The method of obtaining 1,2,5,6,9,10-hexabromocyclododecane
(57) Abstract:Method for obtaining 1,2,5,6,9,10-hexabromocyclododecane by the synthesized cyclododecatriene bromine in aqueous trimethylamine at 0 - 60oC with subsequent treatment of the reaction mixture 5-10% ammonia water. Trimethylarsine easily regenerated from water-alcohol mixture. The only waste product is water runoff containing ammonium salts. 1 C.p. f-crystals. The invention relates to methods of synthesized unsaturated organic compounds, namely, the method of production of hexabromocyclododecane (GB CD), used as flame additives to plastics and fabrics (polystyrene, polypropylene, phenolic resins, and others).Known methods for producing GB CD when interacting 1,5,9-cyclododecatriene (CDT) with molecular bromine in various inert to the action of bromine solvents. Most often as solvents, synthesized using a lower aliphatic primary alcohols [1-3] hydrocarbons  dioxane  carboxylic acid esters of ethylene glycol  as well as mixtures of alcohols with galogenovodorodov  or esters 
The disadvantages of these methods include the need Trudie selection of the target product and the regeneration of solvents, the use of resistant to the action of bromine materials for equipment, and in some cases and low outputs GB SDD.The closest in technical essence to the proposed method is a method for GB CD bromirovanii CDT at 10-50oC alcohols, C3-C4, for example, isobutyl alcohol, containing 2-5% water  the Outputs of the product 90-98% the Disadvantage of this method is the use of primary alcohols, subjected to some degree of oxidation and interaction with bromine, which leads to excess bromine and the high toxicity of the waste solvent (tear). In addition, there are difficulties with the regeneration of the solvent.The purpose of the invention increase the safety of the process and simplify technology.The objective is achieved by the synthesized CDT at 0-60oC in solution resistant to the action of bromine trimethylarsine (TMK), containing 10-30% of water, followed by neutralization of the excess of bromine and hydrogen bromide in the reaction mixture at 5-10% ammonia water, a division of GB SDD and easy regeneration of the solvent. The molar ratio of bromine: CDT 3,1:1, number of TMK 6 g/1 g CST, the number of MMA.water 0.1 g/1 g CST (based on ammonia).TMK easily regenerated from water-alcohol mixture (azeotrope contains only 12% of water).The only waste product water runoff containing ammonium salts.Example 1. In a reactor equipped with a mechanical stirrer, a load of 30.6 g (191,4 mmole) of elemental bromine and 50 g TMK containing 30% of water, and cooled to 0oC. Then, with stirring, add 10 g cyclododecatriene 15,9 (61,7 mmole) in 10 g of TMK, keeping the temperature below 60oC. the Reaction mixture is stirred at a temperature of 10-50oC for 1 h and then gradually add 20 g of 5% aqueous ammonia and incubated for 15-20 min the precipitate GB SDD is separated, washed with 20 g of water and dried at a temperature of 60-75oC. will Receive a total of 38.4 g (97%) of product with a melting point 170-175oC.The filtrate is neutralized ammonia diluted sulphuric or hydrochloric acid and the mixture is distilled. Get up to 52 g TMK, containing a series of 12% water (return of experience 1).Get to 37.6 g of product (95) with Tpl.169-173oC.Example 3. Carried out analogously to example 1, but used to neutralize the reaction mixture, 10 g of 10% aqueous ammonia.Get to 38.8 g (98%) GB CD with Tpl.171-174oC.Literature
1. The application of Germany N 3013002, class C 07 C 17/02, publ.1980.2. U.S. patent N 4783563, class C 07 C 17/02, publ.1988.3. Application France N 2616429, class C 07 C 17/02, publ.1988.4. Auth. mon. Czechoslovakia N 197633, class C 07 C 17/02, publ.1982.5. Auth. mon. USSR N 1031104, class C 07 C 17/02, C 07 C 23/02,publ.1983.6. U.S. patent N 3652688, class C 07 C 17/02, publ.1972.7. The Japan patent N 50-5187, class C 07 C 23/02, publ.1975.8. The Japan patent N 49-24475, class C 07 C 23/02, publ.1974.9. U.S. patent N 5043492, CL 17/02, publ.1991 (prototype). 1. The method of obtaining 1,2,5,6,9,10-hexabromocyclododecane bromirovanii cyclodextrin-1,5,9 elemental bromine at 0 60oWith in aqueous lower aliphatic alcohol as solvent, followed by neutralization of the resulting reaction mixture, wherein the solvent used trimethylarsine containing 10-30 wt. water.2. The method according to p. 1, characterized in that the neutralization of the reaction is
FIELD: industrial organic synthesis.
