RU2374276C1 - Method of recycling organochloride wastes from epichlorohydrin production (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to method of recycling organochloride wastes from epichlorohydrin production, obtaining polymer products. According to the first version, the process is carried out by extracting wastes from epichlorohydrin production in the presence of 2 to 10 g/l caustic soda, separation of the aqueous layer, azeotropic distillation of the residue of the organic layer and separation of 1,2,3-trichloropropane, which is treated with 8 to 10% alcohol solution sodium hydroxide at room temperature for 3.5 to 4.5 hours, obtaining 2,3-dichloropropene-1, with subsequent radical copolymerisation of the obtained 2.3-dichloropropene-1, obtaining polymer products. According to the second version, the obtained 2,3-dichloropropene-1 is reacted with aliphatic amines to form tertiary or quaternary nitrogen-containing unsaturated salts with their subsequent radical copolymerisation, obtaining polymer products.

EFFECT: obtaining polymer products with sufficiently high breaking temperature, with high output without formation of hazardous substances (elementary chlorine, carbon monoxide, phosgene, dioxins etc) using a readily producible method.

2 cl, 18 ex

Description

The invention relates to the field of chemistry, in particular to the disposal of organochlorine wastes for the production of epichlorohydrin, and in particular to technologies for the disposal of organochlorine wastes for the production of epichlorohydrin by producing polymer products.

In the production of 20 thousand tons of epichlorohydrin, more than 8 thousand tons of dichloropropane and more than 2 thousand tons of trichloropropane fractions are formed (Khaliullin AK, Salaurov VN Fundamentals of industrial ecology. Irkutsk, ISTU, 2002, p.70). The total mass of organochlorine wastes on a global scale is estimated at millions of tons (Voronkov M.G., Tatarova L.A., Trofimova K.S., Verkhozina E.I., Khaliullin A.K. Processing industrial chlorine and sulfur-containing wastes // Chemistry in the interests of sustainable development. - 2001. - T. 9, No. 3. - S.393-403). Therefore, the processing of organochlorine wastes from the production of epichlorohydrin will reduce the technogenic impact on the biosphere.

A known method of processing liquid organic and organochlorine wastes, including mixing these wastes with bitumen (Application for invention RU No.2001132501, C08L95 / 00, date of publication of the application 02.20.2004).

The disadvantages of this method are the complete absence of any interactions of organochlorine wastes with bitumen. Only simple mechanical mixing takes place, and with a slight increase in temperature during the operation of such a product, toxic organochlorine compounds are formed, as well as hydrogen chloride, carbon monoxide.

A known method for the disposal of chlorine-containing compounds, including the homogeneous oxidation of organochlorine compounds with atmospheric oxygen in a lined furnace at a temperature of at least 600 ° C (US Patent No. 4018879, priority from 06/21/77, published 04/19/77, IPC C01B 7/00).

The disadvantages of this method are the low efficiency of converting the initial chlorine-containing waste into non-toxic, easily utilizable compounds (hydrogen chloride, water, carbon dioxide), as well as the formation of a significant amount of dangerous oxidation products (elemental chlorine, phosgene, carbon monoxide, dioxins, nitrogen oxides).

A known method of neutralizing organochlorine waste by burning at 1320-1580 ° C in excess air, followed by wet cleaning of flue gases in the presence of sulfur-containing products or elemental sulfur (Patent RU No. 1580929, F23G 7/00, C01B 7/01, 20. 07. 2000 )

The disadvantages of this method are the formation of harmful by-products of oxidation, a sufficiently high oxidation temperature, virtually eliminating the possibility of its practical application.

Known methods for the disposal of organochlorine wastes based on the oxidation of organochlorine compounds in the presence of a catalyst. In particular, a method is known that includes the use of catalysts based on zirconium, vanadium, manganese, cobalt or cerium oxides, as well as at least one of the platinum group metals (US Patent No. 5578283, priority from 12.30.94, IPC C01B 7 / 00, publ. 26.11. 96).

