JPH02123131A - Novel diglycidyl ether and production thereof - Google Patents

Abstract

PURPOSE:To obtain a useful compound having an arbitrarily adjustable polymerization degree, being made into a resin of ultraviolet-curing type, being blended with an amine, etc., as it is and curable as an epoxy resin, having a specific structure and high fluorine content. CONSTITUTION:A diglycidyl ether shown by formula I (n is 0 or positive integer; m is 1-4 integer). The diglycidyl ether is obtained by reacting a diol shown by formula II with epichlorohydrin in the presence of an alkali. The diglycidyl ether having an arbitrary molecular weight can be obtained by controlling an amount of epichlorohydrin used as the raw material and reaction temperature.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is applicable to resins for optical materials that utilize low refractive properties due to high fluorine content, UV-curable composite resins, and non-adhesive resins that utilize low surface energy properties. This paper relates to a new diglycidyl ether used as a raw material for synthetic resins and a method for producing the same.

[Prior Art and Problems to be Solved] Conventionally, a typical epoxy resin made from 4,4-dioxydiphenylpropane (hereinafter abbreviated as bisphenol A) is well known. These have characteristics such as good dimensional stability, good water resistance, and high strength, and are widely used in cast products, molded products, paints, etc. in addition to being used as adhesives.

However, no known aromatic compound with a high fluorine content has the structure of the present invention, in which fluorine is directly bonded to the benzene nucleus.

[Means for Solving the Problems] The present inventor uses the below-described diol, which is a new aromatic compound with a high fluorine content, as a raw material, and increases the degree of polymerization with the diol by reacting it in epichlorohydrin. The present invention has been achieved by discovering that the compound of the present invention can be obtained with arbitrarily adjusted .

That is, the present invention is based on the general formula (where n represents 0 or a positive integer, and Maro represents 1 to 1).
This invention relates to a diglycidyl ether represented by the following integer 4) and a method for producing the same, and is characterized by reacting a diol represented by the following general formula (■) with epichlorohydrin in the presence of an alkali.

(however, During the ceremony Heat indicates an integer from 1 to 4.

Examples of the compound represented by the general formula (II) which is a raw material of the present invention include 2,4-bis(2-hydroxyhexafluoro-2-propyl)fluorobenzene, 2,6-bis(2-hydroxyhexafluoro- 2-propyl)-
Examples include 1,4-difluorobenzene, 2.5-bis(2-hydroxyhexafluoro-2-propyl)1,4-difluorobenzene, and the like.

The reaction temperature of the present invention is preferably 50 to 100°C, more preferably 70 to 100°C, and the degree of 3 reaction points is 50°C.
If it is lower than 100°C, the reaction will not proceed, and if it is higher than 100°C, it will approach the boiling point of epichlorohydrin and the vapor pressure will rise rapidly, making it difficult to carry out the reaction.

Since epichlorohydrin, which is one of the reaction raw materials, is a liquid, it can be reacted without particularly adding a solvent. At that time, the degree of polymerization can be controlled by the amount of epichlorohydrin used in the reaction. That is, when the amount of epichlorohydrin is large, the concentration of the chemical compound becomes low, so that polymerization does not proceed much, resulting in a low molecular weight polymer. On the other hand, if the amount of epichlorohydrin is small,
As the concentration of the product increases, polymerization proceeds further and a product with a high molecular weight is produced.

The reaction of the present invention requires an alkali compound as a catalyst, but this compound is not particularly limited, and examples include hydroxides and carbonates of alkali metals or alkaline earth metals, among which KOH , NaOH is preferred; these compounds are normally used in aqueous solution.

After the reaction is completed, the produced diglycidyl ether can be obtained by removing epichlorohydrin by distillation.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 10 g (23.4 mmol) of 24-bis(2-hydroxyhexafluoro-2propyl)fluorobenzene was added to 2
2g of epichlorohydrin dissolved in <471ml;
50% potassium hydroxide aqueous solution 6g (53.6viol)
was added and stirred vigorously. With the generation of heat, the solution became homogeneous, and when the mixture was heated to 90°C and stirring was continued, precipitation of KCI was observed. After reacting for 1 hour, the mixture was cooled, washed with water until neutral, and after liquid separation, the organic layer was dried over anhydrous magnesium sulfate. 12.5 g of a colorless viscous liquid was obtained as a residue after distilling 1-pichlorohydrin under reduced pressure.
It was confirmed by R,'H NMR that it was the desired diglycidyl ether. The measurement results for 19F NMH are shown in FIG.

In this case, the solvent is CDCl3 and the reference material is CFCl3
It is. Moreover, the measurement results of HNMR are shown in FIG.

In this case, the solvent is CDCl3 and the reference material is TMS. The epoxy value of this product was 326. This is distilled to boiling point range 136-146°C/1.5gm)Ig
7.6 g of fraction was obtained, the epoxy value of this product was 298, and the mass spectrum of the main component was 540 (M"0.I
X), 411 (2, Oz), 395 (5,0”),
394(10,97>273(7,3Z),73(6,
4Z), 57 (35°2χ), 43 (7,8χ>), which were confirmed to be 2,4-bis(glycidyloxyhexafluoro-2-propyl)fluorobenzene.

[Effect of the invention 1] According to the production method of the present invention, by controlling the amount of epichlorohydrin used as a raw material, the reaction temperature, etc., a novel diol as shown in the present invention can be obtained with any molecular weight. The obtained compound can be made into an ultraviolet curable resin by reacting with another compound containing an unsaturated group, or it can be cured as an epoxy resin by directly mixing it with a curing agent such as an amine. It is a useful compound.

[Brief explanation of the drawing]

Figure 1 shows the measurement results for 19F NMH, and Figure 2 shows the measurement results for 19F NMH.
1 The measurement results of NMH are shown.

Claims (2)

[Claims] (1) Diglycidyl ether represented by general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (However, in the formula, n represents 0 or a positive integer, and m represents 1 to
Indicates an integer of 4. ) (2) A method for producing diglycidyl ether represented by general formula (I), which is characterized by reacting a diol represented by general formula (II) with epichlorohydrin in the presence of an alkali ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼(II) (However, in the formula, m represents an integer from 1 to 4.)