CN100402584C - Method for preparing organic polysilane - Google Patents
Method for preparing organic polysilane Download PDFInfo
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- CN100402584C CN100402584C CNB2005100613228A CN200510061322A CN100402584C CN 100402584 C CN100402584 C CN 100402584C CN B2005100613228 A CNB2005100613228 A CN B2005100613228A CN 200510061322 A CN200510061322 A CN 200510061322A CN 100402584 C CN100402584 C CN 100402584C
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- polysilane
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Abstract
The present invention relates to a method for preparing organic polysilane. The method solves technical problem that the method can synthesize organic polysilane with special functional groups (such as halogen, carbonyl, amide, etc.) via convenient operation and moderate reaction. In the method for preparing organic polysilane of the present invention, a low-valent titanium agent (Ti) is prepared via TiClx/M in organic solvent, dichlorosilane is used as a raw material, and the polysilane can be synthesized via the low-valent titanium agent (Ti).
Description
Technical field
The present invention relates to organic high molecular compound, specifically is a kind of preparation method of organopolysilane.
Background technology
The synthetic method of polysilane mainly contains in the prior art: a) poly of the promoted dichlorosilane of ultrasonic wave reaction [J.Am.Chem.Soc., 110 (1988), 3324]; B) the open loop poly of unsettled cyclic silane reaction (spy opens flat 5-170913 communique); C) the dehydrogenation polycondensation of transition metal complex compound inductive hydrosilanes (spy opens flat 7-17753 communique); D) the coupling poly of the promoted dichlorosilane of electrochemistry reaction (spy opens flat 7-309953 communique); E) poly of lithium salts and the promoted dichlorosilane of MAGNESIUM METAL reaction (CN1240459A); F) and the anionic polymerisation (spy opens flat 1-23063 communique) that carries out of exposed disilane etc.But method is the method for the synthetic polysilane in a kind of laboratory a), is difficult in the industrial production; B) and f) need synthesize complicated silane monomer, and in synthetic, use lithium alkylide, aspect security, have certain problem, actually operating difficulty; C) molecular-weight average of method synthetic polysilane is not too high; D) though can synthesize some high-quality organopolysilanes, needing the electrolyzer of special reaction device, is not too suitable on the lower polysilane of production added value; When e) method is synthesized polysilane, in electrolyzer, use in a large amount of lithium salts and MAGNESIUM METAL, also need a large amount of metal halides, operate more loaded down with trivial details.
Up to now, the Wurtz coupling poly that remains promoted dichlorosilane under basic metal (sodium, the potassium) high temperature the most commonly used reacts [J.Am.Chem.Soc., 103 (1981), 7352] in the polysilane preparation.But, because the promoted reaction of basic metal is thermopositive reaction, in reaction process, emit a large amount of heat, therefore, in Industrial processes for the control of speed of response, produce on a large scale and all be faced with very big difficulty, and because severe reaction conditions, some functional groups (as, halogen, carbonyl, amide group etc.) often destroyed in reaction process.The Wurtz linked reaction also is accompanied by the generation of Si-O-Si forming Si-Si simultaneously simultaneously, has a strong impact on the purity of synthetic polysilane, has reduced the various performances of polysilane material.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of easy to operate, and reaction is relatively gentleer, and can synthesize the method for the organopolysilane that has particular functional group's (as halogen, carbonyl, amide group etc.).
The present invention through repetition test research, finds titanium (TiCl at a low price on the basis of existing various synthetic organopolysilanes
X/ Mg, TiCl
X/ Zn, TiCl
X/ Mg-Hg, TiCl
X/ Cu, TiCl
X/ Sm, TiCl
X/ SmI
2, TiCl
X/ LiAlH
4, TiCl
X/ C
8K, X=3 in the formula, 4) be a kind of reductive polymerization agent of good dichlorosilane, synthesize organopolysilane with titanium at a low price, can solve problem more existing in the prior art well.
The preparation method of organopolysilane of the present invention, in organic solvent with TiCl
x/ M prepares low valent titanium reagent [Ti], is raw material with the dichlorosilane, and [Ti] synthesizes polysilane by low valent titanium reagent, and its reaction formula (1) is:
R
1，R
2＝CH
3，CH
2CH
3，Vinyl，Allyl，H，CH
2CH
2OR；
Work as R
1, R
2Be aryl:
N is the positive integer of 50-1500;
Solvents is that solvent is a tetrahydrofuran (THF), 1,2-glycol dimethyl ether, benzene, a kind of in the toluene; TiCl
xBe TiCl
4, TiCl
3In one or both mix reagent; M is metal M g, Zn, Mg-Hg, Cu, Sm, SmI
2, LiAlH
4, C
8The mixture of one or more among the K.
