JP2012131732A - Method for producing dichloroepoxybutane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing dichloroepoxybutane which is a compound capable of imparting functions such as flame retardancy, gas barrier properties and abrasion resistance to a raw material for a polyol which is an intermediate raw material for a resin component used in a coating, adhesive, foam and the like, or to a resin, and of imparting adhesiveness and the like to a plastic base material, by reaction of dichlorobutene with hydrogen peroxide to epoxidize the same, and efficiently recovering dichloroepoxybutane from the reaction solution.SOLUTION: In producing dichloroepoxybutane by reacting dichlorobutene with hydrogen peroxide in the presence of a transition metal compound containing tungsten and/or molybdenum and an organic ammonium salt, the reaction solution after finishing the reaction is washed with one selected from the group consisting of sodium thiosulfate, sodium sulfite, alkaline compounds, aqueous sodium thiosulfate solutions, aqueous sodium sulfite solutions, and aqueous solutions of the alkaline compounds, subsequently the organic phase is separated and subjected to distillation and purification to recover dichloroepoxybutane by fractional distillation at ≤90°C boiling point.

Description

  The present invention relates to a method for producing dichloroepoxybutane, and more specifically, a flame retardant, gas barrier property to a polyol raw material or resin which is an intermediate raw material of a resin component used in paints, adhesives, foams and the like. Dichloroepoxybutane, a compound capable of imparting functions such as abrasion resistance and adhesion to plastic substrates, by epoxidation by the reaction of dichlorobutene and hydrogen peroxide, and efficiently dichloroepoxybutane from the reaction solution It is related with the method of collect | recovering.

  Numerous documents have been known so far regarding the process for producing dichloroepoxybutane. As a method of dehydrochlorination of 1,2,4-trichlorobutan-3-ol with an alkali compound, generally called a chlorohydrin method, 1,4-dichloro-2,3-epoxybutane and 1,2-dichloro-3, A method of synthesizing a mixture of 4-epoxybutane (see, for example, Patent Document 1), oxidizing an olefin moiety of 3,4-dichloro-1-butene with peracetic acid or performic acid, which is an organic peroxide, 3, A method for producing 4-dichloro-1,2-epoxybutane (see, for example, Non-Patent Document 1), and further, an epoxidation reaction of an olefin moiety of 3,4-dichloro-1-butene is realized in a high yield. As a method, a method for synthesizing 3,4-dichloro-1,2-epoxybutane using metachloroperbenzoic acid under mild conditions near room temperature (for example, non-patented Document 2 reference.), And the like have been proposed.

  As another method for synthesizing dichloroepoxybutane, liquid chlorine is added to 3,4-epoxy-1-butene at −30 ° C. to produce 3,4-dichloro-1,2-epoxybutane (for example, Non-Patent Document 3), 3,4-epoxy-1-butene and a halogen molecule are reacted in the presence of a tertiary amine or a halogenated salt of a primary, secondary or tertiary amine. A method (for example, see Patent Document 2) consisting of the above has been proposed.

  On the other hand, in recent years, a method for producing an epoxy compound by a catalyst using hydrogen peroxide and a tungsten compound, which is inexpensive and easy to handle, has attracted attention. For example, an organic phase containing a quaternary ammonium salt, a tungsten compound, and phosphoric acids. An epoxidation method in which hydrogen peroxide is added to a two-phase system solution containing an aqueous phase (see, for example, Patent Document 3), α-aminomethylphosphonic acid, a phase transfer catalyst, and tungstic acids in the presence of olefins and peroxidation A method of reacting hydrogen (for example, see Non-Patent Document 4), and the like have been proposed.

