CN1173498A - Method for prepn. of hexamethyldisilane by utilizing recovered metal Li and tetrahydrofuran - Google Patents
Method for prepn. of hexamethyldisilane by utilizing recovered metal Li and tetrahydrofuran Download PDFInfo
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- CN1173498A CN1173498A CN 97104025 CN97104025A CN1173498A CN 1173498 A CN1173498 A CN 1173498A CN 97104025 CN97104025 CN 97104025 CN 97104025 A CN97104025 A CN 97104025A CN 1173498 A CN1173498 A CN 1173498A
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Abstract
A process for preparing hexamethyldisilane by means of recovered metal lithium and tetrahydrofuran (THF) features that the mixture of metal lithium and recovered metal lighium and trimethyl chlorosilane are use as raw materials, recovered THF as solvent, they take part in reation at 25-65 deg. C for 10-60 hr to obtain hexamethyldisilane. Its advantages are high yield up to 60-80%, low cost, less consumption of raw materials, and no enviromental pollution.
Description
The present invention relates to a kind of compound, particularly a kind of preparation method of organodisilane compound with one or more C-Si keys.
Disilane is a compounds that contains the Si-Si key, in recent years since they at photoelectron material, ceramic precursor, the pharmacy catalyzer, the multiple application of aspects such as polysilane intermediate causes people's attention and attention.
Hexamethyldisilane is important basic compound in the disilane, knows that so far hexamethyldisilane has two kinds of chemical preparation process: (1) at US 4,309, disclosed many chlorine disilane methylation method in 556 (1982).It is to utilize the high boiling material of organosilane monomer in producing, and therefrom isolates many chlorine disilane, methylates and makes with the methyl grignard reagent.Because it is very complicated that high boiling material is formed, the few separation difficulty of disilane content, the grignard reagent consumption is big, and this method is used and is restricted.(2) reducing couple of trimethylchlorosilane and alkali metallic sodium or lithium is legal.At SU 1,833, the method with sodium Metal 99.5 reductive coupling trimethylchlorosilane is disclosed among 390 A3 (1993), it reacts under high temperature and pressure in organic solvent with sodium Metal 99.5 and trimethylchlorosilane, there is serious potential safety hazard in severe reaction conditions, generally is difficult to adopt.
With the method for metallic lithium reductive coupling trimethylchlorosilane under mild conditions, be at J.Organomet.Chem., 13, at first propose in 323 (1968), thereafter at J.Organomet.Chem., 36, C13 (1972), Z.Anorg.Allg.Chem., 473,59 (1981), the spy opens among the flat 5-230077 (1993), basically having continued to use this method, is a kind of method that relatively has preparation to be worth at present.This method is to be reaction reagent with metallic lithium and trimethylchlorosilane, and mol ratio is Li: Me
3SiCl=1.1-1.7 makes solvent with THF, under reflux temperature or room temperature, reacts 12-60 hour formation hexamethyldisilane, and productive rate is 36-76%.Yet this method also must solve following problems as a kind of practical system Preparation Method of hexamethyldisilane.Prepare hexamethyldisilane with this method, its productive rate is relevant with the excessive degree of metallic lithium, productive rate is lower under low mol ratio condition, must use excessive metallic lithium and a large amount of organic solvent THF in order to obtain high yield, because reacted residual metal lithium is used as waste treatment, THF is run off in the washing product is handled, and therefore causes the wasting of resources and environmental pollution.Metallic lithium and THF are somewhat expensive starting material, and hexamethyldisilane price in the world is very expensive, and domestic also do not have a commercial production.Make full use of raw material resources, increase productive rate, reduce preparation cost, decontamination is the problem that must solve in this method practicability process.
The object of the invention is to overcome the waste of residual metal lithium and THF and the shortcoming of contaminate environment, provides a kind of the utilization to reclaim metallic lithium and reclaim the method that THF prepares hexamethyldisilane.By the recovery and reuse of residual metal lithium and THF, make productive rate reach 60-80%, save starting material, reduce cost.
