JPS6245851B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing hydroxy hydrocarbon ethers. Specifically, epoxy hydrocarbons having a halogen atom or an unsaturated group in the molecule are reacted with alcohols or phenols in the presence of a specific heteropolyacid or a metal salt thereof.Having a halogen atom or an unsaturated group in the molecule This is a method for producing hydroxy hydrocarbon ethers. Hydroxy hydrocarbons having a halogen atom or an unsaturated functional group in the molecule are known and are used for various intermediate raw materials. For example, 1-allyloxy-3, which is the raw material for allyl glycidyl ether, is produced by reacting epichlorohydrin with allyl alcohol.
It is known to produce -chloro-2-propanol, as well as to react epichlorohydrin with bisphenol A. In these known reactions, sulfuric acid or aromatic sulfonic acids have conventionally been used as catalysts. However, the above-mentioned known reactions not only require a large amount of catalyst due to the slow reaction rate, but also require the reaction to be carried out at high temperatures for a long time, producing many side reactants and producing the target product with high selectivity. I couldn't get it. Therefore, the above-mentioned hydroxy hydrocarbon ethers have become expensive raw materials. For example, 1-allyloxy-3, which is a raw material for allyl glycidyl ether used as a raw material for epoxy resin and a copolymerization component of polyether.
-Chloro-2-propanol is also expensive, so it is currently used for limited purposes. Therefore, establishing a technology for producing hydroxy hydrocarbon ethers with high selectivity has been a major technical challenge. The present inventor has continued to earnestly study the above reaction. As a result, they found that the hydroxy hydrocarbon ethers can be obtained with high selectivity when the above reaction is carried out using a specific heteropolyacid as a catalyst, leading to the completion of the present invention. That is, the present invention combines an epoxy hydrocarbon having a halogen atom or an unsaturated group in the molecule and alcohols or phenols with molybdophosphoric acid, molybdosilicic acid, tungstophosphoric acid, tungstosilicic acid,
This is a method for producing hydroxy hydrocarbon ethers having a halogen atom or an unsaturated group in the molecule, characterized in that the reaction is carried out in the presence of a heteropolyacid selected from the group consisting of tungstoboric acid and metal salts thereof. The epoxy hydrocarbon used in the present invention is an epoxy hydrocarbon having a highly reactive halogen atom or unsaturated group in the molecule. More specifically, the epoxy hydrocarbons include epichlorohydrin, epibromohydrin, 4-chloro-1,2-
Epoxybutane, 3-chloro-2-methyl-1,
2-epoxypropane, 3,4-epoxy-1-
Epoxy hydrocarbons such as butene can be particularly preferably used. Furthermore, the functional group, ie, the halogen atom or unsaturated group, may be selected from a group containing a plurality of the same type or different types, as required. As is clear from the above description, alcohols and phenols which are other raw materials of the present invention may be any known alcohols having a hydroxyl group in the molecule without particular limitation. Examples of commonly used substances include methanol, ethanol, propanol, isopropyl alcohol, allyl alcohol, butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol, propylene glycol, polyalkylene glycol, phenol, and bisphenol A. be. In particular, alcohols having unsaturated groups, phenols, and polyalcohols having a plurality of hydroxyl groups are preferably used. As is clear from the above description, the most important feature of the present invention lies in the catalyst used for the reaction between the epoxy hydrocarbon and alcohol or phenol. That is, the catalyst used in the present invention is not particularly limited and may be used as long as it imparts a heteropolyacid group in the reaction system, but the following are examples of catalysts that are generally suitably used. For example, molybdophosphoric acid, molybdosilicic acid, tungstophosphoric acid, tungstosilicic acid, tungstoboric acid, or metal salts thereof are preferably used. Various metal salts of the above-mentioned heteropolyacids are known, but so-called acid salts in which at least one hydrogen atom remains are particularly suitable. The amount of the heteropolyacid group that serves as the catalyst in the reaction system varies depending on the type of raw material such as epoxy hydrocarbons, alcohols, phenols, etc., or the type of substance imparting the heteropolyacid group, etc. Cannot be limited. Usually, the above-mentioned heteropolyacid or its metal salt is used in an amount of 0.05 to 10% (by weight), preferably 0.1 to 10%, based on the total of raw materials, ie, epoxy hydrocarbons and alcohols or phenols.
It may be selected based on the range of 5% (by weight). The reaction operation between the epoxy hydrocarbons and alcohols or phenols in the present invention is not particularly limited and any conditions may be selected, but generally the reaction is sufficient at a temperature in the range of 20 to 100°C. proceed. In addition, it is generally preferable to carry out the reaction system while maintaining a liquid phase. Furthermore, the reaction system is generally preferably carried out without using a solvent;
This can be carried out using an inert solvent such as tetrahydrofuran or dioxane, if necessary. In addition, by selecting these reaction conditions as necessary, the reaction can proceed sufficiently under atmospheric pressure.
It can also be carried out under increased pressure or reduced pressure as necessary. Since the catalyst used in the present invention has excellent catalytic activity, the reaction can be completed in a short time. Moreover, the selectivity of the target product is extremely good and can be increased to over 99% by selecting various conditions.
Further, the catalyst of the present invention is a stable catalyst in the reaction system of the present invention and has good sustainability, so that after recovering the desired product as necessary, the catalyst can be recycled and reused. The detailed mechanism of action by which these effects are exerted is still unclear. However, the completion of the present invention is of great industrial significance since it provides surprising reaction rates and selectivity for the desired product compared to conventional catalysts. EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but the present invention is not limited to these Examples. Example 1 The heteropolyacids shown in Table 1 were added to a mixture of 30 ml (0.38 mol) of epichlorohydrin and 100 ml (1.47 mol) of allyl alcohol, and the reaction was carried out at 97°C for 15 minutes in an oil bath to produce 1-allyloxy-3- Chloro-2
- Propanol (hereinafter abbreviated as AOCP) was obtained. The results were as shown in Table 1.

[Table] Example 2 12-
Tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀・27H ₂ O) 0.45g
was added and reacted for 30 minutes at 97°C in an oil bath. 1-Propoxy-3-chloro-2-propanol was obtained with an epichlorohydrin conversion rate of 100% and a selectivity of 97%. Example 3 3.21 g of 12-molybdophosphoric acid (H ₃ PMo ₁₂ O ₄₀ ·27H ₂ O) was added to a mixture of 30 ml (0.38 mol) of epichlorohydrin and 150 g (1.59 mol) of phenol.
The reaction was carried out for 30 minutes at 60°C in a water bath. 1-Phenoxy with 100% epichlorohydrin conversion and 99% selectivity
3-chloro-2-propanol was obtained. Example 4 A mixture of 30 ml (0.38 mol) of epichlorohydrin and 200 ml (3.59 mol) of ethylene glycol was
Add 4.34g of tungstosilicic acid and heat in a water bath at 35℃ for 2 hours.
Time reacted. Epichlorohydrin conversion rate 100
%, selectivity 90%, ethylene glycol mono(3
-chloro-2-hydroxypropyl) ether was obtained, the remainder being ethylene glycol di-(3-chloro-2-hydroxy-propyl) ether. Example 5 4-chloro-1,2-epoxybutane 40g
Add 0.45 g of 12-tungstosilicic acid (H ₄ SiW ₁₂ O ₄₀・26H ₂ O) to a mixture of (0.38 mol) and 100 ml (1.34 mol) of allyl alcohol at 97°C in an oil bath.
It reacted for 15 minutes. 1-allyloxy-4-chloro-2-butanol was obtained with a 4-chloro-1,2-epoxybutane conversion rate of 100% and a selectivity of 90%. Example 6 12-molybdophosphoric acid (H ₃ PMo ₁₂ O ₄₀ .
27H ₂ O) was added thereto, and the mixture was reacted at 40° C. for 60 minutes with stirring. Conversion rate of 3,4-epoxy-1-butene
At 100%, the products are 1-allyloxy-3-buten-2-ol (75% selectivity) and 2-allyloxy-3-buten-1-ol (21% selectivity)
It was hot. Example 7 After dissolving 43.4 g (0.19 mol) of bisphenol A in 100 ml of tetrahydrofuran, 1.0 g of 12-tungstophosphoric acid (H ₃ PW ₁₂ O ₄₀・27H ₂ O) was added.
Warm to 60℃. 30 ml (0.38 mol) of epichlorohydrin was added dropwise to this while stirring. The time required from the start to the end of dropping was 60 minutes. After the dropwise addition was completed, the reaction was further carried out at 60°C for 60 minutes. After the reaction
After adding 10 g of sodium bicarbonate and stirring at room temperature for 30 minutes, the reaction solution was filtered and the product was separated and recovered under reduced pressure. 65 g of di-3-chloro-2-hydroxypropyl ether of bisphenol A was obtained. Comparative Example 1 In Example 1, when 0.45 g of 98% concentrated sulfuric acid was used instead of 12-molybdophosphoric acid and the reaction was carried out at 97°C for 30 minutes, the epichlorohydrin conversion rate was 13%,
The selectivity for 1-allyloxy-3-chloro-2-propanol was 98%. This result shows that the heteropolyacid has a significantly high catalytic activity for this reaction. Comparative Example 2 In Example 5, when 0.45 g of 98% concentrated sulfuric acid was used instead of 12-tungstophosphoric acid and the reaction was carried out at 97°C for 30 minutes, the epichlorohydrin conversion rate was 12%.
The selectivity of 1-propoxy-3-chloro-2-propanol was 98%. This result shows that the heteropolyacid has a significantly high catalytic activity for this reaction.

Claims (1)

[Claims] 1 An epoxy hydrocarbon having a halogen atom or an unsaturated group in the molecule and an alcohol or a phenol selected from the group consisting of molybdophosphoric acid, molybdosilicic acid, tungstophosphoric acid, tungstosilicic acid, tungstoboric acid, and metal salts thereof. 1. A method for producing hydroxy hydrocarbon ethers having a halogen atom or an unsaturated group in the molecule, the method comprising carrying out the reaction in the presence of a heteropolyacid.