The method of obtaining vinylidenechloride

 

(57) Abstract:

The invention relates to a method for vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst. Water-alkaline dehydrochlorination subjected 1,1,2-trichloroethane contained in the clarified waste production of vinyl chloride, the obtained gas-phase dehydrochlorination of 1,2-dichloroethane, without separating it from the waste mixture containing (wt.%) 1,1,2-trichloroethane 50-70, dichloroethane 10-15, perchloroethylene 15-20, tetrachlorethane 2-3. The process is carried out at a temperature of 15-20C in the presence of diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyls2-C4with further addition of water to dissolve the precipitated NaCl, separation of the organic phase and the division into individual products: vinylidenechloride, 1,2-dichloroethane and perchlorethylene, when the molar ratio of alcohol to catalyst - 1-3:1. As a result of waste vinyl chloride receive vinylidenechloride.

The invention relates to organic synthesis, in particular, to a method for vinylidenechloride, prima is vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane 6-24% aqueous solution of hydroxide of an alkali metal at a temperature of 90oC in the presence of the catalyst alkylbenzene chloride of the formula (R1R1R2C6H5CH2N)Cl, where R1- CH3or HOCH2-CH2-, R2- C10-C18. Vinylidenechloride formed with the yield up to 85% (Japan patent N 164416, 1961 ).

Expensive raw materials limits the possibility of using this method.

The closest technical solution to the same destination on the totality of symptoms is the way to get vinylidenechloride with odnowionym the dehydrochlorination 1,1,2-trichloroethane action 33-40% aqueous NaOH solution in the presence of 0.3-1% of the catalyst to 1,1,2-trichloroethane ( Savanov S. C., Tolstikov, A. and others "On the liquid-phase catalysis dehydrochlorinating 1,1,2-trichloroethane". ZH N 1, 1987, S. 150-1530).

For reasons that impede the achievement of specified following technical result when using the known method include:

- expensive raw materials;

- inaccessibility of the used catalysts.

The task of the invention is to develop a method of obtaining vinylidenechloride from waste products of vinyl chloride, the resulting gas-phase dehydrochlorination of dichloroethane.

During implementation of the invention can be obtained the following technical result:

- the problem of waste disposal production of vinyl chloride, the resulting gas-phase dehydrochlorination of dichloroethane;

- mark dichloromethane and perchloroethylene from waste products of vinyl chloride;

- obtaining relatively inexpensive vinylidenechloride.

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 by the action of NaOH in the presence of a catalyst, is h the production of vinyl chloride, the obtained gas-phase dehydrochlorination of 1,2-dichloroethane, without separating it from the waste mixture containing (wt.%) 1,1,2-trichloroethane - 50-70, dichloroethane - 10-15, perchlorethylene - 15-20 at a temperature of 5-10oC in the presence of diethylether--chloropropylamine chloride or di-oxicillin--chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyl (C2-C4, HOCH2-CH=CHCl, when the molar ratio of alcohol to catalyst equal 1-3 : 1, with the further addition of water to dissolve the precipitated NaCl, separation of the organic phase and the division into individual products: vinylidenechloride, dichloromethane and perchloroethylene.

The method consists in the following.

Waste of vinyl chloride after their clarification is subjected to selective (1,1,2-trichloroethane) dehydrochlorination aqueous NaOH at a temperature of 5-10oC in the presence of 0.8-1% 1,1,2-trichloroethane catalyst diethylether--chloropropylamine chloride or di-oxicillin--- chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyl (C2-C4, HOCH2-CH=CHCl, at a molar ratio to the catalyst, is 1-3:1. The addition of water provides the dissolution of precipitated salt NaC is ATM.