The disadvantages of this method are the deactivation and low stability of the catalyst, as well as the formation of harmful by-products of oxidation.

A known method for the disposal of chlorine-containing waste by passing the vapor of chlorine-containing compounds through a layer of acid-resistant zeolite molecular sieves (US Patent No. 4423024, priority from 05.26.82, IPC C01B 21/20, C01B 7/01, publ. 12/27/83).

The disadvantages of this method are the low catalytic activity of the zeolite, its rapid deactivation.

A known method for the disposal of organochlorine compounds by passing the vapors of organochlorine compounds in the composition of the oxygen-containing reaction gas mixture through a catalyst bed that provides oxidation of the starting organochlorine compounds. A catalyst is used, which is a geometrically structured system of microfibers with a diameter of 5-20 μm, having active centers that are characterized in the IR spectra of adsorbed ammonia by the presence of an absorption band with wave numbers in the range ν = 1410-1440 cm ^-1 containing the active component, which is one of the platinum group metals, and a fiberglass carrier. The active component of the catalyst may be at least one of the metals of the platinum group, in particular platinum (Patent RU No. 2252208, C07C 19/01, C07C 19/045, C07C 25/06, B01J 21/08, B01J 23/42, C01B 7/01, published 05/20/2005).

The disadvantages of this method are:

1. Difficulties in creating a certain number of specific active centers on the catalyst surface at the stage of its preparation, providing high selectivity for the oxidation of organochlorine compounds. Failure to comply with these conditions in the modification of the catalyst leads to a decrease in its selectivity and the formation of toxic by-products.

2. Organochlorine compounds are oxidized to hydrogen chloride, carbon dioxide and water, although all these organochlorine compounds are promising raw materials for the production of valuable materials and the demand for which is growing steadily.

A known method of processing organochlorine wastes by hydrogenolysis, which is carried out in the presence of heterogeneous catalysts containing platinum group metals at a temperature of 250 -350 ° C in an inert high-boiling hydrocarbon solvent with its 10-20-fold excess in relation to the mass of organochlorine wastes (Application for invention RU No.2000102841, C07C 17/354, C07C 17/25, 10.27.2001).

The disadvantages of this method are the use of a large amount of inert high-boiling hydrocarbon solvent and the inability to regenerate it, as well as the formation of toxic compounds (elemental chlorine, hydrogen chloride, carbon monoxide, dioxins, nitrogen oxides) as a result of hydrogenolysis.

A known method of processing organochlorine wastes by hydrodechlorination with molecular hydrogen at elevated pressure and temperature in the presence of an alkaline reagent, aromatic or aliphatic hydrocarbon and catalyst - palladium on a carrier (Application for invention RU No. 2005129519, C07C 17/395, A62D 3/00, published 20.08 .2007).

The disadvantages of this method are the use of high pressure, which is extremely undesirable in industry, and the formation of toxic substances (elemental chlorine, phosgene, carbon monoxide, dioxins, nitrogen oxides).

A common disadvantage of the known known methods is that organochlorine compounds are not considered as valuable intermediates for the synthesis of a large number of organic compounds with a complex of valuable operational properties.

A known method of disposal of organochlorine wastes of epichlorohydrin production, including the preparation of thiocols, by reacting various types of wastes with sulfur in an aqueous hydrazine-alkali system (Korchevin N.A., Sukhomazova E.N., Levanova E.P., Russavskaya N.V., Deryagina E.N. Systems for sulfur recovery and utilization of its industrial waste // Chemistry in the interests of sustainable development. - 2002. - V. 10, No. 3. - S.325-330).

The disadvantages of this method are the low yield of the main product (61%) and the use of toxic hydrazine.

