (en) * | 1991-02-15 | 1992-08-04 | Dow Corning Corporation | Olefinic and acetylenic azasilacyclopentanes |
| CN103113399A (en) * | 2013-03-08 | 2013-05-22 | 嘉兴学院 | Method for preparing dimethyl vinyl chlorosilane |
Non-Patent Citations (1)
| Title |
|---|
| Syntheses and pharmacological characterization of achiral and chiral enantiopure C/Si/Ge-analogous derivatives of the muscarinic antagonist cycrimine: a study on C/Si/Ge bioisosterism;Reinhold Tacke et al.;《Journal of Organometallic Chemistry》;20011101;第640卷(第1-2期);第140-165页 * |
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