A method of producing copolymers of hydrocarbons jordanovic

 

(57) Abstract:

Describes a method of producing copolymers jordanovic hydrocarbons by the chlorination of butadiene, water-base catalytic dehydrochlorination formed WITH4-chlorohydrocarbons and subsequent polymerization of the resulting jordanovic hydrocarbons in the presence of polymerization regulators, characterized in that conduct liquid-phase chlorination of butadiene in ethyl chloride boiling at a molar ratio of butadiene:chlorine, equal to 1.2-3:1, respectively, the process is conducted recycle ethyl chloride, then the resulting mixture WITH4-chlorohydrocarbons from 3,4-dichlorobutene-1,1,4-dichlorobutene-2, trichloroethene, tetrachlorobutane dihydrochloride boiling in the environment of ethyl chloride at a weight ratio of ethyl chloride to the mixture WITH4-chlorohydrocarbons, equal 1-3:1, 13-20oWith 42-45% aqueous NaOH in the presence of 0.3-0.8 wt. % (based on C4-chlorohydrocarbons triethyl-, tributyl-1-harbutt-2-yl of ameriglide obtained directly in a mixture WITH4-chlorohydrocarbons plus trialkylamines to alcohol selected from the group comprising 1,4-butandiol, R-OH, where R=C1-C4alkyl, -CH2WITH6H5oC in the presence of radical initiators and regulators of polymerization within 20-40 h followed by distillation of ethyl chloride with unreacted lardenoye hydrocarbons, planting polymer with methanol, the selection of the polymer, Department of methanol containing 1,4-dichlorobutene-2, and the allocation of 1,4-dichlorobutene-2. The technical result - the creation of low-waste method of producing a copolymer of 2,3-dichlorobutadiene and-chloroprene derived from butadiene. 2 C.p. f-crystals.

The invention relates to organic synthesis, in particular, to a method for producing copolymers jordanovic hydrocarbon - chloroprene and 2,3-dichlorobutadiene used as the basis of adhesive compositions and mastics.

A method of obtaining copolymers of light fractions of waste from stages of gas-phase chlorination of butadiene and stage isomerization of 1,4-dichlorobutene-2. The polymerization is carried out in the environment of aromatic solvent selected from the group comprising benzene, toluene, xylene, with a volumetric ratio of the light fraction to the solvent is from 2:1 to 5:1 ratio is rusty aluminum [1].

The disadvantage of this method is the use as a catalyst, aluminum chloride, as this requires stringent conditions on moisture as waste production of chloroprene and to solvents. In addition, the main drawback is the inability to obtain copolymers of a given structure and, therefore, they can't find qualified use.

These copolymers is that known technological process of production of chloroprene rubber according to the scheme of gas-phase chlorination of butadiene, the isomerization of 1,4-dichlorobutene-2, high-temperature dehydrochlorination of 3,4-dichlorobutene-1 to B-chloroprene with subsequent polymerization is accompanied by a large number of chlorinated wastes (up to 250 kg per 1 ton of rubber) [2].

The main components of waste are and-B-chloroprene, monochloroethene, dichlorobutene and tetrachlorobutane. These wastes are disposed of by incineration, which is energy-intensive, as they have low Flammability.

Closest to the claimed is a method of obtaining a polymer product of the organochlorine wastes generated according to [3]. The process of recycling carried out the initial full chlorine is , consisting mainly of Tetra - and pentachlorobutane, which is subjected to water-alkaline dehydrochlorination, catalyzing the reaction by Catalina - a,B (dimethylbenzylamine chloride). Polymerization obtained by dehydrochlorination of 2,3-dichlorobutadiene and 1,2,3-trichlorobutane carried out in the presence of a polymerization regulator - disulfide, diisopropylaniline [3].

The resulting copolymers are used as additives to other rubbers, as independent applications they don't have what is the main disadvantage.

The objective of the invention is the development of low-waste method of producing a copolymer of 2,3-dichlorobutadiene and B-chloroprene derived from butadiene.

The method consists in the following.