The prototype is the method closest to the claimed methods, including the involvement of organochlorine wastes of epichlorohydrin production in the polycondensation process with sodium polysulfides and leading to polymer products (Voronkov MG, Tatarova L.A., Trofimova K.S., Verkhozina E.I ., Khaliullin AK Recycling of industrial chlorine and sulfur-containing waste // Chemistry in the interests of sustainable development. - 2001. - T. 9, No. 3. - S.393-403). In the prototype, the polycondensation reaction was carried out in a two-phase system (aqueous solution of Na ₂ S _m - non-polar organic solvent) and phase transfer catalysts. Low molecular weight tetraalkylammonium compounds: ammonium bromide, tetraoctylammonium bromide, cetyltrimethylammonium bromide and alkyl (C _10-18 ) benzyl dimethyl ammonium chloride (catamine-AB) were used as phase transfer catalysts. The catalytic effect of the quaternary tetraalkylammonium salts is confirmed by the fact that in their absence during the interaction of organochlorine wastes with Na ₂ S _m in the two-phase system, the polymer does not form.

Common features of the prototype with the essential features of the proposed methods (according to the first and second options) are the purpose (disposal of organochlorine wastes of epichlorohydrin production) and production of polymer products as the final product.

The disadvantages of this method are:

1. The softening temperature of the copolymers is from 55 to 170 ° C, which is an extremely small value for polymers.

2. The use of expensive organic solvents and the impossibility of their recycling.

3. The use of expensive phase transfer catalysts and the impossibility of their regeneration.

4. During polycondensation, unwanted toxic substances are released (elemental chlorine, hydrogen sulfide and low molecular weight reaction products).

The technical result of the invention is to obtain polymer products with a sufficiently high decomposition temperature, with a high yield without the formation of harmful substances (elemental chlorine, carbon monoxide, phosgene, dioxins, etc.) in a more technological way.

The technical result is achieved by the fact that in the method for the disposal of organochlorine wastes of the production of epichlorohydrin according to the first embodiment (claim 1), comprising the preparation of polymer products according to the invention, before the production of polymer products, the wastes of the production of epichlorohydrin are extracted in the presence of 2-10 g / l calcined soda, the aqueous layer is separated, the remainder of the organic layer is subjected to azeotropic distillation and 1,2,3-trichloropropane is isolated, which is treated with 8-10% alcohol solution sodium at room temperature for 3.5-4.5 hours to obtain 2,3-dichloropropene-1. The preparation of polymer products in the inventive method according to the first embodiment is carried out by radical copolymerization of the obtained 2,3-dichloropropene-1.

The technical result is achieved by the fact that in the method for the disposal of organochlorine wastes of the production of epichlorohydrin according to the first embodiment (claim 1), comprising the preparation of polymer products according to the invention, before the production of polymer products, the wastes of the production of epichlorohydrin are extracted in the presence of 2-10 g / l calcined soda, the aqueous layer is separated, the remainder of the organic layer is subjected to azeotropic distillation and 1,2,3-trichloropropane is isolated, which is treated with 8-10% alcohol solution sodium at room temperature for 3.5-4.5 hours to obtain 2,3-dichloropropene-1, which is subjected to reaction with aliphatic amines with the formation of tertiary or quaternary nitrogen-containing unsaturated salts. The preparation of polymer products in the inventive method according to the second embodiment is carried out by radical copolymerization of the obtained tertiary or quaternary nitrogen-containing unsaturated salts based on 2,3-dichloropropene-1.

The technical result is achieved by obtaining polymer products without the formation of side impurities (elemental chlorine, carbon monoxide, phosgene, dioxins, etc.).

The developed method is characterized by improved technical and economic characteristics due to the conduct of reactions under mild conditions, the absence of expensive reagents, and high yields of reaction products.

The essence of the claimed group of inventions, united by a single inventive concept, is to obtain by radical copolymerization of polymer products based on 2,3-dichloropropene-1, as well as tertiary and / or quaternary nitrogen-containing unsaturated salts based on 2,3-dichloropropene-1.

A positive effect of the invention is the possibility of processing organochlorine wastes of the production of epichlorohydrin into polymer products with a high decomposition temperature, without the formation of harmful side impurities (elemental chlorine, carbon monoxide, phosgene, dioxins, etc.).

