CN104387415A - Method for preparing hexamethyl-disilane amine lithium solution and reaction device thereof - Google Patents
Method for preparing hexamethyl-disilane amine lithium solution and reaction device thereof Download PDFInfo
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- CN104387415A CN104387415A CN201410685152.XA CN201410685152A CN104387415A CN 104387415 A CN104387415 A CN 104387415A CN 201410685152 A CN201410685152 A CN 201410685152A CN 104387415 A CN104387415 A CN 104387415A
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Abstract
The invention discloses a method for preparing a hexamethyl-disilane amine lithium solution and a reaction device thereof. The method has the following reaction principle: the structural formula is as shown in the specification. The method comprises the following specific reaction steps: batching, dropwise adding and carrying out a deep reaction. The reaction device comprises a reactor, an inert gas filling device, a stirring device, an electron carrier dropwise adding device, a reflux condensing device, a temperature control device, a suction filtration device and a storage device. The method disclosed by the invention is simple, high in reaction speed, complete in reaction and fewer in byproducts; and the adopted reaction device is simple in structure and convenient to use.
Description
Technical field
The present invention relates to the preparation method of hexamethyldisilane amine base an alkali metal salt, be specifically related to a kind of method and the reaction unit thereof of preparing hexamethyldisilane amine base lithium solution.
Background technology
Hexamethyldisilane amine base an alkali metal salt conventional at present has hexamethyldisilane amine base lithium salts, hexamethyldisilane amine base sodium salt, hexamethyldisilane amine base sylvite, and the method for these three kinds of hexamethyldisilane amine base an alkali metal salts is similar.
The synthetic method of current hexamethyldisilane amine base lithium salts mainly contains following several, and a kind of is the proton adopting n-Butyl Lithium to capture hexamethyldisilazane, and under protection of inert gas, the organic solvent through anhydrous and oxygen-free process does reaction solvent, low-temp reaction.This method speed of response is fast, mild condition, but the use of n-Butyl Lithium is more dangerous, dangerous.Other two kinds of conventional methods adopt Lithamide and hexamethyldisilazane reaction or prepare with lithium hydride and hexamethyldisilazane reaction, but the lithium compound in these two kinds of methods can not react completely, and there will be some not expected by products.As Chinese patent CN101492466A discloses a kind of preparation method of hexamethyldisilane amine sodium solution, the method adopt hexamethyldisilazane and sodium hydride high boiling solvent or solvent-free in carry out, after question response is complete, use tetrahydrofuran solvent again, obtained hexamethyldisilane amine sodium tetrahydrofuran solution, the method is simple, and speed of response is fast, but easily occurs some not expected by products.A kind of mode is also had to be adopt metallic lithium and hexamethyldisilazane reaction, this temperature of reaction is higher than the fusing point (>190 DEG C) of metallic lithium, use iron trichloride as catalyzer simultaneously, this method shortcoming is that temperature of reaction is higher, pressure is larger, as European patent ER0699684 describes a kind of preparation method of hexamethyldisilane amine sodium solution, hexamethyldisilane amine and sodium Metal 99.5, react in tetrahydrofuran solvent, temperature of reaction is up to 225 DEG C, reaction times reaches 24 hours, temperature required for reaching reaction, must react in pressurized vessel, reaction conditions is harsher.
Summary of the invention
The object of the invention is to be to provide a kind of method preparing hexamethyldisilane amine base lithium solution, the method is also applicable to the preparation of hexamethyldisilane amine base sodium solution and hexamethyldisilane amine base potassium solution simultaneously.The method applied in the present invention is simple, and speed of response is fast, and react completely, by product is few.
Reaction principle of the present invention, is shown in lower reactive mode.
A kind of method preparing hexamethyldisilane amine base lithium solution comprises the steps (as shown in Figure 1):
(1) feed intake: in reactor, pass into protection of inert gas, then in reactor, add the organic solvent after anhydrous and oxygen-free process, then add hexamethyldisilazane and metallic lithium.