In the formula, Solvents is that solvent is a tetrahydrofuran (THF), 1,2-glycol dimethyl ether, benzene, second hydrogen, a kind of in the toluene; TiCl
xBe TiCl
4, TiCl
3In one or both mix reagent; M is metal M g, Zn, Mg-Hg, Cu, Sm, SmI
2, LiAlH
4, C
8The mixture of one or more among the K.
The present invention uses the low price titanium as the reductive polymerization agent, synthesizes organopolysilane by reduction dichlorosilane in non-proton organic solvent, can reach following significant effect:
A) use industrial raw material, reaction conditions is relatively gentleer;
B) metal of Shi Yonging and titanium metal halogenide are relatively inexpensive, safety and environmentally safe;
C) since low valent titanium reagent be easy to reaction system in a spot of water that contains or oxygen reaction, therefore in the process that generates Si-Si, can suppress the formation of Si-O-Si key effectively, some organopolysilane purity height of synthetic;
D) because the low price titanium is a kind of original reagent of going back of gentleness, and in reaction process, some particular functional groups such as carbonyl in its substrate, amide group, alkylene etc. can be not destroyed, the dehalogenation reaction can not take place simultaneously yet.
Embodiment
Below by embodiment, technical scheme of the present invention is described further.
Embodiment 1.
At one magnetic stirring apparatus is housed, place in three mouthfuls of round-bottomed flasks of the 100mL of constant pressure funnel, reflux condensing tube and air guide port device (0.097g, 4mmol) metal magnesium powder vacuumizes, and inflated with nitrogen carries out 3 times repeatedly.Inject the new distillatory tetrahydrofuran solvent of 40mL then, under nitrogen protection, in reaction flask, add (0.25ml, 2.2mmol) TiCl
3Behind the reflux 2h, be cooled to room temperature, promptly get the low valent titanium reagent of brownish black mud shape.Under the nitrogen protection, in reaction flask, be added dropwise to the THF solution (2ml) that contains dichloromethyl phenylsilane (2mmol), drip 10-60min down at 67 ℃.Mixture reacted about 12 hours down at 67 ℃ then.After reaction finishes, be cooled to room temperature after, add the 2mL dehydrated alcohol.Then reaction mixture is poured among the dilute hydrochloric acid 20mL of 1N, with extracted with diethyl ether (3 * 20mL), merge organic layer with saturated sodium bicarbonate wash secondary (2 * 10mL), saturated common salt solution washing three times (3 * 10mL).The organic layer anhydrous magnesium sulfate drying, boil off solvent after, obtain containing low-molecular-weight thick polysilane, with anhydrous tetrahydro furan (2mL) dissolving after, use the dehydrated alcohol redeposition, obtain highly purified organopolysilane.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.4, molecular-weight average is M
n=13000 aminomethyl phenyl polysilane, yield are 50%.
Embodiment 2
Described tiron is a titanium tetrachloride, and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.3, molecular-weight average is M
n=16000 aminomethyl phenyl polysilane, yield are 52%.
Embodiment 3
Described reacting metal M is a zinc powder, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.5, molecular-weight average is M
n=6000 aminomethyl phenyl polysilane, yield are 39%.
Embodiment 4
Described reacting metal M is magnesium-mercury alloys (Mg=80%, Hg=20%), and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.2, molecular-weight average is M
n=17600 aminomethyl phenyl polysilane, yield are 55%.
Embodiment 5
Described reacting metal M is magnesium-mercury alloys (Mg=80%, Hg=20%), and described tiron is a titanium tetrachloride, and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.3, molecular-weight average is M
n=16500 aminomethyl phenyl polysilane, yield are 53%.
Embodiment 6
Described reacting metal M is that copper powder replaces the magnesium powder, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.6, molecular-weight average is M
n=4500 aminomethyl phenyl polysilane, yield are 38%.
Embodiment 7
Described reacting metal M is the samarium powder, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.0, molecular-weight average is M
n=8000 aminomethyl phenyl polysilane, yield are 40%.
Embodiment 8
Described reacting metal M is a samarium diodide, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.8, molecular-weight average is M
n=12100 aminomethyl phenyl polysilane, yield are 42%.
Embodiment 9
Described reacting metal M is a Lithium Aluminium Hydride, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.6, molecular-weight average is M
n=17100 aminomethyl phenyl polysilane, yield are 45%.
Embodiment 10
Described reacting metal M is a Lithium Aluminium Hydride, and described tiron is a titanium tetrachloride, and the reaction times is to replace taking the identical operations step to react with embodiment 1 outside 12 hours in 24 hours.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.3, molecular-weight average is M
n=18800 aminomethyl phenyl polysilane, yield are 51%.
Embodiment 11
Described reacting metal M is C
8K takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.3, molecular-weight average is M
n=7100 aminomethyl phenyl polysilane, yield are 37%.