Well known in organic chemistry, especially in organic synthesis, the reaction of haloalkanes with an alcohol solution of alkali, the so-called dehydrochlorination reaction (Temnikova TI Course on the theoretical foundations of organic chemistry. Leningrad, Goskhimizdat, 1962, S.375).

We experimentally found the optimal conditions for this reaction for 1,2,3-trichloropropane. The reaction scheme is shown below:

It is known that amines easily react with halogen derivatives to form substituted ammonium salts - the Menshutkin reaction (Temnikova TI Course of Theoretical Foundations of Organic Chemistry. Leningrad, Goskhimizdat, 1962, P.235).

Based on 2,3-dichloropropene-1, tertiary (I) and / or Quaternary (II, III) salts of nitrogen-containing unsaturated salts are obtained. For the first time, optimal conditions for the preparation of these salts were found. Reaction schemes are given below:

The difference of the proposed method from the prototype is to obtain polymer products in the process of radical copolymerization of 2,3-dichloropropene-1, as well as tertiary and / or quaternary nitrogen-containing unsaturated salts based on 2,3-dichloropropene-1.

Thus, two known reactions (the dehydrochlorination reaction and the Menshutkin reaction) in the inventive method for the disposal of organochlorine wastes of epichlorohydrin production in a new set of features indicate a new mechanism unknown from the prior art for the influence of the features on the technical result achieved, which indicates the compliance of the proposed method with the patentability "Inventive step".

The method of disposal of organochlorine waste production of epichlorohydrin according to the first embodiment is as follows.

Before obtaining polymer products, epichlorohydrin production wastes are extracted in the presence of 2-10 g / l of soda ash. The aqueous layer was separated and the remainder of the organic layer was subjected to azeotropic distillation. 1,2,3-trichloropropane is isolated. Processing it with a 10% alcohol solution of sodium hydroxide at room temperature for 4 hours gives 2,3-dichloropropene-1. A radical copolymerization of the obtained 2,3-dichloropropene-1 is carried out. A copolymer of 2,3-dichloropropene and styrene is obtained, which has a decomposition temperature 95 ° C higher than the decomposition temperature of polystyrene.

The method of disposal of organochlorine waste production of epichlorohydrin according to the second embodiment is as follows.

Before obtaining polymer products, the waste products of epichlorohydrin production are extracted in the presence of 2-10 g / l of soda ash, the aqueous layer is separated, the remainder of the organic layer is subjected to azeotropic distillation and 1,2,3-trichloropropane, which is treated with a 10% alcohol solution of sodium hydroxide, is isolated at room temperature for 4 hours to obtain 2,3-dichloropropene-1, which is subjected to reaction with aliphatic amines to form tertiary or quaternary nitrogen-containing unsaturated salts, and obtaining limernyh products obtained by radical copolymerization is carried tertiary or quaternary nitrogen-containing unsaturated salts.

The invention is illustrated by examples.

Example 1. Isolation of 1,2,3-trichloropropane. Organochlorine wastes containing 1,2,3-trichloropropane were extracted from water-soluble impurities (epichlorohydrin, dichloropropanols, chloroesters) with distilled water containing 1 g / l of soda ash (or alkali - to maintain a pH of 7-8). The residue was subjected to azeotropic distillation and 1,2,3-trichloropropane with a purity of ≥79% was isolated by distillation (according to gas-liquid chromatography).

Example 2. Isolation of 1,2,3-trichloropropane. Organochlorine wastes containing 1,2,3-trichloropropane were extracted from water-soluble impurities (epichlorohydrin, dichloropropanols, chloroesters) with distilled water containing 12 g / l of soda ash (or alkali - to maintain a pH of 7-8). The residue was subjected to azeotropic distillation and 1,2,3-trichloropropane with a purity of ≥82% was isolated by distillation (according to gas-liquid chromatography).

The use of 1 g / l of soda ash (example 1) or 12 g / l (example 12) of soda ash when isolating 1,2,3-trichlopropane does not allow to obtain the claimed technical result.

