CN104370857A - Synthesis method of epoxy chloropropane - Google Patents
Synthesis method of epoxy chloropropane Download PDFInfo
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- CN104370857A CN104370857A CN201410632160.8A CN201410632160A CN104370857A CN 104370857 A CN104370857 A CN 104370857A CN 201410632160 A CN201410632160 A CN 201410632160A CN 104370857 A CN104370857 A CN 104370857A
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- epoxy chloropropane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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Abstract
The invention discloses a synthesis method of epoxy chloropropane. The method comprises the following steps: carrying out chlorination reaction on raw materials 95% industrial glycerol and anhydrous hydrogen chloride by using acetic acid as a catalyst to synthesize dichloropropanol, and carrying out cyclization reaction on the dichloropropanol-water mixed solution and 30 wt% sodium hydroxide alkali liquor to obtain the epoxy chloropropane. The yield is up to 87% above, and the purity is up to 98.8%. The method has the characteristics of low energy consumption, mild reaction conditions, simple technical process, high product purity, no secondary pollution and the like.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, a kind of synthetic method of epoxy chloropropane.
Background technology
Non-renewable and the price of petroleum resources high rapidly, force people to seek its substitute, utilizing natural fats and oils to replace oil becomes focus.Natural fats and oils has recyclability, can manufacture biofuel and tensio-active agent, meets tensio-active agent Green Development trend.Biological diesel oil byproduct glycerin deep processing has important meaning for promotion biofuel and green surfactant industry, and what wherein have most industrialization development prospect is glycerine epoxy chloropropane.
Epoxy chloropropane (ECH) is a kind of important industrial chemicals and synthetic intermediate, and in epoxidised compound, the output of ECH is only second to oxyethane and propylene oxide, occupies second.Its purposes is very extensive, be mainly used to synthetic epoxy resin chlorohydrin rubber etc., the throughput of global ECH in 2006 is more than 1.3Mt/a, and the place of production mainly concentrates on the U.S., West Europe and Japan, and the output of the companies such as Tao Shi, Su Wei, shell accounts for 51%. of whole world total amount
At present, the industrial process of ECH mainly contains propylene high-temperature nitriding and propylene acetate method, and the former accounts for 90%.The requirement of propylene high-temperature chlorination process to the corrosion resistance nature of reactor is higher, and energy consumption is comparatively large, and consumption chlorine is more, and by product is more, needs purifying treatment, and environmental pollution is serious; Propylene acetate method have employed acetoxylation technology, and reaction conditions is gentle, and chlorine consumption reduces half, and by product is less, but method steps is many, and technical process is long, and three wastes discharge amount is large.
Summary of the invention
The energy consumption that the present invention is directed to traditional technology is large, by product is many, complex steps, environmental pollution are serious, provides the synthetic method of the epoxy chloropropane that a kind of reaction conditions is simple, productive rate is high, non-secondary pollution, by product are few.
For achieving the above object, the synthetic route of epoxy chloropropane of the present invention is:
The building-up process of the epoxy chloropropane that the present invention relates to comprises the following steps:
1, chlorination reaction
(1) in the 500mL four-hole bottle that thermometer, electric mixer and water trap are housed, add 112.6g glycerine and the stirring of 10.8g Glacial acetic acid, be warming up to 95-100 DEG C, slowly pass into the hydrogen chloride gas through vitriol oil drying, be incubated when temperature reaches 120 DEG C;
(2) water generated in reaction is isolated by water trap, absorb unreacted hydrogen chloride gas with device for absorbing tail gas simultaneously, to the reaction later stage, every the density of 1h sampling and measuring reaction solution, reaction end is controlled, when the density of reaction solution reaches 1.32-1.34g/cm by the density of reaction solution
3;
(3) cool, by reaction solution underpressure distillation, collect the cut of 80-120 DEG C/35mmHg, obtain 119.8g dichlorohydrine.
