Method of production of vinylidene chloride

FIELD: chemical industry; methods of production of vinylidene chloride.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of vinylidene chloride by the dehydrochlorination of 1,1,2- trichloroethane with formation of the target product and the quaternary ammonium salts. As the reactant of the dehydrochlorination they use the water-alcoholic solutions of hydroxides - dimethyl-β or γ- chlorodipropenyl of ammonium gained by the electrolysis of the solutions of dimethyl-β or γ- chlorodipropenyl of ammonium chloride in the water at presence of methyl, ethyl or butyl alcohols in the electrolyzers with the ion-exchange membranes. At that the gained hydroxides are sent to the dehydrochlorination. The technical result of the invention is creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.

EFFECT: the invention ensures creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.

3 cl, 3 ex, 1 dwg

 

Izobreteyonija to organic synthesis, in particular, to a method for vinylidenechloride.

Vinylidenechloride used to obtain polyvinylidenechloride, copolymers with vinyl chloride, Acrylonitrile, and other technically important copolymers, which are synthetic fibers, lacquers, plastics.

A method of obtaining vinylidenechloride alkaline dehydrochlorination 1,1,2-trichloroethane calcium hydroxide at a temperature of 60÷70° (Lebedev N.N. Chemistry and technology of basic organic and petrochemical synthesis. - 2nd ed., Rev. - M.: Chemistry, 1975. 733 S.: ill. s).

The main disadvantage of this method is the formation of large quantities of wastewater containing calcium chloride.

Closest to the claimed, i.e. the prototype is the way to get vinylidenechloride aqueous-alkaline dehydrochlorination 1,1,2-trichloroethane by the action of aqueous NaOH at a temperature of 15÷20°in the presence of a catalyst - diethylether-γ-chloropropylamine chloride or di-β-oxicillin-γ-chloropropylamine chloride with the addition of alcohol of the formula ROH, where R is alkyl With2-C4with further addition of water to dissolve the precipitated NaCl. (U.S. Pat. 2167140 of the Russian Federation, IPC C 07 C 17/25, 21/08 C 07 C. The method of obtaining vinylidenechloride / Savenow S., Abdrashitov AM, Dmitriev J.K., Miniba is in F.M., Japryncev, Y.M., Gubaidullin A.I. No. 99121345/04; Claimed 08.10.1999. Published 20.05.2001).

The disadvantages of the prototype method include education in the process of obtaining vinylidenechloride aqueous solution of sodium chloride, which must be separated from other reaction products and the use of hard-to-catalyst.

The invention solves the technical problem of creating a waste-free, high-performance and environmentally friendly technologies for vinylidenechloride without the use of aqueous solutions of hydroxides of alkali metals and in the absence of catalysts.

This object is achieved in that vinylidenechloride obtained by dehydrochlorination 1,1,2-trichloroethane, and according to the invention as a reagent dehydrochlorinating 1,1,2-trichloroethane use water-alcohol solutions of hydroxides dimethyl-β or γ-chloropropanol ammonium produced by the electrolysis of solutions of dimethyl-β or γ-chloropropanol ammonium chloride in water in the presence of a methyl, ethyl or butyl alcohols in cells with ion-exchange membranes.

The invention consists in the following. The anode chamber of two-chamber electrolytic cell 1 with a cation exchange membrane (see figure 1) fill the 50÷70% (mainly 60%) water-alcohol solution of the Quaternary ammonium salt. The molar ratio is s of water to alcohol is 4:1÷ 2. In the cathode chamber is placed 0,5÷1% aqueous-alcoholic solution of the corresponding Quaternary ammonium hydroxide.

In water-alcohol solution causes dissociation of molecules Quaternary ammonium salt

[(R1)2(R2)2N]+Cl-→[(R1)2(R2)2N]++Cl-

with the formation of the cation [(R1)2(R2)2N]+and anions Cl-,

where R1- -CH3;

R2- -CH2-CCl=CH2, -CH2-CH=CHCl.

In the electric field generated in the electrolytic cell when a voltage is applied to the electrodes, there is a transfer of the cations [(R1)2(R2)2N]+from the anode chamber through the cation exchange membrane into the cathode chamber. In a cathode chamber of the electrolysis is the decomposition of water with evolution of hydrogen and formation of the corresponding Quaternary ammonium hydroxide

2[(R1)2(R2)2N]++2H2O+2e→2[(R1)2(R2)2N]OH+H2↑,

and in the anode chamber, the emission of chlorine

2Cl--2nd→Cl2↑.