Example 3. Isolation of 1,2,3-trichloropropane. Organochlorine wastes containing 1,2,3-trichloropropane were extracted from water-soluble impurities (epichlorohydrin, dichloropropanols, chloroesters) with distilled water containing 2 g / l of soda ash (or alkali - to maintain a pH of 7-8). The residue was subjected to azeotropic distillation and 1,2,3-trichloropropane with a purity of ≥99% was isolated by distillation (according to gas-liquid chromatography).

Example 4. Isolation of 1,2,3-trichloropropane. Organochlorine wastes containing 1,2,3-trichloropropane were extracted from water-soluble impurities (epichlorohydrin, dichloropropanols, chloroesters) with distilled water containing 5 g / l of soda ash (or alkali to maintain a pH of 7-8). The residue was subjected to azeotropic distillation and 1,2,3-trichloropropane with a purity of ≥99% was isolated by distillation (according to gas-liquid chromatography).

Example 5. Isolation of 1,2,3-trichloropropane. Organochlorine wastes containing 1,2,3-trichloropropane were extracted from water-soluble impurities (epichlorohydrin, dichloropropanols, chloroesters) with distilled water containing 8 g / l of soda ash (or alkali to maintain a pH of 7-8). The residue was subjected to azeotropic distillation and 1,2,3-trichloropropane with a purity of ≥99% was isolated by distillation (according to gas-liquid chromatography).

Example 6. Isolation of 1,2,3-trichloropropane. Organochlorine wastes containing 1,2,3-trichloropropane were extracted from water-soluble impurities (epichlorohydrin, dichloropropanols, chloroesters) with distilled water containing 10 g / l of soda ash (or alkali - to maintain a pH of 7-8). The residue was subjected to azeotropic distillation and 1,2,3-trichloropropane with a purity of ≥99% was isolated by distillation (according to gas-liquid chromatography).

Example 7. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with 20% alcohol NaOH at room temperature for 4 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, yield 115 g (60%). T. bale. 94 ° C. n _D ²⁰ 1.4609 (n _D ²⁰ 1.4603).

Example 8. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with a 15% alcohol solution of NaOH at room temperature for 4 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, yield 115 g (67%). T. bale. 94 ° C. n _D ²⁰ 1,4609 (n _D ²⁰ 1.4603).

The use of a 20% alcohol solution of NaOH (example 7) or a 15% alcohol solution of NaOH (example 8) does not lead to the claimed technical result: the yields of the target product are 60 or 67%, respectively.

Example 9. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with an 8% alcohol solution of NaOH at room temperature for 3.5 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, and the yield was 115 g (80%). T. bale. 94 ° C. n _D ²⁰ 1.4609 (n _D ²⁰ 1.4603).

Example 10. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with a 10% alcohol solution of NaOH at room temperature for 4 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, yield 115 g (80%). T. bale. 94 ° C. n _D ²⁰ 1.4609 (n _D ²⁰ 1.4603).

Example 10. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with an 8% alcohol solution of NaOH at room temperature for 4.5 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, yield 115 g (80%). T. bale. 94 ° C. n _D ²⁰ 1.4609 (n _D ²⁰ 1.4603).

Based on the data obtained (examples 9, 10, 11 and 12), an 8-10% alcohol solution of NaOH should be used, and the reaction time is 3.5-4.5 hours.

Synthesized 2,3-dichloropropene-1 is a colorless liquid, fairly stable, does not darken when stored under normal conditions, and does not dehydrochlorinate during prolonged storage. The structure of 2,3-dichloropropene-1 was proved by IR, ¹ H, and ¹³ C NMR spectroscopy. The ¹ H NMR spectrum of 2,3-dichloropropene-1 contained signals from the protons of the vinyl group at 5.48 ppm. and a chloromethyl group at 4.19 ppm. The ¹³ C NMR spectrum shows absorption signals of the chloromethyl group at 47.49 ppm, of the group = CH ₂ at 116.44 ppm. and = CCl groups at 138.44 ppm In the IR spectrum there is an absorption band at 1605 cm ^-1 corresponding to the vinyl group. The absorption band at 680 cm ^-1 can be attributed to the C-Cl bond.