Hawkins, J .; Chem. Soc. , 248 (1959) D. F. Taber et al. Org. Chem. 67, 3847 (2002) Movsumzade et al., Chem. Abstr. 82: 86251k (1975) Kazuhiko Sato et al., Catalyst, Vol. 46, no. 5,328 pages (2004)

British Patent No. 864880 (see claims) Japanese translation of PCT publication No. 08-508494 (refer to claims) JP 2004-115455 A (refer to claims)

  However, the method proposed in Patent Document 1 cannot produce a structural isomer of dichloroepoxybutane at an arbitrary ratio, and has a problem in productivity. Further, the reaction with performic acid proposed in Non-Patent Document 1 has a problem that the yield of the reaction is as low as 35%, and a large amount of glycols and glycol esters are produced as by-products. Furthermore, in the method proposed in Non-Patent Document 2, high selectivity and yield can be realized, but a very expensive metachloroperbenzoic acid as an oxidizing agent is at least equimolar or more with respect to dichlorobutene. As a result, a large amount of metachlorobenzoic acid containing unreacted peroxide is discharged as waste. Furthermore, the reaction time was as long as 72 hours, and there was a problem that it was not an industrially effective production method.

  The method proposed in Non-Patent Document 3 has a problem that its practicality is low as a method for producing 3,4-dichloro-1,2-epoxybutane on an industrial scale in terms of raw material procurement. In the method proposed in Patent Document 2, it is necessary to carry out the reaction under low temperature conditions, and there is a problem in practicality as a manufacturing method on an industrial scale.

  In addition, the method proposed in Patent Document 3 requires a complicated process such as separation from an epoxy compound to be produced, such as using an excessive amount of an aromatic hydrocarbon solvent such as toluene or xylene with respect to the substrate. The method proposed in Non-Patent Document 4 uses aminomethylphosphonic acid which is expensive, hygroscopic and requires careful handling, and is not necessarily satisfactory industrially. In either case, sufficient catalytic activity is often not obtained depending on the substrate to be oxidized, and it is necessary to examine the conditions.

  And, until now, there has been no report on an epoxidation method of olefins such as dichlorobutenes containing a chlorine group which is an electron-withdrawing group in a method of producing an epoxy compound using a tungsten compound and hydrogen peroxide. is the current situation. Also, compounds that are difficult to solidify at a high boiling point, such as dichlorobutenes, are difficult to separate from the catalyst remaining in the reaction solution, and it is very difficult to efficiently recover the epoxy compound obtained by the reaction. .

  Therefore, the production of dichloroepoxybutane, which is a compound capable of imparting a function to the polyol raw material or resin, which is an intermediate raw material for the resin component, and recovery from the reaction solution can be carried out efficiently and inexpensively at an industrial level. There was a need to provide a method.

  As a result of intensive studies on the above problems, the present inventors have conducted a reaction solution after performing dichlorobutene and hydrogen peroxide in the presence of a transition metal compound having tungsten and / or molybdenum and an organic ammonium salt. The inventors have found that dichloroepoxybutane can be efficiently produced by washing under specific conditions and recovering dichloroepoxybutane from the organic phase under specific conditions, and the present invention has been completed.

  That is, in the present invention, when producing dichloroepoxybutane by the reaction of dichlorobutene and hydrogen peroxide in the presence of a transition metal compound having tungsten and / or molybdenum and an organic ammonium salt, the reaction solution after the reaction is treated with thiosulfuric acid. Boiling temperature when separating the organic phase and fractionating the organic phase after washing with one selected from the group consisting of sodium, sodium sulfite, alkaline compound, sodium thiosulfate aqueous solution, sodium sulfite aqueous solution and alkaline compound aqueous solution The present invention relates to a method for producing dichloroepoxybutane, which comprises distillation purification at 90 ° C. or less to recover dichloroepoxybutane.

  The present invention is described in detail below.

  In the method for producing dichloroepoxybutane of the present invention, when epoxidation is performed by the reaction of dichlorobutene and hydrogen peroxide, the reaction is performed in the presence of a transition metal compound having tungsten and / or molybdenum and an organic ammonium salt, The reaction solution after the reaction is washed with one selected from the group consisting of sodium thiosulfate, sodium sulfite, alkaline compound, aqueous sodium thiosulfate solution, aqueous sodium sulfite solution, and aqueous alkaline compound solution, and then the organic phase is separated and the organic Distillation purification is performed at a boiling point temperature of 90 ° C. or lower when fractionating the phase, and dichloroepoxybutane is recovered.

