CN102030736A - Method for synthesizing chlorinated carbonate - Google Patents
Method for synthesizing chlorinated carbonate Download PDFInfo
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- CN102030736A CN102030736A CN2009100932607A CN200910093260A CN102030736A CN 102030736 A CN102030736 A CN 102030736A CN 2009100932607 A CN2009100932607 A CN 2009100932607A CN 200910093260 A CN200910093260 A CN 200910093260A CN 102030736 A CN102030736 A CN 102030736A
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Abstract
The invention relates to a method for synthesizing chlorinated carbonate, which comprises: introducing excessive chlorine into liquid carbonate; performing chlorination under certain reaction conditions to form chlorinated carbonate; and performing chlorination of excessive chlorine in the reaction and paraffin oil again to form chlorinated carbonate paraffin. The reaction tail gas is hydrogen chloride gas containing a micro amount of chlorine. The method has the advantages of lowering production cost and reducing environmental pollution. The method is particularly suitable for producing chloroethylene carbonate, dichloroethylene carbonate and chloropropylene carbonate by using ethylene carbonate or propylene carbonate as a raw material.
Description
Technical field
The present invention relates to a kind of synthetic method of chlorinated carbonates.
Background technology
Carbonic ether is the main component of lithium battery electrolytes solvent.Its chlorization product can be used for the flame-retardant additive of lithium battery electrolytes, also is crucial synthetic intermediate simultaneously, by more and more widely application.Chlorocarbonic acid vinyl acetate particularly, it can simultaneously, also be the important source material of synthesized vinylene carbonate and fluorinated ethylene carbonate directly as the lithium battery electrolytes flame-retardant additive not only.
The technology of once reporting:
In United States Patent (USP) 3021340, the example one with NSC 11801 and chlorine reaction, under the catalysis of Anhydrous Ferric Chloride, is heated to boiling point reaction 30 hours with reaction mixture, obtains 62.5% chlorocarbonic acid vinyl acetate and 32.8% dichloro-NSC 11801.This method is difficult to realize suitability for industrialized production because the harshness of its processing condition is very high to the production unit requirement.
In United States Patent (USP) 6384239, with NSC 11801 and SULPHURYL CHLORIDE reaction, under UV-irradiation, temperature of reaction is controlled at 0-70 ℃, obtains product chlorocarbonic acid vinyl acetate.The example one, the mol ratio of NSC 11801 and SULPHURYL CHLORIDE are 1.35, temperature of reaction 20-40 ℃.This method is owing to use SULPHURYL CHLORIDE as chlorizating agent, and 1 mole of product can produce 1 mole of hydrogenchloride and 1 mole of sulfurous gas mixed tail gas, can't recycle, and environmental pollution is serious.Again it, removing excessive SULPHURYL CHLORIDE also can increase cost.
Summary of the invention
The present invention relates to a kind of synthetic method of chlorinated carbonates, its characteristics are: with the excessive feeding liquid carbon of chlorine acid esters, carry out chlorination reaction under certain reaction conditions, generate chlorinated carbonates, react excessive chlorine process gas-liquid refrigerated separation device, carry out chlorination reaction again with paraffin oil, generate clorafin, reaction end gas is the hydrogen chloride gas that contains micro-chlorine.
The chlorocarbonic acid vinyl acetate that the present invention relates to is the boiling point height, and the carbonic ether chlorinated compound that volatility is low comprises a chlorocarbonic acid vinyl acetate, dichloro-NSC 11801, a chlorocarbonic acid propylene ester etc.
The synthetic method of a kind of chlorinated carbonates that the present invention relates to is:
The technical grade carbonic ether is joined in the chlorination reaction still, and heat temperature raising is to certain temperature, and optimal temperature range is: 40-75 ℃; Under UV-light initiation or chemical initiator, feed chlorine or chlorine nitrogen mixture with certain speed; The reaction heating by regulating chlorination reaction still chuck water coolant and logical chlorine speed, is controlled at temperature of reaction below the certain temperature, and optimal temperature range is 60-85 ℃; Chlorination reaction still tail gas is the excessive chlorine and the hydrogen chloride gas of reaction generation, or also has nitrogen; Chlorination reaction still tail gas with the liquid separation of carrying secretly in the gas, then enters the chlorination of paraffin reactor through gas-liquid refrigerated separation device; The chlorination of paraffin reactor can almost all consume excessive chlorine, and the tail gas of discharge is the hydrogen chloride gas that contains micro-chlorine, or also has nitrogen; The water multistage absorption transfers hydrogen chloride gas to hydrochloric acid again, and tail gas can qualified discharge.When the sampling analysis carbonic ether chlorination degree of depth reaches technical requirements, stop logical chlorine, be used for dry air or rare gas element, carbonic ether chlorination reaction still reaction mixture is carried out air purge, remove the wherein chlorine and the hydrogen chloride gas of small amount of residual, thereby obtain satisfied chlorinated carbonates product.