The method that the present invention prepares hexamethyldisilane is to adopt the reductive coupling reaction of trimethylchlorosilane and metallic lithium.Mixture, trimethylchlorosilane with metallic lithium and recovery metallic lithium are reaction reagent, are solvent to reclaim THF, generate hexamethyldisilane by the reductive coupling reaction, and its preparation method is undertaken by following sequential steps:
(1) reclaims metallic lithium and the method that reclaims THF
At first press J.Organomet.Chem., the method described in 13,323 (1968) is done initial action one time.Metallic lithium and solvent THF are added in the dry reaction bottle, add trimethylchlorosilane at logical nitrogen with under fully stirring, reinforced finishing finished 25 ℃ of reactions in 60 hours.The mol ratio of above-mentioned metallic lithium and trimethylchlorosilane is 1.0-1.3, and the weight ratio of above-mentioned THF and trimethylchlorosilane is 0.8-2.0.
Reaction finishes static 1 hour of back, makes the lithium chloride precipitation of formation, and the residual metal lithium floats on liquid level.Under nitrogen protection, remaining lithium and reaction solution are transferred in the complementary tank, lithium are separated with reaction solution, reclaim lithium and place the drying nitrogen protection, to guarantee the surfactivity of lithium with suction strainer or press filtration method.Filtering-depositing is collected filtrate.Isolating reaction solution and filtrate merging are carried out fractionation, and the cut of collecting 60-80 ℃ of boiling range is mainly THF, and preferable boiling range is 66-76 ℃.The THF that reclaims is merged with the recovery metallic lithium, be used for next step reaction.The cut of collecting 111-113 ℃ of BP is a hexamethyldisilane, and the initial action productive rate is 35-50%.
(2) utilize recovery metallic lithium and recovery THF to prepare hexamethyldisilane
The metallic lithium of step (1) recovery and the THF of recovery are added in the dry reaction bottle, press Li: Me again
3The consumption of SiCl=1.0-1.3 (mol ratio) adds metallic lithium, adds trimethylchlorosilane under logical nitrogen and abundant the stirring, and reinforced finishing is 25-65 ℃ of reaction end reaction in 10-60 hour down.The post-reaction treatment program method of (1) is still set by step carried out, and entire reaction and removal process are carried out in drying nitrogen, and it is 60-80% that reaction obtains the hexamethyldisilane productive rate.
Above-mentioned recovery metallic lithium is 0.1-03 with the mol ratio that adds metallic lithium.
The mixture of above-mentioned metallic lithium and recovery metallic lithium and the mol ratio of trimethylchlorosilane are 1.1-1.6, and preferable mol ratio is 1.3-1.5.
The weight ratio of above-mentioned recovery THF and trimethylchlorosilane is 0.8-2.0, and preferable weight ratio is 1.0-1.5.
According to the method for preparing hexamethyldisilane provided by the invention, can reach following effect: (1) saves starting material THF and metallic lithium in a large number.The present invention only requires in initial action and to add new THF, and the THF that once reclaims before all using with afterreaction, each reacted residual metal lithium reclaim and usefulness again, are not therefore wasting any starting material in the preparation process continuously.(2) Li/THF of Hui Shouing can promote reaction, increase productive rate.Owing to reclaim the surfactivity that metallic lithium has kept response behaviour, reclaim THF quilt further dry (lithium, trimethylchlorosilane, lithium chloride all are siccative) in reaction process, therefore, when they are used for reacting again, reaction there is obvious promoter action.As mentioned above, by the initial action that literature method carries out, the productive rate of hexamethyldisilane is 36-50%, and the present invention utilizes recovery Li/THF to prepare hexamethyldisilane, and productive rate reaches 60-80%.This can find out from the result of continuous 4 embodiment, sees the following form.(3) reduce preparation cost, eliminate environmental pollution.The present invention has made full use of various starting material in preparation hexamethyldisilane process, and at low charging capacity Li: Me
3Increased the hexamethyldisilane productive rate under SiCl=1.0-1.3 (mol ratio) condition, so preparation cost can reduce significantly.In addition, the present invention has reclaimed residual metal lithium and THF effectively and has utilized, and the by product lithium chloride is again to be easy to reclaim and useful material, does not have the waste of contaminate environment, has avoided the pollution problem to environment.Embodiment Me
3SiCl Li THF Me
3SiSiMe
3
(g) (g) (ml)) productive rate %1 520 40.0 800 512 520 40.0 72
(8.2 recovery) 800 (recovery) 3 520 40.0 70
(6.9 recovery) 800 (recovery) 4 520 40.0 74
(9.1 recovery) 800 (recovery)
Further specify the present invention with specific embodiment below:
Embodiment 1: in being equipped with the 2L there-necked flask of reflux condensing tube, feed hopper, airway and induction stirring, logical nitrogen drying 15 minutes, add 40.0g (5.8mol) metallic lithium and 800ml THF, fully stirring adds 520g (4.8mol) trimethylchlorosilane down, finishes 25 ℃ of reaction end reactions in 60 hours down.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen, residual metal lithium and reaction solution are transferred in the complementary tank together, the two are separated, reclaim the heavy 8.2g of lithium, place under the nitrogen protection with filter press technique.Filtering-depositing is collected filtrate, and isolating reaction solution and filtrate merging are carried out fractionation, collects 60-80 ℃ of cut 830ml of BP, is mainly THF, will reclaim THF and merge with the recovery metallic lithium, is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 179g, productive rate 51%, purity 98%.
