CN1113681A - Preparing method for cycocel - Google Patents

Abstract

It uses a reducing fractionation method to collect 80-100 deg.C/640-6600 mmHg fraction, and uses it as raw material for extracting 2,3-dichloropropylene. The preparation of 2,3-dichloropropylene is implemented by using the following procedures: a certain dose of industrial solid alkali is added in a reactor, and then 1,2,3-trichloropropane whose dose is 1/3-1/4 of that of former is added in the reactor, and then they are heated, stirred and reacted, and when its temp. is 70-100 deg.C, the rest of 1,2,3-trichloropropane is dripped in the reactor, and then stirred and reflux-reacted for 0.5-1.5 h. so as to collect 70-100 deg.C fraction by using normal-pressure fractionation. A trimethylamine aqueous solution is added in the dichloropylene at 35-60 deg.C, and stirred and reacted, and then its reacted product is distilled to remove free amine, and then naturally deposited to separate out its oil layer, so that an aqueous solution containing cycocel can be obtained.

Description

Preparing method for cycocel

The present invention relates to a kind of preparation method of quaternary amine type plant growth regulator cycocel.

The cycocel formal name used at school is a 2-Chloroallyl trimethyl ammonium chloride, is a kind of quaternary amine type plant growth regulator, and its molecular structural formula is:

Molecular weight is 170, and fusing point is 168-170 ℃ (decomposition), and is soluble in water.The pure product of cycocel are white powdery crystallization, and the crude product that contains impurity is the ecru powder.

Cycocel is similar to chlormequat (2-chloroethyl trimethyl ammonium chloride), can impel the crops root system development that plant is downgraded, and cane increases slightly, and the leaf look dark green, and blade is generous.Can strengthen resistant to lodging to wheat crops, increase the plant effective tiller, improve output.Can prevent excessive growth for cotton, reduce coming off of cotton buds and bolls.Can strengthen anti-saline and alkaline drought-resistant ability for some crop, and the activity of cycocel and drug effect are higher than chlormequat, toxicity is lower, and the drug effect phase is longer.

The cycocel manufacturing process by 1,2, the 3-trichloropropane produces, 1,2,3-trichloropropane and sodium hydroxide reaction produce 2, the 3-dichloropropylene, 2, the 3-dichloropropylene produces cycocel three parts formation with the trimethylamine condensation.

Make at present that cycocel uses 1,2, the 3-trichloropropane is to adopt the epoxychloropropane inferior horn that produces in the synthetic glycerine production process to make raw material it is carried out the normal pressure fractionation to collect 153-159 ℃ of fraction, or earlier its normal pressure fractionation being steamed low fraction carries out vacuum fractionation again and collects 75-92 ℃/660-680mm fraction and obtain.In the fraction that above-mentioned two kinds of methods are collected 1,2,3-trichloropropane content is more than 90%, utilize behind normal pressure fractionation or the first normal pressure that vacuum fractionation produces 1,2,3-trichloropropane heating-up temperature height, energy resource consumption is big, and equipment requires high, the fraction yield is low, generally has only the 25-30% of dress still liquid.

1,2, the reaction of 3-trichloropropane and oxychloride sodium produce 2, the 3-dichloropropylene, existing method has three kinds, a kind of is the solid caustic soda method, be the industrial solid caustic soda of inventory slowly directly to be put in the trichloropropane react, though its output is high, reaction is fierce, and is wayward, the material spray phenomenon very easily takes place, so the commercial Application that is unrealized so far.Another is pure alkaline process, is the part industry solid caustic soda of inventory to be put in the trichloropropane instead to cause earlier, then the alkali of surplus is mixed with the aqueous solution and and a certain proportion of ethanol mix back stream and be added in the trichloroethanes.The alcohol alkaline process operation cycle is long, and ethanol need be set reclaim and recycle unit, the operating cost height, late phase reaction is slow, and the reaction time is long, and a large amount of ethanol circulate in technology in the production process, and production security is poor.The loss of ethanol increases production cost.The third method is the liquid caustic soda method, be with sodium hydrate aqueous solution add react in the trichloropropane produce 2, the 3-dichloropropylene.Shortcoming is that the reaction time is long, generally needs more than 10 hours, and device efficiency is low, 2,3-dichloropropylene yield is low, generally is no more than 65%.

2, cycocel is produced in 3-dichloropropylene and trimethylamine condensation, existing method is to utilize trimethylamine hydrochloride and sodium hydroxide reaction to produce trimethylamine, then free trimethylamine gas is fed to be dissolved in 2 in the toluene, the 3-dichloropropylene and carry out condensation reaction, water dissolved and tells toluene and obtains the cycocel aqueous solution at last after reaction was finished.This method is toluene with an organic solvent, and the loss of toluene can cause the rising of cycocel cost, in the ventilation trimethylamine loss big, increased consumption of raw materials, production less economical, and equipment is easily stifled.

