Method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)- ethylene

FIELD: chemistry of organochlorine compounds, chemical technology.

SUBSTANCE: method involves treatment of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane with solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide with the content of sodium hydroxide in mixture 30%, not above, in the molar ratio 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane to alkali = 1:(1.5-1.75) at heating in the presence of catalyst. As catalysts method involves benzyltrialkyl ammonium halides, preferably, benzyltriethyl ammonium chloride or benzyltrimethyl ammonium bromide, tetraalkyl ammonium halides, preferably, tetrabutyl ammonium bromide taken in the amount 0.0005-0.005 mole. Invention provides the development of a new method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene allowing to enhance ecological safety of technological process and to improve quality of the end product.

EFFECT: improved method preparing.

2 cl, 15 ex

 

The invention relates to the field of chemistry and technology of organochlorine compounds, and in particular to a method for producing 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene of the formula

which can be used to produce polymeric products to a wider consumer demand, in particular its copolymer with methyl methacrylate, raw material for manufacturing products for domestic use (waste containers, containers for non-food products and others), and also as an additive to polyester resins to improve their fire resistance.

A method of obtaining 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene removal of hydrogen chloride alcohol alkali solution of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane[Grummit O., Buck, A., Steams J., J. Am. Chem. Soc., 1945, v.67, No.1, R; Janota X., Alov E.M., Moskvichev Y.A - Zhur.org.chem., 1985]. Also known is a method of obtaining 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane as acceptor of hydrogen chloride used amines [Lord K.A.J. Chem Soc., 1948, pp.1657-1661].

Closest to the claimed method is a method of obtaining 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane using as eliminating agent crystalline alkali (NaOH) and catalyst - benzyltriethylammonium chloride (prototype) [Patent RU 2109721 from 27.04.1998 g].

How about Westlaw as follows: the reaction mass, consisting of 0.5 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 0.75 mol of NaOH, of 0.0005 mol benzyltriethylammonium chloride, is heated under stirring for 40-60 min and a temperature of 90-100°C. Then neutralized with an aqueous solution of hydrochloric acid. The precipitate was filtered and dried. With the release of 93-97% receive 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene with MP. 88-89°, MP. lit. 88-89° [O. Grummitt, Buck A., Steams J., J. Am. Chem. Soc., 1945, v.67, No.1, R]. It should be noted that after filtering the precipitate and drying receive technical product with the content of the main component 74%. To obtain the target product with TPL 88-89°it is additionally clear: repeatedly washed with hot water to remove the byproduct sodium chloride and excess alkali and recrystallized from isopropyl alcohol.

With the development of technology for production of 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene of the pre-cleaned (up to TPL to 108.5-109° (C) 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane in semi-industrial conditions on the basis of the prototype method is established that the process of obtaining the latter consists of the following main stages:

1. To download components.

2. Heating of the reaction mass up to 90-100°C.

3. The exposure at 90-100°C for 40-60 minutes

4. Cooling the reaction mass to 70°C.

5. Dilution of the reaction mixture with water (14 mol).

6. Neutralize the Oia diluted hydrochloric acid.

7. Filtering the target product.

8. Download technical product in the reactor.

9. Download water (14 mol).

10. The mixture heated to 70-80°C.

11. Cooling to room temperature.

12. The filtering technical product.

13. Wash the precipitate on the filter with water (2.5 mol).

14. Drying of the technical product. The product yield is 93-97%, the content of the main substance of 74%.

15. Recrystallization of a technical product, filtering the precipitate, drying. Obtain the target product with TPL 88-89°C.

16. Packaging product in a plastic container.

The disadvantages of the prototype method:

1. For elimination of hydrogen chloride used lye NaOH - matter relating to the 2nd class of hazard, i.e. high-risk substances. Maximum permissible concentration of NaOH in the air of working zone is 0.5 mg/m3[Harmful substances in industry, V. 3, ed. 7th, Izd-vo “Chemistry”, 1977, str].

In accordance with GOST 12.1.007 clause 2.2. in the development of technology chemical processes measures to ensure safety when in contact with hazardous substances must provide for the replacement of harmful substances in the production of less harmful.

2. A byproduct of the reaction is sodium chloride, related to N hazard class. For the separation of sodium chloride tekhnicheskiy product melted in hot water, precipitated after cooling the product is filtered, the operation is repeated twice. On receipt of 0.5 mol of a technical product with a basic substance content of 74%, it is necessary to 30.5 mol of water.

3. This method is effective when using 1.1.1-trichloro-2.2-bis(4-chlorophenyl)ethane with TPL to 108.5-109°i.e. pre recrystallized.

The purpose of the invention is a new method that extends the range of known ways to obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene, allowing to improve the environmental safety of the process, to simplify the overall process and improve the quality of the target product.