(2) drip: to utilize mixture in reactor by temperature regulating device to 25 DEG C ~ 50 DEG C, in reactor, drip unsaturated conjugated olefines electron carrier, dropwise reaction under normal pressure, control rate of addition, make temperature be no more than 50 DEG C, because of exothermic heat of reaction, adopt external device cooling simultaneously.
(3) deep reaction: drip after terminating, material is warmed up to organic solvent boiling point and carries out backflow deep reaction.
(4) reaction terminates: back flow reaction, after 5 ~ 8 hours, observes metal solid without residue, sampling analysis, and content is cooled to 20 DEG C ~ 30 DEG C, Büchner funnel suction filtration after reaching desired value requirement, and sealing is preserved.
As preferentially, described protection of inert gas is argon gas or nitrogen.
As preferentially, described organic solvent is the one in toluene, THF, normal hexane, methyl-formiate.
As preferentially, described unsaturated conjugated olefines electron carrier is the one in vinylbenzene, isoprene, 2,4-hexadienes.
Based on the above-mentioned method preparing hexamethyldisilane amine base lithium solution, the reaction unit used comprises reactor, rare gas element charging device, whipping appts, electron carrier Dropping feeder, reflux condensate device, temperature regulating device, Suction filtration device and storing apparatus; Described reactor is provided with rare gas element charging device interface, whipping appts interface, electron carrier Dropping feeder interface, reflux condensate device interface, dog-house and drain hole, described reactor is connected with temperature regulating device, Suction filtration device, described whipping appts is arranged in the middle of reactor, and described rare gas element charging device, electron carrier Dropping feeder, reflux condensate device are arranged on the corresponding interface of reactor respectively.
As preferentially, described whipping appts is mechanical stirring device or magnetic stirring apparatus.
As preferentially, described electron carrier Dropping feeder is for dripping pipe.
As preferentially, described reflux condensate device is reflux exchanger.
As preferentially, described Suction filtration device is Büchner funnel.
During work, rare gas element charging device passes into rare gas element in reactor, then adds the organic solvent after anhydrous and oxygen-free process by the dog-house in reactor, then adds hexamethyldisilazane and metallic lithium; Utilize, by temperature regulating device, mixture in reactor is warmed up to 25 DEG C ~ 50 DEG C, in reactor, drip unsaturated conjugated olefines electron carrier by electron carrier Dropping feeder, dropwise reaction under normal pressure, control rate of addition; After dropping terminates, material is warmed up to organic solvent boiling point by temperature regulating device, then carries out backflow deep reaction by reflux condensate device; After reaction terminates, reaction solution flows through Suction filtration device, and the reaction soln after suction filtration is stored in storing apparatus, packaging after cooling.
The method applied in the present invention is simple, and speed of response is fast, and react completely, by product is few; The reaction unit structure adopted is simple, easy to use.
Figure of description
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is reaction unit figure of the present invention.
Accompanying drawing illustrates: 1 is reactor, and 2 is rare gas element charging device, and 3 is whipping appts, 4 be electron carrier Dropping feeder 4,5 is reflux condensate device, and 6 is temperature regulating device, 7 is Suction filtration device, 8 is storing apparatus, and 1.1 is reflux condensate device interface, and 1.2 is electron carrier Dropping feeder interface, 1.3 is whipping appts interface, 1.4 is rare gas element charging device interface, and 1.5 is dog-house 1.5, and 1.6 is drain hole.
Embodiment
Below by embodiment, the present invention is described in detail, should be understood that, these embodiments only can be used for explaining the present invention and can not being used for explaining limitation of the present invention.
