CN106938977A

CN106938977A - A kind of preparation method of unifor

Info

Publication number: CN106938977A
Application number: CN201710303582.4A
Authority: CN
Inventors: 李博强
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-05-03
Filing date: 2017-05-03
Publication date: 2017-07-11

Abstract

The invention provides a kind of preparation method of unifor, this method is using para toluene sulfonamide, ketazine and water as raw material, the unifor of reaction synthesis at a certain temperature, reaction terminate after by the solid matter centrifugal filtration of precipitation, filter cake is scrubbed, dry after obtain unifor finished product.The inventive method technique is simple, and reaction yield is high, and the few purity of product impurity is high；The ammonia and acetone that by-product is reclaimed can be back to synthesis ketazine, the filtrate containing ketazine and para toluene sulfonamide can direct reuse in preparing unifor, raw material availability is high, and production cost is low；Make solvent without benzene, do not produce with corrosive hydrogen chloride gas and hydrochloric acid, not high to equipment requirement, waste discharge is few, be a kind of environmental type production technology.

Description

A kind of preparation method of unifor

Technical field

The invention belongs to chemosynthesis technical field, and in particular to a kind of preparation method of unifor.

Background technology

Unifor alias 4- Methyl benzenesulfonyl hydrazines, are white crystalline powder, are soluble in alkali, be dissolved in methanol, ethanol And butanone, water, aldehydes are slightly soluble in, insoluble in benzene, toluene.Foaming agent as natural rubber, synthetic rubber and a variety of plastics, makes Plastics and rubber produce trickle hole-closing structure, and the shrinkage factor of product is small, and tearing toughness is big.It is also a kind of important organic Synthetic intermediate, in the organic syntheses such as medicine, pesticide producing.

At present, the synthetic method of unifor is mainly by paratoluensulfonyl chloride and hydrazine hydrate（Or hydrazonium salt）It is situated between in benzene React and be made in matter, its processing step is as follows：Hydrazine hydrate is diluted with water into 10% aqueous solution, input enamel reaction still, The lower sulfuric acid that adds of stirring is reacted, generation sulfuric acid hydrazine solution.After benzene and p-methylphenyl sulfonic acid chloride stirring and dissolving, reaction is added Kettle is mixed with hydrazine sulfate, is stirred continuously at normal temperatures, occurs condensation reaction, generates unifor.Because tolysulfonyl Hydrazine does not dissolve in benzene, and is only very slightly soluble in water, therefore is separated out with solid.The hydrogen chloride produced in course of reaction is inhaled after drawing with water Receive, and obtain by-product hydrochloric acid.After unifor reaction of formation is complete, stop stirring, reaction product is stood through filtering, filtrate Layering, upper strata can be recycled for benzene, and water layer reclaims unreacted hydrazine sulfate.Filter cake is washed, and washes away acid and water-soluble thing Afterwards, then through dehydration, it is dried, gets product in 60 DEG C or so.

Prior art has the drawback that：（1）Used benzene to make solvent in the reaction, benzene be it is a kind of it is volatile, to human body The poisonous carcinogen of toxic action can be caused, benzene a small amount of escape in use and volatilization all can be to health and rings Border causes damage and polluted；（2）Corrosivity extremely strong hydrogen chloride gas and hydrochloric acid can be produced during the course of the reaction, to equipment requirement Height, containing a small amount of more intractable removal of benzene in by-product hydrochloric acid, limits the use of by-product hydrochloric acid, its harmless treatment difficulty Greatly, it is costly, easily cause environmental pollution；（3）Current synthetic method is all that, using expensive hydrazine hydrate as raw material, yield is only Have 80% or so, production cost is higher.

The content of the invention

In order to overcome prior art exist disadvantages mentioned above, the invention provides a kind of technique it is simple, low for equipment requirements, Accessory substance reusable edible, high income, production cost are low, environmental protection unifor novel preparation method.

The technical solution adopted by the present invention is：Using para toluene sulfonamide, ketazine and water as raw material, at a certain temperature The ammonia and acetone generated in reaction synthesis unifor, course of reaction can be back to and prepare ketazine, after reaction terminates By the solid matter centrifugal filtration of precipitation, filter cake is scrubbed, dry after obtain unifor finished product.

