CN103833781B - Preparation method of phenyl chlorosilane - Google Patents
Preparation method of phenyl chlorosilane Download PDFInfo
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- CN103833781B CN103833781B CN201410103908.5A CN201410103908A CN103833781B CN 103833781 B CN103833781 B CN 103833781B CN 201410103908 A CN201410103908 A CN 201410103908A CN 103833781 B CN103833781 B CN 103833781B
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Abstract
The invention relates to a preparation method of phenyl chlorosilane. The preparation method comprises the following steps: adding phenyl disilane and a catalyst into a reactor, uniformly mixing, then inhaling inert gas into the reactor and exhausting air, stirring, heating, continuously inhaling pyrolysis gas for reaction under a normal pressure condition, stopping the reaction, rectifying and separating the reaction liquid to prepare different types of phenyl chlorosilane monomers. The target products prepared by the method disclosed by the invention are various types of phenyl chlorosilane monomers; the method can be used for simultaneously preparing various types of high value-added phenyl chlorosilane such as methyl phenyl dichloromethylsilane, dimethyl phenyl chlorosilane, methyl diphenyl chlorosilane and the like; moreover, the yield is high, the yield of byproduct methyl chlorosilane is low, and high-value utilization of a silicon resource is realized.
Description
Technical field
The present invention relates to a kind of preparation method of phenyl chlorosilane, belongs to organic silicon monomer preparing technical field.
Background technology
Organosilicon material has many excellent properties such as preferable temperature tolerance, radioresistance, intermiscibility and specific function, extensively
It is applied to the every field such as science and techniques of defence, Aero-Space, chemical industry, medicine.With with methyl chlorosilane monomer as prepared by raw material having
Machine silicon materials are compared, and the organosilicon material prepared with phenyl chlorosilane monomer is had more excellent temperature tolerance, radioresistance, mixed
The characteristics such as property so that the characteristic of organosilicon material has great lifting.
The preparation method of phenyl chlorosilane mainly includes：Condensation method, Grignard methods, Wurtz methods, catalystic pyrolysis etc..
Patent document CN101628917A discloses the synthesis technique that a kind of condensation method prepares phenyl chlorosilane monomer, that is, adopt
It is raw material with chlorobenzene, methyl hydrogen dichlorosilane, chloroform is catalyst, in 0.2-0.8Mpa, methyl is prepared under the conditions of 350-600 DEG C
Diphenyl dichlorosilane.But the reaction condition of the method HTHP, the security requirement to equipment and operating personnel is high, increase
Production cost, especially generates the accessory substance benzene of substantial amounts of strong carcinogenicity, is extremely unfavorable for industrial production.
Patent document US6541651 and patent document CN102225949A employ Grignard methods and prepare phenylchloride silicon
Alkane.Under anaerobic, with chlorobenzene and magnesium metal as raw material, in alkyl ether be obtained phenyl-magnesium-chloride, then again with methyl three
Chlorosilane reaction obtains dichloromethyl phenylsilane.This method adopts a large amount of organic solvents, and Grignard reagents to live very much
Sprinkle, easily explode, dangerous high, the subsequent treatment of a large amount of metal halides of generation is bothered very much, the product for ultimately producing
Hardly possible is separated.
Patent document CN101077877A discloses the alcoholysate phenyl alcoxyl for preparing phenyl chlorosilane monomer with Wurtz methods
, specifically with chlorobenzene and methyl alkoxy silane as raw material, there is condensation reaction in the presence of sodium and obtain octadecyloxy phenyl in base silane
TMOS.The shortcoming of this kind of method be raw material costly, methyl alkoxy silane is higher than chlorosilane price, according to chlorine
Silane then reacts violent for raw material, the difficult control of process, easily causes danger, the use of excess sodium, and in subsequent treatment, operating procedure is numerous
It is trivial and than relatively hazardous.
Patent document US3772347 and patent document CN101195633A are disclosed using noble metal platinum or palladium and its complexing
Thing is catalyst, is catalyzed the cracking reaction of disilane and chlorine aromatic hydrocarbons, prepares phenyl chlorosilane monomer.But this kind of reaction gained target
Product category is relatively simple, while generating the accessory substance methyl chlorosilane monomer of equivalent, required catalyst is expensive, it is difficult to
Circulating and recovering, production cost is high.
