CN106146344B - Ethylene glycol is double（Propionitrile）The preparation method of ether - Google Patents
Ethylene glycol is double（Propionitrile）The preparation method of ether Download PDFInfo
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- CN106146344B CN106146344B CN201610591391.8A CN201610591391A CN106146344B CN 106146344 B CN106146344 B CN 106146344B CN 201610591391 A CN201610591391 A CN 201610591391A CN 106146344 B CN106146344 B CN 106146344B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
It is double the invention discloses ethylene glycol（Propionitrile）The preparation method of ether, preparation process are as follows：Using ethylene glycol and acrylonitrile as reaction raw materials, reaction generation ethylene glycol is double under the catalysis of 30 DEG C~70 DEG C of reaction temperature and aqueous catalyst solution（Propionitrile）Ether, the aqueous catalyst solution are the compound base catalyst aqueous solution, and the compound base catalyst aqueous solution is mixed by triethylbenzyl ammonium hydroxide aqueous solution with sodium hydrate aqueous solution.As a result of the compound base catalyst aqueous solution mixed by the relatively low triethylbenzyl ammonium hydroxide aqueous solution of alkalescence and sodium hydrate aqueous solution, so that the alkalescence in reaction solution weakens significantly, so as to greatly reduce the generation of the double propionitrile ethers of by-product, such ethylene glycol is double（Propionitrile）The molar yield of ether will greatly improve, and molar yield can reach more than 90%, and the ethylene glycol that can be more easily purified to obtain high-purity is double（Propionitrile）Ether, its purity can reach more than 95%.
Description
Technical field
The present invention relates to lithium-ion battery electrolytes additive agent field, and in particular to can add as lithium-ion battery electrolytes
Add the preparation method of double (propionitrile) ethers of ethylene glycol of agent.
Background technology
The structural formula of double (propionitrile) ethers of ethylene glycol is：Second two
Double (propionitrile) ethers of alcohol are a kind of new additive agents that lithium-ion battery electrolytes using effect can be made more excellent, add ethylene glycol
The Swelling that the lithium ion battery of double (propionitrile) ethers can suppress to store at high temperature or occur during discharge and recharge, in addition, may be used also
To improve the cycle life of lithium ion battery discharge and recharge.Double additives of (propionitrile) ether as lithium-ion battery electrolytes of ethylene glycol
There is strict purity requirement, so double (propionitrile) ethers of the ethylene glycol of high-purity could preferably be used as lithium-ion battery electrolytes
Additive, but the preparation method of double (propionitrile) ethers of existing ethylene glycol is due to being all to use single alkaline hydrated oxide conduct
Catalyst, and in order that reaction can be normally carried out, the concentration of single alkaline hydrated oxide can not be very low, so allows for reacting
During solution alkalescence it is stronger, will be more so as to hydrolyze the by-product of generation, by-product more than one in reactant will shadow significantly
The molar yield of double (propionitrile) ethers of ethylene glycol is rung, and can also greatly improve the purification difficulty of double (propionitrile) ethers of ethylene glycol so that
The purity of double (propionitrile) ethers of ethylene glycol is difficult to improve.
The content of the invention
The technical problems to be solved by the invention are：The ethylene glycol that a kind of by-product is few, molar yield is high, is easily purified will be provided
The preparation method of double (propionitrile) ethers.
In order to solve the above problems, the technical solution adopted in the present invention is：The preparation method of double (propionitrile) ethers of ethylene glycol,
It is characterized in：Preparation process is as follows：Using ethylene glycol and acrylonitrile as reaction raw materials, reaction temperature be 30 DEG C~70 DEG C and
Double (propionitrile) ethers of reaction generation ethylene glycol under the catalysis of aqueous catalyst solution, the aqueous catalyst solution is compound base catalyst
The aqueous solution, the compound base catalyst aqueous solution mixed by triethylbenzyl ammonium hydroxide aqueous solution with sodium hydrate aqueous solution and
Into.