Example 11. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with a 10% alcohol solution of NaOH at room temperature for 6 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, yield 115 g (65%). T. bale. 94 ° C. n _D ²⁰ 1.4609 (n _D ²⁰ 1.4603).

Example 12. Obtaining 2,3-dichloropropene-1. 147.5 (1 mol) of 1,2,3-trichloropropane was treated with a 10% alcohol solution of NaOH at room temperature for 2 hours. The precipitated NaCl was filtered off, the liquid phase was distilled, and the yield was 115 g (45%). T. bale. 94 ° C. n _D ²⁰ 1,4609 (n _D ²⁰ 1.4603).

Increasing the reaction time (example 11) or reducing the reaction time (example 12) leads to a decrease in the yield of 2,3-dichloropropene-1.

Example 14. Obtaining N, N-diethyl-N- (β-chloroallyl) amine (I). In a solution of 31 ml (22 g) (0.3 mol) of freshly distilled diethylamine in 31 ml of distilled water, 27.5 ml (33.3 g) (0.3 mol) of freshly distilled 2,3-dichloropropene-1 and 37.5 g (0.375) were poured with vigorous stirring for 15 min. mol) of a 40% aqueous NaOH solution. The mixture was heated at 65-70 ° C for 4-5 hours, cooled, the organic layer was separated and dried over MgSO ₄ . By distillation in vacuo, 14.3 g (67.5%) (I) were obtained, boiling point 56-58 ° C (3 mmHg), n _D ²⁰ 1.443. IR spectrum, ν, cm ^-1: 1250, 1050 (CN); 1648 (C = C). ¹ H NMR (C ₂ D ₅ OD), δ, ppm: 5.35 d (2H, = CH ₂ , j 82.7 Hz), 3.17 s (2H, CH ₂ ), 2.55 q (4H, 2CH ₂ , j 6.9 Hz), 0.99 t (6H, 2CH ₃ , 6.9 Hz). Spectrum ¹³ C, δ. ppm: 141.69 (= CCl), 113.88 (= H ₂ C), 60.66 (CH ₂ ), 47.97 (CH ₂ ), 12.55 (CH ₃ ). Found,%: C 56.55; H 9.48; N, 9.17; Cl 25.11. C ₇ H ₁₄ NCl. Calculated,%: C 56.95; H 9.49; N, 9.49; Cl 24.07.

Example 15. Obtaining N, N, N-triethyl-N- (β-chloroallyl) ammonium bromide (II).

To a mixture of 10 g of N, N-diethyl-N- (β-chloroallyl) amine in 18 ml of nitromethane, 20 g of ethyl bromide in 36 ml of nitromethane was added with stirring. The salt that crystallized upon cooling was filtered off and dried. Yield 12 g (80%), mp. 168-170 ° C. IR spectrum, ν, cm ^-1 : 1280 (CN); 1618, 2875, 3050 (C = C). ¹ H NMR spectrum (C ₂ D ₅ OD), δ, ppm: 6.08 (2H, = CH ₂ , j 109.6 Hz), 4.45 s (2H, CH ₂ N), 3.55 k (4H, 2CH ₂ , j 7.1 Hz), 1.41 (6H, 2CH ₃ , j 7.1 Hz). ¹³ C NMR spectrum, δ, ppm: 130.02 (= CCl), 129.58 (= H ₂ C), 62.91 (CH ₂ ), 54.93 (CH ₂ ), 8.76 (CH ₃ ). Found,%: C 43.09; H 8.34; Br 31.21; N 5.7; Cl 13.85. C ₉ H ₁₉ BrNCl. Calculated,%: C 42.12; H 7.46; Br 31.14; N, 5.46; Cl 13.82.

