JP2543522B2 - Process for producing alkylene oxide adduct of bisphenol compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an alkylene oxide adduct of a bisphenol compound, and particularly to a highly pure alkylene oxide adduct having a small addition molar distribution width. , The manufacturing method.

[Conventional technology]

In general, the alkylene oxide adduct of a bisphenol compound is usually produced by dissolving or dispersing the bisphenol compound at a reaction temperature higher than the melting point or by using a solvent because the melting point of the bisphenol compound is high. As the solvent, an inert organic solvent having no reactivity with alkylene oxide is used.

The addition of alkylene oxide requires the presence of a basic catalyst. Due to the presence of this, those in which bisphenol is bound with an alkylene group have the property of decomposing at high temperature (Japanese Patent Publication No. 38-1368). However, in the case of the reaction above the melting point of bisphenol, Kennis Rosenweig et al. (Japanese Patent Publication No. 55-29308) use lithium hydroxide or lithium acetate as a catalyst as an improved method for oxyalkylation of diphenol. Due to the use of the selected catalyst, the reaction is suppressed from decomposition.

On the other hand, in the reaction in the absence of solvent or in an inert solvent, the reaction rate becomes slow because the bond between the basic catalyst and the bisphenol-based hydroxyl group is difficult to proceed. Therefore, a method of reacting at a high temperature or increasing the amount of catalyst is used. However, this has the disadvantage that the reaction proceeds without distinction between the phenolic hydroxyl group and the alcoholic hydroxyl group, and the width of the added mole distribution of alkylene oxide becomes wider.

[Problems to be solved by the invention]

Alkylene oxide adducts of bisphenol compounds are polymers such as urethanes, polyesters, UV
In order to improve the physical properties of the curable resin and the like, it is often used as a copolymer diol component. Therefore, for example, bisphenols that interfere with the curing reaction may remain, or the purity of the target alkylene oxide addition mole number may be poor,
It should not have defects such as strong coloring. Needless to say, the base itself used as the basic catalyst or the salt or the like after neutralization is also disliked.

An object of the present invention is to suit the use of improving the physical properties of such a polymer, and particularly to solve the problems that the alkylene oxide addition molar distribution width is wide and sufficient physical properties cannot be obtained, and an alkylene of a bisphenol compound. It is to provide a method for producing an oxide adduct.

[Means for solving problems]

In the present invention, an alkylene oxide adduct of a bisphenol compound is produced by adding an alkylene oxide to two hydroxyl groups of a bisphenol compound [excluding bis (4-hydroxyphenyl) sulfone] in the presence of a basic catalyst. In doing so, water, preferably water in an amount equal to or less than that of bisphenol, is used as a solvent, and one alkylene oxide is added to each of the two hydroxyl groups at a temperature of 100 ° C. or less, or 50% by weight or less of water is added. The method is characterized by using the mixed solvent with an inert organic solvent in an amount of 50% by weight or less based on bisphenol to carry out an addition reaction.

Since water is a polar solvent and facilitates dissociation of highly reactive phenolic hydroxyl groups of bisphenol, activation with a basic catalyst effectively proceeds, and addition of alkylene oxide tends to selectively proceed. Further, when the reaction temperature is kept below 100 ° C., the selectivity is particularly excellent.

A similar effect occurs when water is added to the inert solvent. In this case, the reaction temperature does not need to be the temperature at which bisphenol melts, and the reaction rate is also increased by the presence of water, so the reaction proceeds optimally at 100 ± 50 ° C., preferably 100 ± 20 ° C. Inert organic solvents useful in the present invention include benzene, toluene, xylene and cyclohexane.

A polar solvent, especially water, can be mentioned as a negative factor due to addition reaction with alkylene oxide, but by suppressing the amount of water used, the production of alkylene oxide adduct is drastically reduced, and only ethylene glycol is produced under some conditions. And can be easily removed under reduced pressure with water. The alkylene oxide is used in an amount of 2 to 3 mol, preferably 2.1 to 2.5 mol, based on 1 mol of the bisphenol compound. If it is 2 moles, undesired unreacted substances are likely to remain, and if it is 2.6 moles or more, the addition mole distribution width tends to be broad and the amount of by-produced polyalkylene glycols tends to increase. A bisphenol compound having one alkylene oxide at each hydroxyl group is almost insoluble in water, and can be filtered off and washed with water, and at that time, it can be easily separated from the target product.
Further, when washing with water, there is an advantage that the basic compound used as a catalyst or a neutralized salt thereof can be simultaneously removed.

Regarding the inert organic solvent, when the amount used is 50% by weight or less of bisphenol, it is not in a state of being positively dissolved, and can be removed when removing water from the target substance.