This goal is achieved by a new, more environmentally friendly way to obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene, namely, that the elimination of hydrogen chloride from 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane provide solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide containing not more than 30 wt.% NaOH, at a molar ratio of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane and calcium hydroxide equal to 1:(1,5-1,75), in the presence of catalysts heterophase reactions, taken in an amount of 0.0005-0,005 mol at a temperature of 100-120°C.

For the implementation of the proposed method use the following materials:

technical 1,1,1-t is ALOR-2,2-bis(4-chlorophenyl)ethane in THE 113-04-94-83 with TPL 82-104°C;

- solid NaOH according to GOST 4328-77;

- solid CA(Oh)2according to GOST 9262-77;

- catalysts: benzyltrialkylammonium halides, preferably benzyltriethylammonium chloride on THE 6-09-05-542-76 or designed bromide on THE 6-09-37-1144-91, tetraalkylammonium halides, preferably tetrabutylammonium bromide on THE 6-09-1859-77.

The process of obtaining 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene when using calcium hydroxide or a mixture of calcium hydroxide and sodium hydroxide consists of the following main stages:

1. To download components: 0.5 mol 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane,

0.75 mol of CA(Oh)2or a mixture of Ca(OH)2and NaOH,

0,0005-0,005 mol of catalyst.

2. Heating the reaction mass to 100-120°C.

3. The exposure at 100-120°C for 30-40 minutes

4. Cooling the reaction mass to 70°C.

5. Dilution of the reaction mixture with water (15 mol).

6. Neutralization with diluted hydrochloric acid.

7. The filtering.

8. Wash the precipitate on the filter with water (2.5 mol).

9. Drying and obtaining the target product with a basic substance content of 82%.

10. Packaging product in a plastic container.

A distinctive feature of the proposed solutions is to use as eliminating agent solid calcium hydroxide or a mixture of solid hydroxide to Lycia and sodium hydroxide, carrying out the reaction at a temperature of 100-120°C. Replacement of high-risk reagent NaOH at low-risk of CA(Oh)2allows you to:

- to increase the safety of the process, as evidenced by the following data: TLV NaOH in the air of working zone of 0.5 mg/m3II hazard class. MPC Ca(OH)2in the air of working zone 2000 mg/m - IV class of danger [statement by the Ministry of energy and Ministry of natural resources January 25, 10 August 1996, GOST 12.1.007. Harmful substances. Classification and General safety requirements];

- to use for the process of technical 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane;

to simplify the process and improve the quality of the technical product, i.e. to increase the content of the basic substance from 74% in the method prototype to 82%.

A side product of the reaction according to the method prototype is sodium chloride. A side product of the reaction according to the claimed method is calcium chloride. The solubility of NaCl in 100 g of water at 20°makes 35.7, solubility CaCl2in 100 g of water at 20°With 74 g, which is more than 2 times higher than the solubility of sodium chloride. Calcium chloride is easier to remove from the reaction product, thereby reducing the number of main stages of the process, the time of the meeting, the quantity of water used, thereby reducing the volume of wastewater and improving their environmental safety. According to the order of Mi is intersta natural resources from 15.06.2001, No. 511 approval of the Criteria for classification as hazardous waste by hazard class for the environment” entered 5 hazard classes. Calculations were performed according to the method described in the above order, the waste water by the method prototype, containing sodium chloride, refer to hazard class IV waste water by the present method, containing calcium chloride, belong to V hazard class.

The optimal amount of calcium hydroxide is 1,5-1,75 mol per 1 mol of the original 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane. When using CA(Oh)2in the amount of less than 1.5 mol yield and degree of purity of the target 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene worse.

The use of CA(Oh)2in the amount of over 1.75 mol economically unfeasible because not increase output, increase purity, the simplification of the process.

The content of sodium hydroxide in a mixture of solid calcium hydroxide and solid sodium hydroxide should be no more than 30%. When the content of NaOH in the above-mentioned mixture of more than 30% elimination process leads to the production of the target product with a high content of sodium chloride.

As catalysts use benzyltrialkylammonium halides, preferably benzyltriethylammonium chloride, or tetraalkylammonium halides, site is preferably tetrabutylammonium bromide, in the amount of 0.0005-0,005 mol per 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane.

Example 1. Obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene in the prototype method.

A mixture of 0.5 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 0.75 mol of NaOH, of 0.0005 mol benzyltriethylammonium chloride is heated under stirring for 40-60 min and a temperature of 90-100°C. Then the reaction mixture was neutralized with an aqueous solution of hydrochloric acid. The precipitate is filtered off and dried. Yield 97%. Get a technical product with a basic substance content of 74%. After 2-fold processing technical product with hot water (70-80°), filtering the washed product, and drying and subsequent recrystallization TPL 88-89°C. T. plot. 88-89°C.

Example 2. Obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene by the present method.