2, cyclization
(1) leak in 500mL there-necked flask and add 119.8g dichlorohydrine and 40g water being equipped with thermometer, electric mixer and dropping liquid, be heated to 50-55 DEG C;
(2) slowly drip the sodium hydroxide solution 152g of 30% when rapid stirring, be incubated after being warming up to 70 DEG C simultaneously, under the pressure of 280mmHg, steam the epoxy chloropropane of generation, collect 60-65 DEG C of cut;
(3) sodium hydroxide drips off in about 10min, drips off rear continuation reaction 30min, isolates organic phase, obtain 81.6g epoxy chloropropane, calculated yield after reaction terminates from distillate, and by its purity of chromatographic.
Specific embodiments
The building-up process of a kind of epoxy chloropropane that the present invention relates to comprises the following steps:
In the 500mL four-hole bottle that thermometer, electric mixer and water trap are housed, add 112.6g glycerine and the stirring of 10.8g Glacial acetic acid, be warming up to 95-100 DEG C, slowly pass into the hydrogen chloride gas through vitriol oil drying, be incubated when temperature reaches 120 DEG C; The water generated in reaction is isolated by water trap, absorb unreacted hydrogen chloride gas with device for absorbing tail gas, to the reaction later stage, every the density of 1h sampling and measuring reaction solution simultaneously, reaction end is controlled, when the density of reaction solution reaches 1.32-1.34g/cm by the density of reaction solution
3; Cooling, by reaction solution underpressure distillation, collects the cut of 80-120 DEG C/35mmHg, obtains 119.8g dichlorohydrine.Leak in 500mL there-necked flask and add 119.8g dichlorohydrine and 40g water being equipped with thermometer, electric mixer and dropping liquid, be heated to 50-55 DEG C; Slowly drip the sodium hydroxide solution 152g of 30% when rapid stirring, be incubated after being warming up to 70 DEG C simultaneously, under the pressure of 280mmHg, steam the epoxy chloropropane of generation, collect 60-65 DEG C of cut; Sodium hydroxide drips off in about 10min, drips off rear continuation reaction 30min, isolates organic phase, obtain 81.6g epoxy chloropropane, calculated yield after reaction terminates from distillate, and by its purity of chromatographic.
Example 1
In the 500mL four-hole bottle that thermometer, electric mixer and water trap are housed, add 112.6g glycerine and the stirring of 10.8g Glacial acetic acid, be warming up to 95 DEG C, slowly pass into the hydrogen chloride gas through vitriol oil drying, be incubated when temperature reaches 120 DEG C; The water generated in reaction is isolated by water trap, absorb unreacted hydrogen chloride gas with device for absorbing tail gas, to the reaction later stage, every the density of 1h sampling and measuring reaction solution simultaneously, reaction end is controlled, when the density of reaction solution reaches 1.32g/cm by the density of reaction solution
3; Cooling, by reaction solution underpressure distillation, collects the cut of 80 DEG C/35mmHg, obtains 119.8g dichlorohydrine.Leak in 500mL there-necked flask and add 119.8g dichlorohydrine and 40g water being equipped with thermometer, electric mixer and dropping liquid, be heated to 50 DEG C; Slowly drip the sodium hydroxide solution 152g of 30% when rapid stirring, be incubated after being warming up to 70 DEG C simultaneously, under the pressure of 280mmHg, steam the epoxy chloropropane of generation, collect 60 DEG C of cuts; Sodium hydroxide drips off in about 10min, and drip off rear continuation reaction 30min, from distillate, isolate organic phase after reaction terminates, obtain 81.6g epoxy chloropropane, yield reaches more than 87%, and is 98.8% by its purity of chromatographic.