Examples of bisphenol compounds to which this production method can be applied include bis (4-hydroxyphenyl) methane (commonly called bisphenol F) and 2,2-bis (4
-Hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane (commonly called tetrabromobisphenol A), 2,2-bis (4-hydroxy-3,5) -Dibromophenyl) sulfone (commonly known as tetrabromobisphenol S), 2,2-bis (4-hydroxyphenyl) butane and the like. When a mixed solvent of water and an inert organic solvent is used, the method of the present invention can be applied to bis (4-hydroxyphenyl) sulfone.

As the alkylene oxide, ethylene oxide (hereinafter EO), propylene oxide (hereinafter PO), butylene oxide (hereinafter BO) can be used.

As the basic catalyst, potassium hydroxide, sodium hydroxide, amine-based catalysts such as tributylamine and triethylamine, and salts such as sodium acetate and sodium carbonate can also be used.

When the present invention is carried out, it can be produced in an autoclave using steam as a heat medium, like the general addition of alkylene oxide.

〔The invention's effect〕

According to the present invention, it is possible to produce an alkylene oxide adduct of a desired bisphenol compound, which has an extremely narrow alkylene oxide addition molar distribution width and does not contain any unreacted substances, by-produced polyalkylene glycol, inorganic substances and the like. Further, since the reaction proceeds without melting the bisphenol-based compound, it is possible to carry out the reaction in an autoclave using normal steam as a heat medium without requiring high temperature.

〔Example〕

Next, the present invention will be further described with reference to examples. Parts and% in the examples are based on weight unless otherwise specified.

Example 1. 2,2-bis (4-hydroxyphenyl) propane 228
Part, 228 parts of water, and 2.3 parts of triethylamine were placed in an autoclave equipped with a stirrer, and the mixture was heated to 85 ° C.,
Under a pressure of ² kg / cm ² , 100 parts of ethylene oxide are introduced over a period of 1 hour. Further, the reaction temperature is maintained at 80 to 90 ° C., and the reaction is continued for 1 hour. After the reaction was completed, it was washed with water and dried to obtain 305 parts of an ethylene oxide reaction product.

Example 2 In the same manner as in Example 1, the water was made to be 57 parts and the reaction product 309
Got a part.

Example 3 In the same manner as in Example 1, 0.5 part of sodium hydroxide was used in place of triethylamine as a catalyst to obtain 305 parts of a reaction product.

Example 4 In the same manner as in Example 1, using 23 parts of water and 46 parts of toluene as a solvent, 310 parts of a reaction product was obtained.

Example 5. 250 parts of bis (4-hydroxyphenyl) sulfone, water 1
25 parts of toluene, 125 parts of toluene, and 2.5 parts of sodium hydroxide were placed in an autoclave equipped with a stirrer, the mixture was heated to 85 ° C., and 100 parts of ethylene oxide was required for 1 hour under a pressure of ² kg / cm ^2. And introduce. Further, the reaction temperature is maintained at 80 to 90 ° C., and the reaction is continued for 1 hour. After the reaction was completed, it was washed with water and dried to obtain 325 parts of a reaction product.

Example 6. 544 parts of 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 125 parts of water, 125 parts of toluene, and 2.5 parts of sodium hydroxide were placed in an autoclave equipped with a stirrer. The mixture is heated to 85 ° C. and 100 parts of ethylene oxide are introduced under a pressure of ² kg / cm ² for 1 hour. Further, the reaction temperature is maintained at 80 to 90 ° C., and the reaction is continued for 1 hour. After the reaction was completed, it was washed with water and dried to obtain 615 parts of a reaction product.

Comparative Example 1. 2,2-bis (4-hydroxyphenyl) propane 228
Parts and 1 part of triethylamine were charged into an autoclave, heated and melted at 180 ° C., and 100 parts of ethylene oxide was press-fitted under stirring to cause a reaction. Then, it was washed with water and dried to obtain 303 parts of a reaction product.

Comparative Example 2. The same method as in Comparative Example 1 was carried out using 93 parts of ethylene oxide. Then, it was washed with water and dried to obtain 300 parts of a reaction product.

 The results obtained in the above example are shown in Table 1 below.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 43/205 7419-4H C07C 43/205 A 315/04 315/04 317/22 317/22 / / C07B 61/00 300 C07B 61/00 300

Claims (4)

(57) [Claims] 1. An alkylene oxide of a bisphenol compound by subjecting two hydroxyl groups of a bisphenol compound [excluding bis (4-hydroxyphenyl) sulfone] to an addition reaction of one alkylene oxide each in the presence of a basic catalyst. When producing the adduct, use water as the solvent and 100 ℃
A method characterized by reacting at the following temperature. 2. The method according to claim 1, wherein the amount of water is equal to or less than the weight of the bisphenol compound. 3. When an alkylene oxide adduct of a bisphenol compound is produced by adding one alkylene oxide to each of two hydroxyl groups of a bisphenol compound in the presence of a basic catalyst, water (mixed solvent) is used. 50% by weight or less) of benzene, toluene, xylene, and cyclohexane. 4. The method according to claim 3, wherein the inert organic solvent is 50% by weight or less based on the bisphenol compound.