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 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 method is carried out by chlorination of waste produced by oligomerization of ethylene - -olefin fraction C14-C32in the presence of a radical initiator type in the amount of 0.1 - 0.3 wt.% from mass-olefins. The initiator in the reaction of chlorination is served in the form of 0.5-2.0%-aqueous solution in a chlorinated organic solvent. As the initiator of the use dicetylperoxydicarbonate or azo-visitbotanical. As a chlorinated solvent used chlorohydrocarbons1-C12or chlorohydrocarbons fraction14-C32- intermediate chlorination of waste produced by oligomerization of ethylene with bulk chlorine content of 5-15%. The method is carried out at a temperature of 35-700C. Technical result - disposal of waste oligomerization by ecoystem, the use of chlorohydrocarbons in PVC compositions as a secondary plasticizer. 2 C.p. f-crystals, 4 PL.

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 (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. Sciences. - Samara, 2000, S. 23).

The disadvantage of this method is the use of low molecular weight chlorinated olefins and respectively receiving the bottom of the local methods of obtaining 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.

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

Closest to the claimed invention to the technical essence and the expected effect is a low-temperature liquid-phase chlorination of saturated hydrocarbons (hexane) 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 is x initiators. 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 fraction WITH14-C32;

- get chlorohydrocarbons having plasticizing properties and meets 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 fraction14-C32the peculiarity lies in the fact that the chlorination is subjected to-olefins fraction14-C32- the waste product of the oligomerization of ethylene, containing, wt.%: fraction WITH20-C26- not less than 85; light18and below - not more than 5; heavy C28and above - no more than 10; paraffin - not more than 0.6, in the presence of a radical initiator is onata or azo-visitorville in chlorohydrocarbons C1-C12or chlorohydrocarbons fraction14-C32with the bulk chlorine content of 5-15%.

Chlorination of olefins is carried out 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 24-55 wt.% produced by chlorination of olefins in the presence of initiator, taken in an amount 0,10,3 wt.% from-olefins and representing 0.5 to 2% solution of dicetylperoxydicarbonate or azo-visitorville in chlorohydrocarbons C1-C12(chloroform, methylene chloride, Hardeman, tertiary butyl chloride, hardteen and others) or chlorohydrocarbons fraction14-C32with the bulk chlorine content of 5-15%. The chlorination is carried out at a temperature of 35-70°C at a feed rate of chlorine of 0.1-0.6 g/min chlorine Consumption varies depending on the leakage of chlorine from the exhaust gases (not more than 5 wt.% from the supplied volume). The chlorination process flow initiator in the reaction mass is carried out continuously. Chlorination double bond and substitution is 5-70°With the result of a synergic effect of inducing compositions on the basis of the olefin and the initiator processes the substitutive 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 confirmed by examples.

Example 1

In jacketed reactors equipped with a stirrer, a bubbler, reflux condenser, download 77 g-olefins. The chlorination is carried out at a temperature of 35 to 40°C at a feed rate of chlorine of 0.1-0.6 g/min chlorine Consumption in the process of getting chlorohydrocarbons varies depending on the leakage of chlorine from the exhaust gases. The chlorination process flow initiator (1% solution dicetylperoxydicarbonate in the tertiary butyl chloride) in an amount of 0.2 wt.% from-olefins carried out continuously. Time chlorination to 12.0 hours. The chlorine content in the chlorohydrocarbons is to 47.8 wt.%. The mass of the obtained chlorohydrocarbons fraction14-C32- 147,5,

Example 2

Analogously to example 1, the chlorination is carried out at a temperature of 55 to 60°C in the presence of initiator, taken in an amount of 0.2 wt.% from-olefins, and represents a 2% solution of dicetylperoxydicarbonate in methylene chloride. Time chlorination to 12.0 hours. The chlorine content in the chlorohydrocarbons of 48.1 wt.%. The mass of p is 1, the chlorination is carried out at a temperature of 70°C in the presence of initiator, taken in an amount of 0.3 wt.% from-olefins and representing a 0.5% solution of azo-visitorville (porofor) in chloroform. Time chlorination 11.5 hours. The chlorine content in the chlorohydrocarbons to 48.6 wt.%. The mass of the obtained chlorohydrocarbons fraction14-C32- 149,8,

Example 4

Analogously to example 1, the chlorination is carried out at a temperature of 35 to 40°C in the presence of initiator, taken in an amount of 0.1 wt.% from-olefins, and represents a 2% solution of dicetylperoxydicarbonate in Chlordecone. Time chlorination to 12.0 hours. The chlorine content in the chlorohydrocarbons 46,2 wt.%. The mass of the obtained chlorohydrocarbons fraction14-C32- are 148.6,

Example 5

Analogously to example 1, the chlorination is carried out at a temperature of 35 to 40°C in the presence of initiator (1% solution dicetylperoxydicarbonate or intermediate with a degree of chlorination of 10 wt.%), taken in an amount of 0.2 wt.% from-olefins. Time chlorination of 15.5 hours. The chlorine content in the chlorohydrocarbons is 47.2 wt.%. The mass of the obtained chlorohydrocarbons fraction14-C32- 171,8,

Example 6

Example 7

Analogously to example 1, the chlorination is carried out at a temperature of 70°C in the presence of initiator (2% solution of azo-visitorville (porofor) in the semi-product with a degree of chlorination of 15 wt.%), taken in an amount of 0.2 wt.% from-olefins. Time chlorination - of 17.0 hours. The chlorine content in the chlorohydrocarbons reached 46.7 wt.%. The mass of the obtained chlorohydrocarbons fraction14-C32- 156,5,

Example 8

Analogously to example 1, the chlorination is carried out at a temperature of 55 to 60°C in the presence of initiator (0,8% solution of dicetylperoxydicarbonate or intermediate with a degree of chlorination of 10 wt.%), taken in an amount of 0.1 wt.% from-olefins. Time chlorination of 12.5 hours. The chlorine content in the chlorohydrocarbons is to 47.1 wt.%. The mass of the obtained chlorohydrocarbons fraction14-C32- 161,8,

Example 9

Analogously to example 1, the chlorination is carried out at a temperature of 55 to 60°C in the presence of initiator (0.5% solution diceing. Time chlorination 11.5 hours. The chlorine content in the chlorohydrocarbons is to 48.5 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 229,84,

Example 10

Analogously to example 1, the chlorination is carried out at a temperature of 35 to 40°C in the presence of initiator (2% solution of dicetylperoxydicarbonate in the semi-product with a degree of chlorination of 15 wt.%), taken in an amount of 0.3 wt.% from-olefins. Time chlorination 17 hours. The chlorine content in the chlorohydrocarbons is 53.3 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 185,5,

Example 11

Analogously to example 1, the chlorination is carried out at a temperature of 35 to 40°C in the presence of initiator (1% solution dicetylperoxydicarbonate in the semi-product with a degree of chlorination of 10 wt.%), taken in an amount of 0.1 wt.% from-olefins. Time chlorination 7.5 hours. The chlorine content in the chlorohydrocarbons is 31,7% by weight. The mass of the obtained chlorohydrocarbons fraction C14-C32- 122,5,

Example 12

Analogously to example 1, the chlorination is carried out at a temperature of 35 to 40°C in the presence of initiator, taken in an amount of 0.1 wt.% from-olefins and represents 2% of rest the DACH 47.2 wt.%. The mass of the obtained chlorohydrocarbons fraction C14-C32- 149,4,

The data of examples 1-12 are summarized in table 1.

Obtained in the above way the chlorohydrocarbons fraction C14-C32can be used as secondary plasticizers liquid chlorohydrocarbons instead of chloroparaffin CP-470 in PVC compositions, the formulations of PVC tape, sticky, plastic PVC plasticized filled (bottom layer of linoleum), cable plastic stamps OM-40, which allows to produce products at lower cost, while maintaining or improving the desired performance.

The following examples illustrate the use of chlorohydrocarbons fraction C14-C32in compositions based on polyvinyl chloride (table 2-4).

Examples 13-21

Polymer compositions for tape PVC adhesive, with the 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, time thermolabile the P>

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, time thermostability 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 29-34

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. 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, 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 Edinstvo the proposed method is the utilization of production oligomerization of ethylene -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 resistance, and also to reduce the cost of the finished product.

1. The method of obtaining chlorohydrocarbons by the chlorination of hydrocarbons in the presence of a radical type initiator at a temperature of 35-70°C., wherein the chlorination is subjected waste product of the oligomerization of ethylene - -olefin fraction WITH14-C32in the presence of initiator in an amount of 0.1-0.3 wt.% from mass-olefins, and the initiator in the reaction of chlorination is served in the form of 0.5-2.0%-aqueous solution in a chlorinated organic solvent.

2. The method according to p. 1, characterized in that as the initiator of the use dicetylperoxydicarbonate or azo-visitbotanical.

3. The method according to p. 1, characterized in that as chlororhynchos> - intermediate chlorination of waste produced by oligomerization of ethylene with bulk chlorine content of 5-15%.



 

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