JPH0426684A - Production of epichlorohydrin - Google Patents

Abstract

PURPOSE:To obtain the subject highly active compound useful as an intermediate for surfactants, etc., in high yield by reacting allyl chlorides with an organic peroxide in the presence of a molybdenum compound, etc., in the coexistence of an organic phosphine, etc. CONSTITUTION:Allyl chlorides (preferably used in a molar amount of 3-12 times based on an organic peroxide) are reacted with the organic peroxide (preferably tert-butyl hydroperoxide) in the presence of one catalyst (preferably used in an amount of 0.1-0.5mol% based on the organic peroxide) selected from molybdenum compounds, tungsten compounds and vanadium compounds, etc., by using an organic phosphine oxide (e.g. trimethylphosphine oxide) or an organic phosphine (e.g. trimethylphosphine) in a molar amount of preferably 1-10 times to afford the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application L7-] The present invention relates to a method for producing the corresponding epichlorohydrins from allyl chlorides using organic peroxides in the presence of a catalyst. Epichlorohydrin is an important compound as an intermediate for various chemical products such as epoxy resins, synthetic glycerin, surfactants, fiber treatment agents, solvents, and plasticizers.

[Conventional technology]

Conventionally, the method for producing epichlorohydrin from allyl fumicolide involves the so-called chloro-1' phosphorus method, which involves reacting allyl chloride with hydrochlorin and then dehydrochlorinating it with a basic substance such as calcium hydroxide. It has been known. However, since chlorohydrin is used in the reaction, problems such as corrosion of the reaction equipment and treatment of by-product inorganic salts impair economic efficiency.

On the other hand, as a method that does not use rohydrin, a method is known in which an epoxy compound is directly produced using an organic peroxide as an oxidizing agent. For example, Jar Nor/Of/Kakrisis Volume 31 438-443
(1973) and Japanese Patent Publication No. 48-19609 disclose a method for obtaining epichlorohydrin by oxidizing allyl chloride with L-butyl hydroperoxide or α-phenyl hydroperoxide in the presence of a molybdenum compound. Furthermore, methods of adding various solvents are also known in order to obtain high activity and high selectivity. For example, in JP-A-49-55609, sym-tetrachloroethane and 1,2.3-1
- Chlorination of Lichlorp 11pan, etc. ++i A method for producing epichlorohydrin in which allyl chloride is oxidized with L-butylhyde 11 peroxide in the presence of arsenic on an aliphatic aliphatic is described.

[Problem to be solved by the invention]

However, in the above method, ζ is not sufficient in both activity and selectivity. Therefore, there has been a desire for a production method that provides higher activity and higher selectivity.

[Means to solve the problem]

The inventors of the present invention conducted extensive research to solve the above problem, and found that the coexistence of an organic phosphine oxa-ide or an organic bosphine in the reaction system caused an increase in shrimp Ii.
+ 7 Rechtrins were found to be suitable for the selection of products and were used to complete the present invention. That is, the method of the present invention uses molybdenum compounds, tungsten compounds, and vanadium compounds.
In the production of epichlorohydrins from allyl compounds and organic peroxides in the presence of a seed catalyst,
This is a method for producing epichlorohydrin, which is characterized by coexisting an organic phosphine oxide or an organic phosphine.

Examples of molybdenum compounds, tungsten compounds, and vanadium compounds used as catalysts in the present invention include molybdenum compounds such as molybdenum naphthenate, molybdenum oxide acetylacetonate, and molybdenum acetylacetonyl, tungsten chloride,
Examples include tungsten compounds such as tungsten oxide and tungsten carbonyl, vanadium compounds such as vanadium chloride, vanadyl acedelacetono-1, vanadium acetylacetonate, and vanadium carbonyl.

The amounts of catalysts such as molybdenum compounds, tungsten compounds, and vanadium compounds used in the present invention are determined by the amount of the organic peroxide. 01-1 mol%, preferably 0.1-1 mol%
It is in the range of 0.5 mol%.

The organic phosphine oxy (j (middle, R1, 1-2, 1-3c, al-tol group or aryl group having 1 to 10 carbon atoms) used in the method of the present invention 1, and an example of such an organic bosphinyl oxide 1' is trimethylbosphinyl oxide 1.
-Li-ide, 1-ethylbosphine oxide: 1-'IJ-ide, l-propylphosphine butylbosphine oxide, trihexylphosphine oxide, l-lyoctylphosphine oxide, tridecylphosphine oxide, t- Examples include rifenylphosphine oxide and tritosylbosphine oxide.

Furthermore, the organic phosphite used in the method of the present invention (wherein
r? 1, r? 2.I? 3 is an organic phosphine represented by an alkyl W having 1 to 10 carbon atoms or an aryl group), and examples of such organic phosphine include trimethylphosphine, triethylbosphine, tripropylbosphine, triisopropylbosphine, tributyl Examples include bosphine, trihexylbosphine, j-lioctylbosphine, 1-lysosylphosphine, triphenylbosphine, t-butyldiphenylphosphine, l-lidocylphosphine, methyldiphenylphosphine, diethyltunylphosphine, etc. .

If the amount of these organic phosphine oxides or organic phosphines used in the present invention is too small, the effect will be small, but if added in excess, ζ will not have an adverse effect on the reaction, so although there is no upper limit on the amount used, it may be necessary. It is uneconomical to add it to the catalyst, so it is practically preferable to add it in an amount of 1 to 10 times the mole of the catalyst used.

The allyl chloride used in the method of the present invention means allyl chloride or 2-alkylaryl 1:J ride in which hydrogen at the 2-position of allyl chloride is substituted with an alkyl group.

Epichlorohydrin refers to epichlorohydrin or 2-alkylhydrin, and each of the above-mentioned allylchloride groups corresponds to the corresponding epichlorohydrin.

The reaction is usually carried out in such a manner that the amount of allylc1'1lye I is used in excess of the organic peroxide so that the organic peroxide does not remain in the reaction solution after the reaction. The larger the amount of allylchloride fl. used, the faster the conversion rate of organic peroxide becomes.
However, if it is too excessive, the recovery of unreacted allyl chloride compounds will lead to unfavorable economic efficiency. Therefore, the industrially preferable amount of allyl chloride I' 11 to be used is 1 to organic peroxide
The amount is 20 times the mole, more preferably 3 to 12 times the mole.

The process of the invention is usually carried out in a diluent that is inert to the reaction. Examples of such diluents include aromatic hydrocarbons such as toluene, Hensen, xylene, octane,
Examples include aliphatic hydrocarbons such as decane, starting materials for organic peroxides, such as edil, cumene, and the like. The reaction can also be carried out using the allyl chloride itself as a diluent.

The organic peroxides used in the method of the present invention are alkyl hydroperoxides such as t-butylhydride-1-cobaroxy-1', ethylbenzene hydrobatoside, and cumene hydroperoxide. Among these, L-butyl hydroperoxide (hereinafter abbreviated as TB tl P)
is particularly preferred, and may be used by mixing with the diluent in advance at °C.

As for the reaction temperature in the present invention, the lower the reaction temperature, the higher the selectivity to the a-containing peroxide, but the reaction rate becomes lower. on the other hand,
The maximum reaction temperature is determined by the decomposition temperature of the organic peroxide,
If the reaction temperature is raised too high, the selectivity of Epic I:I ruhydrins will decrease, which is undesirable. Therefore, usually 30~
150°C, and the preferred reaction temperature is 80-1
It is 10°C.

The reaction pressure in the present invention is not particularly limited, and the reaction is carried out under vapor pressure that can maintain the liquid state of commonly used allyl chlorides, diluents, and the like. Further, the method of the present invention can be carried out in a batch method, a semi-flow method, or a flow method.

〔Example〕

The method of the present invention will be explained in detail by way of examples.

In the following Examples and Comparative Examples, the selectivity of ζupichlorohydrin is the selectivity based on organic peroxide, and is expressed by the following formula.

