RU2288908C1 - Method for preparing halogenated paraffin based on higher alpha-olefins - Google Patents

Abstract

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of halogenated paraffin. Method involves carrying out electrolysis of higher α-olefins of (C₁₆-C₂₈)-fractions and higher in the presence of hydrohalogenic acid solution (hydrochloric or hydrobromic acid) and its corresponding salt (sodium or potassium). Process is carried out in diaphragm-free electrolyzer by using graphite or platinum, or titanium, or oxide-ruthenium-titanium, or glass-carbon cathode and graphite or platinum, or oxide-ruthenium-titanium, or glass-carbon anode at temperature 20-90°C and current anode density 100-1400 A/m² and in the mole ratio acid : salt : olefin = (2-14.2):(0-3.5):1, respectively. Invention provides synthesis of chloroparaffins with chlorine content 21-50%.

EFFECT: improved method of synthesis.

3 cl, 4 tbl, 16 ex

Description

The invention relates to the field of chemistry of organic compounds, specifically to a method for producing halogen-paraffins C _{16-28 and higher} , which are used as secondary plasticizers of polymeric materials, flame retardants, modifying additives to polyolefins and synthetic rubbers in order to significantly increase the mechanical and operational properties of compositions increase frost resistance, tensile strength at break, reduce flammability.

The most famous industrial method of producing higher chloroparaffins is the classical chlorination of their elemental chlorine in the presence of some additives, as a rule, initiators of radical processes. Such processes were implemented at Khimprom CJSC (Chuvashia, Novocheboksarsk), Kaustik CJSC (Bashkiria, Sterlitamak), Khimprom CJSC (Volgograd). The disadvantages of these processes are the need to use extremely toxic and explosive, difficult to store and use, corrosive and chemically active, and, therefore, environmentally hazardous, gaseous chlorine. As additives, expensive and difficult to separate because of their poor solubility in water reagents, such as dicetyl peroxydicarbonate (0.1-0.3 wt.% Of the amount of α-olefins) are used [Application for RF patent 2003109898, publ. 2004.10.20], azo-bisisobutyronitrile or dicetyl peroxydicarbonate in an organochlorine solvent [RF Patent Application 2003109894, publ. 2004.10.20].

In some cases, chlorination is carried out in two stages: connecting chlorination at a temperature of 35-55 ° C and substitution chlorination at a temperature of 40-105 ° C [RF Patent Application 2003109897, publ. 2004.10.20].

A known method of hot substitution chlorination of olefins with elemental chlorine at high temperatures up to 500-550 ° C for a very short contact for 1 second followed by rapid cooling in order to obtain products of the type CH ₂ Cl-CR = CH ₂ . Propylene and isobutylene are preferably reacted [Patent GB 968931, publ. 1964.09.09]. By-products are dichlorinated olefins.

Among other olefin chlorination processes, a method is known for liquid phase chlorination of butadiene by carrying out a reaction by boiling the reaction mixture in ethyl chloride containing 6-9 wt.% Of butadiene chlorination products. The process is carried out either without catalysts, or using nitrogen-containing compounds as a catalyst [RF Patent 2125036, publ. 1999.01.20]. The catalyst is prepared by adding trialkylamine dissolved in ethyl chloride to the butadiene chlorination products previously or directly during the reaction.

The production of chloroprene based on butadiene or acetylene by classical chlorination with elemental chlorine has been described and implemented in many foreign countries [M. Lynch, Chemico-Biological Interactions 135-136 (2001) 155-167]. Its disadvantages are two-stage (chlorination, and then dehydrochlorination), the use of toxic and corrosive and chemically active chlorine.

Known industrial process in a reactor with a bubble column chlorination of ethylene with elemental chlorine [J.A. Orejas, Chemical Engineering Science 54 (1999) 5299-5309; Chemical Engineering Science 56 (2001) 513-522]. It is characterized by all the disadvantages described above for processes involving chlorine.