The specific processing step of the inventive method is as follows：Para toluene sulfonamide, ketazine and water are put into reactor, Stirring is opened, 80 DEG C~90 DEG C is heated to and is reacted, the gas for reacting generation rectifying column is introduced into, in tower top temperature 55 DEG C~60 DEG C at extraction acetone and reclaim ammonia；Sampling analysis after reacting 8~12 hours, when para toluene sulfonamide in reaction solution Content stops heating, terminates reaction when being down to 1%, question response kettle is cooled to after normal temperature, by the material centrifugal filtration in reactor, Filtrate containing ketazine and para toluene sulfonamide can direct reuse in preparing unifor, filter cake be washed with water after 60 DEG C or so are dried, and produce unifor finished product.

In above-mentioned steps, the mol ratio of para toluene sulfonamide and ketazine is 1: 1~1.2, and the addition of water is to first 0.5~1 times of benzsulfamide quality.Its reaction equation is as follows：

Compared with prior art, beneficial effects of the present invention and advantage are as follows：

The present invention prepares unifor by raw material of ketazine that is with low cost, being readily synthesized, and technique is simple, and reaction is received Rate is high（With ketazine rate of collecting more than 90%）, simply, the few purity of product impurity is high for post processing；The ammonia and third that by-product is reclaimed Ketone can be back to synthesis ketazine, the filtrate containing ketazine and para toluene sulfonamide can direct reuse in prepare to toluene Sulfohydrazide, raw material availability is high, and production cost is low；Make solvent without benzene（Ketazine is both reactant in the inventive method It is solvent）, do not produce with corrosive hydrogen chloride gas and hydrochloric acid, not high to equipment requirement, waste discharge is few, be a kind of Environmental type production technology.

Embodiment

Embodiment 1

Para toluene sulfonamide 171.2g, ketazine 112.8g and water 90ml are placed in four with stirring, thermometer and rectifying column In mouth flask, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated to 80~ 90 DEG C, after the gas that reaction is produced enters rectifying column, extraction acetone and ammonia is reclaimed at 55~60 DEG C of column top temperature；Reaction Sampling analysis after 8~12 hours, stops heating when the content of para toluene sulfonamide in reaction solution is down to 1%, terminates reaction, treat Flask is cooled to after normal temperature, and by the material taking-up in flask, centrifugal filtration, filter cake is dried at 60 DEG C after being washed with water, obtained Unifor 173.1g, content is 99.5%.

Embodiment 2

Para toluene sulfonamide 171.2g, ketazine 125.5g and water 130ml are placed in four with stirring, thermometer and rectifying column In mouth flask, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated to 80~ 90 DEG C, after the gas that reaction is produced enters rectifying column, extraction acetone and ammonia is reclaimed at 55~60 DEG C of column top temperature；Reaction Sampling analysis after 8~12 hours, stops heating when the content of para toluene sulfonamide in reaction solution is down to 1%, terminates reaction, treat Flask is cooled to after normal temperature, and by the material taking-up in flask, centrifugal filtration, filter cake is dried at 60 DEG C after being washed with water, obtained Unifor 174.8g, content is 99.6%.

Embodiment 3

Para toluene sulfonamide 171.2g, ketazine 134.4g and water 170ml are placed in four with stirring, thermometer and rectifying column In mouth flask, the receiver top of rectifying column connects a conduit to absorb ammonia；Stirring is opened, solution is heated to 80~ 90 DEG C, after the gas that reaction is produced enters rectifying column, extraction acetone and ammonia is reclaimed at 55~60 DEG C of column top temperature；Reaction Sampling analysis after 8~12 hours, stops heating when the content of para toluene sulfonamide in reaction solution is down to 1%, terminates reaction, treat Flask is cooled to after normal temperature, and by the material taking-up in flask, centrifugal filtration, filter cake is dried at 60 DEG C after being washed with water, obtained Unifor 175.6g, content is 99.4%.

Claims

1. a kind of preparation method of unifor, it is characterised in that comprise the following steps：Para toluene sulfonamide, acetone are connected Nitrogen and water are put into reactor, are opened stirring, are heated to 80 DEG C~90 DEG C and are reacted, and the gas for reacting generation is introduced Rectifying column, extraction acetone and ammonia is reclaimed at 55 DEG C~60 DEG C of tower top temperature；Sampling analysis after reacting 8~12 hours, when anti- Stop heating when answering the content of para toluene sulfonamide in liquid to be down to 1%, terminate reaction, question response kettle is cooled to after normal temperature, will reacted Material centrifugal filtration in kettle, the filtrate containing ketazine and para toluene sulfonamide can direct reuse in preparing tolysulfonyl Hydrazine, filter cake is dried after being washed with water at 60 DEG C or so, produces unifor finished product；In above-mentioned steps, to toluene sulphur The mol ratio of acid amides and ketazine is 1: 1~1.2, and the addition of water is 0.5~1 times of para toluene sulfonamide quality.