  The transition metal compound having tungsten and / or molybdenum in the present invention is a transition metal compound that acts as a catalyst in the epoxidation reaction, and the transition metal compound is not limited as long as it belongs to these categories. For example, mononuclear metal oxides, isopolyacids, heteropolyacids, and the like. More specifically, tungstic acid, lithium tungstate, sodium tungstate, tungstic acid Tungstic acid such as potassium and ammonium tungstate or a salt thereof; molybdic acid such as molybdic acid, lithium molybdate, sodium molybdate, potassium molybdate, ammonium molybdate or the like; phosphorus-12-tungstic acid, phosphorus-12 Tongs Sodium phosphate, ammonium phosphate-12-tungstate, potassium phosphate-12-tungstate, silicotungstic acid, sodium silicotungstate, phosphovanadotungstic acid, phosphorus-3-molybdo-9-tungstic acid, phosphorus-6-molybdo -6-tungstic acid, phosphorous-9-molybdo-3-tungstic acid, phosphorus-12-molybdic acid and the like, and / or heteropolyacids containing molybdenum, or salts thereof, etc. Can also be used in combination. And since it becomes possible to manufacture dichloro epoxy butane especially efficiently, tungstic acid, sodium tungstate, ammonium tungstate, phosphorus-12-tungstic acid, phosphorus-3-molybdo-9-tungstic acid is preferable.

  The amount of the transition metal compound used in the present invention is not subject to any limitation as long as dichloroepoxybutane can be produced, and among them, the production method is particularly excellent in production efficiency of dichloroepoxybutane. The molar ratio of tungsten atom and / or molybdenum atom in the transition metal compound to 1 mol of dichlorobutene is preferably 0.0001 to 1 times mol, particularly 0.001 to 0.1 times mol. In addition, since the recovery step of the transition metal compound can be omitted, the amount is preferably 0.002 to 0.05 times mol.

