The method of obtaining vinylidenechloride

 

(57) Abstract:

The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive. The process is carried out at 15-20C in the presence as catalyst diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride and an alcohol additive of the formula ROH, where R is alkyl (C2-C4, SSN=CH-CH2HE. The molar ratio of the catalyst to the alcohol additive is 1:3-1. Water-alkaline dehydrochlorination subjected 1,1,2-trichloroethane in a mixture of clarified waste of perchlorovinyl with a further allocation of vinylidenechloride, trichloroethylene and 1,1,1,2-tetrachlorethane from the organic phase. The result is vinylidenechloride of waste production perchlorovinyl.

The invention relates to organic synthesis, in particular, to a method for vinylidenechloride waste disposal production of chlorinated polyvinyl chloride (perchlorovinyl).

A method of obtaining vinylidenechloride the dehydrochlorination individually 1,1,2-trichloroethane 6-24% aqueous solution of hydroxide of alkali metal at Thames6H5CH2N+/-Cl, where R1-CH3or HOCH2-CH2, R2-C10-C18vinylidenechloride formed with the yield up to 85% /Japan patent N 164416, 1961/.

The disadvantage of this method is to conduct the reaction at a high temperature and a low yield of the target product.

Closest to the claimed invention, the technical solution according to the totality of symptoms is the way to get vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive /Savenow C. S. and others "On the liquid-phase catalysis dehydrochlorinating 1,1,2-trichloroethane". Russian journal of applied chemistry, No. 1, 1987, 150-153 C./.

Water-alkaline dehydrochlorination 1,1,2-trichloroethane carry out the action of 40% NaOH at its molar ratio to the trichloroethane 1:1,3 at a temperature of 25oC in the presence of catalysts, such as alkoxides of triethylenediamine or catalytic system triethylmethylammonium chloride: benzyl alcohol.

The authors have shown that the highest catalytic activity possesses benzilate of triethylenediamine or system triethylmethylammonium chloride: benzyl alcohol.

Nedocenene to obtain catalysts hard triethylamine, benzyl alcohol and benzylchloride.

The objective of the invention is to develop a method of obtaining vinylidenechloride waste from the production of chlorinated polyvinyl chloride.

When the chlorination of polyvinyl chloride in 1,2-dichloroethane formed a significant amount of 1,1,2-trichloroethane. After rectification distillation residues (waste of perchlorovinyl) can be used to obtain a carbon tetrachloride /Oshin L. A. "Industrial organochlorine products. M.: Chemistry, 1978, S. 577/.

However, according to the Montreal agreement on the protection of asenavage layer of soil carbon tetrachloride is not recommended for commercial use.

Disposal and recycling of organochlorine products is one of the most urgent problems of the chemical industry.

When using the invention may be obtained from the technical result:

- waste production perchlorovinyl;

- the possibility of obtaining relatively expensive vinylidenechloride;

- allows separation of the remaining components of organochlorine waste of perchlorovinyl and return them in the process for manufacturing the catalyst.

This technical result in the implementation of the invention is achieved in that in the known method of obtaining vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive, the peculiarity lies in the fact that the water is alkaline dehydrochlorination at a temperature of 15-20oC in the presence of a catalyst, which is used as diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride and an alcohol additive of the formula ROH, where R is alkyl (C2-C4, ClCH=CH-CH2OH when the molar ratio of the catalyst to the alcohol additive is 1: 3-1, is exposed to 1,1,2-trichloroethane in a mixture of clarified waste of perchlorovinyl with a further allocation of vinylidenechloride, trichloroethylene and 1,1,1,2-tetrachlorethane from the organic phase.

The method is as follows.

In a reactor equipped with a heating device, a reflux condenser, a stirrer, a thermometer and a separating funnel, put the estimated number of bleached rectification distillation, containing (wt.%) 1,1,2-trichloroethane - 80-90, 1,1,1,2-tetrachlorethane - 3-8, 1,1,2,2-tetrachlorethane-10-12. To this mixture was added 0.8-1.0 m) is one chloride and 1 to 3 mol of alcohol additives of the formula ROH, where R is alkyl (C2-C4, ClCH=CH-CH2OH. Under stirring at a temperature of 15-20oC is added to 1.3 mol to 1,1,2-trichloroethane 28-30% aqueous NaOH, after which the mixture is stirred for further 0.5 hour.

In the reactor, add demineralized water to dissolve the precipitated Sodium chloride and the reaction mixture was placed in a separating funnel. The organic layer is separated, rinsed with nitrogen and distilled under reflux at a temperature not exceeding 65oC, selected fraction, boiling at a temperature of 32oC. Receive vinylidenechloride purity not less than 99%, the conversion of 1,1,2-trichloroethane 93-95%. VAT residue containing trichloroethylene and 1,1,1,2-tetrachlorethane, is subjected to distillation, separating pure trichloroethylene.

The method is illustrated by examples.

Example 1. In a reactor equipped with a stirrer, reflux condenser, separating funnel, thermometer and thermostatic device, placed 160 g of waste production perchlorovinyl of the following composition, wt%: 1,1,2-trichloroethane - 80; 1,1,1,2-tetrachlorethane - 12; 1,1,2,2-tetrachlorethane - 8.

To this mixture products are added 1 g (0.8 wt.% to 1,1,2-trichloroethane) or diethylether--chloropropylamine chloride in the form of a 50% aqueous solution and 1.6 g of butyl spirtes blown off with nitrogen and add 50 g of NaOH, taken in the form of a 30% aqueous solution (the molar ratio of 1,1,2-trichloroethane : NaOH is 1:1,3).

Upon completion of addition of NaOH (15 min), the reaction mass at this temperature, stirred for further 1 hour, add demineralized water to dissolve the precipitated Sodium chloride, the reaction mixture is placed in a separating funnel.

The organic layer is separated, rinsed and distilled under reflux, selecting a fraction having a boiling point 32oC.

Get 89 g vinylidenechloride (yield 96%), 9 g of trichloroethylene, 18 g of 1,1,1,2-tetrachlorethane.

Example 2. In the conditions of example 1, taken 160 g of waste production perchlorovinyl composition, wt. %: 1,1,2-trichloroethane - 90, 1,1,2,2-tetrachlorethane - 7%, 1,1,1,2-tetrachlorethane - 3.

To this mixture is added 1.4 g of di-oxicillin--chloropropylamine chloride in the form of a 50% aqueous solution and 0.8 g - chloropropanediol alcohol (molar ratio of catalyst : alcohol is 1:1). The dehydrochlorination spend 28% aqueous NaOH.

Get 99 g vinylidenechloride (yield 95%), 8 g of trichloroethylene and 4 g of 1,1,2,2 - tetrachlorethane.

The advantages of the proposed method:

- waste production perchlorovinyl;

- receipt not expensive vinylacetate of perchlorovinyl;

- enhanced and safe, as well as the possibility of the formation of explosive dihloratsetilena;

- used catalysts obtained from the available raw material: allyl chloride and diethanolamine.

The method of obtaining vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane in the presence of a catalyst and an alcohol additive, characterized in that the aqueous-alkaline dehydrochlorination at a temperature of 15-20oC in the presence as catalyst diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride and an alcohol additive of the formula ROH, where R is alkyl WITH2-C4, ClCH=CH-CH2OH, when the molar ratio of the catalyst to the alcohol additive is 1:3-1, is exposed to 1,1,2-trichloroethane in a mixture of clarified waste of perchlorovinyl with a further allocation of vinylidenechloride, trichloroethylene and 1,1,1,2-tetrachlorethane from the organic phase.

 

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