JPH0527630B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a novel method for producing glycidyl ether compounds. More specifically, the present invention relates to a method for producing a glycidyl ether compound that provides an epoxy resin exhibiting excellent cured physical properties when used alone as a resin component or in combination with other glycidyl ethers. [Prior Art] Epoxy resins containing glycidyl ethers as a main component are widely used as thermosetting resins in paints, adhesives, coating materials, molding materials, and laminated materials. However, in the case of epoxy resins using conventionally known polyfunctional glycidyl ethers, the curing speed, curing physical properties, etc. are not suitable for all of the various uses of epoxy resins. For example, in the case of epoxy resins using ordinary bisphenol A type diglycidyl ether compounds obtained by reacting bisphenol A and epichlorohydrin in the presence of an aqueous solution of caustic soda, drawbacks include low heat distortion temperature of the cured product. There is. [Object of the Invention] The present invention provides a method for producing a glycidyl ether compound that eliminates the drawbacks of the conventionally known polyfunctional glycidyl ethers and provides a cured epoxy resin product with excellent cured physical properties, particularly excellent heat resistance. It is in. [Structure of the Invention] The present invention is based on the following formula (): The general formula for ditrimethylolpropane is shown by (): (In the formula, R represents a hydrogen atom or a methyl group,
characterized by reacting an epihalohydrin compound represented by (X represents a halogen atom),
General formula (): [In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or

[Embodiments of the invention]

In the present invention, there are two methods for producing a glycidyl ether compound () by reacting ditrimethylolpropane () and an epihalohydrin compound () (epihalohydrin or β-methyl epihalohydrin). (1) Ditrimethylolpropane () and epihalohydrin compound () are reacted in the presence of an alkali metal hydroxide etc. to form the general formula (): [In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom or

^α represented ^{by the} formula (where R ^and - A one-step method for producing a glycidyl ether compound () by simultaneously carrying out an addition reaction to produce a monohalogenohydrin derivative and a ring-closing reaction to form an epoxy ring by dehydrohalogenation of this α-monohalogenohydrin derivative. . (2) Ditrimethylolpropane () and epihalohydrin compound () are first subjected to an addition reaction in the presence of a catalyst such as a phosphonium salt or a quaternary ammonium salt, and then an alkali metal hydroxide is added to perform a ring-closing reaction. A two-step method for producing glycidyl ether compounds (). Of the above two methods, the latter two-stage method has a higher yield and a lower content of high molecular weight substances in the final reaction product obtained.
It is preferable to the one-stage method. In the one-stage process, the reaction is carried out at a temperature ranging from 60 to 150°C, preferably from 80 to 120°C. The amount of epihalohydrin compound () used for ditrimethylolpropane () is 1 to 10 of the theoretical amount.
The amount is twice the molar amount, preferably about 2 to 6 times the molar amount. In addition, the alkali metal hydroxide is at least equimolar to the hydroxyl group of ditrimethylolpropane (),
Preferably, it is used in an amount of 1.05 to 1.5 times the mole. In the two-stage method, the addition reaction in the first stage is 40~
It is carried out at a temperature of 150°C, preferably in the range 40-80°C. The amount of the catalyst used in the addition reaction of the pre-residue is about 0.1 to 10 mol% based on ditrimethylolpropane (). Epihalohydrin compounds ()
The amount of alkali metal hydroxide used in the subsequent reaction is the same as in the one-stage method. The entire reaction in the one-stage process and the subsequent ring-closing reaction in the two-stage process are carried out under normal pressure or reduced pressure (preferably at 50%
~200 mmHg), while the water produced is continuously removed from the system by azeotropy with the epihalohydrin compound (200 mmHg). In either the one-stage method or the two-stage method, after the reaction is completed, the reaction solution is filtered to remove by-product salts, and the unreacted epihalohydrin compound () is removed and recovered to form the glycidyl ether compound ().
It can be grown. In addition, the glycidyl ether compound () obtained in this way can be dissolved in an organic solvent that is sparingly soluble in water, such as methyl ethyl ketone, methyl isobutyl ketone, toluene, etc., and the resulting solution can be chlorinated by contacting with water or hot water. Purification can be achieved by extracting impurities such as sodium into the aqueous layer and then distilling off the organic solvent from the organic layer. Examples of the epihalohydrin compound () used as a raw material include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and β-methylepibromomodrine. Further, as mentioned above, a quaternary ammonium salt, a phosphonium salt, or the like is used as a catalyst in the first stage addition reaction in the two-stage process. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetraethylammonium chloride, triethylmethylammonium chloride,
Examples include tetraethylammonium iodide, cetyltriethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, cetyltriethylammonium bromide, and tetrabutylammonium bromide. Examples of the phosphonium salt include tetraphenylphosphonium halide, triphenylethylphosphonium halide (iodide, bromide, chloride, etc.). Particularly preferred catalysts include tetramethylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, and the like. The glycidyl ether compound () of the present invention is 1
in the molecule