It is short to the purpose of this invention is to provide a kind of flow process, and equipment is few, and is easy and simple to handle, and energy resource consumption is few, the yield height, and product cost is low, is easy to realize the preparation method of the cycocel of suitability for industrialized production.

The present invention realizes in the following manner.

One, carries out with separating under the epoxychloropropane that produces in the synthetic glycerine production process that vacuum fractionation produces 1,2, the 3-trichloropropane, its method is to carry out vacuum fractionation with separating under the epoxychloropropane under vacuum 640-660mmHg, remove fraction below 80 ℃ and collect 80-100 ℃ of fraction, in the fraction of collecting 1,2,3-trichloropropane content is more than 96%, the fraction yield is about 60% of dress still liquid.

Two, 2, the 3-dichloropropylene adopts the solid caustic soda reaction method.

The rate of charge of reaction is 1,2, the 3-trichloropropane is 1 than sodium hydroxide: the 1-1.5(weight ratio, in 100%), by when purity meter calculation fraction and the industrial solid caustic soda inventory of feeding intake, the industrial solid caustic soda of inventory is dropped in the reactor fraction with the 1/3-1/4 of trichloropropane inventory again to be dropped into to stir and heat in the reactor it is reacted, temperature rises to 70-100 ℃ in the reactor, in the presence of stirring, the trichloropropane fraction of surplus is added drop-wise in the reactor when being generally 75-92 ℃, dropwises the back and continue stirring and refluxing and reacted 0.5-1.5 hour.After reaction is finished the normal pressure fractionation is carried out in reaction product heating and collected 70-100 ℃ of fraction, in the fraction 2,3-dichloropropylene content is 70-90%, 2,3-dichloropropylene yield is the 75-90% of theoretical yield.Kettle base solution is a sodium-chloride water solution, can obtain industrial salt through concentrated, crystallization.

Three, 2, cycocel is produced in the reaction of 3-dichloropropylene and trimethylamine aqueous solution.

2, cycocel is produced in 3-dichloropropylene and trimethylamine condensation, and trimethylamine adopts its aqueous solution to feed intake, and rate of charge is 2, the 3-dichloropropylene is 1 than trimethylamine: the 1-1.4(weight ratio, in 100%).By when cubage dichloropropylene fraction inventory and the trimethylamine aqueous solution consumption of feeding intake, the dichloropropylene fraction of inventory put in the reactor stirring and temperature is under the 35-60 ℃ of condition trimethylamine aqueous solution to be added drop-wise in the reactor, dropwise the back and continue stirring and refluxing reaction 1-2 hour, then reaction product is heated to 85-120 ℃ with the unhindered amina Ex-all in the reaction product, naturally place cooling and layering except that the reaction product behind the amine, tell following oil reservoir after the layering fully.The upper strata is the cycocel aqueous solution, outward appearance be shallow cream colour to the mandarin orange yellow, have the stench flavor of fish, cycocel content is about 50%.

Cycocel preparation method heating-up temperature provided by the invention is low, and general industry can satisfy technological requirement with the heating steam that steam boiler provides, thereby realizes the suitability for industrialized production application easily.Energy resource consumption is low, and each goes on foot the operational yield height, and consumption of raw materials is low.Technological process is short, the equipment consumption is few, easy and simple to handle, and operating cost is low, thereby the production cost of final products is low.

Embodiment

1,2, the 3-tri chloropropene produces

Getting the epoxychloropropane height that produces in the synthetic glycerine production process separates 1230 grams under boiling and puts into 1000 milliliters of distillation flasks and load onto the filler still, thermometer is loaded on filler still top, connect condenser by common fractionation operation heat temperature raising and start the vavuum pump step-down and make in the system that to keep vacuum be 640-660mmHg, fractionation begins the back collects fraction below 80 ℃ separately earlier, collect then 80-100 ℃ of fraction as produce 2, the raw material of 3-dichloropropylene.Also can control when carrying out fractionation operation and (or, collect index of refraction n with index of refraction control with the three sealed systems of analysis with index of refraction ²⁰Ol.477-1.4835 section fraction as produce 2, the raw material of 3-dichloropropylene.Obtain 1,2,3-tri chloropropene fraction 580-720 gram, yield is the 45-58% of dress still liquid, in the fraction 1,2,3-trichloropropane content is 96-98%.

2, the 3-dichloropropylene produces

The rate of charge of reaction: in purity be 100%, 1,2, the 3-trichloropropane: sodium hydroxide is 1: the 1-1.5(weight ratio).