Accordingly, it would be desirable to design and develop new technology prepared by a kind of phenyl chlorosilane monomer, the technique not only reaction condition
Gently, simple to operate, raw material is cheap and easily-available, and the species of gained target product phenyl chlorosilane monomer is more, and yield is high, by-product
Thing is few, can realize the higher value application of silicon resource.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of preparation method of phenyl chlorosilane.
The present invention is achieved through the following technical solutions：
A kind of preparation method of phenyl chlorosilane, comprises the steps：
By phenyl disilane and catalyst in mass ratio（10～100）:1 adds in reactor, is well mixed, then to anti-
Answer be passed through in device inert gas discharge air, be heated with stirring to 100～200 DEG C, under condition of normal pressure, be continually fed into cracking gas 8～
24h, cracking gas is with the mol ratio of phenyl disilane（1～8）:1, stop reaction, rectifying separation is carried out to reactant liquor, it is obtained not
Congener phenyl chlorosilane monomer；
Described phenyl disilane structural formula is as follows：
MemPhnX3-m-nSiSiMeaPhbX3-a-b
Wherein：M, n, a, b are 0～3 integer, and n+b >=1, m+n+a+b ＜ 6, and Me is-CH3, Ph is-C6H5, X is
Cl or Br；
Described catalyst be in polyethers, quaternary ammonium salt, organic amine, crown ether, quaternary ammonium base or season phosphonium salt one or two with
On mixing；
Described cracking gas is HX, X2、CH3One or more mixing in X, wherein X is Cl or Br.
It is according to currently preferred, described polyethers：H(OCH2CH2)3OH、H(OCH2CH2)5OH or R (OCH2CH2)4OR；Described quaternary ammonium salt is：Tetramethyl ammonium chloride, tetrabutyl ammonium sulfate or DTAC；Described is organic
Amine is：Nitrogen nitrogen dimethylaniline, tri-n-amyl amine or tri-n-butylamine；Described crown ether is：Cyclodextrin, 15- crown ethers -5 or 18- hat
Ether -6；Described quaternary ammonium base is：TMAH, trimethylethyl ammonium hydroxide or dimethyl ethyl phenethyl hydroxide
Ammonium；Described season phosphonium salt is：Tetramethyl bromide phosphine, tetrabutyl phosphonium bromide phosphine or tetraphenylphosphonium chloride.
According to currently preferred, the phenyl disilane is with the mass ratio of catalyst（40～80）:1.
According to currently preferred, the temperature is 130～180 DEG C.
According to currently preferred, cracking gas is with the mol ratio of phenyl disilane（1～5）:1.
It is nitrogen, helium, neon or argon gas according to currently preferred, described inert gas.
Above-mentioned phenyl disilane can be prepared using prior art, following method may also be employed and prepares in proportion：
The accessory substance organosilicon high-boiling product that industrial " direct method " produces methylchlorosilane generation is carried out into rectifying, 130- is taken
170 DEG C of cut obtains disilane Me2ClSiSiMeCl2、MeCl2SiSiMeCl2、Me2ClSiSiMe2Mixed liquor (the three of Cl
Mol ratio is 1：1：0.5).Under the protection of nitrogen, 184g Na are added in 2130g toluene, while adding 10.65g palmitins
Acid, is stirred and heated to 105 DEG C, is prepared into alkali metal sand, and 450g chlorobenzenes are added in the alkali metal sand of preparation, reaction balance 2h,
Phenyl alkali metal salt is obtained, phenyl alkali metal salt is added to into 529g Me2ClSiSiMeCl2、MeCl2SiSiMeCl2、
Me2ClSiSiMe2(three's mol ratio is 1 to Cl：1：0.5) in mixed liquor, while 2.05g tetrabutyl phosphonium bromide phosphines are added, at 50 DEG C
Under conditions of, after reaction 5h, stop reaction, room temperature is cooled to, the mixture of phenyl disilane is obtained, Jing gas chromatographic analysis contains
247g Me2PhSiSiMePhCl, 105.8g MePhClSiSiMePh2, 155.5g MePhClSiSiClMePh, 91.4g
Me2PhSiSiMe2Cl；
Phenyl disilane is containing Me obtained in said method2PhSiSiMePhCl、MePhClSiSiMePh2、
MePhClSiSiClMePh and Me2PhSiSiMe2The mixture of tetra- kinds of phenyl disilane of Cl, directly can be carried out subsequently using it
Reaction, also can be separated into after single component by prior art, then carry out subsequent reactions.
Compared with prior art, the invention has the advantages that：
1）The species of gained target product phenyl chlorosilane monomer of the invention is more, can simultaneously prepare aminomethyl phenyl dichloro silicon
Various high added value phenyl chlorosilanes such as alkane, 3,5-dimethylphenyl chlorosilane, methyldiphenyl base chlorosilane, and yield is high, by-product
The low yield of thing methylchlorosilane, realizes the higher value application of silicon resource；
2）The course of reaction of the present invention is gentle, simple to operate, organic solvent is not adopted, without carcinogenic by-products in course of reaction
The generation of benzene；
3）The catalyst for cracking of the present invention is marketable material, and cheap and easily-available, reactant phenyl disilane adopts organosilicon
Prepared by high-boiling components, low cost, beneficial to industrialized production.
Specific embodiment
Technical scheme is further elaborated with reference to embodiment, but institute's protection domain of the present invention is not limited to
This.
Each the two of the disilane mixture that organosilicon high-boiling product is rectifying to obtain are analyzed using gas chromatograph-mass spectrometer (GC-MS)
The constituent content of each phenyl chlorosilane monomer in gained reactant liquor in silane components content, and each embodiment, accessory substance benzene
Content.
Raw material phenyl disilane in embodiment is containing Me2PhSiSiMePhCl、MePhClSiSiMePh2、
MePhClSiSiClMePh and Me2PhSiSiMe2The mixture of tetra- kinds of phenyl disilane of Cl, can be prepared using prior art,
Can adopt and prepare in proportion with the following method：
The accessory substance organosilicon high-boiling product that industrial " direct method " produces methylchlorosilane generation is carried out into rectifying, 130- is taken
170 DEG C of cut obtains disilane Me2ClSiSiMeCl2、MeCl2SiSiMeCl2、Me2ClSiSiMe2Mixed liquor (the three of Cl
Mol ratio is 1：1：0.5).Under the protection of nitrogen, 184g Na are added in 2130g toluene, while adding 10.65g palmitins
Acid, is stirred and heated to 105 DEG C, is prepared into alkali metal sand, and 450g chlorobenzenes are added in the alkali metal sand of preparation, reaction balance 2h,
Phenyl alkali metal salt is obtained, phenyl alkali metal salt is added to into 529g Me2ClSiSiMeCl2、MeCl2SiSiMeCl2、
Me2ClSiSiMe2(three's mol ratio is 1 to Cl：1：0.5) in mixed liquor, while 2.05g tetrabutyl phosphonium bromide phosphines are added, at 50 DEG C
Under conditions of, after reaction 5h, stop reaction, room temperature is cooled to, the mixture of phenyl disilane is obtained, Jing gas chromatographic analysis contains
247g Me2PhSiSiMePhCl, 105.8g MePhClSiSiMePh2, 155.5g MePhClSiSiClMePh, 91.4g
Me2PhSiSiMe2Cl。
Embodiment 1
By the mixture of the raw material phenyl disilane of above-mentioned preparation（Wherein Me containing 247g2PhSiSiMePhCl, 105.8g
MePhClSiSiMePh2, 155.5g MePhClSiSiClMePh, 91.4g Me2PhSiSiMe2Cl）, it is added to band material filling type fractionation
In the cracking still of tower, 6.00g tetraphenylphosphonium chlorides are then added, be passed through nitrogen 30min, discharge the air in cracking still, risen
Temperature is continually fed into gaseous state Br to 200 DEG C2, Br2It is 1 with the molar ratio of phenyl disilane mixture:1, it is continuous anti-under normal pressure
After answering 24h, stop reaction, the reactant liquor for obtaining is the mixture of phenyl chlorosilane monomer.