  The organic ammonium salt in the present invention improves the solubility of the transition metal compound acting as a catalyst during the epoxidation reaction in the organic phase, and the organic ammonium salt is generally known as an organic ammonium salt. Any of these can be used as long as they belong to the category, and among them, an organometallic ammonium salt having 9 to 50 carbon atoms because it is particularly easily available and has an excellent effect of improving the solubility of the transition metal compound. In particular, an organic ammonium salt having 16 to 44 carbon atoms is preferable. Specific examples of the organic ammonium salt include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, benzyltributylammonium chloride, phenyltrimethylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, and trioctylmethyl chloride. Tetraalkyl such as ammonium, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium chloride, dicetyldimethylammonium chloride, cetyltrimethylammonium chloride, tricaprylmethylammonium chloride Ammonium chloride; dodecylpyridinium chloride Alkylpyridinium chloride such as cetylpyridinium chloride; benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, benzyltributylammonium bromide, phenyltrimethylammonium bromide, tetrahexylammonium bromide, tetrabromide bromide Octyl ammonium, trioctyl methyl ammonium bromide, trioctyl ethyl ammonium bromide, dilauryl dimethyl ammonium bromide, lauryl trimethyl ammonium bromide, distearyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, dicetyl dimethyl ammonium bromide, Tetraalkylammonium bromides such as cetyltrimethylammonium bromide and tricaprylmethylammonium bromide; Alkylpyridinium bromides such as decylpyridinium and cetylpyridinium bromide; benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltributylammonium iodide, benzyltributylammonium iodide, phenyltrimethylammonium iodide, tetrahexylammonium iodide, iodine Tetraoctylammonium iodide, trioctylmethylammonium iodide, trioctylethylammonium iodide, dilauryldimethylammonium iodide, lauryltrimethylammonium iodide, distearyldimethylammonium iodide, stearyltrimethylammonium iodide, dicetyldimethyl iodide Ammonium, cetyltrimethylammonium iodide, tricaprylmethyl ammonium iodide Tetraalkylammonium iodides such as nium; alkylpyridinium iodides such as dodecylpyridinium iodide and cetylpyridinium iodide; benzyltriethylammonium hydrogen sulfate, benzyltriethylammonium hydrogensulfate, benzyltributylammonium hydrogensulfate, benzyltributylammonium hydrogensulfate, sulfuric acid Phenyltrimethylammonium hydrogen, tetrahexylammonium hydrogensulfate, tetraoctylammonium hydrogensulfate, trioctylmethylammonium hydrogensulfate, trioctylethylammonium hydrogensulfate, dilauryldimethylammonium hydrogensulfate, lauryltrimethylammonium hydrogensulfate, distearyldimethylammonium hydrogensulfate , Stearyltrimethylammonium hydrogen sulfate, dicetyl dihydrogen sulfate Examples include tetraalkylammonium salts such as tilammonium, cetyltrimethylammonium hydrogensulfate, tricaprylmethylammonium hydrogensulfate; alkylpyridinium salts such as dodecylpyridinium hydrogensulfate and cetylpyridinium hydrogensulfate; and organic compounds of the above specific examples. Among the ammonium salts, organic ammonium salts prepared from naturally-derived raw materials may be used which have a partial unsaturated bond or carbon number distribution in the alkyl group. Moreover, you may use this organic ammonium salt individually or in mixture of 2 or more types. Among them, the production method of dichloroepoxybutane is particularly excellent in production efficiency, so trioctylmethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, tetraoctylammonium hydrogensulfate, chloride Preferred are dodecylpyridinium and cetylpyridinium chloride.

  The amount of the organic ammonium salt used in the present invention is not limited as long as dichloroepoxybutane can be produced. Among them, the production method is particularly excellent in production efficiency of dichloroepoxybutane. It is preferably in the range of 0.1 to 5 moles per mole of tungsten and / or molybdenum atoms in the transition metal compound. In particular, when the organic ammonium salt is an alkylpyridinium salt, it is more preferably in the range of 0.1 to 1.5 times mol, and when it is a tetraalkylammonium salt, 0.25 to 1.5 times mol. More preferably, it is the range. The organic ammonium salt may be diluted with water, alcohol, propylene glycol or the like for easy handling.

  The dichlorobutene in the present invention can be used without any limitation as long as it belongs to a category generally referred to as dichlorobutene. For example, 1,4-dichloro-3-butene and / or Mention may be made of 3,4-dichloro-1-butene.

  The hydrogen peroxide in the present invention can be used without any limitation as long as it belongs to a category generally referred to as hydrogen peroxide. In this case, the concentration is preferably a hydrogen peroxide solution having a concentration in the range of 0.01 to 85% by weight, particularly a hydrogen peroxide solution having a concentration in the range of 10 to 60% by weight. It is preferable to use it as it is or diluted with water.

  The amount of hydrogen peroxide used in the present invention is not limited as long as dichloroepoxybutane can be produced, and among them, dichloroepoxybutane is a production method particularly excellent in production efficiency of dichloroepoxybutane. It is preferably in the range of 0.1 to 5.0 times mol, and particularly preferably in the range of 0.3 to 2.0 times mol with respect to 1 mol of butene.

  Moreover, it is preferable that the manufacturing method of this invention uses the hydrogen peroxide solution which adjusted pH using acids, such as phosphoric acids and sulfuric acids. By adjusting the pH with acids, it is possible to suppress the autolysis reaction of hydrogen peroxide and to produce dichloroepoxybutane with high conversion and selectivity. The pH at that time is particularly preferably in the range of 0.3 to 4.0. Examples of the acids include phosphoric acid, polyphosphoric acid, pyrophosphoric acid, potassium phosphate, sodium phosphate, ammonium phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, sulfuric acid, sodium hydrogen sulfate, and the like. Moreover, as the usage-amount in that case, the range of 0.01-100 times equivalent with respect to the tungsten atom and / or molybdenum atom in this transition metal compound as an equivalent of an acid is preferable, More preferably, it is 0.1- 10 times equivalent.

