Chlorohydrocarbon production process

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.

EFFECT: reduced expenses due to using production waste.

4 tbl, 30 ex

 

The invention relates to the technology of organic synthesis, in particular to a method for producing chlorinated hydrocarbons having plasticizing properties of polymer compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers (Chemical industry abroad. - 1975. No. 7. - P80-87).

A method of obtaining a chlorinated paraffin containing 35-65% of chlorine, chlorinated paraffin hydrocarbon, C14-C30a high degree of purity of the oil fractions which contain only 0.1-0.5% oil (application Germany No. 1593702. - 1972).

Expensive raw materials limits the possibility of using this method.

A method of obtaining chlorinated paraffin used for plasticization of polyvinyl chloride, which consists in the chlorination of waste production sultanol - VAT residue of the distillation of paraffin containing 20-57 wt.% alkyl benzenes. The process is carried out at a mass ratio of the cubic residue and chlorine 1:1-3,3 at 110-120°C (AC USSR №1112026. BI, 1984, No. 33).

The disadvantage of this method is the low degree of use of chlorine and the heterogeneity of the composition of the chlorinated paraffin.

A known method of producing polychloroprenes PI is risovaniem paraffin C 24-C25in two stages. In the first stage chlorination is carried out at 80-100°With up to 40% of the chlorine content of the product. To reduce the viscosity of the reaction mixture, it is diluted with chlorinated solvent. The second stage of chlorination is carried out at 50-80°and light irradiation (Muganlinsky FF, Traeger Y.A., Lusin N.M. // Chemistry and technology of halogenorganics compounds. - M.: Chemistry, 1991. - Pp.163).

The disadvantage of this method is the use of high-boiling solvents, the removal of the finished product requires a stage of distillation of the solvent.

Closest to the claimed invention to the technical essence and the expected effect is way induced chlorination. Its essence is that in the presence of olefins-inductors at low temperatures with high speeds radicals are formed and implemented radical chain process in which the chlorinated olefin and a saturated compound contained in the reaction mass (Kazakov, A., Levanova SV, Printers N.G. waste is Reduced in the process of chlorination of hydrocarbons. // Environment for us and future generations: Ecol., business, Ecol. image: proc. Dokl. 5-th international. fo., Samara, Astrakhan, 8-15 Sept., 2000. Samara, 2000. - C.19-20).

The disadvantage of this method is hudsen the quality due to the presence of volatile impurities, produced by the chlorination of low molecular weight olefins.

Object of the present invention to provide an industrial method of obtaining chlorohydrocarbons from waste products of the oligomerization of ethylene -α-olefin fraction C14-C32. In practice, this waste is disposed of because they don't have qualified. During implementation of the invention can be obtained by technical result, which is expressed in the possibility:

- solve waste disposal oligomerization of ethylene -α-olefin fraction C14-C32;

- get chlorohydrocarbons having plasticizing properties;

- use of chlorohydrocarbons in PVC compositions as a secondary plasticizer instead of the chlorinated paraffin wax while maintaining or improving the desired performance.

The above technical result in the implementation of the invention is achieved in that in the known method of obtaining chlorohydrocarbons by chlorination α-olefin fraction C14-C32the peculiarity lies in the fact that the chlorination subject α-olefin fraction C14-C32- the waste product of the oligomerization of ethylene, containing (wt.%): fraction C20-C26at least 85%, light C18and below is not more than 5%, severe28the above is not more than 10%, paraffin is not more than 0.6% and the chlorination process is carried out in two stages.

The proposed method is as follows.

In jacketed reactors equipped with a stirrer, a bubbler for input of chlorine, reflux condenser, load α-olefins. The chlorohydrocarbons produced by chlorination α-olefins at a temperature of 35-105°S, feed rate of chlorine of 0.1-0.6 g/min to the degree of chlorination 24-55 wt.% Chlorine consumption varies depending on the leakage of chlorine from the exhaust gases (not more than 5 wt.% from the supplied volume).

Chlorination α-olefins is carried out in two stages:

- connecting chlorination double bond at a temperature of 35-55°C;

- substitution chlorination of the resulting product to the desired chlorine in chlorohydrocarbons at a temperature of 40-105°C.

After achieving the necessary degree of chlorination conduct stabilization of the product. The product yield is close to theoretical.

The method is confirmed by examples.