Embodiment 1:
Nitrogen replacement is passed in 1000ml reactor, add 161.4g (1mol) hexamethyldisilane ammonia, add the organic solvent toluene 400g after anhydrous and oxygen-free process, metallic lithium 7.9g (1mol), 25 DEG C ~ 50 DEG C are stirred lower dropping isoprene 34g (0.5mol), are then heated to back flow reaction 3 hours.Be cooled to less than 40 DEG C, with hexamethyldisilazane lithium content in test soln after Büchner funnel suction filtration, obtain hexamethyldisilazane lithium 153.4g in solution, collect yield 91.7% with lithium.
Embodiment 2:
Nitrogen replacement is passed in 1000ml reactor, add 161.4g (1mol) hexamethyldisilane ammonia, add the organic solvent tetrahydrofuran 400g after anhydrous and oxygen-free process, metallic lithium 7.9g (1mol), 25 DEG C ~ 50 DEG C are stirred lower dropping vinylbenzene 52g (0.5mol), are then heated to back flow reaction 3 hours.Be cooled to less than 40 DEG C, with hexamethyldisilazane lithium content in test soln after Büchner funnel suction filtration, obtain hexamethyldisilazane lithium 154.3g in solution, collect yield 92.2% with lithium.
Embodiment 3:
Nitrogen replacement is passed in 1000ml reactor, add 161.4g (1mol) hexamethyldisilane ammonia, add the organic solvent tetrahydrofuran 400g after anhydrous and oxygen-free process, metallic lithium 7.9g (1mol), 25 DEG C ~ 50 DEG C are stirred lower dropping vinylbenzene 52g (0.5mol), are then heated to back flow reaction 5 hours.Be cooled to less than 40 DEG C, with hexamethyldisilazane lithium content in test soln after Büchner funnel suction filtration, obtain hexamethyldisilazane lithium 157.8g in solution, collect yield 94.3% with lithium.
Embodiment 4:
Nitrogen replacement is passed in 1000ml reactor, add 161.4g (1mol) hexamethyldisilane ammonia, add the organic solvent-normal hexane 400g after anhydrous and oxygen-free process, metallic lithium 7.9g (1mol), 25 DEG C ~ 50 DEG C are stirred lower dropping vinylbenzene 52g (0.5mol), are then heated to back flow reaction 7 hours.Be cooled to less than 40 DEG C, with hexamethyldisilazane lithium content in test soln after Büchner funnel suction filtration, obtain hexamethyldisilazane lithium 158.1g in solution, collect yield 94.5% with lithium.
Embodiment 5:
Argon replaces is passed in 1000ml reactor, add 161.4g (1mol) hexamethyldisilane ammonia, add the organic solvent-normal hexane 400g after anhydrous and oxygen-free process, metallic lithium 7.9g (1mol), 25 DEG C ~ 50 DEG C are stirred lower dropping vinylbenzene 52g (0.5mol), are then heated to back flow reaction 5 hours.Be cooled to less than 40 DEG C, with hexamethyldisilazane lithium content in test soln after Büchner funnel suction filtration, obtain hexamethyldisilazane lithium 165.3g in solution, collect yield 98.8% with lithium.
As shown in Figure 2, the reaction unit used in above-described embodiment 1-5 comprises reactor 1, rare gas element charging device 2, whipping appts 3, electron carrier Dropping feeder 4, reflux condensate device 5, temperature regulating device 6 and Suction filtration device 7 and storing apparatus 8; Whipping appts 3 is mechanical stirring device, and electron carrier Dropping feeder 3 is for dripping pipe, and reflux condensate device 5 is reflux exchanger, and Suction filtration device 7 is Büchner funnel; Reactor 1 is provided with rare gas element charging device interface 1.4, whipping appts interface 1.3, electron carrier Dropping feeder interface 1.2, reflux condensate device interface 1.1, dog-house 1.5 and drain hole 1.6, described reactor 1 is connected with temperature regulating device 6, Suction filtration device 7, described whipping appts 3 is arranged in the middle of reactor 1, and described rare gas element charging device 2, electron carrier Dropping feeder 4, reflux condensate device 5 are arranged on the corresponding interface of reactor 1 respectively.
