JPS6019907B2 - Method for producing aromatic glycidyl ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing glycidyl ethers from aromatic oxy compounds.

Conventionally known methods for producing glycidyl ether from aromatic oxy compounds include a one-stage method and a two-stage method.

To explain the one-step method using phenylglycidyl ether as an example, an alkali or alkaline metal hydroxide is added, phenol and excess epichlorohydrin are reacted, and etherification and cyclization are performed. A method for producing phenylglycidyl ether by removing metal hydroxides and chlorides from the reaction product by washing with water in a furnace, then removing excess epichlorohydrin, and further milling. be.

To explain the two-step method in the same way, epichlorohydrin is added to phenol, the temperature is raised in the presence of an alkali or alkali metal hydroxide, and the reaction is performed. During the reaction, the hydroxide and chloride of the metal are extracted from the reactants. phenylglycidyl ether, which consists of a first step of separating and removing excess epichlorohydrin, and a second step of adding more than the saponification equivalent of the metal hydroxide to the remaining reactant and further reacting. This is a manufacturing method.

The reaction equation can be explained as follows. However, these have a yield of 74 to 82% and a low purity, which is not industrially satisfactory.

An object of the present invention is to provide a method for producing glycidyl ether from aromatic oxy compounds with high purity and high yield.

The method for producing an aromatic glycidyl ether of the present invention uses a catalyst of the general formula [R, R2R3R4N]X (where R, ~4 are alkyl groups, aralkyl groups, aryl groups,
This method is characterized by reacting an aromatic oxy compound and epihalohydrin in the presence of an aqueous caustic solution using a quaternary amine salt represented by Br) or a base anion exchange resin.

For example, when phenylphenol and epichlorohydrin were used, surprising results were obtained with a yield of 88% or higher and a purity of % or higher.

In the above general formula, when R and ~4 are alkyl groups, the number of carbon atoms is preferably 1 to 18.

Specifically, examples of quaternary amine salts include tetramethylammonium chloride, tetraethylammonium chloride, trimethyllauryl chloride, trimethylstearylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and the like of these amines. I can give you a bromide. The amount of these catalysts added is suitably in the range of 1 to 0.001 mol per 1 mol of phenol.
In addition, as a base anion exchange resin, the general formula R and Gosan (R
5R6R7> (However, R is the polymer X molecule of the resin skeleton, R5R
6 and R7 are alkyl groups, aryl groups or lower hydroxyalkyl groups, X is halogen) or R-N=[R8R9
] (where R is a polymer of the marrow of the resin, and R8 and R9 are lower alkyl groups) can be used.

For example, IRA-400, a product name of Rohm Asodhaas Co., Ltd.
, IRA-401, IRA-402, IRA-405,
IRA-42fu IRA-143stop IRA-900, I
RA-904, IRA-93 IRA-410, mA
-411, IRA-910, IRA-911, mA-9
A house etc. can be mentioned. Aromatic oxy compounds include phenol, alkyl-substituted phenol, phenylphenol,
This includes various phenols such as benzylphenol and naphthol, and counterfeit phenols. Moreover, these can also be used after being dissolved in an organic solvent. Epihalohydrins include epichlorohydrin, epibromohydrin,
Epiiodohydrin is applicable, and epichlorohydrin is industrially advantageous. Regarding the method of the present invention, the production of o-biphenylglycidyl ether from o-phenylphenol and epichlorohydrin will be explained in detail.

First, in the case of using a quaternary amine salt as a catalyst, the amount of the catalyst added is preferably in the range of 1 to 0.001 mol per 1 mol of o-phenylphenol, and a particularly preferable amount is 0.1 to 0.001 mol. It is 0.003 mol. The catalyst can also be recovered and reused after the reaction is completed. Additionally, a solvent such as a liquid lower aliphatic or alicyclic hydrocarbon such as pentane or hexane, an aromatic hydrocarbon such as benzene, toluene, or xylene, or a halogenated aliphatic hydrocarbon such as chloroform is added to the reaction system. However, the catalyst still works effectively. As a caustic alkali aqueous solution, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.
% concentration, and the amount used is in the range of 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of caustic alkali per mol of o-phenylphenol.

The appropriate amount of epichlorohydrin is 1 to 5 mol, preferably 1.5 to 3.0 mol, per 1 mol of o-phenylphenol. The reaction temperature is 10 to 110°C, preferably 20 to 70 qo, and the reaction time is usually several tens of minutes to several hours. Since the reaction system is carried out in two phases, an aqueous phase and an organic phase, and the catalyst acts at the interface between the two incompatible liquid phases, it is necessary to carry out sufficient crossing over the ocean. The method for extracting piphenylglycidyl ether from the reaction product is to remove the inorganic salt by filtration or dissolving it in water, distill off unreacted epichlorohydrin, and remove biphenylglycidyl ether by distillation under reduced pressure. I can put it out. The same applies even when aromatic compounds other than phenylpherol are used as raw materials. Next, when using a base anion exchange resin, the amount of catalyst added is 10 to 10% relative to phenylphenol.
6% by weight, preferably 15-3% by weight.