Example 1

In jacketed reactors equipped with a stirrer, a bubbler, reflux condenser, download 77 g α-olefins. Chlorine consumption in the process of getting chlorohydrocarbons varies in the range of 0.12-0.52 g/min depending on the leakage of chlorine from the exhaust gases. Connecting the chlorine to the double bond is carried out at a temperature of 35-40°will replace the aspects of chlorination to the required mass of chlorine in the product at a temperature of 40-50° C. the Time of chlorination - 18 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32is 47,96 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 148,

Example 2

Analogously to example 1, with the substitution chlorination is carried out at a temperature of 60-65°C. the Time of chlorination - 18 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32- 47,43%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 147,

Example 3

Analogously to example 1, with the substitution chlorination is carried out at a temperature of 80-85°C. the Time of chlorination 13 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32is 47.5%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 147,

Example 4

Analogously to example 1, with the substitution chlorination is carried out at a temperature of 100-105°C. the Time of chlorination 13 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32and 47.0%. The mass of the obtained chlorohydrocarbons - 146,

Example 5

Analogously to example 1. Time chlorination - 3 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32- 14,3%. The mass of the obtained chlorohydrocarbons fraction C14-C3290,

Example 6

Analogously to example 1, with the substitution chlorination is carried out at a temperature of 80-85°C. x is aerovane - 6.5 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32- 23,0%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 100 g

Example 7

Analogously to example 1, with the substitution chlorination is carried out at a temperature of 40-50°C. the Time of chlorination - 9 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32or 34.7%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 117,9,

Example 8

Analogously to example 1, with the substitution chlorination is carried out at a temperature of 80-85°C. the Time of chlorination - 9 hours. The chlorine content in the chlorohydrocarbons fraction C14-C32- 39,7%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 127,7,

The data of examples 1-8 are summarized in table 1.

The chlorohydrocarbons are multifunctional additives to polymeric materials having the properties of a secondary plasticizer and lubricant. The use of liquid chlorohydrocarbons fraction C14-C32instead of chlorinated paraffin wax CP-470 in PVC compositions, the formulations of PVC tape, sticky, plastic PVC plasticized filled (bottom layer of linoleum), cable plastic stamps OM-40 makes it possible to produce products with lower cost, to stabilize the product quality, to increase the number of physico-mechanical pokazatelili. Compositions containing the received chlorohydrocarbons fraction C14-C32when processing is more efficient since it reduces the adhesiveness of their granules due to the additional lubricating effect.

The use of chlorohydrocarbons fraction C14-C32obtained as described above, is illustrated by the following examples.

Examples 9-17

Polymer compositions for tape PVC adhesive, with the compositions according to table 2, is prepared by mixing the components in the mixer at 90-100°C for 30 minutes. The mixture rolls at 162°C for 7 minutes to obtain a sample of the material, which determine the “volume resistivity” according to GOST 23206-78, the time of thermal stability - according to GOST 14044-68 and a melt flow index on the device IIRC according to the method.

Examples 18-24

Polymeric composition for a cable having compositions according to table 3, is prepared by mixing the components in the mixer at 90-100°C for 30 minutes. The mixture rolls at 162°C for 10 minutes to obtain a sample of the material, which determine the “volume resistivity” according to GOST 23206-78, the time of thermal stability - according to GOST 14044-68 and a melt flow index on the device IIRC in accordance with the method. The finished film after conditioning which was analizirovali for compliance with GOST 5960.

Examples 25-30.

Resin composition for flexible PVC polyvinylchloride plasticized filled (bottom layer of linoleum), with the compositions according to table 4, is prepared by mixing the components in the mixer at 90-100°C for 30 minutes. The mixture rolls at 168-170°C for 5 minutes to obtain a sample of the material, which determine the “volume resistivity” according to GOST 23206-78, the time of thermal stability - according to GOST 14044-68 and a melt flow index on the device IIRC according to the method.

The use of the invention enables industrial method of obtaining chlorohydrocarbons from waste products of the oligomerization of ethylene - α-olefin fraction C14-C32.

The obvious advantage of this method is the utilization of production oligomerization of ethylene - α-olefin fraction C14-C32obtaining chlorohydrocarbons having plasticizing properties.

Application chlorophenothane plasticizer in polyvinyl chloride compositions can improve the manufacturability of processing by reducing slidenote granules, significantly improve the tensile strength, relative elongation at break”, “fire” and “specific volume resistivity is our actions”, and also to reduce the cost of the finished product.

The method of obtaining chlorohydrocarbons by the chlorination of hydrocarbons, characterized in that is used as raw material waste product of the oligomerization of ethylene -α-olefin fraction C14-C32and the chlorination is carried out in two stages: connecting the chlorination at a temperature of 35-55°and substitution chlorination at a temperature of 40-105°C.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to manufacturing chloro-containing hydrocarbons, in particular, tert.-butyl chloride used for preparing addition agents and as activator for dehydrogenation catalysts. Method for preparing involves interaction gaseous isobutylene and hydrogen chloride in the presence of catalyst in the amount 0.02-0.3 wt.-% of parent reagents mass. Water is used as a catalyst. Process is carried out at volume rate of feeding reagents from 1400 h-1 to 1500 h-1, at temperature from 0oC to -5oC and in the mole ratio isobutylene : hydrogen chloride = (1.01-1.015):1 in the bubbling reactor. Method provides elevating yield of tert.-butyl chloride up to 99.2-99.5 wt.-%.