During work, rare gas element charging device 2 passes into rare gas element in reactor 1, then adds the organic solvent after anhydrous and oxygen-free process by the dog-house 1.5 in reactor 1, then adds hexamethyldisilazane and metallic lithium; Utilize, by temperature regulating device 6, mixture in reactor 1 is warmed up to 25 DEG C ~ 50 DEG C, in reactor 1, drip unsaturated conjugated olefines electron carrier by electron carrier Dropping feeder 4, dropwise reaction under normal pressure, control rate of addition; After dropping terminates, material is warmed up to organic solvent boiling point by temperature regulating device 6, then carries out backflow deep reaction by reflux condensate device 5; After reaction terminates, reaction solution flows through Suction filtration device 7, and the reaction soln after suction filtration is stored in storing apparatus 8, packaging after cooling.
Claims (9)
1. prepare a method for hexamethyldisilane amine base lithium solution, it is characterized in that comprising the steps:
(1) feed intake: in reactor, pass into protection of inert gas, then in reactor, add the organic solvent after anhydrous and oxygen-free process, then add hexamethyldisilazane and metallic lithium.
(2) drip: to utilize mixture in reactor by temperature regulating device to 25 DEG C ~ 50 DEG C, in reactor, drip unsaturated conjugated olefines electron carrier, dropwise reaction under normal pressure, control rate of addition, make temperature be no more than 50 DEG C, because of exothermic heat of reaction, adopt external device cooling simultaneously.
(3) deep reaction: drip after terminating, material is warmed up to organic solvent boiling point and carries out backflow deep reaction.
(4) reaction terminates: back flow reaction, after 5 ~ 8 hours, observes metal solid without residue, sampling analysis, and after content reaches desired value requirement, 20 DEG C ~ 30 DEG C, Büchner funnel suction filtration, sealing is preserved.
2. a kind of method preparing hexamethyldisilane amine base lithium solution according to claim 1, is characterized in that described protection of inert gas is argon gas or nitrogen.
3. a kind of method preparing hexamethyldisilane amine base lithium solution according to claim 1, is characterized in that described organic solvent is the one in toluene, THF, normal hexane, methyl-formiate.
4. a kind of method preparing hexamethyldisilane amine base lithium solution according to claim 1, is characterized in that described unsaturated conjugated olefines electron carrier is the one in vinylbenzene, isoprene, 2,4-hexadienes.
5. prepare for claim 1 reaction unit that hexamethyldisilane amine base lithium solution methods uses, it is characterized in that described reaction unit comprises reactor, rare gas element charging device, whipping appts, electron carrier Dropping feeder, reflux condensate device, temperature regulating device, Suction filtration device and storing apparatus; Described reactor is provided with rare gas element charging device interface, whipping appts interface, electron carrier Dropping feeder interface, reflux condensate device interface, dog-house and drain hole, described reactor is connected with temperature regulating device, Suction filtration device, described whipping appts is arranged in the middle of reactor, and described rare gas element charging device, electron carrier Dropping feeder, reflux condensate device are arranged on the corresponding interface of reactor respectively.
6. a kind of reaction unit according to claim 5, is characterized in that described whipping appts is mechanical stirring device or magnetic stirring apparatus.
7. a kind of reaction unit according to claim 5, is characterized in that described electron carrier Dropping feeder is for dripping pipe.
8. a kind of reaction unit according to claim 5, is characterized in that described reflux condensate device is reflux exchanger.