SUBSTANCE: invention is dealing with production of chlorohydrocarbons exhibiting plasticizing properties in polymer compositions in production of synthetic building materials, varnishes and paints, artificial films and leathers, in rubber industry, and as fire-retardant additives in polymers. Process comprises chlorination of waste obtained in production of C14-C32 fraction by ethylene-α-olefin oligomerization. Chlorination is accomplished in two steps: addition chlorination at 35-55°C followed by substitution chlorination at 40-105°C. Chlorohydrocarbons thus obtained can, in particular, be used as secondary plasticizer in polyvinylchloride compositions.
EFFECT: reduced expenses due to using production waste.
4 tbl, 30 ex
FIELD: petrochemical and industrial organic synthesis.
SUBSTANCE: process comprises separating gaseous pyrolysis products to recover ethylene-containing fraction with 54-65% ethylene content and C3-C5-hydrocarbon fraction. Ethylene-containing fraction is subjected to liquid-phase catalytic chlorination. Gas phase of chlorination product is purified via adsorption and fed into furnace as fuel. C3-C5-Hydrocarbon fraction is subjected to exhaustive hydrogenation, hydrogenation product is combined with fresh raw material at weight ratio (0.05ч1):1 and sent to pyrolysis plant.
EFFECT: achieved integration of process, increased reliability thereof, and reduced expenses.
1 dwg, 1 tbl, 15 ex
FIELD: organic chemistry.
SUBSTANCE: 1,2-dichloroethane is obtained by liquid phase ethylene chlorination with discharging of reaction heat due to operation medium boiling. In claimed process nitrogen is added to chlorine and ethylene reagents. Ratio of chlorine volume consumption to nitrogen volume consumption is maintained as 1:1. Reaction is carried out at temperature lower than 1,2-dichloroethane boiling point, and discharging of reaction heat is carried out by evaporative cooling of operation medium in nitrogen.
EFFECT: process of increased selectivity; decreased yield of by-products.
1 tbl, 5 dwg
FIELD: chemical industry; designs of the bubble-type reactors for production of 1.2-dichloroethane.
SUBSTANCE: the invention is pertaining to the design of the bubble-type reactors for production of 1.2-dichloroethane by the method of the liquid-phase chlorination of ethylene with the reaction heat removal at boiling of the working medium. As the contact device the reactor uses two layers of the metallic nozzle. The liquid 1.2-dichloroethane is fed from above to the nozzle, into the space between the layers of the nozzle feed the gaseous chlorine with nitrogen, and under the lower layer of the nozzle feed the gaseous ethylene with nitrogen, that allows to reduce the diameter of the reactor in 1.5-2 times due to the increased effectiveness of stirring and formation of the developed contact surface of the phases. At that the heat of the reaction is removed by evaporation of 1.2-dichloroethane in nitrogen. At that the temperature of the liquid is maintained below the boiling temperature. The technical result of the invention is the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
EFFECT: the invention ensures the increased selectivity of the process, reduction of the outlet of the by-products (the highest ethane chlorides) and the decreased overall dimensions of the reactor.
1 ex, 4 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. The process is carried out by direct feeding gaseous reagents chlorine and ethylene in liquid reaction medium of reactor. Before feeding into reactor chlorine and ethylene are heated preliminary in heat-exchangers to temperature equal to that of liquid in reactor. Method provides enhancing selectivity of process and reducing formation of by-side substances representing higher chlorine-derivatives of ethane.
EFFECT: improved method of synthesis.
4 dwg, 1 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,2-dichloroethane by method of liquid-phase chlorination of ethylene. Method involves maintaining the optimal ratio of heat eliminated based on evaporation and heat eliminated based on cooling a liquid medium in a heat exchanger in the process. One-sixth part of heat formed in reactor is eliminated based on evaporation of synthesized compound in boiling and 5/6 part of formed heat is eliminated based on circulation of liquid working medium in external heat exchanger. The temperature gradient in the reaction zone is maintained equal 52°C. Invention provides enhancing selectivity of process and reducing amount of by-side products of reaction (higher chlorine-derivate of ethane).