After the reaction is completed, the catalyst can be recovered by a method such as filtration or heating and can be reused in the next reaction. Alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.
Used as a 20-5% by weight aqueous solution. The appropriate amount of alkali to be used is 1 to 3 moles per mole of phenylphenol. The amount of epichlorohydrin is 1 to 5 mol, preferably 1.5 mol, per 1 mol of phenylphenol.
~3.0 mol. The reaction temperature is 10-110 pm, preferably 20-7000 pm. The reaction time is usually several tens of minutes to several hours. The reaction system is an aqueous phase and an organic phase.
Since it is carried out in phases and the catalyst is an insoluble solid, it is necessary to thoroughly mix the mixture to ensure sufficient contact. The method for recovering biphenyl glycidyl ether from the reaction product involves removing by-product inorganic salts and catalysts through a furnace. Thereafter, unreacted epichlorohydrin is distilled off, and biphenyl glycidyl ether can be recovered by distillation under reduced pressure. The same applies when aromatic oxy compounds other than phenylphenol are used as raw materials. The present invention will be explained below with reference to Examples. Example 1 255.0 mol of o-phenylphenol (1.5 mol),
A mixture of 416.3 mols of epichlorohydrin (4.5 moles) and 1.71 mols of triethylbenzyl ammonium chloride was heated to 30 to 35 mils, and 168 mols of a 5% by weight aqueous solution of caustic soda (2.1 mols of NaOH) was poured into the mixture. 3
One female was added.

After that, 2.50~60oo. After drying in the field, the reaction mixture was cooled, the organic layer was separated, washed with water, excess epichlorohydrin was distilled off, and then distilled under reduced pressure to obtain 301 g of o-piphenyl glycidyl ether (yield: 88. .8%). The purity of o-biphenyl glycidyl ether was determined by gas chromatography analysis and was found to be 98.5%.
Example 2 A mixture of 94.1 moles (1.0 moles) of phenol, 277.5 moles (3.0 moles) of epichlorohydrin, and 0.54 moles of tetramethylammonium chloride was flooded to 30-35°C and the weight of 5. % caustic soda aqueous solution 104% (NaOH
I. 3 mol) was added over 25 minutes while stirring.

After that, 1. After cooling for a while, the product was treated in the same manner as in Example 1 to obtain 1,283 phenylglycidyl ether (yield: 86.0%). Purity is Satoshi. It was 4%. Example 3○-Phenylphenol 170.0 evenings (1
．． 0 mol), Amberlite IRA-91044-2 in a mixture of Epichlorohydrin 13 & 8 mol (1.5 mol)
Add chlorine and raise the temperature to maintain the reaction temperature at 50-60°C.
While stirring, 120 g (1.5 mol) of a 50% aqueous NaOH solution was added dropwise over 20 minutes.

After that, 1.60qo. I reacted while waiting for hours.
The product was filtered through a furnace to recover the resin and creation salt, and the organic layer was separated from the furnace solution, washed with water, and excess epichlorohydrin was removed by distillation, followed by o-biphenyl glycidyl ether 19
A yield of 9.1% was obtained (yield: 88.0%). The purity was determined by gas chromatography analysis and was 98.6%. Example 4 Amberlite IRA-90024.5 was added to a mixed solution of 94.1 mol of phenol (1.0 mol) and 185.0 mol of epichlorohydrin (2.0 mol), and the temperature was raised to a reaction temperature of 50 to 50 mol. Keep it at 6000 and add 50% NaO while worshiping.
120 g (1.5 mol) of an aqueous H2 solution was added dropwise over 30 minutes.

Thereafter, the mixture was allowed to react at 60° C. for 2.0 hours under lighting. The product was treated in the same manner as in Example 3 to obtain 126.8 g of phenylglycidyl ether. (Yield 85.0%). The purity of the product is 98.1% as determined by gas chromatography analysis.
Met. Example 5 Paratertiary butyl phenol 150 m (1.0
Amberlite IRA-91039.0 was added to a mixed solution of 138.8 mole (1.5 mole) of epichlorohydrin, and the temperature was raised to 50% NaOH aqueous solution while maintaining the reaction temperature at 50 to 60 qo. 120 moles (1.5 mol) was added dropwise over 30 minutes.

Claims (1)

[Claims] 1 General formula [R_1R_2R_3R_4N] as a catalyst
Using a quaternary amine salt represented by X (where R_1_ to_4 are alkyl, aralkyl, or aryl groups; 1. A method for producing an aromatic glycidyl ether, which comprises reacting in the presence of an aromatic glycidyl ether. 2. The manufacturing method according to claim 1, in which biphenyl glycidyl ether is obtained from phenylphenol and epichlorohydrin.