By 1,2,3-trichloropropane 147.5 grams feed intake, according to 1 of used fraction, 2,3 trichloropropane content are converted into trichloropropane fraction inventory with 147.5 gram trichloropropanes, calculate industrial solid caustic soda inventory according to used industrial solid caustic soda purity and rate of charge, then the industrial solid caustic soda of inventory is put in the reactor again the trichloropropane fraction of the 1/3-1/4 of inventory put into to start in the reactor and stirred and heating, temperature of charge reaches 70-100 ℃ in reactor, be added drop-wise to the trichloropropane fraction of surplus in the reactor slowly when being generally 75-92 ℃ and make reactor temperature be no more than 100 ℃, generally be no more than 92 ℃.Dropwise the back and continue stirring and refluxing reaction 0.5-1.5 hour.After reaction is finished reaction product being put into distillation flask loads onto the filler still and carries out the normal pressure fractionation and collect 70-100 ℃ of fraction, the fraction of collecting is put into separatory funnel leave standstill the natural subsidence layering, layering fully back divides that water-yielding stratum gets 2,3-dichloropropylene 93 grams-99.9 grams, 2,3-dichloropropylene content is 70-90%, 2,3-dichloropropylene collection rate is the 75.4-90% of theoretical amount.

Three, 2, cycocel is produced in 3-dichloropropylene and trimethylamine condensation.

The condensation reaction rate of charge, in purity be 100%, 2,3-dichloropropylene weight: trimethylamine weight is 1: 1-1.4, inventory: 2, the 3-dichloropropylene is 111 grams (100%).

By inventory and used 2, dichloropropylene content is put into the dichloropropylene fraction of inventory in the reactor after calculating dichloropropylene fraction consumption in the 3-dichloropropylene fraction, it is the trimethylamine aqueous solution of 25-55% that trimethylamine adopts weight percent concentration, the inventory of calculating according to rate of charge converses used trimethylamine aqueous solution consumption again, the trimethylamine aqueous solution of inventory put into drip bottle and on reactor, install thermometer and reflux condenser starts and stirs and heat temperature raising at night, when reactor temperature reaches 35-60 ℃, slowly trimethylamine aqueous solution is added drop-wise to and carries out condensation reaction in the reactor.Trimethylamine aqueous solution dropwises the back and continues stirring and refluxing reaction 1-1.5 hour, be warming up to 85-120 ℃ of steaming again and remove unhindered amina, unhindered amina is poured reaction product in separatory funnel natural subsidence layering after removing and separating, layering back fully divides oil-yielding stratum to obtain light beige to the yellow cycocel aqueous solution 282.2 grams of mandarin orange-313 grams, cycocel content is 45-50.1%, and the cycocel yield is the 83-90% of theoretical amount.

Claims (2)

1, a kind of preparation method of cycocel comprises

(1) by the epoxychloropropane inferior horn that produces in the synthetic glycerine production produce 1,2, the 3-trichloropropane;

(2) 1,2, the reaction of 3-trichloropropane and sodium hydroxide produce 2, the 3-dichloropropylene;

(3) 2, cycocel is produced in 3-dichloropropylene and trimethylamine condensation;

It is characterized in that:

(1) the epoxychloropropane inferior horn that produces in the synthetic glycerine production being carried out vacuum fractionation, is to steam fraction below 80 ℃ under the 640-660mmHg to close 80-100 ℃ of fraction of collection in vacuum;

(2) in 100%, 1,2,3-trichloropropane weight: sodium hydroxide weight is 1: the ingredient proportion of 1-1.5 with the industrial solid caustic soda of inventory put in the reactor again with the 1/3-1/4 of inventory 1,2,3-trichloropropane fraction puts into and stirs in the reactor and heating, when reactor temperature rises to 70-100 ℃ in the presence of stirring lentamente with surplus 1,2,3-trichloropropane fraction is added drop-wise in the reactor, dropwise the back and continue stirring and refluxing reaction 0.5-1.5 hour, 70-100 ℃ of fraction of normal pressure fractionation collection carried out in heating then;

(3) in 100%, 2,3-dichloropropylene: trimethylamine weight is 1: the ingredient proportion of 1-1.4 with inventory 2,3-dichloropropylene fraction puts in the reactor that temperature is under the 35-60 ℃ of condition trimethylamine aqueous solution to be added drop-wise in the reactor in the presence of stirring, dropwise the back and continue stirring and refluxing reaction 1-2 hour, then reaction product is heated to 85-120 ℃ of steaming and removes unhindered amina, except that the reaction product natural subsidence layering behind the amine, dividing oil-yielding stratum to obtain outward appearance after the layering fully is that light beige is to the yellow cycocel aqueous solution of mandarin orange.

2, preparation method by the described cycocel of claim 1, it is characterized in that in 100%, 1,2, the 3-trichloropropane: sodium hydroxide weight is 1: the ingredient proportion of 1-1.5 puts in the reactor the more industrial solid caustic soda of inventory with 1 of the 1/3-1/4 of inventory, 2,3-trichloropropane fraction is put into and is stirred in the reactor and heating, when reactor temperature rises to 75-92 ℃ in the presence of stirring lentamente with 1 of surplus, 2,3-trichloropropane fraction is added drop-wise in the reactor, dropwise the back and continue stirring and refluxing reaction 0.5-1.5 hour, 70-100 ℃ of fraction of normal pressure fractionation collection carried out in heating then.