A known method of producing chloroalkanes by adding chlorine to C-C double and triple bonds by the reaction of an olefin in the gas or liquid phase with elemental chlorine by illuminating the mixture with ultraviolet light having a wavelength> = 280 nm. [Patent EP 1189856, publ. 2002.03.27. Abstract of corresponding document: US 2002125122].

Known methods for producing brominated organic compounds useful as flame retardants by reacting unsaturated compounds with bromine in an inert solvent [Patent TW 434204, publ. 2001.05.16] or in the presence of a solution of an inorganic salt in water or an organic solvent [Patent JP 56008331, publ. 1981.01.28].

The disadvantages of all the above processes are the need to use extremely toxic and explosive, difficult to store and use, corrosive and chemically active and, accordingly, environmentally hazardous chlorine and bromine.

Electrochemical halogenation of olefins has certain advantages. It uses metal halides as the source of the halogenating agent, rather than elemental halogens. Some examples of electrochemical halogenation are known. So, the process of oxidation and halogenation of hydrocarbons is described, which is carried out in a cell containing a selective membrane that separates the cell space into anolyte and catholyte equipped with a porous anode and a porous cathode. Anolyte and catholyte respectively contain a mixture of electrolyte and unsaturated hydrocarbon and a mixture of electrolyte and in situ generated halogen or oxygen. The process proceeds at room or elevated temperature and pressure. Halogenated or oxidized hydrocarbon is recovered, and the electrolyte, unsaturated hydrocarbon, gaseous halogen or oxygen is re-launched into the cell [Patent CA 1292273, publ. 1991.11.19, Patent US 4731168, publ. 1988.03.15].

Another embodiment of the electrochemical process for halogenating compounds in situ is claimed. In this process, anhydrous hydrogen halide is fed into the anode compartment of the electrochemical cell, where halogenation occurs by oxidation of the halide at the anode [Application WO 9800580, publ. 1998-01-08, Abstract of WO 9800580]. The product is drained from the bottom of the cell, that is, its density should be greater than the density of the electrolyte.

The electrochemical process of electrolysis of an aqueous solution of an alkali metal halide to produce halogenated hydrocarbons is described [Patent US 4834847, publ. 1989.05.30]. The cell is equipped with a diaphragm and an anode and a cathode depolarizing gases. An alkali is formed in the cathode space as a by-product.

A process for producing halogenated hydrocarbons is proposed, which includes the reaction of a hydrocarbon or halogenated feedstock with a solution of a halogen carrier [Patent US 4376019, publ. 1983.03.08]. Halogenation is carried out in a cell with three compartments, equipped with ion-exchange membranes or a diaphragm and a membrane, by electrolysis of a non-aqueous solution of a halogen carrier, in which the halide salts of metals of variable valency, in which the metal has a higher valence, especially copper chloride or iron chloride, act. After depletion and expenditure of the carrier, the stage of its regeneration by electrolysis of the solution in the presence of halide ions follows.

A method for the electrolytic chlorination of butadiene by electrolysis of non-aqueous solutions of cobalt and iron chlorides is described [Patent JP 57-161076, publ. 1982.10.04]. Due to the low solubility of chlorides in non-aqueous solvents, the simultaneous presence of several different in nature chlorides is necessary. The cell is separated by a diaphragm, and the chlorination process takes place in the anode region.

Known electrolytic synthesis of organohalogen compounds on the anode of complex composition, representing a gas diffusion electrode of carbon and tetrafluoroethylene, coated with a catalyst of noble metals [Patent JP 04-006290, publ. 1992.01.10]. Used only for gaseous substrates.

All the above methods for the synthesis of halogenated paraffins are based on the use of either toxic elemental chlorine and bromine, often using catalysts, organic solvents and high temperatures, or electrolytic decomposition of halides in structurally complex multisection electrolyzers, often using expensive electrodes of complex design, sometimes modified with catalysts and polymers , in electrolytes of complex composition, sometimes in organic solvents, often using expensive Olay transition metal - cobalt, iron or copper, are used as the source of the chlorinating agent that is in large quantities. The increasing complexity of the electrolyte composition leads to difficulties in the isolation and purification of products, increases the amount of chlorine-containing, toxic, and corrosive waste. In most cases, processes are designed to produce chlorinated hydrocarbons only. The main disadvantage of almost all of the above methods is the use of only lower olefins as substrates.