Embodiment 2: the metallic lithium 8.2g (1.18mol) of example 1 recovery and the THF 800ml that reclaims are added in the reaction flask, logical nitrogen adds metallic lithium 40.0g (5.8mol) down, fully stir and add 520g (4.8mol) trimethylchlorosilane down, finish 25 ℃ of reactions 24 hours, react again at 55 ℃ and finished reaction in 24 hours.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen protection, the residual metal lithium is transferred in the complementary tank together with reaction solution, the two is separated, reclaim the heavy 6.9g of lithium, place under the nitrogen protection with filter press technique.Filtering-depositing is collected filtrate, and isolating reaction solution and filtrate merging are carried out fractionation, and 66-72 ℃ of cut 790ml of collection BP is THF, with receiving THF and reclaiming the metallic lithium merging, is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 253g, productive rate 72%.
Embodiment 3: the metallic lithium 6.9g (1.0mol) of example 2 recovery and the THF 790ml that reclaims are added in the reaction flask, add the THF 10ml that example 1 reclaims.Logical nitrogen adds metallic lithium 40.0g (5.8mol) down, fully stirs down to add 520g (4.8mol) trimethylchlorosilane, finishes 25 ℃ of reactions and finishes reaction in 60 hours.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen protection, the residual metal lithium is transferred in the complementary tank together with reaction solution, the two is separated, reclaim the heavy 9.1g of lithium, place under the nitrogen protection with suction filtration.Filtering-depositing is collected filtrate, and reaction solution and filtrate merging are carried out fractionation, and collecting 66-76 ℃ of cut 800ml of BP is THF, reclaims THF and reclaim metallic lithium to merge, and is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 246g, productive rate 70%.
Embodiment 4: the lithium 9.1g (1.31mol) of example 3 recovery and the THF 800ml that reclaims are added in the reaction flask, logical nitrogen adds metallic lithium 40.0g (5.8mol) down, fully stir and add 520g (4.8m0l) trimethylchlorosilane down, finish 25 ℃ of reactions 12 hours, react again at 55 ℃ and finished reaction in 36 hours.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen protection, the residual metal lithium is transferred in the complementary tank in company with reaction solution, the two is separated, reclaim the heavy 7.5g of lithium, place under the nitrogen protection with suction filtration.Filtering-depositing is collected filtrate, and reaction solution and filtrate are merged fractionation, and collecting 66-76 ℃ of cut 800ml of BP is THF, reclaims THF and reclaim metallic lithium to merge, and is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 259g, productive rate 74%.
Embodiment 5: the lithium 7.5g (1.08mol) of example 4 recovery and the THF 800ml that reclaims are added in the reaction flask, logical nitrogen adds metallic lithium 45.0g (6.48mol) down, fully stir and add 520g (4.8mol) trimethylchlorosilane down, finish 25 ℃ of reactions 8 hours, finished reaction in 40 hours 55 ℃ of reactions.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen protection, the residual metal lithium is transferred in the complementary tank in company with reaction solution, the two is separated, reclaim the heavy 7.3g of lithium, place under the nitrogen protection with suction filtration.Filtering-depositing is collected filtrate, and reaction solution and filtrate are merged fractionation, and collecting 66-80 ℃ of cut 810ml of BP is THF, reclaims THF and reclaim metallic lithium to merge, and is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 273g, productive rate 78%.
