CN1298687C - Process for preparing 2,3-dichloropropylene - Google Patents
Process for preparing 2,3-dichloropropylene Download PDFInfo
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- CN1298687C CN1298687C CNB2004100648078A CN200410064807A CN1298687C CN 1298687 C CN1298687 C CN 1298687C CN B2004100648078 A CNB2004100648078 A CN B2004100648078A CN 200410064807 A CN200410064807 A CN 200410064807A CN 1298687 C CN1298687 C CN 1298687C
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- dichloropropylene
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- chlorallylene
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Abstract
The present invention relates to technology for preparing 2, 3-dichloropropene, which solves the problems of high reaction yield of products and high production cost of the prior art for preparing 2, 3-dichloropropene. TEBA as a catalyst is added during the reacting process of 1, 2, 3-trichloropropane and alkali liquor to generate 2, 3-dichloropropene. The technology is characterized in that allyl chloride is used as initial raw material to react with chlorine gas to generate 1, 2, 3-trichloropropane. Due to the adoption of production technology without solvent, the material cost is reduced. TEBA is used as a catalyst for reaction in the technology of the present invention, so that the product quality and the product yield are enhanced.
Description
Technical field
The present invention relates to a kind of pesticide intermediate 2, the preparation technology of 3-dichloropropylene.
Background technology
2, the 3-dichloropropylene is the intermediate that can be used for producing agricultural chemicals such as choline dichloride, thiophene worm piperazine etc.Consult known to the patent documentation according to the applicant, produce 2 at present, the technology of 3-dichloropropylene is starting raw material with the glyceryl trichloride, and adopts ethanol to make solvent, and raw materials cost is higher; And quality product is not high, yield is lower.
Summary of the invention
The technical problem to be solved in the present invention is an existing preparation 2, there is the problem that the product reaction yield is on the low side, production cost is high in the technology of 3-dichloropropylene, a kind of product reaction yield that improves is provided, has reduced the preparation 2 of production cost of products, the technology of 3-dichloropropylene.
Of the present invention 2, the preparation technology of 3-dichloropropylene is to generate 2 at glyceryl trichloride and liquid caustic soda reaction, in the process of 3-dichloropropylene, adds catalyzer TEBA.
As improvement, this preparation technology may further comprise the steps: glyceryl trichloride and TEBA are added reaction flask, be warming up to 75-85 ℃, dropwise liquid adds the water distillation after the back flow reaction.
Recited above any 2, the preparation technology of 3-dichloropropylene, mole proportioning that feeds intake of glyceryl trichloride and TEBA is 1: 0.018～0.02.
Recited above any 2, the preparation technology of 3-dichloropropylene is starting raw material and chlorine reaction glyceryl trichloride with the chlorallylene earlier.With the chlorallylene is that starting raw material and chlorine reaction glyceryl trichloride may further comprise the steps: add chlorallylene in reaction flask, cool the temperature to-3 to 5 ℃, feed chlorine, controlled temperature is no more than 25 ℃, when chlorallylene＜3%, stop logical chlorine, take out excessive chlorine after the stirring.
The present invention and existing production 2, the technology that the 3-dichloropropylene generally adopts relatively has following beneficial effect: (1) existing manufacturing technique adopts ethanol to make solvent, the present invention adopts solvent-free production technique, thereby has reduced raw materials cost, and useful to the raising of quality product, yield.(2) existing processes does not adopt catalyzer, and the present invention adopts TEBA as catalyst for reaction, has improved quality, the yield of product.(3) existing processes is starting raw material with the glyceryl trichloride, and the present invention is starting raw material with the chlorallylene, thereby has reduced the raw materials cost of product effectively, and the range of decrease can reach 20%.Because this product is the intermediate of agricultural chemicals, application of the present invention, make some agricultural chemicals as: the production cost of choline dichloride, thiophene worm piperazine etc. reduces, thereby makes peasant's use cost also obtain decline.(4) adopt Synthetic 2 of the present invention, the reaction conditions gentleness of 3-dichloropropylene, the existing technology of step is simple, and no special equipment requirements has reduced by 2, and the production cost of 3-dichloropropylene has reduced the generation of " three wastes ".(5) by 2 of the present invention's production, 3-dichloropropylene content can reach 96%, and yield can reach more than 71%.
Description of drawings
Fig. 1 is the FB(flow block) of preparation glyceryl trichloride;
Fig. 2 is preparation 2, the FB(flow block) of 3-dichloropropylene.
Embodiment
Comparative Examples:
(1) glyceryl trichloride 147 grams (93%) is dropped in the stainless steel reactor, and add 10 gram sodium hydroxide.Stir, heat, when being warming up to 95 ℃, beginning reaction and emit heat, reacted 1 hour down in 98～105 ℃ temperature condition.
(2) 38 gram sodium hydroxide are made into 50% aqueous solution, add 70 gram ethanol, slowly splash into after the mixing in the reactor, under the maintenance reflux state, in 3～3.5 hours, dropwise.Under 80～90 ℃ condition, continue reaction 6 hours again.(3) add cold water in reaction soln, thorough washing allows it leave standstill layering until neutrality then.Take out oil reservoir, 93～105 ℃ of cuts are collected in distillation, obtain 2,3-dichloropropylene 79 grams, and content 92%, yield are 70.01%.
Embodiment 1:
(1) be earlier that starting raw material and chlorine reaction generate glyceryl trichloride with the chlorallylene
A, reaction equation
B, working specification
Drop into the 1000g chlorallylene in reaction flask, stirring, chilled brine cool the temperature to about 0 ℃; Open the chlorine main valve, beginning feeds chlorine in reaction flask, and controlling moisture is no more than 25 ℃, feeds about 946g chlorine about 5 hours, and tracks to raw material＜3% with the gas spectrum, stops to lead to chlorine then; About 25 ℃, stirred 1 hour, take out excessive chlorine with little negative pressure then.About 20 minutes, blowing, weigh, the about 1900g of glyceryl trichloride.
C, charge ratio
Chlorallylene: chlorine=1: 1.02 (mol ratio)
(2) generate 2, the 3-dichloropropylene with glyceryl trichloride and liquid caustic soda reaction again
A, reaction equation
B, working specification
In reaction flask, drop into 951g1,2,3-trichloropropane, 25gTEBA stir, and behind the intensification degree to 80 ℃, drip the 960g liquid caustic soda; After dropwising, back flow reaction is about 2 hours, branch vibration layer; Add 400g left and right sides water in reaction flask, change back stream for distillation, use water-and-oil separator, oil advances receiver, until there not being oil droplet to produce.Get 2, the about 530g of 3-dichloropropylene, content＞96%.
C, charge ratio
Glyceryl trichloride: liquid caustic soda: TEBA=1: 1.2: 0.018～0.02 (mol ratio)
Embodiment 2:
(1) in reaction flask, drop into 951g1,2,3-trichloropropane (93%), 25gTEBA start stirring, intensification degree to 80 ℃.
(2) in the 960g liquid caustic soda, add 453g ethanol, slowly be added dropwise in the reactor after the mixing, drip off the back back flow reaction about 2 hours, branch vibration layer; In reaction flask, add 400g water, change back stream, collect 93～105 ℃ of cuts, get 2,3-dichloropropylene 512g, content 95.1%, yield 72.5% for distillation.
Embodiment 3:
(1) in reaction flask, drops into the 1000g chlorallylene, open stirring, chilled brine, cool the temperature to about 0 ℃; Open the chlorine main valve, beginning feeds chlorine in reaction flask, and controlling moisture is no more than 25 ℃, feeds about 946g chlorine about 5 hours, and to track to raw material with the gas spectrum be 3%, stops to lead to chlorine then; About 25 ℃, stirred 1 hour, take out excessive chlorine with little negative pressure then.About 20 minutes, blowing, weigh, glyceryl trichloride 1908g, content 93.5%, yield 92.5%.
(2) in reaction flask, drop into 951g1,2,3-trichloropropane, 25gTEBA start stirring, behind the intensification degree to 80 ℃, drip the 960g liquid caustic soda; After dropwising, back flow reaction is about 2 hours, branch vibration layer; Add 400g water in reaction flask, change back stream for distillation, use water-and-oil separator, oil advances receiver, until there not being oil droplet to produce.Get 2,3-dichloropropylene 528g, content 96.8%, yield 75.7%.
Embodiment 4:
(1) in reaction flask, drops into the 1000g chlorallylene, open stirring, chilled brine, cool the temperature to about 0 ℃; Open the chlorine main valve, beginning feeds chlorine in reaction flask, and controlling moisture is no more than 25 ℃, feeds about 946g chlorine about 5 hours, and tracks to raw material＜3% with the gas spectrum, stops to lead to chlorine then; About 25 ℃, stirred 1 hour, take out excessive chlorine with little negative pressure then.About 20 minutes, blowing, weigh, the about 1893g of glyceryl trichloride, content 94.7%, yield 93.0%.
(2) in reaction flask, drop into 951g1,2,3-trichloropropane, 27.5gTEBA start stirring, behind the intensification degree to 80 ℃, drip the 960g liquid caustic soda; After dropwising, back flow reaction is about 2 hours, branch vibration layer; Add 400g water in reaction flask, change back stream for distillation, use water-and-oil separator, oil advances receiver, until there not being oil droplet to produce.Get 2, the about 532g of 3-dichloropropylene, content 96.5%, yield 75.1%.
Can find out that from above embodiment the present invention starts with from catalyzer, filter out TEBA and make catalyzer, and technology is optimized, adopt solvent-free production technique, and do initial raw material, thereby improve the reaction yield of product, reduce production cost with chlorallylene.
Claims (3)
1, a kind of 2, the preparation technology of 3-dichloropropylene is characterized in that: 1,2,3-trichloropropane and liquid caustic soda reaction generate 2, in the process of 3-dichloropropylene, are catalyzer with TEBA, with 1,2,3 trichloropropanes and TEBA add in the reaction flask by 1: 0.018～0.02 molar ratio, are warming up to 75-85 ℃, dropwise liquid adds the water distillation after the back flow reaction.
2, according to claim 12, the preparation technology of 3-dichloropropylene is characterized in that: be earlier starting raw material and chlorine reaction generation glyceryl trichloride with the chlorallylene.
3, according to claim 22, the preparation technology of 3-dichloropropylene, it is characterized in that: be that starting raw material and chlorine reaction generate 1 with the chlorallylene, 2, the 3-trichloropropane comprises the steps: to add propyl chloride in reaction flask, cools the temperature to-3 to 5 ℃, feed chlorine, controlled temperature is no more than 25 ℃, stops logical chlorine when chlorallylene＜3%, takes out excessive chlorine after the stirring.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100648078A CN1298687C (en) | 2004-09-30 | 2004-09-30 | Process for preparing 2,3-dichloropropylene |
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| CNB2004100648078A CN1298687C (en) | 2004-09-30 | 2004-09-30 | Process for preparing 2,3-dichloropropylene |
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| CN1634818A CN1634818A (en) | 2005-07-06 |
| CN1298687C true CN1298687C (en) | 2007-02-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299151B (en) * | 2018-02-09 | 2020-03-10 | 浙江大学 | Method for preparing 2-methylallyl chloride from 1, 2-dichlorotert-butyl alkane |
| CN108640811A (en) * | 2018-04-26 | 2018-10-12 | 山东海益化工科技有限公司 | The method that chloropropene is synthetically prepared 1,2,3- trichloropropanes |
| CN108640812A (en) * | 2018-06-21 | 2018-10-12 | 岳阳景嘉化工有限公司 | The synthetic method of one kind 2,3- dichloropropylenes |
| CN109912384A (en) * | 2019-04-04 | 2019-06-21 | 浙江大学 | A kind of catalysis process recycling dichloropropylene from dichloropropylene polymer |
| CN110746267A (en) * | 2019-12-03 | 2020-02-04 | 湖南莱万特化工有限公司 | Preparation method and preparation device of 2, 3-dichloropropene compound |
| CN112191270A (en) * | 2020-10-14 | 2021-01-08 | 湖南莱万特化工有限公司 | Catalyst for converting 1, 2, 3-trichloropropane into 2, 3-dichloropropene and application method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4535194A (en) * | 1983-07-06 | 1985-08-13 | Monsanto Co. | Process for producing 1,1,2,3-tetrachloropropene |
| CN1113681A (en) * | 1994-05-27 | 1995-12-27 | 天津市农药研究所 | Preparing method for cycocel |
-
2004
- 2004-09-30 CN CNB2004100648078A patent/CN1298687C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4535194A (en) * | 1983-07-06 | 1985-08-13 | Monsanto Co. | Process for producing 1,1,2,3-tetrachloropropene |
| CN1113681A (en) * | 1994-05-27 | 1995-12-27 | 天津市农药研究所 | Preparing method for cycocel |
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