Advantage of the present invention is:
1, uses chlorine as chlorizating agent, use the SULPHURYL CHLORIDE cost low.Its reason is that the molecular weight of chlorine is 71 to be 132 little than the SULPHURYL CHLORIDE molecular weight, and the chlorination dosage of every mole of product needed is little.Again it, the price of chlorine is low than SULPHURYL CHLORIDE.
2, chlorine is as chlorizating agent, and the tail of generation is narrow-minded, and tail gas is single component hydrogenchloride, and used water is absorbed as hydrochloric acid as byproduct.Use SULPHURYL CHLORIDE as chlorizating agent, the tail gas amount of generation is relatively than the people, and the tail gas component is the blending ingredients of hydrogenchloride and sulfurous gas, and the discharging that can only neutralize is difficult to obtain the byproduct of use value.
3, the carbonic ether chlorination is connected with the chlorination of paraffin reaction, can make carbonic ether chlorating excessive chlorine, obtains the utilization of high value, simultaneously, feeds the excessive upper limit of chlorine in the time of can improving the carbonic ether chlorination, thereby, improve speed of response, reduce technique controlling difficulty.
Example 1,
After the thawing of 1000kg NSC 11801, join in the enamel reaction still of 1000L, it is warming up to 60 ℃, under UV-irradiation, feed dry chlorine gas, exothermic heat of reaction, by reactor cooling system and the logical chlorine speed of adjusting, temperature of reaction is controlled at below 80 ℃.18 hours reaction times, logical chlorine total amount 2000kg.Obtain the 1200kg reaction mixture, sampling is analyzed with GC: chlorocarbonic acid vinyl acetate content is 80.1%, and the dichloro-ethylene carbonate content is 5.2%.The tail gas that the back reaction produces feeds the 4000L enamel reaction still that 2000kg paraffin is housed, and under UV-irradiation, carries out thermopositive reaction, tail gas absorbs through three grades of water absorption towers, but qualified discharge, the 2800kg clorafin that obtains, clorafin cl content are 28.6%.
Example 2,
After the thawing of 1000kg NSC 11801, join in the enamel reaction still of 1000L, it is warming up to 60 ℃, add 1kg azo-bis-isobutyl cyanide and 2kg methylene dichloride mixing solutions, feed dry chlorine gas, exothermic heat of reaction by reactor cooling system and the logical chlorine speed of adjusting, is controlled at temperature of reaction below 85 ℃.25 hours reaction times, logical chlorine total amount 2400kg.Obtain the 1300kg reaction mixture, sampling is analyzed with GC: chlorocarbonic acid vinyl acetate content is 61.2%, and the dichloro-ethylene carbonate content is 27.8%.The tail gas that the back reaction produces feeds, and the 4000L enamel reaction still of 2000kg paraffin is housed, under UV-irradiation, carry out thermopositive reaction, tail gas absorbs through three grades of water absorption towers, but qualified discharge, the 2900kg clorafin that obtains, clorafin cl content 31.0%.
Example 3
The 1000kg propylene carbonate is joined in the enamel reaction still of 1000L, it is warming up to 60 ℃, add 1kg azo-bis-isobutyl cyanide and 2kg methylene dichloride mixing solutions, feed dry chlorine gas, exothermic heat of reaction, by reactor cooling system and the logical chlorine speed of adjusting, temperature of reaction is controlled at below 75 ℃.18 hours reaction times, logical chlorine total amount 2000kg.Obtain the 1200kg reaction mixture, sampling is analyzed with GC: chlorocarbonic acid propylene ester content is 79.5%, and dichloro-propylene carbonate ester content is 4.8%.The tail gas that the back reaction produces feeds, and the 4000L enamel reaction still of 2000kg paraffin is housed, under UV-irradiation, carry out thermopositive reaction, tail gas absorbs through three grades of water absorption towers, but qualified discharge, the 2800kg clorafin that obtains, clorafin cl content are 28.6%.