Embodiment 12
Described reacting metal M is C
8K, described tiron are titanium tetrachloride, and the reaction times is to replace taking the identical operations step to react with embodiment 1 outside 12 hours in 24 hours.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.9, molecular-weight average is M
n=10800 aminomethyl phenyl polysilane, yield are 45%.
Embodiment 13
Described dichlorosilane is a dimethyldichlorosilane(DMCS), and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.5, molecular-weight average is M
n=9800 dimethyl polysiroxan, yield are 47%.
Embodiment 14
Described dichlorosilane is the methylethyl dichlorosilane, and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.5, molecular-weight average is M
n=5800 methylethyl polysilane, yield are 46%.
Embodiment 15
Described dichlorosilane is the methyl ethylene dichlorosilane, and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.0, molecular-weight average is M
n=7800 methyl ethylene polysilane, yield are 38%.
Embodiment 16
Described dichlorosilane is the methylpropenyl dichlorosilane, and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.1, molecular-weight average is M
n=5800 methylpropenyl polysilane, yield are 38%.
Embodiment 17
Described dichlorosilane is that methyl p-methylphenyl dichlorosilane replaces dichloromethyl phenylsilane, and the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.1, molecular-weight average is M
n=15800 methyl p-methylphenyl polysilane, yield is 48%.
Embodiment 18
Described dichlorosilane be methyl to the formyl radical diphenyl dichlorosilane, the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=2.1, molecular-weight average is M
n=17000 methyl is to formyl radical phenyl polysilane, and yield is 46%.
Embodiment 19
Described dichlorosilane be methyl to N, dinethylformamide base diphenyl dichlorosilane, the reaction times is 24 hours, takes the identical operations step to react with embodiment 1.Its result obtains molecular-weight average and is distributed as M
w/ M
n=1.5, molecular-weight average is M
n=15000 methyl is to N, dinethylformamide base phenyl polysilane, and yield is 45%.
Claims (1)
1. the preparation method of an organopolysilane, in organic solvent with TiCl
x/ M prepares low valent titanium reagent [Ti], is raw material with the dichlorosilane, and [Ti] synthesizes polysilane by low valent titanium reagent, and its reaction formula (2) is:
R
1, R
2=CH
3, CH
2CH
3, vinyl, allyl group, H;
Work as R
1, R
2Be aryl:
N is the positive integer of 50-1500;
Described in organic solvent with TiCl
x/ M prepares low valent titanium reagent [Ti]: at one magnetic stirring apparatus is housed, places 0.097g in three mouthfuls of round-bottomed flasks of the 100mL of constant pressure funnel, reflux condensing tube and air guide port device, the 4mmol metal magnesium powder vacuumizes, and inflated with nitrogen carries out 3 times repeatedly; Inject the new distillatory tetrahydrofuran solvent of 40mL then, under nitrogen protection, in reaction flask, add 0.25ml, 2.2mmol TiCl
3Behind the reflux 2h, be cooled to room temperature, promptly get the low valent titanium reagent of brownish black mud shape.
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|---|---|---|---|
| CNB2005100613228A CN100402584C (en) | 2005-10-31 | 2005-10-31 | Method for preparing organic polysilane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100613228A CN100402584C (en) | 2005-10-31 | 2005-10-31 | Method for preparing organic polysilane |
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|---|---|
| CN1880361A CN1880361A (en) | 2006-12-20 |
| CN100402584C true CN100402584C (en) | 2008-07-16 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2135844A1 (en) * | 2008-06-17 | 2009-12-23 | Evonik Degussa GmbH | Method for manufacturing higher hydridosilanes |
| WO2013133100A1 (en) | 2012-03-07 | 2013-09-12 | 日本曹達株式会社 | Method for producing polydialkylsilane |
| US8865850B2 (en) | 2012-06-14 | 2014-10-21 | Dow Corning Corporation | Method of selectively forming a reaction product in the presence of a metal silicide |
| CN113429573B (en) * | 2021-07-19 | 2023-09-26 | 王军 | Method for preparing polydimethylsilane by ultrasonic sodium condensation and polydimethylsilane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309953A (en) * | 1994-03-22 | 1995-11-28 | Osaka Gas Co Ltd | Production of polysilane |
| CN1240459A (en) * | 1996-12-27 | 2000-01-05 | 大阪瓦斯株式会社 | Process for preparing polysilanes |
-
2005
- 2005-10-31 CN CNB2005100613228A patent/CN100402584C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309953A (en) * | 1994-03-22 | 1995-11-28 | Osaka Gas Co Ltd | Production of polysilane |
| CN1240459A (en) * | 1996-12-27 | 2000-01-05 | 大阪瓦斯株式会社 | Process for preparing polysilanes |
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