  The method for producing dichloroepoxybutane of the present invention can be carried out in the presence or absence of a solvent. Examples of the solvent include halogenated hydrocarbons such as methylene chloride and chloroform; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, cyclooctane, and 2,6-dimethylcyclooctane; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene and cumene; alcohols such as isopropanol, butanol and higher aliphatic alcohols. Among these, from the viewpoint of suppressing reaction efficiency and side reactions, a solvent that can be easily separated into an organic phase and an aqueous phase is preferable, and halogenated hydrocarbons such as methylene chloride and chloroform, and aromatic hydrocarbons such as toluene and xylene are preferable.

  The amount of the solvent used is preferably 0.01 to 5 times the weight of dichlorobutenes.

  The reaction temperature for producing dichloroepoxybutane is preferably 0 to 100 ° C. because the hydrogen peroxide self-decomposition reaction is kept low and the selectivity per hydrogen peroxide can be kept high. Further, it is particularly preferably in the range of 25 to 75 ° C. from the viewpoint of increasing the speed of the epoxidation reaction and suppressing the progress of side reactions and the self-decomposition of hydrogen peroxide. The production can be carried out under atmospheric pressure, under pressure or under reduced pressure. The reaction atmosphere is not particularly limited, and is preferably carried out in an inert gas such as nitrogen or argon in consideration of safety.

  The method for producing dichloroepoxybutane of the present invention comprises a solution system using a solvent, a bulk system using dichlorobutene as a solvent, a two-phase solvent and / or dichlorobutene as an organic phase, and an aqueous phase using hydrogen peroxide as an aqueous solution. It is possible to carry out by a method such as a system, and among them, it is preferable to carry out in a two-phase system because it can be produced particularly efficiently. As a two-phase system at that time, for example, a method in which an organic phase containing dichlorobutene and an organic ammonium salt is added to an aqueous phase containing a transition metal compound containing tungsten and / or molybdenum and hydrogen peroxide and the reaction is performed; dichlorobutene A method of adding hydrogen peroxide as an aqueous solution to a two-phase system solution comprising an organic phase containing an organic ammonium salt and an aqueous phase containing a transition metal compound having tungsten and / or molybdenum; dichlorobutene and an organic ammonium salt Examples thereof include a method of adding an aqueous solution of hydrogen peroxide in which a transition metal compound having tungsten and / or molybdenum is dissolved to the organic phase to be contained. Further, the organic phase at this time may be diluted with a solvent. Further, it may be a hydrogen peroxide solution that is an aqueous solution of hydrogen peroxide, and the pH of the hydrogen peroxide solution may be adjusted with acids such as phosphoric acid and sulfuric acid.

  The method for producing dichloroepoxybutane of the present invention is obtained by removing sodium thiosulfate, sodium sulfite, alkaline compound, aqueous sodium thiosulfate, sodium sulfite after removing the aqueous phase of the reaction solution after completion of the reaction by decantation or without removing it. Washing is performed with a member selected from the group consisting of an aqueous solution and an aqueous alkaline compound solution. In this case, the alkaline compound is not particularly limited as long as it is a compound having a pH of more than 7 when made into an aqueous solution, and examples thereof include compounds represented by sodium hydroxide, sodium hydrogen carbonate, sodium acetate and the like. And as a usage-amount of sodium thiosulfate, sodium sulfite, and an alkaline compound, 0.5-5 times equivalent is mentioned, for example with respect to the hydrogen peroxide which remains after completion | finish of reaction. Moreover, washing can be performed according to a known method. That is, it can be carried out batchwise or continuously. Moreover, it can also carry out using a countercurrent extraction apparatus etc. Here, sodium thiosulfate, sodium sulfite, alkaline compound, sodium thiosulfate aqueous solution, sodium sulfite aqueous solution and alkaline compound aqueous solution are not used for washing, or sodium thiosulfate, sodium sulfite, alkaline Production with poor distillation efficiency during distillation purification and poor recovery efficiency of dichloroepoxybutane when washed with a compound other than those selected from the group consisting of compounds, aqueous sodium thiosulfate, aqueous sodium sulfite, and aqueous alkaline compound solutions Become a method. In addition, in the manufacturing method of the dichloro epoxy butane of this invention, after performing these washing | cleaning, you may wash | clean with water etc. further.