EFFECT: improved preparing method, enhanced yield.

2 cl, 1 tbl, 4 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to technology manufacturing halide-substituted hydrocarbons, in particular, to stabilization of halogenated paraffins that are used as plasticizers, antipyrenes and special additives for polymeric materials and rubber mixtures, and in leather industry and in manufacturing depressants and lubricants also. Method is carried out by addition of stabilizing system comprising epoxy-compound and chelate compound forming chelate with iron ions. Stabilizing system comprises additionally acceptor of hydrogen chloride as a stabilizing agent that represents aliphatic carboxylic acid ketene comprising carbon number in chain in the ranges (C10-C23) and alkaline-earth metal of the 2-d group of periodic system in the following ratio of components as measured for the parent halogenated paraffin, wt.-%: chelate compound, 0.03-0.50; acceptor of hydrogen chloride as a stabilizing agent, 0.05-0.30; epoxy-compound, 0.20-0.80. Addition of indicated components of stabilizing system to halogenated paraffin is carried out simultaneously or successively at temperature in the ranges 40-90oC. Stabilizing system can comprise additionally also antioxidant - a stabilizing agent of phenol type representing sterically hindered di- or trialkylphenol or its derivative, or their mixtures taken in the mount 0.01-0.15 wt.-%. Addition of indicated antioxidant - stabilizing agent is carried out before blowing or steaming acid mixtures at temperature in the ranges 40-90oC in common or separately with chelate compound. Halogenated paraffin represents chlorinated paraffin with mass part of chlorine in the ranges 12-75%. Invention provides enhancing quality of stabilized halogenated paraffins by indices "color index" and "mass part of acids", reducing consumption norm of epoxy-compound.

EFFECT: improved stabilizing method.

8 cl, 1 tbl, 16 ex

The invention relates to the technology of organic synthesis, in particular, to a method for producing chlorinated hydrocarbons having plasticizing properties of polymer compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers

The invention relates to the technology of organic synthesis, in particular to a method for producing chlorinated hydrocarbons used as plasticizers for polymeric compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers

The invention relates to a process for the simultaneous receipt of chloroform and chlorinated paraffin wax and catalysts used for their production

The invention relates to the technology of organic synthesis, in particular to a method of stabilizing chlorinated hydrocarbons
The invention relates to methods of obtaining and purification of 3,3-dimethylbutyramide

The invention relates to the production of hexachlorethane, which is used in the production of halon 113, tablets for degassing at low tide aluminum parts, upon receipt of deodorants, antibacterial drugs and smoke blends

The invention relates to the production of 1,1,1,3,3-pentachlorobutane

The invention relates to new derivatives of tamilcanadian with the General formula (I) wherein R' represents 2-thienyl or 3-thienyl radical, R represents ceanorhaditis or a radical of the formula-C(O) - and R2 is optional saturated or unsaturated cyclic hydrocarbon radical or aryl radical

The invention relates to the technology of organic synthesis, in particular, to a method for producing chlorinated hydrocarbons having plasticizing properties of polymer compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers

The invention relates to the technology of organic synthesis, in particular to a method for producing chlorinated hydrocarbons used as plasticizers for polymeric compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers

The invention relates to the production of chlorinated derivatives of methane, ethane, ethylene catalytic hydrochloridebuy of carbon tetrachloride

The invention relates to the technology of organic synthesis, in particular, to a method for producing chlorinated hydrocarbons having plasticizing properties of polymer compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers

The invention relates to the technology of organic synthesis, in particular to a method for producing chlorinated hydrocarbons used as plasticizers for polymeric compositions in the industry of synthetic building materials, paints and varnishes, synthetic films and leathers, rubber industry, as well as ontamarama additives to various polymers

The invention relates to the management of chemical-technological processes carried out in a cascade of reactors for producing 1,2-dichloroethane by chlorination of ethylene in recogida reaction mass

The invention relates to the production of 1,2-dichloroethane by direct chlorination of ethylene in the liquid dichloroethane

The invention relates to the production of dichloroethane by direct chlorination of ethylene in the liquid dichloroethane

The invention relates to a method of producing allylchloride gas-phase chlorination of propylene under pressure at 430-470°C

The invention relates to the production of 1,2-dichloroethane (ethylene dichloride , ejh) by introducing ethylene and chlorine in the circulating ejh under vigorous stirring and heat recovery
Up!