Example 16. Obtaining N, N-dimethyl-N, N-di (β-chloroallyl) ammonium chloride (III). To 68.2 g (0.5 mol) of a 33% aqueous solution of dimethylamine and at a temperature not exceeding 40 ° C with vigorous stirring 55 ml (0.5 mol) of freshly distilled 2,3-dichloropropene-1 and 50 g of 50% aqueous solution of NaOH (0.625 mol), the temperature was raised to 60 ° C and heated for 4–6 h. The organic layer was separated, and quaternary salt crystals precipitated upon standing (1 or more days). Yield 58 g (80%). The resulting salt decomposes at 165 ° C, not reaching the melting point. IR spectrum, ν, cm ^-1 : 1030, 1230 (CN); 1648, 2975, 3080 (C = C). ¹ H NMR: (C ₂ D ₅ OD), δ ppm, 6.18 d (4H, = H ₂ C; j 96.7 Hz), 4.70 s (4H, 2CH ₂ ), 3.41 s (6H, 2CH ₃ ) . ¹³ C NMR spectrum, δ, ppm: 126.12 (= CH ₂ ), 125.33 (= CCl), 66.51 (CH ₂ ), 47.33 (CH ₃ ). Found,%: C 41.68; H 6.6; N, 6.84; Cl 44.34. C ₈ H ₁₄ NCl ₃ . Calculated,%: C 41.65; H 6.07; N 6.08; Cl 46.2.

Example 17. Obtaining a copolymer of 2,3-dichloropropene-1 and styrene. The copolymerization of 2,3-dichloropropene-1 and styrene was carried out in sealed ampoules in bulk at 60 ° C in the presence of azobisisobutyric acid dinitrile in an argon atmosphere. The copolymerization products were precipitated with methanol and reprecipitated several times. The copolymerization of 2,3-dichloropropene-1 with styrene gave powdered products that were readily soluble in aromatic hydrocarbons, carbon tetrachloride, acetone and insoluble in alcohols and liquid saturated hydrocarbons. The decomposition temperature is 95 ° C higher than the decomposition temperature of polystyrene.

Example 18. Obtaining a copolymer of nitrogen-containing unsaturated salts based on 2.3-dichloropropene-1 and methyl methacrylate.

The copolymerization of nitrogen-containing unsaturated salts based on 2.3-dichloropropene-1 and methyl methacrylate was carried out in sealed ampoules in bulk at 60 ° C in the presence of azobisisobutyric acid dinitrile in an argon atmosphere. The copolymerization products were precipitated with methanol and reprecipitated several times. The copolymerization of nitrogen-containing unsaturated salts based on 2.3-dichloropropene-1 and methyl methacrylate gave powder products.

Claims (2)

1. A method of disposing of organochlorine wastes of the production of epichlorohydrin, including the production of polymer products, characterized in that before receiving the polymer products, the waste products of epichlorohydrin are subjected to extraction in the presence of 2-10 g / l of soda ash, the aqueous layer is separated, the remainder of the organic layer is subjected to azeotropic distillation and isolated 1,2,3-trichloropropane, which is treated with an 8-10% alcohol solution of sodium hydroxide at room temperature for 3.5-4.5 hours to obtain 2,3-dichloropropene-1, and the preparation of polymer products is carried out by radical copolymerization of the obtained 2,3-dichloropropene-1. 2. A method of disposing of organochlorine wastes of the production of epichlorohydrin, including the production of polymer products, characterized in that prior to the preparation of polymer products, the waste products of epichlorohydrin are subjected to extraction in the presence of 2-10 g / l of soda ash, the aqueous layer is separated, the remainder of the organic layer is subjected to azeotropic distillation and isolated 1,2,3-trichloropropane, treated with trichloropropane 8-10% alcoholic solution of sodium hydroxide at room temperature for 3.5-4.5 hours to obtain 2,3-dichloropr Foam-1, which is reacted with aliphatic amines to form tertiary or quaternary nitrogen-containing unsaturated salts, the preparation of polymer product obtained by radical copolymerization is carried tertiary or quaternary nitrogen-containing unsaturated salts.