The electrolysis is carried out at a temperature of 20÷25°and a cathode current density of 30÷60 mA/cm2to achieve the hydroxide concentration in the cathode chamber 25÷35%.

Obtained in the electrolysis of aqueous-alcoholic solution of hydroxide che is vertices ammonia at a temperature of 40÷ 60°served in the reactor 2, is equipped with heating and mixing devices. In the same reactor under stirring add 1,1,2-trichloroethane based on 1 mol 1,1,2-trichloroethane 1,05÷1,1 mole of hydroxide. When 1,1,2-trichloroethane with a Quaternary ammonium hydroxide, the formation of vinylidenechloride and the corresponding Quaternary ammonium salt.

ClCH2-CHCl2+[(R1)2(R2)2N]OH→CH2=CCl2+[(R1)2(R2)2N]Cl+H2O

Vinylidenechloride boils at a temperature of 31.7°therefore its isolation from the reaction mass is not difficult. Water-alcohol solution of the Quaternary ammonium salt formed by 1,1,2-trichloroethane with a Quaternary ammonium hydroxide in the reactor 2, after adjusting the concentration is served in the anode chamber of the electrolytic cell 1 for hydroxide.

Chlorine generated in the anode chamber of the electrolytic cell 1 can be used for 1,1,2-trichloroethane.

Example 1

In the anode chamber membrane of the cell, separated by cation-exchange membrane brand MK-40, pour 200 ml of 60% aqueous-methanolic solution of [(CH3)2N(CH2-CH=CHCl)2]Cl. The molar ratio of N2O:CH3IT is 4:1. In the cathode chamber of the electrolytic cell pour 200 ml of water and m is analnogo solution, containing 0.5% [(CH3)2N((CH2-CH=CHCl)2]IT. As electrodes using titanium plates coated with ruthenium oxide. The process was performed at room temperature, amperage of 3 And a cathode current density of 60 mA/cm2within 3 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end of the process in the cathode chamber get to 34.8% water-methanol solution of [(CH3)2N(CH2-CH=CHCl)2]HE contains to 69.6 g of hydroxide.

Obtained in a cathode chamber of a membrane electrolyzer water-methanol solution of [(CH3)2N(CH2-CH=CHCl)2]IT is transferred into a reactor equipped with a heating device, a stirrer and reflux condenser. Later in the reactor is supplied nitrogen to create an inert atmosphere. After that, the reactor at a temperature of 60C° and continuous stirring was added 27.5 ml 1,1,2-trichloroethane. The molar ratio of hydroxide to 1,1,2-trichloroethane is 1.1:1. Released from the reaction vinylidenechloride through the reflux condenser output in the receiver, the cooled brine. After 5 min after the start of the process to obtain 28.8 g of vinylidenechloride. The resulting aqueous-methanol solution of the Quaternary ammonium salt after adjusting again pokeweed is in the anode chamber membrane of the cell to obtain a water-methanol solution of Quaternary ammonium hydroxide. Conversion of 1,1,2-trichloroethane in vinylidenechloride is 99.7 per cent.

Example 2

In the anode chamber membrane of the cell, separated by cation-exchange membrane brand MK-40, pour 200 ml of 50% ethanol-water solution of[(CH3)2N(CH2-CH=CHCl)2]Cl. The molar ratio of N2A:C2H5IT is 4:1,5. In the cathode chamber of the electrolytic cell pour 200 ml of ethanol-water solution containing 1% [(CH3)2N(CH2-CH=CHCl)2]IT. As electrodes using titanium plates coated with ruthenium oxide. The process was performed at room temperature, amperage 2 a, a cathode current density of 40 mA/cm2within 4 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end of the process in the cathode chamber receive a 31% aqueous-ethanolic solution of [(CH3)2N((CH2-CH=CHCl)2]IT containing 62,0 g hydroxide.