Claims (4)
1. the synthetic method of a chlorinated carbonates, its characteristics are: with the excessive feeding liquid carbon of chlorine acid esters, temperature of reaction is at 50-110 ℃, optimal temperature range is: under 40-75 ℃, under UV-light or chemical initiator effect, carry out chlorination reaction, generate chlorinated carbonates.React excessive chlorine process gas-liquid refrigerated separation device, carry out chlorination reaction again, generate clorafin with paraffin oil.Reaction end gas is the hydrogen chloride gas that contains micro-chlorine.
2. the synthetic method described in the claim 1, its characteristics are: the liquid carbon acid esters is NSC 11801 or propylene carbonate.
3. the synthetic method described in the claim 1, its characteristics are: chlorinated carbonates is a chlorocarbonic acid vinyl acetate, dichloro-NSC 11801 or chlorocarbonic acid propylene ester.
4. the synthetic method described in the claim 1, its characteristics are: gas-liquid refrigerated separation device is a reflux exchanger.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100932607A CN102030736A (en) | 2009-09-24 | 2009-09-24 | Method for synthesizing chlorinated carbonate |
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| CN2009100932607A CN102030736A (en) | 2009-09-24 | 2009-09-24 | Method for synthesizing chlorinated carbonate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772344A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院理化技术研究所 | Photochemical synthesis method of monochloroethylene carbonate and photochemical reactor |
| CN104058961A (en) * | 2014-06-07 | 2014-09-24 | 李安民 | Process and equipment for continuously producing di(trichloromethyl)carbonate by adopting two-step chlorination method |
| CN106083805A (en) * | 2016-06-20 | 2016-11-09 | 天津市职业大学 | A kind of preparation method of bromo carbonic ester |
| CN110437202A (en) * | 2019-08-27 | 2019-11-12 | 许兆石 | A kind of chloridization process of ethylene carbonate |
| 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 |
| CN114437016A (en) * | 2022-02-28 | 2022-05-06 | 济源市恒顺新材料有限公司 | Production and manufacturing method of chlorinated ethylene carbonate |
| CN115626907A (en) * | 2022-11-03 | 2023-01-20 | 多氟多新材料股份有限公司 | Preparation method of 4-trifluoromethyl vinyl carbonate |
| CN115677646A (en) * | 2022-11-15 | 2023-02-03 | 福建致尚生物质材料发展有限公司 | Method for co-producing bio-based plasticizer by using chloroethylene 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 |
-
2009
- 2009-09-24 CN CN2009100932607A patent/CN102030736A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 孙浩: "碳酸亚乙烯酯的合成", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 黄建平 等: "氯化石蜡生产尾气治理", 《郑州工学院学报》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772344A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院理化技术研究所 | Photochemical synthesis method of monochloroethylene carbonate and photochemical reactor |
| CN103772344B (en) * | 2012-10-18 | 2015-11-04 | 中国科学院理化技术研究所 | Photochemical synthesis method of monochloroethylene carbonate and photochemical reactor |
| CN104058961A (en) * | 2014-06-07 | 2014-09-24 | 李安民 | Process and equipment for continuously producing di(trichloromethyl)carbonate by adopting two-step chlorination method |
| CN104058961B (en) * | 2014-06-07 | 2020-03-27 | 李安民 | Process and equipment for continuously producing di (trichloromethyl) carbonate by two-step chlorination method |
| CN106083805A (en) * | 2016-06-20 | 2016-11-09 | 天津市职业大学 | A kind of preparation method of bromo carbonic ester |
| CN110437202A (en) * | 2019-08-27 | 2019-11-12 | 许兆石 | A kind of chloridization process of ethylene carbonate |
| 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 |
| CN114437016A (en) * | 2022-02-28 | 2022-05-06 | 济源市恒顺新材料有限公司 | Production and manufacturing method of chlorinated ethylene carbonate |
| CN115626907A (en) * | 2022-11-03 | 2023-01-20 | 多氟多新材料股份有限公司 | Preparation method of 4-trifluoromethyl vinyl carbonate |
| CN115626907B (en) * | 2022-11-03 | 2024-04-16 | 多氟多新材料股份有限公司 | Preparation method of 4-trifluoro methyl ethylene carbonate |
| CN115677646A (en) * | 2022-11-15 | 2023-02-03 | 福建致尚生物质材料发展有限公司 | Method for co-producing bio-based plasticizer by using chloroethylene 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: 20110427 |