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 [4] dioxane [5] carboxylic acid esters of ethylene glycol [6] as well as mixtures of alcohols with galogenovodorodov [7] or esters [8]

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 [9] 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

 

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