EFFECT: improved method of synthesis.
3 dwg, 1 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to a process of liquid-phase chlorination of ethylene wherein reaction heat is removed by means of vaporization of reaction medium. Process is conducted at vacuum-mediated reduction of reaction medium boiling temperature below 60°C, vacuum being developed because of condensation of vapors formed in external condenser accompanied by removal of non-condensed gases by vacuum pump.
EFFECT: enhanced selectivity of process and decreased yield of by-products (higher chlorine derivatives of ethane).
FIELD: chemical industry.
SUBSTANCE: vacuum reactor comprises tower (1), distributors of chlorine (2) and ethylene (3), circulation pipe (5), perforated plates (6), condenser (7), pump (8), vacuum-pump (9), and hydraulic valve (10).
EFFECT: improved quality of the product.
FIELD: chemical industry; apparatuses for production of the chlorinated allyl.
SUBSTANCE: the invention presents the reactor for production of the chlorinated allyl intended for realization of the method of production of the chlorinated allyl by the direct gaseous phase chlorination of the propylene. The reactor includes the closed circuit of circulation of the reaction gases, the devices of injection of the source propylene and chlorine, the device of the forced circulation of the part of the reaction gases and the device of withdrawal of the other part of the reaction gases. At that the closed circuit of the reaction gases circulation forms the jet pump, which includes in series connected the reception chamber, the mixing chamber and the diffuser, and the pipe of the circulation circuit connecting the outlet of the diffuser with the appropriate inlet of the reception chamber of the injector and acting as the main reaction zone of the ideal displacement with the presence time of 0.7-0.9 s, in which the scatter of the temperatures does not exceed ±10°С. The reception chamber contains the nozzles used as the devices for injection of the source propylene and chlorine. The jet pump ensures fulfillment of the concerted functions: introduction of the streams of the source propylene and chlorine, which are the working injecting streams; the forced circulation pump with the repetition factor of 5-10 of the reaction gases stream, which is the injected stream; the high-velocity mixer and the preheater of the source reactants in the mixing chamber due to the strong turbulence during (0.01-0.04)s, which is formed by the combination of the nozzles of the injected gases at the arrangement of the nozzle/ nozzles of the chlorine coaxially to the main nozzle of the propylene arranged on the shaft of the mixing chamber. The technical result of the invention is, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.
EFFECT: the invention provides, that the presented design of the reactor allows to increase the selectivity of the process of production of the chlorinated allyl.
1 ex, 1 dwg
SUBSTANCE: invention relates to method of producing high purity 1,2-dichloroethane from dissolved chlorine and dissolved ethylene which are brought into contact with each other while using a liquid reaction medium excited for circulation, where the said medium essentially consists of 1,2-dichloroethane and a catalyst and at least passes through a vertical reaction zone which forms a loop, where both knees of the loop are joined by a gas separator lying above, from which the reaction product is tapped in gaseous and/or liquid form, characterised by that: at least 3 supply sections are located in the knee of the loop along which the liquid flows upwards; and each of these supply sections consists of a unit for supplying dissolved or gaseous ethylene located at the inlet of the section, and a unit for supplying dissolved chlorine located at the output of the section, and can also have static mixing devices. The invention also relates to a device for implementing the said method.
EFFECT: method is more cost-effective, enables increase of power without increasing outside dimensions of the reactor and simultaneous production of high purity dichloroethane.
3 cl, 1 dwg
FIELD: organic chemistry.
SUBSTANCE: claimed method includes reaction between corresponding hydrocarbons with tetra bromomethane at 150-180°C in liquid phase in presence of copper chloride or copper bromide complex with nitrogen-containing substance, wherein as nitrogen-containing substance amine of general formula Ph-CH(OH)-Q-NHR' is used. In formula: Q is group -CH(CH3)- or -(CH2)n, wherein n = 1-3; R' is lower alkyl.
EFFECT: increased catalyst productivity, simplified process of decreased cost.
12 ex, 1 tbl