To 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane was added 1.5 mol CA(Oh)2and 0.0005 mol of benzyltriethylammonium chloride. The mixture is heated to 100-120°C and maintained at this temperature for 30-40 minutes and Then the mixture is cooled to 70-80°add 10 mol H2O, neutralized with diluted (1:1) hydrochloric acid. The precipitate is filtered, washed with water (5 mol)and dried. Yield 98%. The content of the basic substance in the technical product is 82%, TPL recrystallized product 88-89°C.

Example 3. Analogously to example 2 after conducting the Oia reaction at a temperature of 120° To obtain the target product with a yield of 98% and a content of the basic substance 82%. TPL recrystallized product 88-89°C.

Example 4. Analogously to example 2 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, a 1.75 mol CA(Oh)2and 0.0005 mol of tetrabutylammonium bromide, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 97%. The basic substance content of 82%. TPL (recrystallized) 88-89°C.

Example 5. Analogously to example 2 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1 mol CA(Oh)2 and 0.0005 mol of the designed bromide, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 94%. The basic substance content of 78%. TPL (recrystallized) 88-89°C.

Example 6. Analogously to example 3 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 2 mol of solid CA(Oh)2and 0.0005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 97%. The basic substance content of 82%. TPL (precrystallization) 88-89°C.

Example 7. Analogously to example 3 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol of solid CA(Oh)2and 0.0005 mol of tetrabutylammonium bromide, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 96%. The content of the main substance of 81%. TPL (Perekrest Lisovenko) 88-89° C.

Example 8. Analogously to example 2 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol solid mixture of CA(Oh)2and NaOH (70:30 wt.%) and 0.0005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 96%. The basic substance content of 82%. TPL (recrystallized) 88-89°C.

Example 9. Analogously to example 3 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol solid mixture of CA(Oh)2and NaOH (70:30 wt.%) and 0.0005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 96%. The basic substance content of 82%. MP (recrystallized) 88-89°C.

Example 10. Analogously to example 2 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol solid mixture of CA(Oh)2and NaOH (60:40 wt.%) and 0.0005 mol of tetrabutylammonium bromide, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 94%. The basic substance content of 78%. MP (recrystallized) 88-89°C.

Example 11. Analogously to example 3 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol solid mixture of CA(Oh)2and NaOH (60:40 wt.%) and 0.0005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 94%. The basic substance content of 78%. TPL (recrystallized) 8-89° C.

Example 12. Analogously to example 2 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, a 1.75 mol CA(Oh)2and 0.005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 97%. The basic substance content of 82%. TPL (recrystallized) 88-89°C.

Example 13. Analogously to example 3 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol of solid CA(Oh)2and 0.005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 96%. The content of the main substance of 81%. TPL (precrystallization) 88-89°C.

Example 14. Analogously to example 2 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol solid mixture of CA(Oh)2and NaOH (70:30 wt.%) and 0.005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 96%. The basic substance content of 82%. TPL (recrystallized) 88-89°C.

Example 15. Analogously to example 3 from a mixture containing 1 mol of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,5 mol solid mixture of CA(Oh)2and NaOH (70:30 wt.%) and 0.005 mol of benzyltriethylammonium chloride, receive technical 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene yield of 96%.

The basic substance content of 82%. TPL (recrystallized) 88-89°C.

Thus, carried away the above examples demonstrate the effectiveness of the proposed method obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene.

Because the inventive method previously not described in literature, it meets the criterion of novelty. The use of solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide containing the latter in the mixture is not more than 30% in the claimed conditions resulted in non-obvious result of increasing the effectiveness of the proposed method, the improvement of environmental safety of the process, enhance the content of the basic substance in the technical product, i.e. improve its quality.

The proposed method meets the requirements of inventive step, because they are based on known for the connection of the reaction, the terms of which were not known earlier.

Industrial applicability. The inventive method can be used, on the one hand, as a cheap and affordable way of disposing of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane with expired and, on the other hand, in the chemical industry for more monomers of polymer products to a wider consumer destination.

The release of three pilot batches scheduled for the I quarter of 2004 in the experimental production of IOPC them. A.Ye.Arbuzov KSC RAS, which possesses the necessary facilities, equipment, instrument Park and specialists.

1. The way to obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene by processing 1,11-trichloro-2,2-bis(4-chlorophenyl)ethane alkali when heated in the presence of a catalyst at a molar ratio of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane and alkali 1:1,5-1,75, characterized in that the alkalis are used as solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide containing sodium hydroxide in a mixture of not more than 30%.

2. The method according to claim 1, characterized in that the catalysts used benzyltrialkylammonium halides, preferably benzyltriethylammonium chloride or designed bromide, tetraalkylammonium halides, preferably tetrabutylammonium bromide, taken in an amount of 0.005-of 0.0005 mol.



 

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