Copolymers jordanovic of hydrocarbons obtained by the chlorination of butadiene, water-base catalytic dehydrochlorination formed C4-chlorohydrocarbons and subsequent polymerization of the resulting jordanovic hydrocarbons in the presence of polymerization regulators, the peculiarity lies in the fact that carry out liquid-phase chlorination of butadiene in ethyl chloride boiling at a molar ratio of butadiene:chlorine, equal to 1.2-3:1 southwestairline-1, 1,4-dichlorobutene-2, trichloroethene, tetrachlorobutane dihydrochloride boiling in the environment of ethyl chloride at a weight ratio of ethyl chloride to a mixture of C4-chlorohydrocarbons, equal 1-3:1 when 13-20oC, 42-45% aqueous NaOH in the presence of 0.3-0.8 wt.% in the calculation of C4-chlorohydrocarbons triethyl-, tributyl-1-harbutt-2-yl of ameriglide obtained directly in a mixture of C4-chlorohydrocarbons by adding appropriate trialkylamines and alcohol, selected from the group comprising 1,4-butandiol, R-OH, where R=C1-C4alkyl, -CH2C6H5when a molar ratio of trialkylamine and alcohol from the group of 1:1-5, respectively, followed by the separation after dehydrochlorinating organic phase comprising at least ethyl chloride, chloroprene, 2,3-dichlorobutadiene, 1,4-dichlorobutene-2, and their subsequent polymerization in ethyl chloride at a temperature of 40-80oC in the presence of radical initiators and regulators of polymerization within 20-40 h followed by distillation of ethyl chloride with unreacted lardenoye hydrocarbons, planting polymer with methanol, the selection of the polymer, Department of methanol containing 1,4-dichlorobutene-2 and the allocation of 1,4-dichlorobut util-1-harbutt-2-yl-ameriglide in the amount of 0.005-0.05 wt.% to ethyl chloride, and the catalyst dihydrochloride is obtained directly in a mixture of C4-chlorohydrocarbons after chlorination of butadiene, adding triethylamine or tributylamine and alcohol, selected from the group comprising 1,4-butandiol, R-OH, where R=C1-C4alkyl, -CH2C6H5and maintaining the mixture for one hour.

The structure of the obtained copolymer install UV spectroscopy and can be represented by the formula:

< / BR>
where m=30000-60000

The method is realized in the following way.

Example 1. Chlorination of butadiene is carried out in the presence of 0.05 wt.% to ethyl chloride nitrogen-containing catalyst triethylammonium.

In a cylindrical reactor with a height of 100 cm and a diameter of 1.2 cm, filled with attachment and is equipped with three nozzles in the lower part of the reactor (low to output products of the chlorination of butadiene, average for the supply of butadiene, and the third is above average for input of chlorine) and fitting in the middle part of the reactor to enter recirculated ethyl chloride, serves 75 g of ethyl chloride, and then into the corresponding fitting serves 0,249 g/min of styrene and 0.273 g/min of chlorine (the molar ratio of butadiene:chlorine 1,2:1). Chloride of ethyl top bath ethyl chloride together with dissolved butadiene enters the cooled receiver, where to recycle the mixture is fed to the middle portion of the reactor. The products of the chlorination of butadiene together with chloride ethyl deduce from the bottom of the reactor. For five hours the reactor received 240 g of the reaction mixture consisting of 120 g of ethyl chloride and C4-chlorohydrocarbons composition: 3,4-dichlorobutene-1 - 60%, 1,4-dichlorobutene-2 - 25%, 1,2,3-trichlorobutane-4 - 4.2% and 1,2,3,4-tetrachlorobutane - 10,8%.

100 g of the mixture C4-chlorohydrocarbons, consisting of 3,4-dichlorobutene-1, 1,4-dichlorobutene-2, trichloroethene, tetrachlorobutane and ethyl chloride, is subjected to an aqueous-alkaline dehydrochlorination in the presence of a catalyst obtained as a mixture of C4-chlorohydrocarbons by adding 0.6 g of triethylamine and 0.5 g benzilovogo alcohol in a reactor equipped with thermostation and mixing devices. With stirring to a mixture of C4-chlorohydrocarbons added to the reactor for 0.5 h 60 g of NaOH in the form of a 45% aqueous solution. The temperature of the reaction mixture 14-18oC. of Boiling ethyl chloride through the condenser is sent to the collector, where return to the reactor. After addition of NaOH in the reaction mixture at this temperature, stirred for further 0.5 h until complete dissolution of the precipitated NaCl and the reaction mass is placed Uglevodorodov composition, wt.%: In-chloroprene - 60, 1,4-dichlorobutene-2 - 25, 2,3-dichlorobutadiene - 15.

The organic phase obtained by dehydrochlorination, saturated with nitrogen, was added with stirring 2.6 g of a polymerization regulator - peroxide distributel. After that polymerizat placed in the autoclave, equipped with a mixing device. The temperature in the autoclave was raised to 60oC and the polymerization is carried out at this temperature for 20 hours

After that polymerizat cooled and placed in a flask, distilled ethyl chloride together with unreacted lardenoye hydrocarbons, mainly B-chloroprene. After removal jordanovic hydrocarbons in polymerizat add 50 g of methanol. The resulting copolymers wikidot methanol, to obtain 45 g of the polymer (depth conversion of 50%), soluble in a mixture of ethyl acetate-petrol Galosh. The average molecular weight is 40,000.

Example 2. In the conditions of example 1, the chlorination is carried out at a molar ratio of butadiene:chlorine 3:1. Received 100 g C4-chlorohydrocarbons composition, wt. %: 3,4-dichlorobutene-1 - 69, 1,4-dichlorobutene-2 - 21, 1,2,3-trichlorobutane - 3,5, 1,2,3,4-tetrachlorobutane - 6,5.

The resulting mixture of 100 g of ethyl chloride dihydrochloride presence in anorganisch compounds of the composition, wt.%: B-chloroprene - 69, 2,3-dichlorobutadiene - 10, 1,4-dichlorobutene-2 - 21.

The polymerization carried out for 40 hours at a temperature of 40oC in the presence of 0.4% to Jordanova hydrocarbons benzoyl peroxide and 4% of dodecylmercaptan. Received 63 g of copolymer. The depth of polymerization of 80%, molecular weight of 60000.

Example 3.

Under the conditions of example 1, butadiene glorious, the mixture C4-chlorohydrocarbons dihydrochloride. The polymerization is carried out in the presence of benzoyl peroxide and dodecylmercaptan for 20 hours at a temperature of 80oC. Received 49 g of copolymer. The depth of polymerization of 63%, a molecular weight of 38000.

The use of the proposed method will allow you to:

to obtain copolymers B-chloroprene and 2,3-dichlorobutadiene, soluble in ethyl acetate, which will without their plasticization to get a basis for the adhesive compositions and mastics;

- to carry out the process of obtaining the copolymer of the monomers based on butadiene technology, providing maloothodnoj.

References

1. Author's certificate N 1608201, class C 11/02 08, 1990

2. "Industrial organochlorine products" edited by L. A. Osina. Handbook, M.: Chemistry, 1978, S. 307-314.

3. Marnel "Industry Of Armenia", 1985, No. 2, S. 38-40.

1. A method of producing copolymers jordanovic hydrocarbons by the chlorination of butadiene, water-base catalytic dehydrochlorination formed C4-chlorohydrocarbons and subsequent polymerization of the resulting jordanovic hydrocarbons in the presence of polymerization regulators, characterized in that conduct liquid-phase chlorination of butadiene in ethyl chloride boiling at a molar ratio of butadiene : chlorine, equal to 1.2 - 3 : 1, respectively, the process is conducted recycle ethyl chloride, then get a mixture of C4-chlorohydrocarbons from 3,4-dichlorobutene-1,1,4-dichlorobutene-2, trichloroethene, tetrachlorobutane dihydrochloride boiling in the environment of ethyl chloride at a weight ratio of ethyl chloride to a mixture of C4-chlorohydrocarbons equal to 1 to 3 : 1, 13 - 20oC, 42 - 45% aqueous NaOH in the presence of 0.3 - 0.8 wt.% in the calculation of C4-chlorohydrocarbons triethyl-, tributyl-1-harbutt-2-yl of ameriglide obtained directly in a mixture of C4-chlorohydrocarbons by adding appropriate trialkylamines to alcohol selected from the group comprising 1,4-butandiol, ROH, where R = C1- C4alkyl, -CH2C6H5when the molar sootnoshyeniya organic phase, including at least ethyl chloride, chloroprene, 2,3-dichlorobutadiene, 1,4-dichlorobutene-2 with subsequent polymerization in ethyl chloride at 40 - 80oC in the presence of radical initiators and regulators of polymerization for 20 to 40 hours, followed by distillation of ethyl chloride with unreacted lardenoye hydrocarbons, planting polymer with methanol, the selection of the polymer, Department of methanol containing 1,4-dichlorobutene-2 and the release of 1,4-dichlorobutene-2.

2. The method according to p. 1, characterized in that the chlorination of butadiene is carried out in the presence of nitrogen-containing catalyst is triethyl - or tributyl-1-harbutt-2-yl-ammonium chloride in the amount of 0.005 - 0.05 wt.% to ethyl chloride.

3. The method according to p. 1, characterized in that the catalyst dihydrochloride is obtained directly in a mixture of C4-chlorohydrocarbons after chlorination of butadiene, adding triethylamine or tributylamine and alcohol, selected from the group comprising 1,4-butandiol, ROH, where R = C1- C4alkyl, -CH2C6H5and maintaining the mixture for one hour.

 

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