Obtained in a cathode chamber of a membrane electrolyzer water-ethanol solution of [(CH3)2N((CH2-CH=CHCl)2]IT is transferred into a reactor equipped with a heating device, a stirrer and reflux condenser. Later in the reactor is supplied nitrogen to create an inert atmosphere. After that, the reactor at a temperature of 50C° and continuous re is eshiwani add 26 ml of 1,1,2-trichloroethane. The molar ratio of hydroxide to 1,1,2-trichloroethane is 1.05:1. Released from the reaction vinylidenechloride through the reflux condenser output in the receiver, the cooled brine. After 5 min after the start of the process get to 26.9 g vinylidenechloride. The resulting aqueous-ethanolic solution of Quaternary ammonium salt after adjusting again placed in the anode chamber membrane of the cell to obtain a water-ethanol solution of Quaternary ammonium hydroxide. Conversion of 1,1,2-trichloroethane in vinylidenechloride 99.5%.

Example 3

In the anode chamber membrane of the cell, separated by cation-exchange membrane brand MK-40, pour 200 ml of 70% aqueous-butanole solution of [(CH3)2N(CH2-CCl=CH2)2]Cl. The molar ratio of N2O:4H9OH is 4:2. In the cathode chamber of the electrolytic cell pour 200 ml of water butanole solution containing 1% [(CH3)2N(CH2-CCl=CH2)2]OH. As electrodes using titanium plates coated with ruthenium oxide. The process was performed at room temperature, amperage of 1.5 And a cathode current density of 30 mA/cm2within 5 hours. The concentration of the solution during electrolysis in the anode chamber of the electrolyzer support permanent add salt crystal. At the end of protsessov cathode chamber receive 26.7% of water-butanolic a solution of [(CH 3)2N(CH2-CCl=CH2)2]OH containing at 53.4 g of hydroxide.

Obtained in a cathode chamber of a membrane electrolyzer water-methanol solution of [(CH3)2N(CH2-CCl=CH2)2]OH transferred into a reactor equipped with a heating device, a stirrer and reflux condenser. Later in the reactor is supplied nitrogen to create an inert atmosphere. After that, the reactor at a temperature of 40C° and continuous mixing add a 21.5 ml of 1,1,2-trichloroethane. The molar ratio of hydroxide to 1,1,2-trichloroethane is 1.1:1. Released from the reaction vinylidenechloride through the reflux condenser output in the receiver, the cooled brine. After 5 min after the start of the process to obtain 22.1 g of vinylidenechloride. The resulting water butanolic solution of Quaternary ammonium salt after adjusting again placed in the anode chamber membrane electrolyzer for receiving water butanole solution of Quaternary ammonium hydroxide. Conversion of 1,1,2-trichloroethane in vinylidenechloride is 99,3%.

Using the proposed method to obtain vinylidenechloride compared with existing has the following advantages:

a) create the possibility of organizing a virtually waste-free, high-performance, environmentally friendly technologies;

b) the absence of alkali inthe receiving vinylidenechloride eliminates the necessity of selection of salts (NaCl, CaCl2) the reaction mass;

C) the proposed method provides for obtaining stoichiometric to vinylidenechloride the amount of chlorine that can be used in obtaining 1,1,2-trichloroethane;

g) in addition to chlorine in the electrolysis of Quaternary ammonium salt is a trademark hydrogen.

1. The method of obtaining vinylidenechloride the dehydrochlorination 1,1,2-trichloroethane, wherein the dehydrochlorination is carried 1,1,2-trichloroethane with a water-alcohol solutions of hydroxides of Quaternary ammonium salts of the formula [(R1)2(R2)2N]+OH-where R1- -CH3; R2- -CH2-CCl=CH2; -CH2-CH=CHCl, with the formation of the target product and Quaternary ammonium salts, which are used to produce hydroxides of Quaternary ammonium salts, directed to the dehydrochlorination 1,1,2-trichloroethane.

2. The method according to claim 1, characterized in that the aqueous-alcoholic solutions of hydroxides of Quaternary ammonium salts obtained by electrolysis of an aqueous-alcohol solutions of the corresponding Quaternary ammonium salts in the electrolytic cells with ion-exchange membranes.

3. The method according to claim 1, characterized in that as the alcohol components of the water-alcohol solutions used methyl, ethyl and butyl alcohols based 1-2 mol of alcohol is 4 mol of water.



 

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61 cl, 8 tbl, 32 ex

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EFFECT: increased productivity of process and improved economical characteristics.

26 cl, 1 tbl

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