Embodiment 6: the lithium 7.3g (1.05mol) of example 5 recovery and the THF 810ml that reclaims are added in the reaction flask, logical nitrogen adds metallic lithium 35.0g (5.04mol) down, fully stir and add 520g (4.8mol) trimethylchlorosilane down, finish 25 ℃ of reactions 24 hours, react again at 55 ℃ and finished reaction in 24 hours.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen protection, the residual metal lithium is transferred in the complementary tank together with reaction solution, the two is separated, reclaim the heavy 8.6g of lithium, place under the nitrogen protection with suction filtration.Filtering-depositing is collected filtrate, and with filtrate and reaction solution merging carrying out fractionation, collecting 66-80 ℃ of cut 810ml of BP is THF, reclaims THF and reclaims the metallic lithium merging, is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 231g, productive rate 66%.
Embodiment 7: the lithium 8.6g (1.24mol) of example 6 recovery and the THF 820ml that reclaims are added in the reaction flask, logical nitrogen adds metallic lithium 40.0g (5.8mol) down, fully stir adding 520g (4.8mol) trimethylchlorosilane down, finish 55 ℃ of reactions and finished reaction in 12 hours.Reaction mixture sat 1 hour precipitates the lithium chloride of formation, and remaining metallic lithium floats on liquid level.Under nitrogen protection, the residual metal lithium is transferred in the complementary tank together with reaction solution, the two is separated, reclaim the heavy 7.5g of lithium and place under the nitrogen protection with suction filtration.Filtering-depositing is collected filtrate, and with filtrate and reaction solution merging carrying out fractionation, collecting 66-76 ℃ of cut 800ml of BP is THF, reclaims HF and reclaims the metallic lithium merging, is used for reacting next time.Collecting 111-113 ℃ of cut of BP is hexamethyldisilane 245g, productive rate 70%.
Claims (8)
1, a kind of method for preparing hexamethyldisilane is to adopt metallic lithium and trimethylchlorosilane to make by the reductive coupling reaction in THF, it is characterized in that described metallic lithium is that metallic lithium is a solvent with the mixture that reclaims lithium, to reclaim THF, described reductive coupling temperature of reaction is 25-65C, and the reaction times is 10-60 hour.
2, the method for preparing hexamethyldisilane according to claim 1 is characterized in that described metallic lithium and reclaims in the lithium mixture that the mol ratio that reclaims lithium and metallic lithium is 0.1-0.3.
3, the method for preparing hexamethyldisilane according to claim 1 is characterized in that the weight ratio of described recovery THF and trimethylchlorosilane is 0.8-2.0.
4, the method for preparing hexamethyldisilane according to claim 3 is characterized in that the weight ratio of described recovery THF and trimethylchlorosilane is 1.0-1.5.
5, the method for preparing hexamethyldisilane according to claim 1 is characterized in that described metallic lithium and the mol ratio that reclaims metallic lithium mixture and trimethylchlorosilane are 1.1-16.
6, the method for preparing hexamethyldisilane according to claim 5 is characterized in that described metallic lithium and the mol ratio that reclaims lithium and trimethylchlorosilane are 1.3-1.5.
7, the method for preparing hexamethyldisilane according to claim 1 is characterized in that the boiling range of described recovery THF is BP60-80 ℃.
8, the method for preparing hexamethyldisilane according to claim 7 is characterized in that the boiling range of described recovery THF is BP66-76 ℃.
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| CN97104025A CN1056613C (en) | 1997-04-18 | 1997-04-18 | Method for prepn. of hexamethyldisilane by utilizing recovered metal Li and tetrahydrofuran |
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| CN97104025A CN1056613C (en) | 1997-04-18 | 1997-04-18 | Method for prepn. of hexamethyldisilane by utilizing recovered metal Li and tetrahydrofuran |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457762C (en) * | 2006-12-11 | 2009-02-04 | 扬州三友合成化工有限公司 | Synthesis process of hexamethyldisilane |
| CN117624214A (en) * | 2024-01-24 | 2024-03-01 | 全椒亚格泰电子新材料科技有限公司 | Preparation method of tetramethylsilane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU1833390C (en) * | 1991-12-23 | 1993-08-07 | ѕЛЧФБ@ ГЦѕьТГ | Method of hexamethyldisilane synthesis |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457762C (en) * | 2006-12-11 | 2009-02-04 | 扬州三友合成化工有限公司 | Synthesis process of hexamethyldisilane |
| CN117624214A (en) * | 2024-01-24 | 2024-03-01 | 全椒亚格泰电子新材料科技有限公司 | Preparation method of tetramethylsilane |
| CN117624214B (en) * | 2024-01-24 | 2024-05-17 | 全椒亚格泰电子新材料科技有限公司 | Preparation method of tetramethylsilane |
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