In a reactor equipped with a stirrer, thermometer, reflux condenser, separating funnel, and a thermostatic device, put the estimated amount of the clarified waste of vinyl chloride, containing (wt. %) 1,1,2-trichloroethane - 50-70, dichloroethane - 10-15, perchlorethylene - 15-20, tetrachlorethane - 2-3. To this mixture are added 1% to 1,1,2-trichloroethane catalyst in the form of a 50% aqueous solution of 1-3 mol to Quaternary ammonium salt of the corresponding alcohol. Under stirring at a temperature of 5-10oC add 1.3 to 1.5 mole to 1,1,2-trichloroethane NaOH, taken in the form of 33-35% aqueous solution. Before the addition of NaOH mixture chlorohydrocarbons blown off with nitrogen. Upon completion of addition of NaOH (10-15 min) the reaction mixture is stirred for another 0.5-1 h and add demineralized water to dissolve the precipitated NaCl. The organic layer is separated, rinsed with nitrogen and distilled under reflux at a temperature in the cube is not above 65oC, selecting the fraction with boiling point 32oC.

Get vinylidenechloride purity not less than 99%, the conversion of 1,1,2-trichloroethane is 98-99%. VAT residue containing mainly 1,2-dichloroethane and perchlorethylene, is distilled in a distillation column.

The method is illustrated Satnam refrigerator, a separating funnel and thermostatic device is placed 204 g of clarified waste of vinyl chloride, containing (wt. %) 1,1,2-trichloroethane - 65, 1,2-dichloroethane - 15,6, perchlorethylene - 18,4, tetrachlorethane - 1. To this mixture was added 1.3 g (1% trichloroethane) diethylether--chloropropylamine chloride in the form of a 50% aqueous solution and 1.4 g (2 mol of a catalyst) - chloropropanediol alcohol. With vigorous stirring and at a temperature of 5-10oC added 52 g of NaOH (molar ratio trichloroethane : NaOH is 1:3), taken in the form of a 35% aqueous solution for 10-15 minutes After which the reaction mixture is stirred at the same temperature for another 0.5-1 hours After that, the reactor add demineralized water to dissolve the precipitated salt is NaCl. The reaction mass is placed in a separating funnel. The mixture defend 0.5 h and separated the organic layer, is placed in an alembic, equipped with a reflux condenser and a fridge, blown off with nitrogen and the temperature, first 55-65oC, distilled vinylidenechloride selected fraction, boiling at a temperature of 32oC (yield 97%), then distilled dichloromethane (yield 92%) at the corresponding temperature and then perchlorethylene (yield of 92.5%).

Example 2. In the conditions of example 1 as the catalysis of the hours get 94 g vinylidenechloride (yield 96%), 29 g of 1,2-dichloroethane (yield 92%), 36 g of perchloroethylene (yield of 91.5%).

Example 3. In the conditions of example 1 as alcohol Supplement take 3 mol of ethanol. The output vinylidenechloride was 92%, dichloroethane 92 percent, of perchloroethylene - 91%.

The advantages of the proposed method of obtaining vinylidenechloride expressed in the following:

- in opportunities from waste products of vinyl chloride valuable individual products - vinylidenechloride, dichloroethane, perchloroethylene, each of which has its own practical application;

- to obtain relatively inexpensive vinylidenechloride.

The method of obtaining vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH in the presence of a catalyst, characterized in that the aqueous-alkaline dehydrochlorination subjected 1,1,2-trichloroethane contained in the clarified waste production of vinyl chloride, the obtained gas-phase dehydrochlorination of 1,2-dichloroethane, without separating it from the mixture of waste containing, wt.%: 1,1,2-trichloroethane 50-70, dichloroethane 10-15, perchloroethylene 15-20, tetrachlorethane 2-3, at a temperature of 15-20oC in the presence of diethylether--chloropropylamine chloride (/(S2nilamani chloride (/(NON2-CH2)2-CH2-CH= CH2, -CH2CH=Cl-N+/Cl-) add alcohol of the formula ROH, where R is alkyls2-C4NON2CH=HCl, when the molar ratio of alcohol to catalyst equal 1-3:1, with the further addition of water to dissolve the precipitated NaCl, separation of the organic phase and the division into individual products: vinylidenechloride, 1,2-dichloroethane and perchlorethylene.

 

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