The method of producing diepoxides conjugated aliphatic dienes

 

(57) Abstract:

The invention relates to the field of reception of diepoxides conjugated aliphatic dienes, which are used as raw materials for epoxy resins, rubbers, adhesives, stabilizers, blowing agents, surface-active substances are used in biotechnology, the leather industry. The purpose of the invention is to increase the output of diepoxides conjugated aliphatic dienes, reducing the reaction time. To address this problem, the oxidation of unsaturated monoepoxides encouraged to not nagkakamali, and aliphatic hydroperoxides. The latter are introduced into the reaction mixture in the environment of a non-polar solvent with a speed of 0.8-2.0 mol SE/H. the Reaction proceeds when the calculated molar ratio of unsaturated monoepoxide : hydroperoxide 1: (1-2) at 110-140oIn the presence of soluble hydrocarbons molybdenum catalyst in the amount of 1-10103mol Mo/DM3and nitrogen and/or oxygen-containing compounds as polymerization inhibitor in the amount of 0.5-510-3mol/DM3. table 1.

The invention relates to an improved process for the preparation of diepoxides paired aliphatic resins, rubbers, adhesives, stabilizers, blowing agents, surface-active substances are used in biotechnology, the leather industry.

A method of obtaining these diepoxides from the corresponding Gilardino. The process consists of two stages. In the first stage receive dichlorvos interaction of the corresponding dienes with chlorine water. However, because of the formation of polyvinyl chloride, the output does not exceed 50%. Good output were obtained by gradual addition of concentrated hypochlorous acid cooled and vigorously stirred mixture consisting of a liquid diene, water and excess carbon dioxide [Brooks B. T. , Burd S. E. , Kurtz, S. C. , Sperling L. Chemistry of petroleum hydrocarbons. - M. : Costoptimized, 1959. - so 3 - S. 371. ] . In the second stage obtained dichlorvos subjected to dehydrochlorination aqueous alkali at 30-60oS, followed by extraction diepoxide CH2Cl2. Diepoxide allocate fractionation with yields of 80% [patent Poland 93504, class C 07 D 301/26, 1975 Rehim 23 N 23 N, 1978] . The total yield of the target product in the above method does not exceed 40%. A significant drawback is the large amount of waste and wastewater.

The closest to p is monoepoxides nagkakamali. The process is carried out in organic solvents (ether, chloroform) at 0-20oAnd duration of the reaction up to 17 days. As the oxidant used peracetic, natantia and other nagkalat [Pancewicz-Carol C. I. Oxidation Arkadievich hydrocarbons asymmetric structure with hydropredict acetyl //GOH - 1956. So 26. - vol. 8. - S. 2161-2170; Pudovik L. I. , Ivanov B. E. Oxidation of butadiene, isoprene, piperylene hydropredict acetyl //Joh. - 1956. - so 26. - Vol. 10. - S. 2771-2775] . The disadvantage of this method is the low output diepoxide (12 - 25%), a large number of by-products, a long reaction time.

The purpose of the invention is to increase the output of diepoxides conjugated aliphatic dienes, reducing the reaction time.

This goal is achieved by the fact that in contrast to the known method as oxidizing agent for the epoxidation of unsaturated monoepoxides use aliphatic hydroperoxides, which are introduced gradually into the reaction environment in a non-polar solvent with a speed of 0.8-2.0 mol SE/h, while the calculated molar ratio of unsaturated monoepoxide : hydroperoxide - 1: (1-2).

Epoxidation proceeds at 110-140oSince, in the presence of restvg">

To reduce the proportion of the polymerization reaction of unsaturated epoxides in the reaction mixture is added to the polymerization inhibitors in the amount of 0.5-510-3mol/DM3, which used nitrogen-containing and/or oxygen-containing compounds containing secondary and tertiary amino groups and/or hydroxy-group.