Example 2
In the 500mL four-hole bottle that thermometer, electric mixer and water trap are housed, add 112.6g glycerine and the stirring of 10.8g Glacial acetic acid, be warming up to 98 DEG C, slowly pass into the hydrogen chloride gas through vitriol oil drying, be incubated when temperature reaches 120 DEG C; The water generated in reaction is isolated by water trap, absorb unreacted hydrogen chloride gas with device for absorbing tail gas, to the reaction later stage, every the density of 1h sampling and measuring reaction solution simultaneously, reaction end is controlled, when the density of reaction solution reaches 1.33g/cm by the density of reaction solution
3; Cooling, by reaction solution underpressure distillation, collects the cut of 100 DEG C/35mmHg, obtains 119.8g dichlorohydrine.Leak in 500mL there-necked flask and add 119.8g dichlorohydrine and 40g water being equipped with thermometer, electric mixer and dropping liquid, be heated to 53 DEG C; Slowly drip the sodium hydroxide solution 152g of 30% when rapid stirring, be incubated after being warming up to 70 DEG C simultaneously, under the pressure of 280mmHg, steam the epoxy chloropropane of generation, collect 63 DEG C of cuts; Sodium hydroxide drips off in about 10min, and drip off rear continuation reaction 30min, from distillate, isolate organic phase after reaction terminates, obtain 81.6g epoxy chloropropane, yield is more than 87%, and is 98.8% by its purity of chromatographic.
Example 3
In the 500mL four-hole bottle that thermometer, electric mixer and water trap are housed, add 112.6g glycerine and the stirring of 10.8g Glacial acetic acid, be warming up to 100 DEG C, slowly pass into the hydrogen chloride gas through vitriol oil drying, be incubated when temperature reaches 120 DEG C; The water generated in reaction is isolated by water trap, absorb unreacted hydrogen chloride gas with device for absorbing tail gas, to the reaction later stage, every the density of 1h sampling and measuring reaction solution simultaneously, reaction end is controlled, when the density of reaction solution reaches 1.34g/cm by the density of reaction solution
3; Cooling, by reaction solution underpressure distillation, collects the cut of 120 DEG C/35mmHg, obtains 119.8g dichlorohydrine.Leak in 500mL there-necked flask and add 119.8g dichlorohydrine and 40g water being equipped with thermometer, electric mixer and dropping liquid, be heated to 55 DEG C; Slowly drip the sodium hydroxide solution 152g of 30% when rapid stirring, be incubated after being warming up to 70 DEG C simultaneously, under the pressure of 280mmHg, steam the epoxy chloropropane of generation, collect 65 DEG C of cuts; Sodium hydroxide drips off in about 10min, and drip off rear continuation reaction 30min, from distillate, isolate organic phase after reaction terminates, obtain 81.6g epoxy chloropropane, yield is more than 87%, and is 98.8% by its purity of chromatographic.
Claims (2)
1. a synthetic method for epoxy chloropropane, is characterized in that chlorination reaction:
(1) in the 500mL four-hole bottle that thermometer, electric mixer and water trap are housed, add 112.6g glycerine and the stirring of 10.8g Glacial acetic acid, be warming up to 95-100 DEG C, slowly pass into the hydrogen chloride gas through vitriol oil drying, be incubated when temperature reaches 120 DEG C;
(2) water generated in reaction is isolated by water trap, absorb unreacted hydrogen chloride gas with device for absorbing tail gas simultaneously, to the reaction later stage, every the density of 1h sampling and measuring reaction solution, reaction end is controlled, when the density of reaction solution reaches 1.32-1.34g/cm by the density of reaction solution
3;
(3) cool, by reaction solution underpressure distillation, collect the cut of 80-120 DEG C/35mmHg, obtain 119.8g dichlorohydrine.
2. the synthetic method of a kind of epoxy chloropropane according to claim 1, is characterized in that cyclization:
(1) leak in 500mL there-necked flask and add 119.8g dichlorohydrine and 40g water being equipped with thermometer, electric mixer and dropping liquid, be heated to 50-55 DEG C;
(2) slowly drip the sodium hydroxide solution 152g of 30% when rapid stirring, be incubated after being warming up to 70 DEG C simultaneously, under the pressure of 280mmHg, steam the epoxy chloropropane of generation, collect 60-65 DEG C of cut;
(3) sodium hydroxide drips off in about 10min, drips off rear continuation reaction 30min, isolates organic phase, obtain 81.6g epoxy chloropropane, calculated yield after reaction terminates from distillate, and by its purity of chromatographic.