  And in the manufacturing method of the dichloro epoxy butane of this invention, an organic layer is isolate | separated from the reaction solution after washing | cleaning, and the boiling point temperature at the time of fractionating this organic layer is 90 degrees C or less, Preferably it distills on the conditions of 80 degrees C or less. By carrying out the purification, dichloroepoxybutane is efficiently recovered. When distillation purification is performed under conditions where the boiling point temperature during fractional distillation exceeds 90 ° C., the side effect of dichloroepoxybutane occurs due to the presence of the transition metal compound, resulting in a significant reduction in the recovery efficiency. As the distillation purification method, a known method can be selected. For example, simple distillation, steam distillation, equilibrium flash distillation, continuous multistage distillation, batch multistage distillation, continuous rectification or molecular distillation using a packed column, Etc. The degree of reduced pressure at which the distillation operation is performed can be arbitrarily selected as long as the boiling point temperature during fractional distillation can be set to 90 ° C. or less, and is preferably 5 kPa or less, particularly 2 kPa or less. Preferably there is. The time required for distillation can be arbitrarily selected. In the case of a batch system, the operation time is preferably within 24 hours, particularly preferably within 8 hours in consideration of the progress of side reactions. The boiling point temperature at the time of fractional distillation in the present invention is the top temperature of the distillation in general distillation purification, and the top temperature of the distillation is the temperature at the top of the distillation purification apparatus used for distillation purification ( Maximum temperature).

  The dichloroepoxybutane obtained by the production method of the present invention can be produced without any limitation as long as it belongs to the category generally referred to as dichloroepoxybutane. For example, 1,4 -Dichloro-2,3-epoxybutane and 3,4-dichloro-1,2-epoxybutane can be mentioned.

  According to the production method of the present invention, flame retardant, gas barrier property, abrasion resistance, adhesion to a plastic substrate, or a polyol raw material or resin, which is an intermediate raw material for resin components used in paints, adhesives, foams, etc. It is possible to produce dichloroepoxybutane capable of imparting functions such as properties with high production efficiency, and its industrial value is extremely high.

  The following examples illustrate the effects of the present invention, but the present invention is not limited thereto.

  The evaluation and measurement methods used from the examples are shown below.

-Gas chromatography (GC) analysis-
A capillary column (type: FFAP, size: length × capillary-diameter 30 m × 0.32 mmφ) was used, and the temperature program was as follows: initial temperature: 100 ° C. (5 minutes), rising temperature pattern: 250 ° C. at 10 ° C./min. The temperature was measured by holding for 5 minutes.

Example 1
In a 3 liter flask equipped with a stirrer, 500 ml (565 g, 5.82 mol) of 35% by weight of hydrogen peroxide adjusted to pH 0.5 with 85% phosphoric acid, phosphorus-12-tungstic acid / 30 water 50.11 g (185.6 mmol) of the Japanese product was added, dissolved at room temperature, and gently stirred for 24 hours. Separately, in a 5 liter flask equipped with a condenser, a stirrer, and a dropping device, 2 liters of 3,4-dichloro-1-butene (2320 g, 18.56 mol), a 95 wt% alcohol solution of trioctylmethylammonium chloride 62 .4g (Wako Pure Chemical Industries, Ltd., (trade name) Aliquote 336: 18.56 milmol) was added and stirred at room temperature.

