JPH0621151B2 - Modified epoxy resin manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified epoxy resin.

Generally, an epoxy resin has excellent properties such as adhesiveness, coatability, weather resistance, solvent resistance, electrical characteristics, transparency and mechanical strength.

Therefore, epoxy resins are used in a wide range of applications.

The present invention is to provide a modified epoxy resin which is useful as an adhesive, a resin improving agent, a fiber treating agent, a coating material, a filling material, an electric component material and the like by utilizing the characteristics of conventional epoxy resins. That is, the general formula (1) And an epoxy resin represented by the general formula (2) The compound represented by the general formula (3) is reacted in the presence of a dehydrohalogenating agent. Is a method for producing an epoxy resin.

As the epoxy resin represented by the general formula (1) used in the present invention, a bifunctional phenol compound represented by the general formula (4),
For example And a compound obtained by reacting epihalohydrin or methylepihalogehydrin.

Examples of the epihalogenhydrin and methylepihalohydrin include epichlorohydrin, epibromudrin, methylepihalochlorbidoline, methylepichlorohydrin and methylepibromohydrin.

Examples of the compound represented by the general formula (2) include: Examples of the dehydrohalogenating agent include amines such as trimethylamine, triethylamine, triacrylamine and tributylamine, pyridine, picoline, diethylaniline, caustic alkali and alkali carbonate.

The method for producing a modified epoxy resin represented by the general formula (3) according to the present invention is a method of preparing the epoxy resin represented by the general formula (1) and the compound represented by the general formula (2) in the presence of the dehalogenating agent. Specifically, the epoxy resin represented by the general formula (1) is converted into a solvent, for example, chlorinated hydrocarbons such as methylene chloride and trichloroethali, dimethylformamide or dimethylsulfoxide, etc. Dissolve, then add and dissolve the dehalogenating hydrogenating agent, keep the temperature in the reaction system at 0 to 40 ° C, and then add the compound represented by the general formula (2) as it is or by dissolving it in a solvent and dropping it. .

After the dropping is completed, the stirring is further continued at the above temperature to complete the reaction.

After completion of the reaction, the salt is removed by filtration to remove the by-product salt, or water is added to the reaction system to dissolve the by-product salt, followed by washing with water, and optionally Na ₂ CO ₃ or NaHCO _{3 at} any concentration. After washing with an aqueous solution, further washing with water is carried out, and the crystals are filtered off and dried, or the solvent is distilled off.

The amount of the compound represented by the general formula (2) is, based on one OH group contained in the epoxy resin represented by the general formula (1),
The compound represented by the general formula (2) is preferably 1 to 1.3 mol.

The amount of the dehydrohalogenating agent used is preferably 1 to 1.1 mol per 1 mol of the compound represented by the general formula (2).

The modified epoxy resin represented by the general formula (3) obtained according to the method for producing a modified epoxy resin of the present invention has improved water resistance,
It has excellent properties such as imparting plasticity, improving electrical properties, cross-linking to improve physical properties, and weather resistance. Adhesives, resin modifiers, fiber treatment agents, coating materials, filling materials, electronic parts Materials, pigments, dispersants for inorganic materials, crosslinking agents,
Most suitable as paint and emulsion improver.

Next, examples of the present invention will be described. In the examples, "%" is based on weight.

Example 1 , And the epoxy equivalent of about 1400, 200 g of epoxy resin is dissolved in 580 g of methylene chloride, and the reaction system is heated to 10 ° C.
Keep below, add 99.9g of triethylamine,
Stir.

Next, keep the inside of the reaction system at 10 to 20 ° C and diphenylphosphinic chloride. 147 g is dropped and reacted.

After the addition is complete, stir at 30 ° C for 3 hours and then at 40% for 3 hours.

Next, 600 g of water, 600 g of 1% Na ₂ CO ₃ aqueous solution and 600 g of water are sequentially added to wash, the lower methylene chloride layer is taken out, dehydrated and dried, the solvent is distilled off, and 308 g of a modified epoxy resin represented by the following formula (Yield 95%) was obtained.

This modified epoxy resin has an epoxy oxygen content of 0.66% (calculated value 0.68%) and a phosphorus content of 5.
96% calculated value 5.94%).

Example 2 And 90.8 g of an epoxy resin having an epoxy equivalent of about 500 is dissolved in 200 g of methylene chloride, and the reaction system is mixed with 10
Keep it below ℃, add 22g of triethylamine,
Stir.

Next, keep the reaction system at 10 to 20 ℃ and dibutylphosphinic chloride. 39.3g is added dropwise and reacted.

After the addition is complete, stir at 20 ° C for 2 hours and then at 30 ° C for 5 hours.