The mixture is analyzed with gas-chromatography, is calculated Me2The yield of PhSiBr is 25.9%,
The yield of MePhSiBrCl is 44.6%, MePh2The yield of SiBr is 6.2%, Me2The yield of SiBrCl is 8.3%, phenyl halosilanes
The total recovery of monomer is 76.7%, and no coupling product benzene is generated.
Rectifying is carried out to the mixture of above-mentioned phenyl-halide silane monomer, 218 DEG C, 228 DEG C, 316 DEG C of cut are taken respectively, point
Do not obtain product Me2PhSiBr、MePhSiBrCl、MePh2SiBr。
Embodiment 2
By the mixture of the raw material phenyl disilane of above-mentioned preparation（Wherein Me containing 247g2PhSiSiMePhCl,
105.8gMePhClSiSiMePh2, 155.5g MePhClSiSiClMePh, 91.4g Me2PhSiSiMe2Cl）, it is added to band filler
In the cracking still of formula fractionating column, 29.98g tri-n-amyl amines are then added, are passed through nitrogen 10min, discharge the air in cracking still,
130 DEG C are warming up to, Cl is continually fed into2, Cl2It is 4 with the molar ratio of phenyl disilane:1, under normal pressure after successive reaction 12h,
Stop reaction, the reactant liquor for obtaining is the mixture of phenyl chlorosilane monomer.
The mixture is analyzed with gas-chromatography, is calculated Me2The yield of PhSiCl is 27.4%, MePhSiCl2
Yield be 47.2%, MePh2The yield of SiCl is 6.6%, Me2SiCl2Yield be 8.78%, the total recovery of phenyl chlorosilane
For：81.2%, no coupling product benzene is generated.
Rectifying is carried out to the mixture of above-mentioned phenyl chlorosilane monomer, 196 DEG C, 206 DEG C, 296 DEG C of cut are taken respectively, point
Do not obtain product Me2PhSiCl、MePhSiCl2、MePh2SiCl。
Embodiment 3
By the mixture of the raw material phenyl disilane of above-mentioned preparation（Wherein Me containing 247g2PhSiSiMePhCl, 105.8g
MePhClSiSiMePh2, 155.5g MePhClSiSiClMePh, 91.4g Me2PhSiSiMe2Cl）, it is added to band material filling type fractionation
In the cracking still of tower, 8.57g tetramethyl bromide phosphines are then added, be passed through nitrogen 20min, discharge the air in cracking still, risen
Temperature is continually fed into CH to 150 DEG C3Cl, CH3Cl is 3 with the molar ratio of phenyl disilane:1, successive reaction 19h under normal pressure
Afterwards, reaction is stopped, the reactant liquor for obtaining is the mixture of phenyl chlorosilane monomer.
The mixture is analyzed with gas-chromatography, is calculated Me2The yield of PhSiCl is 62.2%, MePhSiCl2
Yield be 10.7%, MePh2The yield of SiCl is 6.4%, Me2SiCl2Yield be 8.6%, the total recovery of phenyl chlorosilane is：
79.3%, no coupling product benzene is generated.
Rectifying is carried out to the mixture of above-mentioned phenyl chlorosilane monomer, 196 DEG C, 206 DEG C, 296 DEG C of cut are taken respectively, point
Do not obtain product Me2PhSiCl、MePhSiCl2、MePh2SiCl。
Embodiment 4
By the mixture of the raw material phenyl disilane of above-mentioned preparation（Wherein Me containing 247g2PhSiSiMePhCl, 105.8g
MePhClSiSiMePh2, 155.5g MePhClSiSiClMePh, 91.4g Me2PhSiSiMe2Cl）, it is added to band material filling type fractionation
In the cracking still of tower, 59.97g tetramethyl ammonium chlorides are then added, be passed through nitrogen 5min, discharge the air in cracking still, risen
Temperature is continually fed into HCl gases to 100 DEG C, and HCl is 5 with the molar ratio of phenyl disilane:1, successive reaction 8h under normal pressure
Afterwards, reaction is stopped, the reactant liquor for obtaining is the mixture of phenyl chlorosilane monomer.
The mixture is analyzed with gas-chromatography, is calculated Me2The yield of PhSiCl is 28%, MePhSiCl2's
Yield is 48.2%, MePh2The yield of SiCl is 6.7%, and the total recovery of phenyl chlorosilane is：82.9%, no coupling product benzene is generated.
Rectifying is carried out to the mixture of above-mentioned phenyl chlorosilane monomer, 196 DEG C, 206 DEG C, 296 DEG C of cut are taken respectively, point
Do not obtain product Me2PhSiCl、MePhSiCl2、MePh2SiCl。
Claims (5)
1. a kind of preparation method of phenyl chlorosilane, it is characterised in that comprise the steps：
By phenyl disilane and catalyst in mass ratio（10～100）:1 adds in reactor, is well mixed, then to reactor
In be passed through inert gas discharge air, be heated with stirring to 100～200 DEG C, under condition of normal pressure, be continually fed into the h of cracking gas 8～24,
Cracking gas is with the mol ratio of phenyl disilane（1～8）:1, stop reaction, rectifying separation is carried out to reactant liquor, it is obtained not of the same race
The phenyl chlorosilane monomer of class；
Described phenyl disilane structural formula is as follows：
MemPhnX3-m-nSiSiMeaPhbX3-a-b
Wherein：M, n, a, b are 0～3 integer, and n+b >=1, m+n+a+b ＜ 6, and Me is-CH3, Ph is-C6H5, X is Cl
Or Br；
Described catalyst is tetramethyl ammonium chloride, tetramethyl bromide phosphine, tetraphenylphosphonium chloride or tri-n-amyl amine；
Described cracking gas is HX, X2、CH3One or more mixing in X, wherein X is Cl or Br.
2. preparation method as claimed in claim 1, it is characterised in that the phenyl disilane is with the mass ratio of catalyst
（40～80）:1.
3. preparation method as claimed in claim 1, it is characterised in that the temperature is 130～180 DEG C.
4. preparation method as claimed in claim 1, it is characterised in that the cracking gas is with the mol ratio of phenyl disilane（1
～5）:1.
5. preparation method as claimed in claim 1, it is characterised in that described inert gas is nitrogen, helium, neon or argon
Gas.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772347A (en) * | 1971-12-15 | 1973-11-13 | Dow Corning | Transition metal catalyzed silylations |
| US5288892A (en) * | 1992-06-19 | 1994-02-22 | Wacker-Chemie Gmbh | Separation of methylchlorosilanes from high boiling residues of methylchlorosilane synthesis |
| CN101195633A (en) * | 2007-12-07 | 2008-06-11 | 浙江大学 | Method for producing methyl phenyl dichloresilane |
| CN101628917A (en) * | 2009-07-28 | 2010-01-20 | 江苏宏达新材料股份有限公司 | Method for preparing methyldiphenylchlorosilane and reactor thereof |
| CN102584882A (en) * | 2012-02-17 | 2012-07-18 | 嘉兴学院 | Method for preparing methyl phenyl dichlorosilane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE552814A (en) * | 1955-11-22 |
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2014
- 2014-03-19 CN CN201410103908.5A patent/CN103833781B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772347A (en) * | 1971-12-15 | 1973-11-13 | Dow Corning | Transition metal catalyzed silylations |
| US5288892A (en) * | 1992-06-19 | 1994-02-22 | Wacker-Chemie Gmbh | Separation of methylchlorosilanes from high boiling residues of methylchlorosilane synthesis |
| CN101195633A (en) * | 2007-12-07 | 2008-06-11 | 浙江大学 | Method for producing methyl phenyl dichloresilane |
| CN101628917A (en) * | 2009-07-28 | 2010-01-20 | 江苏宏达新材料股份有限公司 | Method for preparing methyldiphenylchlorosilane and reactor thereof |
| CN102584882A (en) * | 2012-02-17 | 2012-07-18 | 嘉兴学院 | Method for preparing methyl phenyl dichlorosilane |
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Address after: 256401 Tangshan, Shandong, Huantai Town, Zibo Co-patentee after: Institute of Process Engineering, Chinese Academy of Sciences Patentee after: Shandong Dongyue organosilicon material Limited by Share Ltd Address before: 256401 Tangshan, Shandong, Huantai Town, Zibo Co-patentee before: Institute of Process Engineering, Chinese Academy of Sciences Patentee before: Shandong Dongyue Silicon Material co., Ltd. |