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| CN201410632160.8A CN104370857A (en) | 2014-11-11 | 2014-11-11 | Synthesis method of epoxy chloropropane |
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| CN201410632160.8A CN104370857A (en) | 2014-11-11 | 2014-11-11 | Synthesis method of epoxy chloropropane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903222A (en) * | 2017-10-18 | 2018-04-13 | 江苏索普（集团）有限公司 | A kind of method that epoxychloropropane is prepared by biomass glycerol |
| CN107935968A (en) * | 2017-10-18 | 2018-04-20 | 江苏索普（集团）有限公司 | A kind of epoxychloropropane preparation method based on biomass glycerol |
| CN110229123A (en) * | 2019-05-10 | 2019-09-13 | 淮阴工学院 | The method that novel saponification agent prepares epoxychloropropane |
| CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
Citations (7)
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|---|---|---|---|---|
| US2144612A (en) * | 1936-09-10 | 1939-01-24 | Dow Chemical Co | Preparation of glycerol dichlorohydrin |
| CN1845888A (en) * | 2003-09-01 | 2006-10-11 | 化学和冶金生产联合体股份公司 | Method of preparing dichloropropanols from glycerine |
| CN101003523A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing epoxy chloropropane by using glycerol method |
| CN101255099A (en) * | 2008-04-03 | 2008-09-03 | 南京工业大学 | Method for producing dichloropropanol by using glycerin |
| CN102516205A (en) * | 2004-07-21 | 2012-06-27 | 陶氏环球技术有限责任公司 | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
| CN103025691A (en) * | 2010-06-30 | 2013-04-03 | 三星精密化学株式会社 | Method for preparing chlorohydrins composition and method for preparing epichlorohydrin using chlorohydrins composition prepared thereby |
| CN103038200A (en) * | 2010-06-30 | 2013-04-10 | 三星精密化学株式会社 | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby |
-
2014
- 2014-11-11 CN CN201410632160.8A patent/CN104370857A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2144612A (en) * | 1936-09-10 | 1939-01-24 | Dow Chemical Co | Preparation of glycerol dichlorohydrin |
| CN1845888A (en) * | 2003-09-01 | 2006-10-11 | 化学和冶金生产联合体股份公司 | Method of preparing dichloropropanols from glycerine |
| CN102516205A (en) * | 2004-07-21 | 2012-06-27 | 陶氏环球技术有限责任公司 | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
| CN101003523A (en) * | 2007-01-25 | 2007-07-25 | 中国林业科学研究院林产化学工业研究所 | Method for preparing epoxy chloropropane by using glycerol method |
| CN101255099A (en) * | 2008-04-03 | 2008-09-03 | 南京工业大学 | Method for producing dichloropropanol by using glycerin |
| CN103025691A (en) * | 2010-06-30 | 2013-04-03 | 三星精密化学株式会社 | Method for preparing chlorohydrins composition and method for preparing epichlorohydrin using chlorohydrins composition prepared thereby |
| CN103038200A (en) * | 2010-06-30 | 2013-04-10 | 三星精密化学株式会社 | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903222A (en) * | 2017-10-18 | 2018-04-13 | 江苏索普（集团）有限公司 | A kind of method that epoxychloropropane is prepared by biomass glycerol |
| CN107935968A (en) * | 2017-10-18 | 2018-04-20 | 江苏索普（集团）有限公司 | A kind of epoxychloropropane preparation method based on biomass glycerol |
| CN110229123A (en) * | 2019-05-10 | 2019-09-13 | 淮阴工学院 | The method that novel saponification agent prepares epoxychloropropane |
| CN113234041A (en) * | 2021-04-07 | 2021-08-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
| CN113234041B (en) * | 2021-04-07 | 2023-03-10 | 江苏瑞恒新材料科技有限公司 | Preparation method of epichlorohydrin |
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Application publication date: 20150225 |