The problem of developing an effective method of halogenation, primarily the chlorination of technical higher alpha-olefins, obtained from fractions of hydrocarbons of factory labeling C _16-18 , C _20-26 , C _{28 and higher} during oil refining, is currently critical in our country in due to the accumulation of a huge amount of these alpha olefins, which are characterized by low reactivity, and, as a result, the difficulty of involving them in traditional double bond functionalization reactions.

A known method for the synthesis of dichloroethane and ethylene chlorohydrin., Which consists in the electrolysis of a mixture of hydrochloric acid and sodium chloride in a two-section electrolyzer, separated by a diaphragm and equipped with a platinum or graphite anode [M.A. Kalinin, VV Stender, Electrolytic oxidation and chlorination of ethylene, Zh. butt. Chemistry, 1946, v.19, No. 10-11, S.1045-1058] while passing through the electrolyte gaseous ethylene.

Its disadvantages can be called the following: the use of a diaphragm electrolyzer, which complicates the process and increases its cost, increases energy consumption due to high voltages on the cell; the impossibility of chlorinating higher alpha olefins in these specifications, calculated on the gaseous starting compounds and products; the process concerns only chlorination and does not affect the bromination of olefins; chlorination results in a mixture of chlorine-containing products; the impossibility of substitution chlorination, and therefore, varying the composition of the target product by the chlorine content in it, that is, obtaining polychlorinated products.

The closest in technical essence and the achieved result to the proposed method is a method for producing dichloroethane by electrolysis of ethylene in the presence of a 12-36% aqueous solution of hydrochloric acid and the corresponding salt of nickel, cobalt, iron in a diaphragmless electrolyzer at a temperature of 45-70 ° C and anode current density 0.4-1.0 A / cm ² . Its disadvantages include the following: the use of toxic salts of transition metals (Ni, Co, Fe) or their alloys, the impossibility of chlorinating higher alpha-olefins in these specifications, designed for gaseous starting compounds; the process concerns only chlorination and does not affect the bromination of olefins; chlorination results in a mixture of chlorine-containing products; the impossibility of substitution chlorination, and consequently, varying the composition of the target product by the chlorine content in it, that is, obtaining the desired polychlorinated products; the presence of elemental chlorine in the exhaust gases from the electrolyzer.

The objective of the invention is a simple electrochemical method of halogenation, which allows the use of technical fractions of various alpha-olefins as starting compounds: C _16-18 (TU 38.402-69-73-89) C _20-26 (TU 38.402-69-72-89), From _{28 and above} (TU 38.402-69-71-89), perform chlorination and bromination of olefins, produce chloroparaffins with different chlorine content (21-50%), and thus solve the problem of utilizing accumulated alpha olefins into useful products.

The technical result of the claimed invention lies in the possibility of selective radical halogenation of alpha-olefins with a controlled content of halogen (chlorine) in the target products in the conditions of flameless electrolysis. The claimed technical result is achieved due to the proposed method for producing halogen-paraffins, which consists in the fact that a solution of hydrohalic acid, its corresponding salt and olefin is subjected to electrolysis in a non-diaphragm electrolyzer, and graphite or platinum, or titanium, or ruthenium-titanium oxide (ORTA) is used for electrolysis ), or a glassy carbon cathode and graphite or platinum, or ORTA, or a glassy carbon anode, use HCl or HBr as a hydrogen halide acid, as its The appropriate salt - the sodium or potassium salts, as the olefin - higher α-olefins fraction C ₁₆ -C _{28 and higher,} taken in molar ratio of acid: salt: olefin = (2 ÷ 14,2) :( 0 ÷ 3,5) : 1, and the process is conducted at a temperature of 20-90 ° C and an anode current density of 100-1400 A / m ² (0.01-0.14 A / cm ² ).

Distinctive features of the method are the implementation of the halogenation process by electrolysis of an acid solution (HCl, HBr), the corresponding salt of sodium or potassium halide, and alpha olefin fractions C _{16-C28 and higher} , taken in the above ratio at a temperature of 20-90 ° C and anode density current 100-1400 A / m ² (0.01-0.14 A / cm ² ), using graphite, or platinum, or titanium, or OPTA or a glassy carbon cathode and graphite or platinum, or ORTA or a glassy carbon anode, or any combination of them, and this combination does not affect em to achieve a technical result.

The proposed set of features makes it possible to obtain halogen-paraffins with high current and substance yields, avoiding the use of elemental halogens, to obtain products with different halogen contents in them, to use alpha-olefins with different numbers of carbon atoms, and to simplify the process.

The simplification of the process is achieved by carrying out the process under relatively simple conditions in a very simple design of the electrolyzer in the form of a glass in which electrodes are suspended from available materials, including cheap ones, as well as due to the very easy isolation of the product by decantation of a hydrocarbon fraction insoluble in an aqueous electrolyte . There is no need to use transition metal compounds (roads, toxic), take an excess of olefin (as 3-5% in the prototype) and capture gaseous poisonous chlorine.

The proposed set of features is new and has not been used to obtain halogen-paraffins. The possibility of obtaining, depending on the need, products with different halogen contents from one olefin fraction has never been considered.

The advantages of the proposed method are provided by carrying out the electrolysis process in the electrolyte of the above composition in a diaphragmless electrolyzer under appropriate conditions. In this case, the following reactions proceed at the cathode and anode - the evolution of hydrogen at the cathode and halogen radicals (the target reaction for generating a halogenating agent) at the anode:

Exposure to an olefin of anodically generated radical chlorine (halogen) leads to selective chlorination of the olefin to chloro (halogen) paraffin. The radical nature of the process allows it to be carried out not only to the stage of double bond addition (which is typical for non-catalytic chlorination with elemental chlorine), but also to the substitution chlorination stage, increasing the chlorine content in the product with an increase in the reaction time to 50.5%.

The indicated interval of change in the ratio of reagents is optimal. It is determined, firstly, by the requirements of the stoichiometry of the process, secondly, by the need to have a working electrolyte of sufficient electrical conductivity, and thirdly, by the need for acid in the solution to avoid alkalization of the electrolyte.

The temperature range at which electrolysis is carried out (20-90 ° C) is also optimal, since at lower temperatures certain measures are required for cooling and conductivity is reduced, current efficiency is reduced, and the use of higher temperatures complicates the implementation of the method, requiring special measures preventing evaporation from the electrolyte. The range of changes in the working current densities is determined by the complex chemistry of the reactions occurring during electrolysis and is set experimentally to achieve maximum process performance.

In all the examples below, electrolysis is carried out in the electrolyzer without separation of the cathode and anode spaces using graphite or platinum, or titanium, or OPTA, or a glassy carbon cathode with a working surface area of 20-150 cm ² and a graphite or platinum, or ORTA, or glassy carbon anode with a working surface area of 20-150 cm ² .

During electrolysis, the solution is stirred using a magnetic stirrer or a circulation pump. The structure of the obtained halogen-paraffin products was proved by the methods of NMR spectroscopy, elemental analysis, mass spectrometry, as well as by comparing their physical characteristics with literature data from catalogs.

Example 1

A working solution with a total volume of 40 ml is prepared by mixing 30 ml (35.7 g or 362 mmol) of 37% hydrochloric acid and 10 g (42 mmol) of the C ₁₆ -C ₁₈ olefin fraction. A platinum anode and cathode are used. Electrolysis is carried out at 20 ° at an anode current density of 100 A / m ² . 3 F of electricity in terms of olefin C ₁₇ H _{34 is} passed through the electrolyte. At the end of electrolysis, the electrolyte was stratified into two layers, the organic part was decanted and washed with water. Traces of water are removed in a vacuum of a water-jet pump. The yield of chloroparaffin is 13 g (100%). Physico-chemical parameters of chloroparaffin are shown in table 1 (in column I). Calculated for C ₁₇ H ₃₄ Cl ₂ ,%: C 66.02; H 11.00; Cl 22.98. Found,%: C 66.60; H 11.60; Cl 21.80. According to NMR ( ¹ H, ¹³ C), IR spectroscopy in the product there are no double bonds, that is, it is saturated chloroparaffin.

Example 2

A working solution with a total volume of 40 ml is prepared by mixing 14.1 g (143 mmol) of 37% hydrochloric acid and 10 g (42 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A platinum anode and cathode are used. Electrolysis is carried out at 20 ° at an anode current density of 100 A / m ² . 3F of electricity is passed through the electrolyte in terms of the olefin C ₁₇ H ₃₄ . The isolation procedure is similar to 1. The yield of chloroparaffin is 13 g (100%). Calculated for C ₁₇ H ₃₄ Cl ₂ ,%: C 66.02; H 11.00; Cl 22.98. Found,%: C 65.60; H 11.20; Cl 23.20.

Example 3

A working solution with a total volume of 40 ml is prepared by mixing 9.4 g (95 mmol) of 37% hydrochloric acid, 2.8 g (48 mmol) of NaCl, adding 10 g (42 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A platinum anode and a titanium cathode are used. The electrolysis is carried out at 30 ° at an anode current density of 200 A / m ² . 3 F of electricity in terms of olefin C ₁₇ H _{34 is} passed through the electrolyte. The isolation procedure is similar to 1. The yield of chloroparaffin is 13 g (100%). Calculated for C ₁₇ H ₃₄ Cl ₂ ,%: C 66.02; H 11.00; Cl 22.98. Found,%: C 65.60; H 11.20; Cl 23.20.

Example 4

A working solution with a total volume of 40 ml is prepared by mixing 8.2 g (83 mmol) of 37% hydrochloric acid, 4.18 g (71 mmol) of NaCl, adding 10 g (42 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A glassy carbon anode and a titanium cathode are used. The electrolysis is carried out at 50 ° at an anode current density of 100 A / m ² . 3.8 F of electricity in terms of olefin C ₁₇ H _{34 is} passed through the electrolyte. The isolation procedure is similar to 1. The yield of chloroparaffin is 13 g (100%). Calculated for C ₁₇ H ₃₄ Cl ₂ ,%: C 66.02; H 11.00; Cl 22.98. Found,%: C 64.16; H 10.17; C1 25.67.

Example 5

A working solution with a total volume of 40 ml is prepared by mixing 8.2 g (83 mmol) of 37% hydrochloric acid, 5.57 g (95 mmol) of NaCl, adding 10 g (42 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A platinum anode and a titanium cathode are used. The electrolysis is carried out at 60 ° at an anode current density of 200 A / m ² . 4 F of electricity, calculated as C ₁₇ H ₃₄ olefin, is passed through the electrolyte. The isolation procedure is similar to 1. The yield of chloroparaffin is 13 g (100%). Calculated for C ₁₇ H ₃₄ Cl ₂ ,%: C 66.02; H 11.00; Cl 22.98. Found,%: C 66.12; H 11.10; C1 22.78.

Example 6

The experimental conditions and the isolation of the product are similar to example 1, but the electrolysis is carried out at a temperature of 90 ° C.

Example 7e

The experimental conditions are similar to example 1, but they use the ORTA (oxide-ruthenium-titanium) anode and glassy carbon cathode. To achieve the same chlorine content as in Example 1, 3.2 F electricity must be skipped in the product.

Example 8

The experimental conditions are similar to example 1, but use a graphite anode and cathode. To achieve the same chlorine content as in Example 1, 3.2 F of electricity must be skipped.

Example 9

A working solution with a total volume of 40 ml is prepared by mixing 18.0 g (182 mmol) of 37% hydrochloric acid, 5.0 g (85 mmol) of NaCl, adding 5 g (21 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A platinum anode and cathode are used. The electrolysis is carried out at 20 ° at an anode current density of 500 A / m ² . An increasing amount of electricity is passed through the electrolyte, the values of which in terms of olefin C ₁₇ H ₃₄ are shown in table 2. The allocation procedure is similar to 1. The yield of chloroparaffin is 100%, but the chlorine content in it depends on the amount of electricity passed. The found amount of chlorine in the product in each case is shown in table 2.

Example 10

A working solution with a total volume of 80 ml is prepared by mixing 35.7 g (362 mmol) of 37% hydrochloric acid, 17 g (290 mmol) of NaCl, adding 19.8 g (83 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A platinum anode and an OPTA cathode are used. The electrolysis is carried out at 20 ° at an anode current density of 1000 A / m ² . An increasing amount of electricity is passed through the electrolyte, the values of which in terms of olefin C ₁₇ H ₃₄ are shown in table 3. The allocation procedure is similar to 1. The yield of chloroparaffin is 100%, but the chlorine content in it depends on the amount of electricity passed through. The found amount of chlorine in the product in each case is shown in table 3. Physico-chemical parameters of chloroparaffin with a chlorine content of 48-50% are shown in table 1 (in column II). Further transmission of electricity does not increase the chlorine content of the product.

Example 11

The experimental conditions are similar to example 1, but using fractions of olefins With ₂₀ -C ₂₆ (31 mmol). The yield of chloroparaffin is 12.2 g (100%). Calculated for C ₂₃ H ₄₆ Cl ₂ ,%: C 70.23; H 11.70; Cl 18.07. Found,%: C 66.12; H 11.10; Cl 18.40. n _D ²⁰ 1.469.

Example 12

The experimental conditions are similar to example 1, but use fractions of olefins of factory labeling C _{28 and higher} with a predominant content of hydrocarbons C ₂₈ -C ₃₀ (25 mmol). The electrolysis temperature is 75 ° C. The yield of chloroparaffin is 12.2 g (100%). Calculated for C ₂₉ H ₅₈ Cl ₂ ,%: C 72.95; H 12.16; Cl 14.89. Found,%: C 70.65; H 10.95; Cl 18.40. The product is solid, so pl. 72 ° C.

Example 13

A working solution with a total volume of 40 ml is prepared by mixing 20 g (99 mmol) of 40% hydrobromic acid, 4.0 g (39 mmol) of NaBr, adding 10 g (42 mmol) of the C ₁₆ -C ₁₈ olefin fraction and water. A platinum anode and cathode are used. The electrolysis is carried out at 30 ° at an anode current density of 100 A / m ² . 3 F of electricity in terms of olefin C ₁₇ H _{34 is} passed through the electrolyte. The isolation procedure is similar to 1. The output of bromoparaffin is 16.7 g (100%). Calculated for C ₁₇ H ₃₄ Br ₂ ,%: C 51.26; H 8.54; Br 40.20. Found,%: C 51.78; H 7.35; Br 40.87, n _D ²⁰ 1.4822.

Example 14

The experimental conditions and the isolation of the product are similar to Example 9, but the electrolysis is carried out at an anode current density of 1400 A / m ² and 3 F of electricity is passed through the electrolyte. The yield of chloroparaffin is 25.91 g (100%). Calculated for C ₁₇ H ₃₄ Cl ₂ ,%: C 66.02; H 11.00; Cl 22.98. Found,%: C 60.93; H 10.74; Cl 28.33.

Example 15

The experimental conditions, isolation of the product and the result are similar to example 3, but using potassium chloride.

Example 16

The experimental conditions, the isolation of the product and the result are similar to example 14, but using potassium bromide.

