CN106632227A - Method for preparing chloroethylene carbonate - Google Patents
Method for preparing chloroethylene carbonate Download PDFInfo
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- CN106632227A CN106632227A CN201611123538.7A CN201611123538A CN106632227A CN 106632227 A CN106632227 A CN 106632227A CN 201611123538 A CN201611123538 A CN 201611123538A CN 106632227 A CN106632227 A CN 106632227A
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- vinyl acetate
- acid vinyl
- ethylene carbonate
- chlorocarbonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing chloroethylene carbonate. The method comprises a step of synthesizing chloroethylene carbonate through ethylene carbonate and a chlorination agent in an illumination condition by use of a transition metal nanoparticle photosensitizer. The chloroethylene carbonate comprises monochloroethylene carbonate and dichloroethylene carbonate. The adopted catalyst is a transition metal nanoparticle photosensitizer. The illumination condition is ultraviolet illumination or illumination of visible light including sunlight and ordinary lighting. The chlorination agent comprises chlorine, sulfuryl chloride, thionyl chloride, triphosgene, etc. The preparation method provided by the invention is different from the thermal catalysis and ultraviolet catalysis of traditional technology, the reaction conditions are milder, the reaction is fast, and the production efficiency is high; the synthesis equipment can be made of common glass material, and a reactor of special material such as quartz is not needed for transmitting ultraviolet; and moreover, the technology is safer, and the product is easy to separate and purify.
Description
Technical field
The present invention is, with regard to a kind of preparation method of chlorocarbonic acid vinyl acetate, to more particularly relate to nano material sensitising agent and exist
The method that chlorocarbonic acid vinyl acetate is catalyzed and synthesized under visible light conditions, the separated purification of chlorocarbonic acid vinyl acetate prepared by the present invention
After can prepare pharmaceutical preparation, polymer, coating products and battery electrolyte etc. as intermediate.
Technical background
Chlorocarbonic acid vinyl acetate is mainly used in and prepares lithium battery electrolytes fluorinated ethylene carbonate and vinylene carbonate fat.
High-purity chloro can also improve following for lithium battery electrolytes for ethylene carbonate directly as lithium battery electrolytes flame-retardant additive
Ring performance, improves service life.
United States Patent (USP) 3021340 is the method that chlorocarbonic acid vinyl acetate is prepared disclosed in relatively morning.The method that the patent is provided
It is that chlorocarbonic acid vinyl acetate is prepared by ethylene carbonate and chlorine haptoreaction using anhydrous ferric trichloride as initiator, will be anti-
Mixture is answered to be heated to boiling reaction 30h, condition is harsh, high to equipment requirement, is unfavorable for industrialized production.
At present two kinds of conventional methods for preparing chlorocarbonic acid vinyl acetate are：
1. with chlorine as chlorination reagent, chlorocarbonic acid vinyl acetate is prepared by ethylene carbonate under ultraviolet light, advantage is former
Material low cost, has the disadvantage that reaction rate is slow, and product yield is low.
2. using chlorosulfuric acid, solid phosgene etc. as chlorination reagent, in azo-initiator or peroxide type initiators
The lower heating response of effect prepares chlorocarbonic acid vinyl acetate by ethylene carbonate, and advantage is that reaction yield can reach more than 75%, is lacked
Point is product in highly acid, and impurity content is on the high side to be unfavorable for purification of products, and can produce a large amount of waste water and gas, environmental pollution compared with
Greatly.
In sum, a kind of low toxicity, efficient, process is simple are developed, is adapted to the chlorocarbonic acid vinyl acetate conjunction of industrialized production
It is this area problem in the urgent need to address into method.
The content of the invention
The purpose of the present invention is to break through inefficient thermal initiation and the ultraviolet light-initiated method for synthesizing chlorocarbonic acid vinyl acetate.