  The solution of 3,4-dichloro-1-butene and trioctylmethylammonium chloride was heated to 50 ° C. with vigorous stirring, and the previously prepared phosphorus-- was controlled while controlling the temperature of the reaction solution not to exceed 60 ° C. A hydrogen peroxide solution of 12-tungstic acid was added dropwise over 30 minutes. Thereafter, 126 ml (142 g, 1.466 mol) of 35% by weight of hydrogen peroxide adjusted to pH 0.5 with phosphoric acid was added dropwise over 1 hour and 30 minutes while maintaining the reaction temperature at 60 ° C.

  The reaction was carried out with vigorous stirring for 33 hours while the reaction temperature was controlled at 60 ° C. to produce 3,4-dichloro-2-epoxybutane. GC analysis confirmed that the epoxy conversion of 3,4-dichloro-1-butene was 89% and the selectivity was 88%. 2,290 g (14.54 mol) of 3,4-dichloro-2-epoxybutane is present in the reaction solution.

  From the obtained reaction solution, 76 g of a reaction solution containing 61 g of 3,4-dichloro-2-epoxybutane was collected by GC analysis, and 50 ml (10 g / L) of an aqueous sodium sulfite solution was appropriately applied to the reaction solution. The hydrogen peroxide concentration in the aqueous phase was 5 mg / L or less and pH = 7. The aqueous phase was removed by decantation, and the organic phase was washed twice with 50 ml of distilled water and the aqueous phase was removed by decantation to obtain an organic phase.

  The obtained organic phase was extracted from the organic phase with a batch distillation apparatus by distillation under reduced pressure over 1 hour at an operating temperature (oil bath temperature) of 80 ° C., a distillation head temperature of 47 ° C., and a degree of vacuum of 0.4 kPa. Dichloro-2-epoxybutane was recovered by distillation and separated from the catalyst component. As a result of GC analysis, 59 g of 3,4-dichloro-2-epoxybutane (recovery: 96%) was confirmed in the fraction.

Example 2
Operation conditions of distillation apparatus; operating temperature (oil bath temperature) 80 ° C., distillation head temperature 47 ° C., degree of vacuum 0.4 kPa, operating time 1 hour instead of operating temperature (oil bath temperature) 95 ° C., distillation head 3,4-Dichloro-2-epoxybutane was produced and collected in the same manner as in Example 1 except that the temperature was 66 ° C., the degree of vacuum was 1.5 kPa, and the operation time was 1 hour. As a result of GC analysis, 59 g of 3,4-dichloro-2-epoxybutane (recovery: 96%) was confirmed in the fraction.

Example 3
Operation conditions of distillation apparatus; operating temperature (oil bath temperature) 80 ° C, distillation head temperature 47 ° C, degree of vacuum 0.4 kPa, operating time 1 hour instead of operating time (oil bath temperature) 105 ° C, distillation head 3,4-Dichloro-2-epoxybutane was produced and recovered in the same manner as in Example 1 except that the temperature was 78 ° C., the degree of vacuum was 2.6 kPa, and the operation time was 1 hour. As a result of GC analysis, 57 g of 3,4-dichloro-2-epoxybutane (recovery: 93%) was confirmed in the fraction.

Comparative Example 1
A portion of 76 g of the reaction solution mixture obtained in the same manner as in Example 1 was collected, and without washing the reaction solution, the operation temperature (oil bath temperature) 128 ° C., distillation head temperature 97 ° C. 3,4-Dichloro-2-epoxybutane was recovered by distillation under reduced pressure over 4 hours at a reduced pressure of 5.5 kPa, and separated from the catalyst component. From GC analysis, 1.8 g of 3,4-dichloro-2-epoxybutane was confirmed in the resulting fraction. The recovery rate was as low as 3%.