Thus, the proposed method for producing halogen-paraffins has the following technical and economic efficiency:

1) allows you to get halogen-paraffins with a high yield of available non-toxic raw materials - sodium or potassium halide and hydrohalic acid as halogenating agents;

2) product isolation is very simple and economical - by decantation;

3) allows the use of various halogenating agents - chlorides and bromides (salts and acids);

4) one-stage, mild process conditions;

5) low-waste method, since an electrolyte with an excess of halide is regenerated during isolation and can be used in a new cycle of synthesis of target compounds;

6) the method allows to obtain products with different chlorine content in chloroparaffin - from 21 to 50%;

7) the simplification of the process is achieved through the use of an electrolyzer of simple design, characterized by a low voltage on it, and, consequently, cost-effectiveness, as well as a wide range of possible electrode materials.

Based on the proposed method, a pilot plant was created with an electrolyzer working volume of 5 l with forced circulation of an electrolyte for electrochemical halogenation of higher technical alpha olefins, experimental batches of halogen-paraffins with a chlorine content of 23% and 48% of 2 kg in each batch were developed. The technical characteristics of the products obtained by the claimed electrochemical method are in good agreement with the characteristics of chloroparaffins manufactured industrially using the classical technology based on gaseous chlorine at ZAO Khimprom in Novocheboksarsk (table 4).

Table 1.
Physico-chemical characteristics of the chlorination product of alpha-olefins C _l6 -C ₁₈ with different chlorine content. No. Indicator Technical documentation Indicator value I chlorine content: 21-23% II chlorine content: 48-50% one Appearance - Colorless./St. - yellow. liquid Colorless./St. - yellow. liquid 2 Density, d ₄ ²⁰ , g / cm ³ GOST 3900-47 0.9477 1,1346 3 Refractive Index, n _D ²⁰ GOST 18995.2-73 1.4645 1.4940 four Kinematic viscosity at 25 ° С, cSt GOST 33-66 16,4 178.65 5 Flash point in open crucible, ° С GOST 4333-48 ~ 173 ~ 220 6 Pour point, ° C GOST 20287-74 -eighteen -39 7 Iodine number GOST 2070-55 1.98 1,02 8 Molecular weight (cryoscopy) Workshop on the physical. org chemistry. N. Isaac. Peace; M. 1972, p. 45. 347 448

Table 2.
Characteristics of chloroparaffin, depending on the amount of transmitted electricity (as in example 9). The amount of electricity, f n _D ²⁰ % Cl one 1.457 13.1 2 1.461 17.2 3 1.462 18.2 4.5 1.465 21.3 10 1.476 32.0 11.5 1.477 33.0 twenty 1.482 38.5 28 1.487 43.0

Table 3.
Characteristics of chloroparaffin, depending on the amount of transmitted electricity (as in example 10). The amount of electricity, f n _D ²⁰ % Cl 3 1.477 33.0 four 1.486 42.6 4.5 1.492 48.7 10 1.494 50.5

Table 4.
Comparison of the quality indicators of chlorinated paraffins (from alpha-olefins C ₁₆ -C ₁₈ ) Indicator Brand (OJSC "Khimprom") Chloroparaffins R-Cl _n no the claimed method HP-250 HP-470 Connect chlorination Substitution Chlorination Density at 20 ° С, kg / m ³ 950-1020 1180 950 1135 Mass fraction of chlorine (Cl),% 24-29 45-49 24-26 45-50 Iodine number - four 2 one

Claims (3)

1. The method of producing halogenated paraffins, including the electrolysis of olefins in the presence of an aqueous solution of hydrohalic acid and its corresponding salt in a diaphragmless electrolyzer, characterized in that the higher α-olefins of fractions C ₁₆ -C ₂₈ and higher, taken in molar ratio, are used as olefins acid: salt: olefin = (2 ÷ 14.2) :( 0 ÷ 3.5): 1, and the process is carried out at a temperature of 20-90 ° C and anode current density of 100-1400 A / m ² . 2. The method according to claim 1, characterized in that hydrochloric or hydrobromic acids are used as hydrohalic acid, and their sodium or potassium salt is used as salts. 3. The method according to claim 1, characterized in that the diaphragmless electrolyzer is equipped with a graphite, or platinum, or titanium, or ruthenium-titanium oxide, or glassy carbon cathode, and a graphite, or platinum, or ruthenium-titanium oxide, or glassy carbon anode.