Further, the preparation method of double (propionitrile) ethers of foregoing ethylene glycol, wherein：Triethylbenzyl ammonium hydroxide is water-soluble
The mass concentration of liquid and sodium hydrate aqueous solution is 1%~5% respectively, their mixed compound base catalyst aqueous solution
Mass concentration be 2%~5%, and triethylbenzyl ammonium hydroxide aqueous solution and hydrogen-oxygen in the compound base catalyst aqueous solution
The weight ratio for changing sodium water solution is (1~4)：1.
Further, the preparation method of double (propionitrile) ethers of foregoing ethylene glycol, wherein：The mol ratio of ethylene glycol and acrylonitrile
For 1: (2~5).
Further, the preparation method of double (propionitrile) ethers of foregoing ethylene glycol, wherein：The compound base catalyst aqueous solution with
The weight ratio of ethylene glycol is 1: (0.1~10).
Further, the preparation method of double (propionitrile) ethers of foregoing ethylene glycol, wherein：Reaction time is 10~12 hours.
Further, the preparation method of double (propionitrile) ethers of foregoing ethylene glycol, wherein：Reaction temperature is 30 DEG C, during reaction
Between be 12 hours.
Further, the preparation method of double (propionitrile) ethers of foregoing ethylene glycol, wherein：After question response, to reaction solution
Neutralized, then distillation removes unreacted acrylonitrile and recycle-water in reactant, then carries out rectification under vacuum to reactant, receives
Collect cut, so as to ethylene glycol pair (propionitrile) ethers after purify.
The present invention reaction equation be：
Advantages of the present invention is：Catalyst in the present invention is as a result of by the relatively low triethylbenzyl hydroxide of alkalescence
The compound base catalyst aqueous solution that aqueous ammonium and sodium hydrate aqueous solution mix so that the alkalescence of reaction solution is significantly
Weaken, so as to greatly reduce the generation of the double propionitrile ethers of by-product, the molar yield of double (propionitrile) ethers of such ethylene glycol will be significantly
Improve, molar yield can reach more than 90%, and can more be easily purified to obtain double (propionitrile) ethers of ethylene glycol of high-purity, its purity
More than 95% can be reached.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
With mechanical agitation, thermometer, Dropping feeder, condenser pipe three-necked flask in, add ethylene glycol 62g (1mol)
It is stirred with acrylonitrile 159g (3mol), then slowly heating, is added dropwise the compound base catalyst aqueous solution at a temperature of 30 DEG C
(the sodium hydrate aqueous solution that the triethylbenzyl ammonium hydroxide aqueous solution 186g and mass concentration that mass concentration is 5% are 3%
62g) 248g, 12 hours are incubated at a temperature of 30 DEG C after being added dropwise, then reaction solution is neutralized, is then distilled to recover
Unreacted acrylonitrile 60.3g and recycle-water 413g in reactant, then reactant is depressurized under -0.01Mpa pressure
Rectifying, cut is collected, so as to obtain double (propionitrile) the ether 159.0g (purity 98.52%) of the ethylene glycol of high-purity, molar yield
For 93.14%.
Embodiment 2
With mechanical agitation, thermometer, Dropping feeder, condenser pipe three-necked flask in, add ethylene glycol 62g (1mol)
It is stirred with acrylonitrile 106g (2mol), then slowly heating, is added dropwise the compound base catalyst aqueous solution at a temperature of 50 DEG C
(the sodium hydrate aqueous solution that the triethylbenzyl ammonium hydroxide aqueous solution 248g and mass concentration that mass concentration is 4% are 2%
74.4g) 322.4g, 11 hours are incubated at a temperature of 50 DEG C after dripping, then reaction solution is neutralized, then distilled back
Unreacted acrylonitrile 8.4g and recycle-water 524g in reactant are received, then reactant is subtracted under -0.01Mpa pressure
Rectifying is pressed, collects cut, so as to obtain double (propionitrile) the ether 158.5g (purity 98.28%) of the ethylene glycol of high-purity, mole receipts
Rate is 92.61%.
Embodiment 3
With mechanical agitation, thermometer, Dropping feeder, condenser pipe three-necked flask in, add ethylene glycol 62g (1mol)
It is stirred with acrylonitrile 265g (5mol), then slowly heating, compound base catalyst is added dropwise at a temperature of 70 DEG C, and (quality is dense
Spend the triethylbenzyl ammonium hydroxide aqueous solution 217g and sodium hydrate aqueous solution 80.6g that mass concentration is 2% for 3%)
297.6g, 10 hours are incubated at a temperature of 70 DEG C after being added dropwise, then reaction solution is neutralized, is then distilled to recover
Unreacted acrylonitrile 167.8g and recycle-water 468g in reactant, then reactant is subtracted under -0.01Mpa pressure
Rectifying is pressed, collects cut, so as to obtain double (propionitrile) the ether 157.1g (purity 98.16%) of the ethylene glycol of high-purity, mole receipts
Rate is 91.67%.
Claims (5)
1. ethylene glycol is double（Propionitrile）The preparation method of ether, it is characterised in that：Preparation process is as follows：It is anti-using ethylene glycol and acrylonitrile
Raw material is answered, reaction generation ethylene glycol is double in the case where reaction temperature is the catalysis of 30 DEG C~70 DEG C and aqueous catalyst solution（Propionitrile）
Ether, the aqueous catalyst solution are the compound base catalyst aqueous solution, and the compound base catalyst aqueous solution is by triethylbenzyl
Ammonium hydroxide aqueous solution mixes with sodium hydrate aqueous solution, wherein：Triethylbenzyl ammonium hydroxide aqueous solution and hydroxide
The mass concentration of sodium water solution is 1%~5% respectively, and the mass concentration of their mixed compound base catalyst aqueous solution is
2%~5%, and the weight of triethylbenzyl ammonium hydroxide aqueous solution and sodium hydrate aqueous solution in the compound base catalyst aqueous solution
Measuring ratio is（1~4）：1, the weight ratio of compound the base catalyst aqueous solution and ethylene glycol is 1:（0.1~10）.
2. ethylene glycol according to claim 1 is double（Propionitrile）The preparation method of ether, it is characterised in that：Ethylene glycol and acrylonitrile
Mol ratio be 1:（2~5）.
3. ethylene glycol according to claim 1 or 2 is double（Propionitrile）The preparation method of ether, it is characterised in that：Reaction time is
10~12 hours.
4. ethylene glycol according to claim 1 or 2 is double（Propionitrile）The preparation method of ether, it is characterised in that：Reaction temperature is
30 DEG C, the reaction time is 12 hours.
5. ethylene glycol according to claim 1 or 2 is double（Propionitrile）The preparation method of ether, it is characterised in that：Question response finishes
Afterwards, reaction solution is neutralized, then distillation removes unreacted acrylonitrile and recycle-water in reactant, then reactant is carried out
Rectification under vacuum, cut is collected, so as to which the ethylene glycol after being purified is double（Propionitrile）Ether.
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| CN106905189B (en) * | 2017-03-01 | 2019-03-26 | 苏州汶颢微流控技术股份有限公司 | Microreactor system and method for bis- (propionitrile) the ether synthesis of ethylene glycol |
| CN109134309B (en) * | 2018-09-19 | 2020-12-29 | 张家港瀚康化工有限公司 | Method for purifying ethylene glycol bis (propionitrile) ether |
| CN115322119B (en) * | 2022-07-29 | 2023-09-29 | 抚顺顺能化工有限公司 | Preparation method of ethylene glycol bis (propionitrile) ether |
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| CN105418456A (en) * | 2015-12-07 | 2016-03-23 | 张家港瀚康化工有限公司 | Preparation method of butanediol bis(propionitrile) ether |
| CN105481718A (en) * | 2015-12-07 | 2016-04-13 | 张家港瀚康化工有限公司 | Production method of butenediol bis (propionitrile) ether |
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