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but these Examples are merely illustrative and the present invention is not limited by these Examples. Example 1 200 g of ditrimethylolpropane, 1480 g of epichlorohydrin, and 8 g of tetramethylammonium chloride were placed in a container equipped with a thermometer, a cooler, and a stirrer.
The mixture was placed in a three-necked flask, and the reaction was carried out at 75°C for 3 hours. Thereafter, the reaction solution was cooled to 60° C., a water separator was attached, 320 g of a 40% by weight aqueous sodium hydroxide solution was added, and a ring-closing reaction was carried out under reduced pressure (100 to 150 mmHg). The produced water was continuously removed from the system by azeotroping with epichlorohydrin. The reaction was terminated when the amount of produced water reached the theoretical amount (for introducing four glycidyl groups into one molecule of ditrimethylolpropane). After the reaction is complete, remove unreacted epichlorohydrin from 1 to
After recovery by distillation at 60-110° C. under a reduced pressure of 50 mmHg, 0.5 ml of methyl ethyl ketone was added to make the product into a slurry, and then filtered to remove by-product salts. After washing the liquid with 200 ml of water, methyl ethyl ketone was distilled off under reduced pressure to obtain 320 g of a pale yellow liquid. The viscosity (20°C) of this product was 185 poise, and the epoxy equivalent was 126. Example 2 318 g of a pale yellow liquid was obtained in the same manner as in Example 1, except that 12 g of benzyltriethylammonium chloride was used instead of tetramethylammonium chloride. This product had a viscosity (at 20°C) of 183 poise and an epoxy equivalent of 125. Example 3 330 g of pale yellow liquid was obtained in the same manner as in Example 1 except that 1700 g of β-methylepichlorohydrin was used instead of epichlorohydrin. This product (at 20°C) had a poise of 170 and an epoxy equivalent of 141. Application Examples 1 to 2 Using the glycidyl ether compounds of the present invention obtained in Examples 1 to 2 above and Epicote 828 (trade name of glycidyl ether of bisphenol A manufactured by Ciel Chemical Co., Ltd., epoxy equivalent: 190), these was mixed with diaminodiphenylmethane, a curing agent, in the ratio shown in Table 1 to prepare an epoxy resin composition, and each of the resulting compositions was defoamed for several minutes under reduced pressure of 1 to 5 mmHg. The material was injected into a mold and cured. After pretreatment at 80°C for 2 hours, curing was performed by heating at 150°C for 4 hours and then at 175°C for 16 hours to obtain a completely cured product. The heat distortion temperature (ASTM
D 648) and tensile strength (JIS K 6911) were measured. The results are shown in Table 1. As is clear from Table 1, the glycidyl ether compound of the present invention provides a cured product with superior cured physical properties compared to Epicote 828, which is a difunctional bisphenol A glycidyl ether compound.

【table】

【table】

Claims (1)

[Claims] Primary formula (): The general formula for ditrimethylolpropane is shown by (): (In the formula, R represents a hydrogen atom or a methyl group,
characterized by reacting an epihalohydrin compound represented by (X represents a halogen atom),
General formula (): [In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or [Formula] (where R represents the same as above) (However, R ¹ ,
except when R ² , R ³ and R ⁴ are all hydrogen atoms)] A method for producing ditrimethylolpropane glycidyl ether.