CN1047077A - Industrial producing method for alpha-cyano ethylacrylate - Google Patents
Industrial producing method for alpha-cyano ethylacrylate Download PDFInfo
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- CN1047077A CN1047077A CN 89106885 CN89106885A CN1047077A CN 1047077 A CN1047077 A CN 1047077A CN 89106885 CN89106885 CN 89106885 CN 89106885 A CN89106885 A CN 89106885A CN 1047077 A CN1047077 A CN 1047077A
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- ethylacrylate
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Abstract
Industrial producing method for alpha-cyano ethylacrylate, by speed contract refreshing dry reaction, tri-layer drying and dehydrating, the slaking depolymerization, the refining four step operations of filling are formed.Neither with an organic solvent do not use sulfur dioxide gas in the production again, safety non-pollution, technical process is simple, plant factor height, with short production cycle, easy to operate, drying operation are saved the energy, the product yield height based on seasoning, good product quality, stable, product cost is low.
Description
The present invention relates to industrial producing method for alpha-cyano ethylacrylate.
Industrial, mainly be both at home and abroad at present by ethyl cyanoacetate and formaldehyde condensation be alpha-cyanoethyl acrylate oligomer then again the dehydration, depolymerization and purified approach make ethyl.Under this approach, multiple implementation method is arranged again, as: formalin method, Paraformaldehyde 96 methyl alcohol method, Paraformaldehyde 96 chloroparaffin method, formalin dichloroethane law.Condensation in these methods, dehydration operation are carried out in poisonous inflammable organic solvents such as methyl alcohol, benzene and ethylene dichloride mostly.Because the ethyl monomer runs into the easy polymerization of the water capacity of trace, occluding device when serious is forced to parking maintenance, so depolymerization, purification operations generally are to carry out having under the sulfurous gas atmosphere of irritating smell.If with an organic solvent and sulfurous gas, a lot of shortcomings are arranged then in the production.As: dangerous, environmental pollution, complex process, processing trouble are arranged, product yield is on the low side, quality is not good enough and cost is more high.
The objective of the invention is: provide a kind of in production ethyl process, neither with an organic solvent do not use sulfur dioxide gas again, technical process is simple, plant factor is high, with short production cycle, easy to operate, drying operation is based on seasoning, and product yield is up to about 75%, good product quality, stable, production process safety, pollution-free, the industrial producing method for alpha-cyano ethylacrylate of saving the energy.
The present invention is achieved in that a composite assistant aqueous solution drops in the reactor, subsequently ethyl cyanoacetate and formalin are dropped in the reactor, logical steam is in the reactor interlayer, make interior temperature rise to 35～45 ℃ of reaction system, then the aqueous solution of catalyzer hexahydropyridine is dropped in the reactor, temperature of reaction is at 60～90 ℃, and the reaction times is at 2～5 hours, finishes the speed refreshing dry reaction operation that contracts; The alpha-cyanoethyl acrylate oligomer wet powder that the refreshing dry reaction operation that contracts by speed is obtained places outdoor ventilation on the sunny side to carry out the seasoning dehydration, in middle temperature, carry out the second level drying and dehydrating then under the vacuum tightness, under the high temperature condition of high vacuum degree, carry out the tri-layer drying and dehydrating at last, finish tri-layer drying and dehydrating operation; Carry out maturation process sneaking into the slaking auxiliary agent in the alpha-cyanoethyl acrylate oligomer dry powder that obtains by tri-layer drying and dehydrating operation, and then do not use the conventional depolymerization of sulfurous gas, finish slaking depolymerization operation; Putting into flask by the ethyl crude monomer after the slaking depolymerization, under the effect of filling medium, carry out underpressure distillation and handle, finish the filling refining step, obtain purpose product ethyl.
Advantage of the present invention is: in whole process of production, neither use poisonous inflammable organic solvent also not use poisonous sulfur dioxide gas, safety non-pollution, technical process is simple, and the plant factor height is with short production cycle, easy to operate, drying operation is saved the energy based on seasoning; The product yield height, good product quality, stable, product cost is low.
Below the present invention will be further described with embodiment:
Open charging opening, drop into 24.25 kilograms of 3% the sodium alkyl sulfate compound ligand aqueous solution, 30 kilograms of 42 kilograms of 94% ethyl cyanoacetates and 35% formalins in 200 liters of enamel reaction stills.Start stirring, logical steam makes interior temperature rise to 35～45 ℃ of reaction system in reacting kettle jacketing, stop steam heating.Open charging opening, drop into 10 kilograms of the hexahydropyridine aqueous solution, after the question response system temperature no longer rises, logically be steam heated to that temperature is 60～90 ℃ in the reaction system, the reaction times was at 2～5 hours.Open charging opening, drop into pH value that an amount of phosphoric acid adjusts reaction system for less than 8, make the speed refreshing dry reaction termination of contracting.Open the drain hole blowing in the charge basin, the quenching and manually rub crowdedly of throwing cold water on, cold gradually thereupon consolidate beats with mallet and to cause brokenly, weighs and weighs, and the result obtains wet about 63 kilograms in thing powder of alpha-cyanoethyl acrylate oligomer.
With above-mentioned 63 kilograms of alpha-cyanoethyl acrylate oligomer wet powders, with 15～20 millimeters thickness, share in several square material discs, place outdoor ventilation on the sunny side to carry out the seasoning dehydration.Through 1～3 order of classes or grades at school, just can remove wherein most moisture, reach the degree of picking up dust from flying when falling.In order to remove in the oligopolymer residual water-content at normal temperatures and pressures, need material disc placed and carried out in the vacuum drying oven 2～4 hours, temperature is 40～80 ℃, vacuum tightness is the second level drying and dehydrating of 500～650mmHg.In order further to remove in the oligopolymer micro-moisture under the vacuum tightness in middle temperature, the oligopolymer that has passed through two dry levels was finished in vacuum drying oven 10～30 minutes, temperature is 100～160 ℃, vacuum tightness is the tri-layer drying and dehydrating of 700～750mmHg, meet the depolymerization process requirement with the drying and dehydrating of guaranteeing oligopolymer, the result obtains about 46.62 kilograms of alpha-cyanoethyl acrylate oligomer dry powder.
With above-mentioned 46.62 kilograms alpha-cyanoethyl acrylate oligomer dry powder.By per 1.5 kilograms is a unit, and the flask of putting into 5000 milliliters carries out maturation process earlier.By 1～3% mixture that applies slaking auxiliary agent-dihydric phenol and polyphenol that feeds intake.Then flask is dipped in the oil bath that is preheated to 80～150 ℃ in advance, can starts vacuum pump after fixing, when the time comes, maturing process just in bottom oil bath heating, moves under the situation that top vacuumizes.Flavous slaking thing is come to bottle center turnup around the bottle wall gradually, until covering whole materials; Steam bubble in the slaking thing is ascending until arriving surface boiling endlessly internally; The interior temperature of slaking thing constantly raises, until steam temperature reach 60～90 ℃ and have small part impurity in the slaking thing by till being steamed.Stop heating, close vacuum pump, logical atmosphere makes system recovery to normal pressure.Then open the flask opening for feed, pour into about catalyzer 60 grams, after the hand mixing, give heat again, start vacuum pump, promptly begin not use the conventional depolymerization operation of sulfurous gas.The result obtains about 38.875 kilograms of ethyl crude monomers.
With above-mentioned 38.875 kilograms of ethyl crude monomers,, divide that to carry out filling for 10 times refining with 5000 milliliters flask.Filling polyphenol, acid anhydrides and zeolite substitute the effect of sulfurous gas jointly in crude monomer, and the underpressure distillation operation is normally carried out.The result obtains 30～31 kilograms of ethyl, and total recovery (ethyl cyanoacetate in 94%) is 76～78%.
The production ethyl was more than 35 tons altogether with production method of the present invention so far from 1984 for Yucheng, Shandong Province chemical general factory, and product yield is 75～80%, and slip resistance on average reaches 200 kilograms per centimeter
2, be 0.5～1 year storage period, and curing speed is in 40 seconds, and purity is 96%.
Claims (6)
1, industrial producing method for alpha-cyano ethylacrylate, it is characterized in that: the composite assistant aqueous solution is dropped in the reactor, subsequently ethyl cyanoacetate and formalin are dropped in the reactor, logical steam is in the reactor interlayer, make interior temperature rise to 35～45 ℃ of reaction system, then the aqueous solution of catalyzer hexahydropyridine is dropped in the reactor, temperature of reaction is at 60～90 ℃, reaction times is at 2～5 hours, finishes the speed refreshing dry reaction operation that contracts; The alpha-cyanoethyl acrylate oligomer wet powder that the refreshing dry reaction operation that contracts by speed is obtained places outdoor ventilation on the sunny side to carry out the seasoning dehydration, in middle temperature, carry out the second level drying and dehydrating then under the vacuum tightness, under the high temperature condition of high vacuum degree, carry out the tri-layer drying and dehydrating at last, finish tri-layer drying and dehydrating operation; Carry out maturation process sneaking into the slaking auxiliary agent in the alpha-cyanoethyl acrylate oligomer dry powder that obtains by tri-layer drying and dehydrating operation, and then do not use the conventional depolymerization of sulfurous gas, finish slaking depolymerization operation; Putting into flask by the ethyl crude monomer after the slaking depolymerization, under the effect of filling medium, carry out underpressure distillation and handle, finish the filling refining step, obtain purpose product ethyl.
2, industrial producing method for alpha-cyano ethylacrylate according to claim 1 is characterized in that: the said composite assistant aqueous solution is the sodium alkyl sulfate compound ligand aqueous solution.
3, industrial producing method for alpha-cyano ethylacrylate according to claim 1 is characterized in that: the temperature of carrying out the second level drying and dehydrating in said in the temperature under the vacuum tightness is 40～80 ℃, and vacuum tightness is 500～650mmHg.
4, industrial producing method for alpha-cyano ethylacrylate according to claim 1 is characterized in that: the temperature of carrying out the tri-layer drying and dehydrating under the said high temperature condition of high vacuum degree is 100～160 ℃, and vacuum tightness is 700～750mmHg.
5, industrial producing method for alpha-cyano ethylacrylate according to claim 1 is characterized in that: said slaking auxiliary agent is the mixture of dihydric phenol and polyphenol.
6, industrial producing method for alpha-cyano ethylacrylate according to claim 1 is characterized in that: said filling medium is respectively polyphenol, acid anhydrides and zeolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106885 CN1047077A (en) | 1989-12-26 | 1989-12-26 | Industrial producing method for alpha-cyano ethylacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106885 CN1047077A (en) | 1989-12-26 | 1989-12-26 | Industrial producing method for alpha-cyano ethylacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1047077A true CN1047077A (en) | 1990-11-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106885 Pending CN1047077A (en) | 1989-12-26 | 1989-12-26 | Industrial producing method for alpha-cyano ethylacrylate |
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| CN (1) | CN1047077A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062484C (en) * | 1994-08-18 | 2001-02-28 | 陈体义 | Medical adhesive for wound and surgery |
| CN102686687A (en) * | 2009-12-25 | 2012-09-19 | 田冈化学工业株式会社 | Method for purification of ethyl-2-cyanoacrylate adhesive composition, and ethyl-2-cyanoacrylate adhesive composition |
| CN103319369A (en) * | 2013-06-06 | 2013-09-25 | 常熟市江南粘合剂有限公司 | Alpha-ethyl cyanoacrylate production process |
-
1989
- 1989-12-26 CN CN 89106885 patent/CN1047077A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062484C (en) * | 1994-08-18 | 2001-02-28 | 陈体义 | Medical adhesive for wound and surgery |
| CN102686687A (en) * | 2009-12-25 | 2012-09-19 | 田冈化学工业株式会社 | Method for purification of ethyl-2-cyanoacrylate adhesive composition, and ethyl-2-cyanoacrylate adhesive composition |
| CN102686687B (en) * | 2009-12-25 | 2013-09-25 | 田冈化学工业株式会社 | Method for purification of ethyl-2-cyanoacrylate adhesive composition, and ethyl-2-cyanoacrylate adhesive composition |
| US8945299B2 (en) | 2009-12-25 | 2015-02-03 | Taoka Chemical Co., Ltd. | Method for purifying ethyl-2-cyanoacrylate adhesive composition and ethyl-2-cyanoacrylate adhesive composition |
| CN103319369A (en) * | 2013-06-06 | 2013-09-25 | 常熟市江南粘合剂有限公司 | Alpha-ethyl cyanoacrylate production process |
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