9. a kind of reaction unit according to claim 5, is characterized in that described Suction filtration device is Büchner funnel.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011372A (en) * | 2017-05-15 | 2017-08-04 | 江苏维祥生物科技有限公司 | A kind of method for preparing lithium hexamethyldisilazide |
| CN109608487A (en) * | 2018-12-05 | 2019-04-12 | 菏泽医学专科学校 | The preparation method of hexamethl disilamine base sodium |
| CN111171069A (en) * | 2020-01-15 | 2020-05-19 | 浙江硕而博化工有限公司 | Method and device for preparing hexamethyl disilazane lithium amide solution |
| CN112707929A (en) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | Process for preparing bis (trimethyl disilyl) lithium amide |
| CN114874253A (en) * | 2022-06-27 | 2022-08-09 | 浙江江北南海药业有限公司 | Preparation process of lithium bis (trimethylsilyl) amide |
| CN115301187A (en) * | 2022-08-31 | 2022-11-08 | 四川嘉碧新材料科技有限公司 | Method for preparing hexamethyldisilane amine through inverse concentration gradient reaction |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420322A (en) * | 1994-08-31 | 1995-05-30 | Mine Safety Appliances Company | Preparation of alkali-metal hexamethydisilazanes |
| WO1995023803A1 (en) * | 1994-03-02 | 1995-09-08 | Fmc Corporation | Improved method of preparation of lithium alkylamides |
| WO1997002210A2 (en) * | 1995-06-30 | 1997-01-23 | Fmc Corporation | Contaminant free organometallic amide compositions and processes for making same |
| WO1997006173A1 (en) * | 1995-08-09 | 1997-02-20 | Fmc Corporation | High purity formulations of highly substituted lithium amide bases |
| CN1175580A (en) * | 1997-07-17 | 1998-03-11 | 中国科学院化学研究所 | Process for preparing N, N -dimethylamino pentamethyl disilane |
| US6169203B1 (en) * | 1998-02-24 | 2001-01-02 | Mine Safety Appliances Company | Method of preparation of alkali-metal amides |
| CN101492466A (en) * | 2009-03-10 | 2009-07-29 | 陕西大生化学科技有限公司 | Method of preparing hexamethyldisilane amine sodium solution |
-
2014
- 2014-11-25 CN CN201410685152.XA patent/CN104387415A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995023803A1 (en) * | 1994-03-02 | 1995-09-08 | Fmc Corporation | Improved method of preparation of lithium alkylamides |
| US5420322A (en) * | 1994-08-31 | 1995-05-30 | Mine Safety Appliances Company | Preparation of alkali-metal hexamethydisilazanes |
| WO1997002210A2 (en) * | 1995-06-30 | 1997-01-23 | Fmc Corporation | Contaminant free organometallic amide compositions and processes for making same |
| WO1997006173A1 (en) * | 1995-08-09 | 1997-02-20 | Fmc Corporation | High purity formulations of highly substituted lithium amide bases |
| CN1175580A (en) * | 1997-07-17 | 1998-03-11 | 中国科学院化学研究所 | Process for preparing N, N -dimethylamino pentamethyl disilane |
| US6169203B1 (en) * | 1998-02-24 | 2001-01-02 | Mine Safety Appliances Company | Method of preparation of alkali-metal amides |
| CN101492466A (en) * | 2009-03-10 | 2009-07-29 | 陕西大生化学科技有限公司 | Method of preparing hexamethyldisilane amine sodium solution |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011372A (en) * | 2017-05-15 | 2017-08-04 | 江苏维祥生物科技有限公司 | A kind of method for preparing lithium hexamethyldisilazide |
| CN109608487A (en) * | 2018-12-05 | 2019-04-12 | 菏泽医学专科学校 | The preparation method of hexamethl disilamine base sodium |
| CN111171069A (en) * | 2020-01-15 | 2020-05-19 | 浙江硕而博化工有限公司 | Method and device for preparing hexamethyl disilazane lithium amide solution |
| CN112707929A (en) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | Process for preparing bis (trimethyl disilyl) lithium amide |
| CN114874253A (en) * | 2022-06-27 | 2022-08-09 | 浙江江北南海药业有限公司 | Preparation process of lithium bis (trimethylsilyl) amide |
| CN115301187A (en) * | 2022-08-31 | 2022-11-08 | 四川嘉碧新材料科技有限公司 | Method for preparing hexamethyldisilane amine through inverse concentration gradient reaction |
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Application publication date: 20150304 |