The claimed technical solution meets the criterion of novelty. In the literature no known example of an exhaustive epoxidation of conjugated dienes [Tolstikov, A. Reaction hydropeaking oxidation. - M. : Nauka, 1976. - C. 42] . The mention of getting diocese butadiene present in the patent [U.S. patent 3634464, CL 260-348.54 (0l D l (08)). 1969, Rehim 20 N 34 N, 1972] , is not supported by the experimental example and, apparently, is advertising. The difficulty of the implementation process due to the low reactivity of conjugated unsaturated epoxides and high activity of the resulting conjugate diepoxides in polymerization reactions. Replacing nagkalat on thermally stable aliphatic hydroperoxide allows to increase the output diepoxides from 25 to 50-78%. Receiving incremental input of hydroperoxide in the reaction medium allows to increase the output diepoxide C the popular the ratio of the unsaturated hydroperoxide monoepoxide does not exceed 1: 2. Increasing the reaction temperature, the introduction of the catalyst reduces the reaction time from 17 days to 4-6 hours New in this solution is the use of the polymerization inhibitor that increases output diepoxides.

The invention is illustrated by the following examples:

Example 1 (prototype). To 400 cm3Zabolotnogo solution adventurou acid in chloroform (adventurou acid 59.3 g, 0.43 mol) was added gradually and 49.2 cm3solution of 1,2-epoxy-3-butene (1,2-epoxy-3-butene is 27.1 g of 0.39 mol). The mixture was kept in refrigerator at 0-5oWith over 14 days. The mixture is then neutralized with an aqueous solution of soda, washed with water, dried and subjected to fractionation. Output 1,2,3,4-diepoxybutane equal to 15% of the downloaded 1,2-epoxy-3-butene, which is ~ 5,

Example 2. In a titanium autoclave load 140 g (2 mol) of 1,2-epoxy-3 - butene, 460 g (5 mol) of methylbenzol, 0.28 g (0,9810-3mol) of propilenglikolem molybdenite, 0,72 g (0,4810-3mol) tertbutyl-pyrocatechin (TBQ) and 180 g (2 mol) of tert-butylhydroperoxide (TBHP). The mixture was stirred at 110oC for 3 hours under these conditions, the conversion of tert-butylhydroperoxide is 92%, the yield of 1,2,3,4-diepoxybutane on prevremeni autoclave load 140 g (2 mol) of 1,2-epoxy-3-butene, 310 g (3,36 mol) of methylbenzol, 0.28 g (0,9810-3mol) of propilenglikolem molybdenite, 0,72 g (0,4810-3mol) of tert-butylpyrocatechol (TBQ). The mixture is heated with stirring to 110oWith and begin to dose 180 g (2 mol) of tert-butylhydroperoxide 150 g (1,63 mol) of methylbenzol with a speed of 0.8 - 1.0 mol SE/h After 4 h from the beginning of the reaction, the conversion of tert-butylhydroperoxide was 90%, and the yield of 1,2,3,4-diepoxybutane turned on hydroperoxide 80%, uploaded 1,2-epoxy-3-butene - 72,0%.

Example 4. Analogously to example 3 was charged to the reactor unsaturated epoxide, a catalyst, a polymerization inhibitor, a solvent. The mixture is heated with stirring to the reaction temperature and introduced gradually into the reaction zone a solution of the hydroperoxide. The table shows the conditions of the process and its main indicators.

The method of producing diepoxides conjugated aliphatic dienes by their oxidation of unsaturated monoepoxides, characterized in that as the oxidant used aliphatic hydro-peroxides in the environment of a non-polar solvent, which is gradually introduced into the reaction mixture with a speed of 0.8-2.0 mol SE/h with an estimated molar ratio of unsaturated monoepoxide: hydroperoxide as 1-1010-3mol Mo/DM3and nitrogen and/or oxygen-containing compounds as polymerization inhibitor in the amount of 0.5-510-3mol/DM3.

 

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