The method of obtaining chlorohydrocarbons

 

(57) Abstract:

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 method is carried out by chlorination of waste produced by oligomerization of ethylene --olefin fraction C14-C32in the presence of dicetylperoxydicarbonate in the amount of 0.1-0.3 wt.% the number-olefins. The technical result - the disposal of waste oligomerization of ethylene - -olefin fraction C14-C32obtaining chlorohydrocarbons having plasticizing properties, their use in PVC compositions as a secondary plasticizer. 4 table.

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 synthetic building materialographic to various polymers (Chemical industry abroad 1975, No. 7, S. 80-87).

There is a method of liquid-phase chlorination of 3-chloropropene, 2-chloropropene, 2,3-dichloropropene when 0-55°C in media of different polarity, with the addition of catalysts, initiators and inhibitors of radical reactions without them. It is established that in nonpolar environments in addition to the products attachment of chlorine are formed unconventional for low temperatures, the products of replacement - chloroalkane (Strizhakova Y. A. Chlorination of chloroethanol3. Abstract. dis. on saisc. academic step. Kida. chem. of Sciences, Samara, 2000, S. 23).

The disadvantage of this method is to obtain low molecular weight chloroalkanes and, accordingly, low molecular weight chlorohydrocarbons, which do not have a plasticizing effect.

Known methods for producing chlorinated paraffin by hydrochloridebuy-olefins in the presence of metal halides (U.S. Pat. 1568237, Germany, 1971) and chlorinated paraffin by hydrochlorination products telomerization lower olefins (ethylene) at a temperature of 100°C and a pressure of 60 MPa (R. Schreiner//Chem. Proc. - 1981. - V. 44, No. 10. - R. 26-27).

The disadvantage is the complexity of this method, because it requires high pressures.

Closest to the claimed invention tekhnicheskogo in the presence of various olefins. Identified synergies when exposed to inducing compositions based on olefin and azo-visitorville (porofor) on the rate of chlorination of alkanes and chloroalkanes - radical processes of substitution chlorination of saturated compounds at low temperatures (Strizhakova Y. A., Levanova S. C., Sokolov, A. B., Printers, M. G., Ali Tariq Saeed.// Zhur.org.chem.. - 2000. - So 36. No. 5. - S. 670-675).

The disadvantage of this method is the use of low molecular weight olefins and alkanes and respectively receiving low-molecular chlorohydrocarbons, which do not have a plasticizing effect.

Object of the present invention to provide an industrial method of obtaining chlorohydrocarbons from waste products of the oligomerization of ethylene - -olefin fraction C14-C32using as an initiator other than poroporo (CHS-57) - dicetylperoxydicarbonate (lilodocs). In practice, this waste is disposed of because it doesn'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-olefin fractiously the high requirements of the variable “color”;

- the 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 of olefins fraction C14-C32the peculiarity lies in the fact that the chlorination is subjected to-olefins fraction C14-C32- the waste product of the oligomerization of ethylene, containing (wt.%): fraction WITH20-C26at least 85%, light C18and below is not more than 5%, heavy C28and above not more than 10%, the wax is not more than 0.6% in the presence of initiator - lilodocs at low temperatures, providing a colorless chlorohydrocarbons.

The proposed method is as follows.

In jacketed reactors equipped with a stirrer, a bubbler for input of chlorine, reflux condenser, load-olefins. The chlorohydrocarbons with the degree of chlorination 24-53,7 wt.% produced by chlorination of olefins in the presence of initiator - lilodocs, taken in an amount of 0.1-0.3 wt.% from-olefins at a temperature of 35-70&#m ore than 5 wt.% from the supplied volume). The chlorination process flow initiator in the reaction mass to carry out portions at intervals of 30 minutes Chlorination double bond and substitution chlorination flow simultaneously at a temperature of 35-70°With the result of a synergic effect of inducing compositions based on olefin and lilodocs - initiator for radical processes of substitution chlorination of saturated compounds. Upon reaching the desired degree of chlorination is conducted stabilization of the product. The chlorohydrocarbons are obtained colorless. The product yield is close to theoretical.

The method is illustrated by the following examples.

Example 1

In jacketed reactors equipped with a stirrer, a bubbler, reflux condenser, download 77 g-olefins. Chlorine consumption in the process of getting chlorohydrocarbons varies in the range of 0.1-0.6 g/min, depending on the leakage of chlorine from the exhaust gases. The chlorination process flow initiator in an amount of 0.2 wt.% from-olefins in the reaction mass to carry out portions at intervals of 30 minutes the temperature of the chlorination - 35 to 40°C. the Time of chlorination of 14.5 hours. The chlorine content in the chlorohydrocarbons fraction14-C32is 46.6 wt.%. Weight receiving the chlorination is carried out in the presence of initiator, taken in an amount of 0.2 wt.% from-olefins at a temperature of 55 to 60°C. the Time of chlorination - 12 hours. The chlorine content in the chlorohydrocarbons is 48.6 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 149,

Example 3

Analogously to example 1, the chlorination is carried out in the presence of initiator, taken in an amount of 0.2 wt.% from-olefins at a temperature of 70°C. the Time of chlorination is 15.5 hours. The chlorine content in the chlorohydrocarbons - 48,9 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 150g

Example 4

Analogously to example 1, the chlorination is carried out in the presence of initiator, taken in an amount of 0.1 wt.% from-olefins at a temperature of 55 to 60°C. the Time of chlorination 13 hours. The chlorine content in the chlorohydrocarbons, with 47.4 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 146,

Example 5

Analogously to example 1, the chlorination is carried out in the presence of initiator, taken in an amount of 0.3 wt.% from-olefins at a temperature of 55 to 60°C. the Time of chlorination - 11 hours. The chlorine content in the chlorohydrocarbons was 47.1 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 145,

Example 6

Similar is the temperature of 35-40°C. While chlorination is 18 hours. The chlorine content in the chlorohydrocarbons - of 53.7 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 166,

Example 7

Analogously to example 1, the chlorination is carried out in the presence of initiator, taken in an amount of 0.1 wt.% from-olefins at a temperature of 35 to 40°C. the Time of chlorination - 7.5 hours. The chlorine content in the chlorohydrocarbons - 32,0 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 113,

Example 8.

Chlorination carried out without initiator at a temperature of 60-65°C. the Time of chlorination - 18 hours. The chlorine content in the chlorohydrocarbons 47,43 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 147,

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

Use as secondary plasticizers liquid chlorohydrocarbons instead of CP-470 in PVC compositions, the formulations of PVC tape, sticky, plastic PVC plasticized filled (bottom layer of linoleum), cable plastic stamps OM-40 will allow to produce products at lower cost, while maintaining or improving the desired performance.

The essence izobreteniya, having compositions according to table 2, is prepared by mixing the components in the mixer at 90 to 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 to 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-conditioning analyzed 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 to 100°C for 30 minutes. Poluchenie volume electric resistance” - according to GOST 23206-78, time thermostability 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 - -olefin fraction WITH14-C32.

The obvious advantage of this method is the utilization of production oligomerization of ethylene - -olefin fraction WITH14-C32obtaining chlorohydrocarbons fraction14-C32having 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 resistance, and also to reduce the cost of the finished product.

The method of obtaining chlorohydrocarbons by the chlorination of hydrocarbons in the presence of the initiator at a temperature of 35-70°C., wherein the chlorination is subjected waste p is bonate in the amount of 0.1-0.3 wt.% the number-olefins.



 

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