CN1022415C - Prepn. of 2-chloroethyl phosphonic acid - Google Patents
Prepn. of 2-chloroethyl phosphonic acid Download PDFInfo
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- CN1022415C CN1022415C CN 89103982 CN89103982A CN1022415C CN 1022415 C CN1022415 C CN 1022415C CN 89103982 CN89103982 CN 89103982 CN 89103982 A CN89103982 A CN 89103982A CN 1022415 C CN1022415 C CN 1022415C
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- chloroethyl
- hydrogen chloride
- chloride gas
- reaction
- phosphoric acid
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Abstract
The present invention relates to a preparing method for 2-chloroethyl phosphonic acid (with the trade name of ethephon) as a plant growth regulator. Technical conditions under which dry hydrogen chloride gas is fed during decompression to realize the acidolysis of di(2-chloroethyl)-2-chloroethyl phosphonate ester are used in the method. Consequently, the method has the advantages of simplified technology, reduced cost and reduced environmental pollution and is suitable for large-scale industrial production.
Description
The invention relates to the preparation method of a plant growth regulators.
2 chloroethyl phosphoric acid (commodity are called ethrel, external general Ethephon by name) is a kind of efficient plant growth regulator.It has the seed of breaking dormancy, reduces apical dominance, castrates, urges effects such as heat, volume increase, is widely used in crops such as rubber, tobacco, fruit tree, vegetables, cotton, wheat.
About the preparation method of 2 chloroethyl phosphoric acid, many reports were once arranged both at home and abroad, wherein majority is to be starting raw material with oxyethane and phosphorus trichloride, is prepared through following addition, rearrangement, acidolysis three-step reaction.
Current, the acidolysis reaction to above-mentioned the 3rd step adopts two-(2-chloroethyl) 2 chloroethyl phosphoric acid ester and concentrated hydrochloric acid (30～38%) to carry out processing condition (U.S.3,787,486 of acidolysis under high pressure (3～6 normal atmosphere) more; U.S.3,808,265; U.S, 4,322,371).Also be reported in add suitable quantity of water after, logical hydrogen chloride gas carries out acidolysis reaction (G.B.1,592,265) under condition of high voltage.But owing to above-mentioned the whole bag of tricks all needs just can carry out under condition of high voltage, thus all corresponding higher to the requirement of equipment, and complicated operation, wayward, danger is also bigger.Because of the adding of concentrated hydrochloric acid or water, brought very big trouble for the aftertreatment of product in addition.
The objective of the invention is to replace concentrated hydrochloric acid and water, and under the condition of decompression, carry out acidolysis reaction, to eliminate or to reduce above-mentioned drawback with the exsiccant hydrogen chloride gas.
In the present invention, the preparation of the first step three-(2-chloroethyl) phosphinate, adopting phosphorus trichloride and oxyethane is raw material.Temperature of reaction is controlled between 25～35 ℃, and the mol ratio of phosphorus trichloride and oxyethane is 1: 3.12.The preparation of second step, two-(2-chloroethyl) 2-chloroethyl phosphoric acid ester, control three-(2-chloroethyl) phosphinates carry out rearrangement reaction at 155～175 ℃.Reaction times is about about 16 hours.
The present invention takes the processing condition that reduce pressure in the 3rd step of producing 2 chloroethyl phosphoric acid during acidolysis reaction.And under heating and stirring, the exsiccant hydrogen chloride gas is fed two-(2-chloroethyl) 2 chloroethyl phosphoric acid ester solutions slowly.Adopt the decompression method to carry out esterlysis and react requirement, the simplification technology that both can reduce equipment, can reduce environmental pollution again, help strengthen labour protection.The pressure of entire reaction system should be controlled at 100～400mmHg during reaction, is preferably in 100～200mmHg.
Employed dry hydrogen chloride gas among the present invention is to adopt the vitriol oil more than sodium-chlor and 92% to react between 80～90 ℃, and the hydrogen chloride gas of generation gets by the vitriol oil is dry.(the present invention has adopted the cyclic ventpipe for the contact surface of 2-hydrogen ethyl phosphonate, fast reaction speed, and feeds slowly in the bottom of two-(2-chloroethyl) 2 chloroethyl phosphoric acid ester liquid in order to increase hydrogen chloride gas and two-(2-chloroethyl).The logical chlorine time should be controlled at 12～15 hours.
Adopt the water that do not add of the present invention to feed dry hydrogen chloride gas and carry out the prepared 2 chloroethyl phosphoric acid of acidolysis and can directly be made into preparation, and do not need to carry out again any aftertreatment.And under the condition of decompression reaction, the hydrogenchloride in the product does not need to adopt additive method just can reduce to minimum concentration.Superfluous hydrogenchloride water can be applied mechanically or be sold after absorbing, and both can reduce cost, and is free from environmental pollution again.
For the speed that distillates, the shortening reaction times of accelerating the byproduct ethylene dichloride, simultaneously also for the outward appearance of yield, purity and the assurance product that can improve product, temperature of reaction during acidolysis should be controlled between 140～200 ℃, and optimal reaction temperature is 160～170 ℃.
Adopt method of the present invention to prepare 2 chloroethyl phosphoric acid, both simplified technology, reduced cost, be convenient to operate, reduced pollution again, and all increase than additive method at the aspects such as yield, purity, outward appearance and aftertreatment of product to environment.
Example one
Two-(2-chloroethyl) the 2 chloroethyl phosphoric acid esters that add 660 grams 60% in there-necked flask stir down reactant are warming up to 140 ℃.The control reaction pressure feeds dry hydrogen chloride gas at 100～200mmHg from bottom ring-type ventpipe, is warming up to 170～180 ℃ then, reacts 14.5 hours.After treating that ethylene dichloride seldom distillates, stop logical hydrogen chloride gas.Under reduced pressure kept 30 minutes, and removed excessive oxidation hydrogen, content is 71.77% 2 chloroethyl phosphoric acid crude product, 346.6 grams, thick ethylene dichloride 309 grams.
Example two
Two-(2-chloroethyl) the 2 chloroethyl phosphoric acid esters that add 625 grams 60% in there-necked flask stir down reactant are warming up to 140 ℃.The control reaction pressure feeds dry hydrogen chloride gas at 200～300mmHg from bottom ring-type ventpipe, is warming up to 160～170 ℃ then, reacts 12.5 hours.After treating that ethylene dichloride seldom distillates, stop logical hydrogen chloride gas.Under this pressure, kept 30 minutes, and removed excessive hydrogen chloride, content is 72.09% 2 chloroethyl phosphoric acid crude product 362.5 grams, thick ethylene dichloride 257.5 grams.
Example three
Two-(2-chloroethyl) the 2 chloroethyl phosphoric acid esters that add 500 grams 60% in there-necked flask stir down reactant are warming up to 140 ℃.The control reaction pressure feeds dry hydrogen chloride gas at 300～400mmHg from bottom ring-type ventpipe, is warming up to 180～200 ℃ then, reacts 15 hours.After treating that ethylene dichloride seldom distillates, stop logical hydrogen oxide gas.Under this pressure, kept 30 minutes, and removed excessive hydrogen chloride, content is 66.70% 2 chloroethyl phosphoric acid crude product 278.5 grams, thick ethylene dichloride 262 grams.
Claims (6)
1, a kind of method for preparing 2 chloroethyl phosphoric acid from two-(2-chloroethyl) 2 chloroethyl phosphoric acid esters through acidolysis reaction, the invention is characterized in the reaction conditions that adopts decompression, heating, in two-(2-chloroethyl) 2 chloroethyl phosphoric acid ester solutions, feed dry hydrogen chloride gas.
2, by the described acidolysis reaction of claim 1, it is characterized in that the pressure that reduces pressure should be controlled at 100～400mmHg.
3, by the described acidolysis reaction of claim 1, the temperature when it is characterized in that acidolysis reaction is 140～200 ℃.
4,, it is characterized in that the time that feeds dry hydrogen chloride gas should grasp at 12～15 hours by the described acidolysis reaction of claim 1.
5, by the described acidolysis reaction of claim 1, the pipe that it is characterized in that feeding dry hydrogen chloride gas is a ring-type.
6, by the acidolysis reaction of claim 1 and 5 described logical dry hydrogen chloride gas, it is characterized in that the ring-type ventpipe should place the bottommost of reactor, dry hydrogen chloride gas should feed from the bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103982 CN1022415C (en) | 1989-06-14 | 1989-06-14 | Prepn. of 2-chloroethyl phosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103982 CN1022415C (en) | 1989-06-14 | 1989-06-14 | Prepn. of 2-chloroethyl phosphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048043A CN1048043A (en) | 1990-12-26 |
| CN1022415C true CN1022415C (en) | 1993-10-13 |
Family
ID=4855374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89103982 Expired - Fee Related CN1022415C (en) | 1989-06-14 | 1989-06-14 | Prepn. of 2-chloroethyl phosphonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1022415C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074420C (en) * | 1999-10-08 | 2001-11-07 | 常熟市农药厂 | Preparation method of 70%-80% liquid 2-chloroethyl phosphonic acid |
| CN102766161B (en) * | 2012-08-02 | 2015-11-04 | 上海华谊（集团）公司 | A kind of preparation method of 2 chloroethyl phosphoric acid |
| CN103755740B (en) * | 2013-01-24 | 2016-06-01 | 绍兴市东湖生化有限公司 | A kind of serialization pressurization produces the technique of 2 chloroethyl phosphoric acid |
| CN103788126B (en) * | 2014-01-10 | 2015-08-19 | 江苏安邦电化有限公司 | A kind of ethrel continuous acidolysis method |
| CN110150268B (en) * | 2019-05-23 | 2021-08-03 | 苏农（广德）生物科技有限公司 | Preparation process for continuously producing ethephon aqua |
| CN112661607B (en) * | 2020-12-28 | 2023-04-07 | 安道麦安邦(江苏)有限公司 | Method and device for recycling organic waste liquid generated in ethephon production |
-
1989
- 1989-06-14 CN CN 89103982 patent/CN1022415C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1048043A (en) | 1990-12-26 |
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