The chlorocarbonic acid vinyl acetate synthetic method referred in the present invention is referred to by ethylene carbonate and chlorination reagent under visible light illumination
Chlorocarbonic acid vinyl acetate is catalyzed and synthesized by transition metal nanoparticles sensitising agent.The chlorocarbonic acid vinyl acetate for wherein preparing includes one
Chlorocarbonic acid vinyl acetate and dichloro- ethylene carbonate.Dichloro- ethylene carbonate include trans-dichloro for ethylene carbonate and
Cis-dichloro- ethylene carbonate, the content ratio of the two is 20:1~5:1.The thermal initiator that prior synthesizing method is used mostly is
Azo-initiator（Such as AIBN）Or peroxide type initiators（Such as BPO）, reaction efficiency is low, and impurity in products is more, is unfavorable for
Product is purified.Although the ultraviolet light-initiated impurity contents that can be reduced in product of UV, do not refer in presently disclosed document
Using the method for sensitising agent, the reaction time is long, and low production efficiency is higher to equipment requirement, and it is special from quartz glass etc. to need
Material reactor, is unfavorable for industrialized production, and the intense radiation of ultraviolet light has compared with major injury to human body, needs special protection.
The invention provides it is a kind of safer, more efficiently it is catalyzed under visible light conditions by transition metal nanoparticles sensitising agent
The method of synthesis chlorocarbonic acid vinyl acetate.
The present invention provides a kind of method for preparing chlorocarbonic acid vinyl acetate, and wherein the method is included in transition metal nanoparticle
Sub- sensitising agent（Such as Ir/TiO2- CNTs) exist under conditions of, the ethylene carbonate and chlorination reagent haptoreaction under illumination condition
Prepare chlorocarbonic acid vinyl acetate.It can also be sunshine, normal lighting light that wherein described illumination condition can be ultraviolet light
Deng visible ray.
The method that the present invention is provided improves reaction efficiency, simplifies experimental facilities.Compare thermal initiator to be closed by thermal initiation
Into chlorocarbonic acid vinyl acetate, transition metal nanoparticles sensitising agent radiation of visible light catalyzes and synthesizes chlorocarbonic acid vinyl acetate reaction speed
Rate improves about 10 times.Ultraviolet light-initiated synthesis chlorocarbonic acid vinyl acetate is compared, the addition of transition metal nanoparticles sensitising agent makes
Visible light catalytic synthesis chlorocarbonic acid vinyl acetate is possibly realized, building-up process more safety and environmental protection, and reaction rate also has substantially
Improve.Add and chlorocarbonic acid vinyl acetate is catalyzed and synthesized under visible light conditions after nanometric photosensitizer, it is anti-using common transparent glass
Device is answered, equipment investment is few, reaction rate is fast, production efficiency is high, reaction condition is gentleer, reaction more safety, product
Impurity content is few, and product is easy to purification, is more suitable for industrialized production.Chlorocarbonic acid prepared by the method provided using the present invention
Vinyl acetate can be a kind of important organic synthesis intermediate as the raw material of synthesizing lithium ion battery electrolyte.
The chemical equation of the present invention can be expressed as：
The catalyst for wherein using is a kind of transition metal nanoparticles sensitising agent.The carrier that the sensitising agent is used is titanium dioxide
Titanium-carbon nano tube compound material, the transition metal for using is one or more of Pt, Pd, Rh, Ir, Ru, Os, Co, Ni, Cu, its
In one or more preferably in Pt, Pd, Ir, Cu.
Preferably, described chlorocarbonic acid vinyl acetate includes monochloroethylene carbonate and dichloro- ethylene carbonate.
Dichloro- ethylene carbonate includes trans-dichloro for ethylene carbonate and cis-dichloro- ethylene carbonate, structure
Formula is as follows：
Preferably, described trans-dichloro is 20 for the ratio of ethylene carbonate and cis-dichloro- ethylene carbonate:1~5:
1。
Preferably, described chlorination reagent is one or more of chlorine, chlorosulfuric acid, thionyl chloride, solid phosgene.
Preferably, ethylene carbonate and the mol ratio of chlorination reagent are 1:1~1:5, preferably 1:1~1:3, more preferably
1:1.2~1:2。
Preferably, the consumption of sensitising agent is chlorination reagent mole 0.05% ~ 5%, and preferred consumption is 0.1% ~ 1%, more excellent
Choosing is 0.45% ~ 0.75%.
The preparation method that the present invention is provided is different from the thermal initiation of conventional method and ultraviolet light-initiated, and reaction condition is more warm
Fast with, reaction rate, production efficiency is high, and synthesis device can use simple glass material, it is not necessary to select for ultraviolet transmissive light
The special substance reactor such as quartz, technology is safer, and product is easily isolated purification.
Specific embodiment
Following examples contributes to understanding the present invention, but is not limited to these embodiments：
Embodiment 1
352g ethylene carbonates are added in four mouthfuls of 1L flasks with thermometer boss, mechanical agitation and reflux condenser,
478g thionyl chlorides, 4.2g Pt metal nano-particle sensitising agents, condensator outlet connects gas sparger and device for absorbing tail gas, stirs
Mix and be uniformly dissolved, the stir about 1h under sunlight irradiation, discharge to obtain 508g crude products, rectifying（82 ~ 89 DEG C, 3 ~ 4mmHg）Obtain 456g to evaporate
Point, monochloroethylene carbonate purity 95.9%, yield about 89.6%.
Embodiment 2
528g ethylene carbonates are added in four mouthfuls of 2L flasks with thermometer boss, mechanical agitation and reflux condenser,
1626g chlorosulfuric acids, 12.6g metal Ir nano-particle sensitising agents, wherein chlorosulfuric acid can disposably be added and can also added in batches,
Condensator outlet connects gas sparger and device for absorbing tail gas, and stirring and dissolving is uniform, and stir about 2h, discharges under blue light illumination
891g crude products.Rectifying（62 ~ 65 DEG C, 9 ~ 11mmHg）409g cuts 1, be trans-dichloro for ethylene carbonate and cis-dichloro
For ethylene carbonate ester admixture, ratio 12:1, purity total 93.5%；Rectifying（82 ~ 89 DEG C, 3 ~ 4mmHg）399g cuts 2 are obtained, is
Monochloroethylene carbonate, purity 95.9%, total recovery about 90.6%.
Embodiment 3
528g ethylene carbonates are added in four mouthfuls of 2L glass kettles with thermometer boss, mechanical agitation and reflux condenser,
832g dichloromethane, 7.0g metal Pd nano-particle sensitising agents, condensator outlet connects gas sparger and device for absorbing tail gas, stirs
Mix and be uniformly dissolved, chlorine is led into glass reaction kettle, control 2 ~ 3g/min of chlorine flowrate, stir about 5h under white light, revolving
The most of dichloromethane of removing, obtains material 1029g.Rectifying（62 ~ 65 DEG C, 9 ~ 11mmHg）395g cuts 1 are obtained, is dichloro- carbonic acid
Ethene ester admixture, purity 91.5%, wherein trans-dichloro are for ethylene carbonate and the ratio of cis-dichloro- ethylene carbonate
About 20:1；Rectifying（82 ~ 89 DEG C, 3 ~ 4mmHg）415g cuts 2, be monochloroethylene carbonate, purity 95.3%, total recovery is about
78.7%。
Embodiment 4
528g ethylene carbonates are added in four mouthfuls of 2L flasks with thermometer boss, mechanical agitation and reflux condenser,
500g chloroforms, 1184g solid phosgenes, 4.2g Ni metal nano-particle sensitising agents, condensator outlet connect gas sparger and
Device for absorbing tail gas, is heated to being stirred after dissolving, stops heating stir about 1.5h under white light illumination, and discharge to obtain 1402g
Crude product.Revolving removes most of solvent chloroform, and rectifying collects 62 ~ 65 DEG C, the cut 359.9g of 9 ~ 11mmHg, be it is trans-
Dichloro- ethylene carbonate and cis-dichloro- ethylene carbonate ester admixture, ratio 5:1, purity total 91.6%；Rectifying is collected
82 ~ 89 DEG C, the cut 395.5g of 3 ~ 4mmHg is monochloroethylene carbonate, purity 90.9%, total recovery about 80.0%.
Embodiment 5
2000g ethylene carbonates, 6136g chlorosulfuric acids, 11.6g metal Rh nanometers are sequentially added in the glass storage tank of 10L photosensitive
Agent, with the feed rate of 50ml/min through glass plate type reactor（Volume about 8ml）It is well mixed, then is passed through homemade tubular type
Reactor（About 300ml）Chlorination reaction is carried out under blue light illumination, material collection storage tank connects device for absorbing tail gas, about 2h charging knots
Beam, discharge to obtain 4268g crude products.Decompression pumping removes unreacted material, and rectifying collects 62 ~ 65 DEG C, the cut of 9 ~ 11mmHg
1878g is trans-dichloro for ethylene carbonate and cis-dichloro- ethylene carbonate ester admixture, ratio 11:1, purity adds up to
95.3%；Rectifying collects 82 ~ 89 DEG C, and the cut 1001g of 3 ~ 4mmHg is monochloroethylene carbonate, purity 96.9%, total recovery
About 85%.
Embodiment 6
2000g ethylene carbonates, 200g chloroforms, 21.4g metal Os nanometric photosensitizers are sequentially added in the glass storage tank of 10L,
Heating（50±2℃）To material dissolution, channel glass plate is squeezed into the feed rate of 20ml/min after stirring mixing about 20min
Formula reactor, while chlorine squeezes into reactor with the feed rate of 15 ~ 21g/min, Reactor inlet keeps 0.8 ~ 1.5MPa pressures
Power, through 10 blocks of glass reaction plates（About 80ml）Blue light illumination, material enter rewinding tank in, rewinding tank connect tail gas absorption dress
Put.About 1.5h chargings terminate, and discharge to obtain 3068g crude products.Decompression pumping removal light component acid gas, 62 ~ 65 DEG C of rectifying collection, 9 ~
The cut 1378g of 11mmHg is trans-dichloro for ethylene carbonate and cis-dichloro- ethylene carbonate ester admixture, ratio
14:1, purity total 97.3%；Rectifying collects 82 ~ 89 DEG C, and the cut 1201g of 3 ~ 4mmHg is monochloroethylene carbonate, purity
98.9%, total recovery about 80.5%.
Claims (11)
1. a kind of preparation method of chlorocarbonic acid vinyl acetate, it is characterised in that：Ethylene carbonate and chlorination reagent are in illumination condition
Under chlorocarbonic acid vinyl acetate is catalyzed and synthesized by transition metal nanoparticles sensitising agent, wherein described illumination condition can be ultraviolet
Light irradiation can also be radiation of visible light.
2. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 1, it is characterised in that：Described chloro carbon
Vinyl acetate includes monochloroethylene carbonate and dichloro- ethylene carbonate.
3. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 2, it is characterised in that：Described dichloro-
Ethylene carbonate includes trans-dichloro for ethylene carbonate and cis-dichloro- ethylene carbonate, and structural formula is as follows：
4. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 3, it is characterised in that：It is described it is trans-
The ratio of dichloro- ethylene carbonate and cis-dichloro- ethylene carbonate is 20:1～5:1.
5. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 1, it is characterised in that：Described chlorination examination
Agent is one or more of chlorine, chlorosulfuric acid, thionyl chloride, solid phosgene.
6. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 1, it is characterised in that：Described transition gold
The carrier that category nano-particle sensitising agent is used is titanium dioxide-carbon nano tube compound material.
7. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 1 or 6, it is characterised in that：Described mistake
Cross one or more that the transition metal that metal nanoparticle sensitising agent uses is Pt, Pd, Rh, Ir, Ru, Os, Co, Ni, Cu.
8. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 7, it is characterised in that：Described transition gold
The preferred transition metal that category nano-particle sensitising agent is used is one or more in Pt, Pd, Ir, Cu.
9. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 1, it is characterised in that：Ethylene carbonate with
The mol ratio of chlorination reagent is 1:1～1:5.
10. the preparation method of a kind of chlorocarbonic acid vinyl acetate according to claim 9, it is characterised in that：Ethylene carbonate
1 is preferably with the mol ratio of chlorination reagent:1～1:3, more preferably 1:1.2～1:2.
A kind of 11. preparation methods of chlorocarbonic acid vinyl acetate according to claim 1, it is characterised in that：The use of sensitising agent
Amount is chlorination reagent mole 0.05%～5%, and preferred consumption is 0.1%～1%, more preferably 0.45%～
0.75%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611123538.7A CN106632227A (en) | 2016-12-08 | 2016-12-08 | Method for preparing chloroethylene carbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611123538.7A CN106632227A (en) | 2016-12-08 | 2016-12-08 | Method for preparing chloroethylene carbonate |
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| CN201611123538.7A Pending CN106632227A (en) | 2016-12-08 | 2016-12-08 | Method for preparing chloroethylene carbonate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586421A (en) * | 2018-01-23 | 2018-09-28 | 长园华盛(泰兴)锂电材料有限公司 | A kind of production method of chlorocarbonic acid vinyl acetate |
| CN112940029A (en) * | 2019-12-11 | 2021-06-11 | 新特能源股份有限公司 | Methyl chlorosilane, preparation method and device |
| CN112979607A (en) * | 2021-03-11 | 2021-06-18 | 泰兴华盛精细化工有限公司 | Method for continuously preparing chlorinated ethylene carbonate |
| CN117229253A (en) * | 2023-11-16 | 2023-12-15 | 山东海化集团有限公司 | Method for continuously preparing high-purity chloroethylene carbonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091605A (en) * | 2005-09-27 | 2007-04-12 | Nippon Light Metal Co Ltd | Method for producing chloroethylene carbonate |
| CN101205226A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparing monochlorin ethylene carbonate ester and vinylene carbonate |
| CN103772344A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院理化技术研究所 | Method for photochemical synthesis of monochloroethylene carbonate and photochemical reactor |
-
2016
- 2016-12-08 CN CN201611123538.7A patent/CN106632227A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091605A (en) * | 2005-09-27 | 2007-04-12 | Nippon Light Metal Co Ltd | Method for producing chloroethylene carbonate |
| CN101205226A (en) * | 2006-12-22 | 2008-06-25 | 比亚迪股份有限公司 | Method for preparing monochlorin ethylene carbonate ester and vinylene carbonate |
| CN103772344A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院理化技术研究所 | Method for photochemical synthesis of monochloroethylene carbonate and photochemical reactor |
Non-Patent Citations (1)
| Title |
|---|
| 刘超程等: ""碳酸亚乙烯酯的合成工艺改进"", 《精细化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586421A (en) * | 2018-01-23 | 2018-09-28 | 长园华盛(泰兴)锂电材料有限公司 | A kind of production method of chlorocarbonic acid vinyl acetate |
| CN112940029A (en) * | 2019-12-11 | 2021-06-11 | 新特能源股份有限公司 | Methyl chlorosilane, preparation method and device |
| CN112979607A (en) * | 2021-03-11 | 2021-06-18 | 泰兴华盛精细化工有限公司 | Method for continuously preparing chlorinated ethylene carbonate |
| CN117229253A (en) * | 2023-11-16 | 2023-12-15 | 山东海化集团有限公司 | Method for continuously preparing high-purity chloroethylene carbonate |
| CN117229253B (en) * | 2023-11-16 | 2024-04-05 | 山东海化集团有限公司 | Method for continuously preparing high-purity chloroethylene carbonate |
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Application publication date: 20170510 |