Comparative Example 2
Operation conditions of distillation apparatus: operation temperature (oil bath temperature) 128 ° C, distillation head temperature 97 ° C, degree of vacuum 5.5 kPa, operation time 4 hours instead of operation temperature (oil bath temperature) 95 ° C, distillation head 3,4-Dichloro-2-epoxybutane was produced and recovered in the same manner as in Comparative Example 1 except that the temperature was 78 ° C., the degree of vacuum was 2.6 kPa, and the operation time was 9 hours. As a result of GC analysis, 46 g of 3,4-dichloro-2-epoxybutane was confirmed in the fraction. The recovery rate was as low as 76%.

Comparative Example 3
Operation conditions of distillation apparatus; operation temperature (oil bath temperature) 128 ° C, distillation head temperature 97 ° C, degree of vacuum 5.5 kPa, operation time 4 hours instead of operation temperature (oil bath temperature) 97 ° C, distillation head Production and recovery of 3,4-dichloro-2-epoxybutane was attempted in the same manner as in Comparative Example 1 except that the temperature was 89 ° C. and the degree of vacuum was 5.5 kPa. As a result of GC analysis, 24 g of 3,4-dichloro-2-epoxybutane was confirmed in the fraction, but the recovery rate was as low as 40% and could hardly be recovered.

Example 4
Using a batch-type distillation apparatus, operating conditions of the distillation apparatus; operating temperature (oil bath temperature) 80 ° C., distillation head temperature 47 ° C., vacuum degree 0.4 kPa, operating time 1 hour, instead of flash distillation device The operating conditions of the distillation apparatus; operating temperature (external jacket temperature) 85 ° C., distillation head temperature 62 ° C., vacuum degree 1.1 kPa, average residence time 2 minutes in heating section, similar to Example 1 3,4-Dichloro-2-epoxybutane was produced and recovered by the method. The recovery rate of 3,4-dichloro-2-epoxybutane was 96%.

Example 5
Production of 3,4-dichloro-2-epoxybutane by the same method as in Example 1 except that 50 ml (10 g / L) of sodium thiosulfate was used instead of 50 ml (10 g / L) of the aqueous sodium sulfite solution. Recovery was performed. The recovery rate of 3,4-dichloro-2-epoxybutane was 96%.

Example 6
Production and recovery of 3,4-dichloro-2-epoxybutane by the same method as in Example 1 except that 50 ml of a 1 mol wt% aqueous sodium hydroxide solution was used instead of 50 ml of an aqueous sodium sulfite solution (10 g / L). Went. The recovery rate of 3,4-dichloro-2-epoxybutane was 96%.

  Dichloroepoxy that can impart functions such as flame retardancy, gas barrier properties, abrasion resistance, and adhesion to plastic substrates to polyol raw materials or resins that are intermediate raw materials for resin components used in paints, adhesives, foams, etc. Butane can be produced with high production efficiency.

Claims (3)

In producing dichloroepoxybutane by the reaction of dichlorobutene and hydrogen peroxide in the presence of a transition metal compound having tungsten and / or molybdenum and an organic ammonium salt, the reaction solution after the reaction is mixed with sodium thiosulfate, sodium sulfite, After washing with a material selected from the group consisting of an alkaline compound, an aqueous sodium thiosulfate solution, an aqueous sodium sulfite solution, and an aqueous alkaline compound solution, the organic phase is separated and distilled at a boiling point of 90 ° C. or lower when the organic phase is fractionated. A method for producing dichloroepoxybutane, comprising purifying and collecting dichloroepoxybutane. The transition metal compound having tungsten and / or molybdenum is selected from the group consisting of tungstic acid, sodium tungstate, phosphorus-12-tungstic acid and phosphorus-3-molybdo-9-tungstic acid. The method for producing dichloroepoxybutane according to claim 1. The method for producing dichloroepoxybutane according to claim 1 or 2, wherein the organic ammonium salt has a carbon number of 9 or more and less than 50.