Epichlorohydrin selectivity - (8/(B-C))
100A - Number of moles of epichlorohydrin produced in the reaction B
- Number of moles of organic peroxide used C - Number of moles of residual organic peroxide after reaction Example 1 In a 300 d stainless steel autoclave, 0.79 g of molybdenum naphthenate (<0.41 mmol I atoms) and tributylphosphine oxide were added. id 0. IOg (0,458mm
ol), and allyl chloride 96. old g(], 254
mo1), 69% T1311P toluene solution 16.31
1 g (0,125 mol) was added and reacted at 90'C for 1 hour. After the reaction was completed, it was cooled and the reaction solution was analyzed using a gask 1:J madograph and 'I''B HI' was analyzed using a chemical analysis method. As a result, the 3MjR ratio of epichlorohydrin ss
, ct, '3 II I' conversion rate 89, 96
2 'j' Arata.

Examples 2 to 8 Reactions were carried out in the same manner as in Example 1 except that the type and amount of organic phosphine oxidation or organic bosphine were changed as shown in Table 1.The results are shown in Table 1. Shown in the table.

Comparative Example I A reaction was carried out in the same manner as in Example I except that no organic bosphinoid or organic bosphin was used. The results are shown in Table 1.

Example 9 A reaction was carried out in the same manner as in Example 1 except that molybdenum acetylacetonate (0,444 mmol atom) was used instead of molybdenum naphthenate. The results are shown in Table 1.

Comparative Example 2 A reaction was carried out in the same manner as in Example 9 except that tributylphosphine oxide was not used. The results are shown in Table 1.

Example IO To molybdenum instead of molybdenum naphthenate: Tozatricarbonyl (0,444 mmol atom) and also T
B Ethylbenzene hydrocarbon instead of HP;
The reaction was carried out in the same manner as in Example 1 except that Toshi 1' was used. The results are shown in Table 1.

Comparative Example 3 A reaction was carried out in the same manner as in Example IO except that tributylbosphine oxide was not used. Results first
Shown in the table.

Examples 11-12 Vanadate acedelace 1 instead of molybdenum compound
The reaction was carried out in the same manner as in Example 1, except that the reaction mixture was changed to Nato (0.45 mmol original 1') or tungsten hexacarbonyl (0.438 mmol atom).

The results are shown in Table 1.

Comparative Examples 4-5 Reactions were carried out in the same manner as in Examples 11-12 except that I.lidylphosphine oxide was not used. The results are shown in Table 1.

Example 13 In a 300 ml stainless steel autoclave, 0.62 g (0.32 mmol atoms) of molybdenum naphthenate and 0.09 g (0.41 mmol atoms) of tributylphosphine oxide were placed in a 300 ml stainless steel autoclave.
mol), and 2-methylallyl chloride 105.
21g (1,149mol), 69% TB11P+-
16.50 g (0.126 mol) of the toluene solution was placed in the apparatus of Example 1, and reacted at 90°C for 1 hour. As a result, the selectivity of 2-methylepichlorohydrin was 8512%,
'r 13 HP conversion rate was 91.35%.

Comparative Example 6 A reaction was carried out in the same manner as in Example I3, except that tripudylbosphin oxide was not used.

As a result, the selectivity of 2-methylepichlorohydrin was 72
．． 50%, and the conversion rate of T B HP was 84.72%.

〔Effect of the invention〕

By coexisting an organic phosphine oxa-ide or an organic phosphine according to the present invention, the selectivity of epichlorohydrin can be improved by 10% or more and the conversion rate of organic peroxide can be improved by 5% or more, which is an industrially advantageous method. .

Patent applicant: Sanno 1 Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] In producing epichlorohydrins from allyl chlorides and organic peroxides in the presence of a type of catalyst selected from molybdenum compounds, tungsten compounds and vanadium compounds, an organic phosphine oxide or an organic phosphine is allowed to coexist. Method for producing epichlorohydrin.