Next, 100 g of water, 100 g of 1% Na ₂ CO ₃ aqueous solution and 100 g of water are sequentially added to wash, the lower methylene chloride layer is taken out, dehydrated and dried, and then the solvent is distilled off to obtain a modified epoxy resin represented by the following formula. 116.3 g (yield 96%) was obtained.

This modified epoxy resin has 2.63% epoxy oxygen (calculated value
2.16%) and phosphorus content was 5.10% (calculated value 5.06%).

Example 3 1016 g of epoxy resin represented by
Is dissolved in, and the reaction system is kept at 10 ° C or lower, 205 g of triethylamine is added thereto, and the mixture is stirred.

Next, keep the temperature inside the reaction system at 10 to 20 ° C and diphenylphosphinic chloride. Add 473 g dropwise to react.

After the addition is complete, stir at 20 ° C for 1 hour and then at 30 ° C for 3 hours.

Next, after adding 5000 g of water to the reaction system to wash it, 500 g of a 1% Na ₂ CO ₃ aqueous solution and 5000 g of water were added, and after washing twice, the lower methylene chloride layer was removed, dehydrated and dried, and the solvent was distilled off. 1427 g (yield 98.8%) of the modified epoxy resin represented by the formula was obtained.

This modified epoxy resin has an epoxy oxygen content of 2.1% (calculated value 2.3%) and a phosphorus content of 4.31% (calculated value 4.29%).
Met.

Example 4 257 g of an epoxy resin containing Br and F atoms shown in (3) is dissolved in 1000 g of methylene chloride, the inside of the reaction system is maintained at 10 ° C., 41.0 g of triethylamine is added, and the mixture is stirred.

Next, keep the inside of the reaction system at 10 to 20 ℃, 100.2 g is added dropwise to react.

After the addition is complete, stir at 20 ° C for 1 hour and then at 30 ° C for 3 hours.

Next, after adding 3000 g of water to the reaction system and washing it, 500 g of 1% Na ₂ CO ₃ aqueous solution and 3000 g of water were added, and after washing twice, the lower methylene chloride layer was removed, dehydrated and dried, and the solvent was distilled off to denature it. 334 g (yield 97%) of epoxy resin was obtained.

This modified epoxy resin has an epoxy oxygen content of 0.90%
(Calculated value 0.93%), phosphorus content 3.65% (calculated value 3.61%)
Met.

Example 5 And an epoxy resin having an epoxy equivalent of 633
Dissolve 126 g in 300 g of trichloroethane and add 10 g to the reaction system.
Keep below ℃, add 29.5g of pyridine and stir.

Next, keep the inside of the reaction system at 10 to 20 ° C and diphenylphosphinic chloride. A solution prepared by dissolving 87.5 g in 100 g of trichloroethane is added dropwise and reacted. After completion of dropping, at 20 ℃ for 1 hour, then at 40 ℃
Stir for 3 hours.

Next, it is filtered off, and 500 g of water, 300% of 1% Na ₂ CO ₃ aqueous solution and 500 g of water are sequentially added to the filtrate for washing, the lower layer of trichloroethane is taken out, dehydrated and dried, and then the solvent is distilled off. As a result, 190 g (yield 95%) of a modified epoxy resin was obtained.

Modified epoxy resin has an epoxy oxygen content of 1.51% (calculated value
1.60%) and phosphorus content was 8.10% (calculated value 8.16%).

Application Example 1 To 100 parts of a commercially available epoxy resin (Epicoat 828), 27 parts of a curing agent diaminodiphenylmethane, 5 parts of silica, and 20 parts of the modified epoxy resin of Example 4 were added, thoroughly mixed, cast, and then at 80 ° C. for 2 hours. After heating, the impact strength, tensile strength, transverse rupture strength, water absorption test (100 ° C, 1 hour) and specific resistance of the molded product obtained by further curing at 160 ° C for 3 hours were measured.
Similarly, a comparison was made with the case where no modified epoxy resin was added.

The results are shown in Table 1.

Application Example 2 A molding obtained by adding 100 parts of a commercially available epoxy resin (Epicoat 828) with 27 parts of a curing agent diaminodiphenylmethane, 5 parts of silica, and 25 parts of the modified epoxy resin of Example 3 and curing the same as in Application Example 1. The same evaluation was performed.

The results are shown in Table 2.

Claims (1)

[Claims] 1. A general formula (1) And an epoxy resin represented by the general formula (2) The compound represented by the general formula (3) is reacted in the presence of a dehydrohalogenating agent. A method for producing a modified epoxy resin, which comprises obtaining an epoxy resin represented by: