JPS61186376A - Novel polyepoxy compound - Google Patents

Abstract

NEW MATERIAL:The polyepoxy compound of formula (R is H or CH3). USE:The compound has high heat-resistance, gives a cured product having excellent mechanical characteristics and waer-resistance, and is useful as a molding material, sealant for electronic parts, adhesive, paint, matrix resin for composite material, etc. It keeps a liquid state having low viscosity and is resistant to crystallization even at a low temperature. It has no self-polymerization tendency, and has excellent storage stability and remarkably improved workability. PREPARATION:The compound of formula I can be produced by reacting the resorcinol sulfide of formula II with the epihalohydrin of formula III (X is Cl or Br) in the presence of a catalyst such a quaternary ammonium slat, tertiary amine, etc. at 40-100 deg.C, and subjecting the reaction product to dehydrohalogenation reaction with an alkali metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyepoxy compound having a novel chemical structure. When the polyepoxy compound of the present invention is used alone or in a mixture with other polyepoxy compounds, the cured product has high heat resistance and excellent mechanical properties and water resistance, and is a molding material that requires heat resistance and water resistance. It can be used in a wide range of applications, including encapsulating materials for electronic components, circuit boards, adhesives, coating materials, paints, and matrix resins for composite materials. In particular, the polyepoxy compound of the present invention is liquid even at room temperature, does not crystallize at low temperatures, has good storage stability, and has significantly improved workability compared to conventional heat-resistant epoxy resins. That is.

[Prior Art] Epoxy resins are widely used in various fields. Among epoxy resins, diglycidyl ether of bisphenol A is most commonly used, but it has a low heat distortion temperature and cannot be used for applications requiring heat resistance. Therefore, we use heat-resistant epoxy resin.

As a result, polyfunctional glycidyl ether compounds such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, and tetraglycidyl ether of 1.1', 2゜2'-tetrakis(P-hydroxyphenyl)ethane have been used. It is either solid at room temperature or has a fairly high viscosity, and must be heated to melt or lower the viscosity when mixed with a hardening agent, resulting in poor workability.

In addition, N, N, and N' are widely used as heat-resistant epoxy resins in the field of carbon fiber composite materials.

Polyfunctional glycidylamine compounds such as N'-tetraglycidyldiaminodiphenylmethane have a nitrogen atom in the molecule and are therefore self-polymerizable, resulting in poor storage stability and poor water resistance of cured products.

[Problems to be Solved by the Invention] The present inventors took into consideration the above-mentioned drawbacks of conventional heat-resistant epoxy resins, and arrived at the present invention as a result of intensive study on a new polyepoxy compound that improves these drawbacks. It is.

[Means for solving the problem] That is, the above problem is solved by using a new polyepoxy compound having the chemical structure of the following general formula (1), which is obtained by using resorcinol sulfide as a starting material and converting its phenolic hydroxyl group into glycidyl ether. I discovered that I could solve the problem.

R: H or CH3 The novel polyepoxy compound of the present invention is synthesized by the following polyepoxy compound synthesis method. First, resorcinol sulfide having the following chemical structure is reacted with epihalohydrin in the presence of a catalyst to generate shrimp helohydrin ether of resorcinol sulfide, and then shrimp helohydrin ether of resorcinol sulfide and shrimp helohydrin ether of resorcinol sulfide are produced. By reacting with an alkali metal compound, the novel polyepoxy compound of the present invention represented by general formula (1) can be obtained.

The epihalohydrin used in the present invention includes:
It is represented by the general formula (2), x:cg or Br R:H or CH3 Specific examples include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. The amount of epihalohydrin used is in the range of 2 to 15 moles, preferably 3 to 7 moles, based on the phenolic hydroxyl group of the phenol compound as a raw material.

Catalysts used in the present invention include tetramethylammonium chloride, tetraethylammonium bromide, triethylmethylammonium chloride,
Examples include quaternary ammonium salts such as benzyltrimethylammonium chloride, amine salts such as triethylamine hydrochloride, tertiary amines such as triethylamine, and triphenylethylphosphonium diethyl phosphate. The amount of these catalysts used is 0.1 mol% to 50 mol% based on 1 mol of the raw material phenol compound.
is within the range of

In the synthesis method of the present invention, this epihalohydrin etherification reaction is carried out at 20'C to 150°C, preferably from 40'C to 150°C.
It is carried out in a substantially anhydrous state at a temperature range of 100° C. for 2 to 50 hours.

After completion of this epihalohydrin etherification reaction, a dehydrohalogenation reaction using an alkali metal compound is carried out, but before that, it is preferable to include a step of removing the catalyst by washing the reaction solution with water. This step improves the purity and yield of the desired polyepoxy compound.

In the synthesis method of the present invention, the dehydrohalogenation reaction is carried out in the presence of an alkali metal compound.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, and sodium methylate.

The amount of these alkali metal compounds used is 0.8 per mole of phenolic hydroxyl group of the raw material phenol compound.
~1.2 mol. In the synthesis method of the present invention,
The dehydrohalogenation reaction is carried out at a temperature of 50'C to 120'C, but when alkali hydroxide is used as the alkali metal compound, the water produced in the reaction is removed from the reaction system by azeotroping with epihalohydrin. It is preferable to proceed with the reaction, and it is preferable to proceed with the reaction under reduced pressure in order to roughly lower the azeotropic temperature.

After the dehydrohalogenation reaction is completed, the desired new polyepoxy compound can be obtained by separation and purification by a conventional method.

As the curing agent to be added when using the novel polyepoxy compound of the present invention, all compounds conventionally known as curing agents for epoxy resins can be used. Specifically, aliphatic polyamines such as diethylene triamine, triethylene tetramine, and isophorone diamine, and their adducts such as epoxy compounds such as ethylene oxide and propylene oxide, or acrylic compounds such as acrylonitrile and acrylic acid, diaminoethyl modified aliphatic polyamines such as diethylene triamine, polyamide amines such as dimer acid/diethylene triamine condensates, aromatic polyamines such as methylene dianiline, m-phenylene diamine, diaminodiphenylsulfone, adducts of these with epoxy compounds, trifluorocarbons, etc. Lewis acids such as boron oxide, and their salts and
Complexes, polymercaptan compounds such as polysulfide resins, imidazole compounds such as 2-ethyl-4-methylimidazole, and salts of these with organic acids, acid anhydrides such as hexahydrophthalic anhydride and methylnadic anhydride, and phenol. Examples include compounds having a phenolic hydroxyl group such as novolak, dicyandiamide, urea, and derivatives thereof.

The novel polyepoxy compound of the present invention may be used alone or as a condensate thereof, or in combination with other epoxy compounds as long as the useful advantages of the novel polyepoxy compound of the present invention are not impaired. can not use.

Roughly speaking, the epoxy resin composition using the FR polyepoxy compound of the present invention contains a hardening agent and, if necessary, a filler,
Various additives such as flame retardants, heat stabilizers, antioxidants, thickeners, flexibility imparters, lubricants, and curing accelerators can be used.

Furthermore, the epoxy resin composition using the novel polyepoxy compound of the present invention can be used as a matrix resin for fiber-reinforced plastics in combination with reinforcing fibers such as carbon fiber, boron fiber, alumina fiber, aramid fiber, and glass fiber.

[Effects of the Invention] The novel polyepoxy compound of the present invention is tetrafunctional, so it has excellent heat resistance, and since it does not contain nitrogen atoms in the molecule, it is not self-polymerizable and has excellent storage stability, and the cured product has improved mechanical properties and water resistance. The quality is also good. In addition, the most important feature of the new polyepoxy compound of the present invention is that it is liquid at room temperature and does not crystallize even at low temperatures, and its workability is significantly improved, so it can be used in a wide variety of applications. can. Further, the novel polyepoxy compound of the present invention has a high reactivity of the epoxy group, and is also characterized in that it cures at a lower temperature and in a shorter time than conventional heat-resistant epoxy resins.

[Example code] The specific content of the present invention will be explained below with reference to Examples.

Example 1 Resorcinol sulfide 75.0Q (0.3 mo
l > and x Bichlorochtrine 472.5ml (6
, 0 mol> and heated to dissolve at 50°C in an oil bath.
．． 440 (0,024 mo I) and heated at 50°C.
The mixture was heated and stirred for 4 hours. During this time, the reaction solution changed from dark brown to light brown. After 24 hours, 300 ml of distilled water was poured into the reaction solution, stirred, and then allowed to stand still to remove the upper water layer, thereby washing the reaction solution with water.

Next, dissolve 48g of NaOH in 100ml of steam water for 4 hours.
It was dripped over 30 minutes. The reaction system was depressurized to 100 mmH (7), and the reaction proceeded while removing water in the system azeotropically with epichlorohydrin.
After continued heating, NaCff generated was removed by washing with water.

Next, after removing excess epichlorohydrin under reduced pressure and heating, 200 ml of methyl isobutyl ketone was added and the solid content was removed by suction filtration, and the methyl isobutyl ketone was distilled off using a rotary evaporator to produce a brown liquid product 13C)Qe. Obtained.

The infrared absorption spectrum of this liquid product is shown in FIG.

In addition, NMR and MS analysis results revealed that this liquid product was an epoxy compound in which R is H in general formula (1).

The viscosity of this epoxy compound at 40°C was 750 poise, and the epoxy equivalent measured by the hydrochloric acid-dioxane method was 145 (theoretical value: 118°5).

Example 2 An epoxy resin composition containing diaminodiphenylsulfone 42 (II) mixed with 100 CI of the epoxy compound obtained in Example 1 was heated to uniformly dissolve the mixture, and after degassing under vacuum, it was placed in a 120 mm x 120 mm x 2 mm silicone mold. Pour in oven at 150℃ x 1hr, 190℃
It was cured under the conditions of 4 hours to create a casting plate. The tensile properties of this cast plate were measured according to JIS K-6911. In addition, the weight increase rate after 20 hours of boiling was measured to evaluate water resistance. The results are shown in Table 1.

Example 3 The epoxy compound obtained in Example 1 was sealed and left in an atmosphere at 80° C. for one month, but no changes such as viscosity change were observed and the storage stability was good.

Comparative Example 1 Ep-154 as an epoxy compound (phenol novolak type epoxy resin manufactured by Dioilka Shell Epoxy Co., Ltd.)
A casting plate was prepared in exactly the same manner as in Example 2, except that an epoxy resin composition containing 100 g of diaminodiphenylsulfone 34q as a curing agent was used, and its physical properties were measured. The results are shown in Table 1.

Comparative example 2 ELM-434 (N, N) as an epoxy compound.

A casting plate was prepared in exactly the same manner as in Example 2, except that an epoxy resin composition containing 100q of N',N'-tetraglycidylaminodiphenylmethane (manufactured by Sumitomo Chemical Co., Ltd.) and 40g of diaminodiphenylsulfone as a hardening agent was used. The material was prepared and its physical properties were measured. The results are shown in Table 1.

Comparative Example 3 When the storage stability was evaluated in the same manner as in Example 3 except that the epoxy resin composition used in Comparative Example 2 was used, the viscosity increased significantly and it became unusable.

As described above, the novel polyepoxy compound of the present invention is tetrafunctional, so it has excellent heat resistance, and since it does not contain a nitrogen atom in the molecule, it is not self-polymerizable and has excellent storage stability, and the cured product has excellent mechanical properties and water resistance. is also good.

Table 1

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of the polyepoxy compound obtained in Example 1 of the present invention.

Claims (1)

[Claims] A new polyepoxy compound having a chemical structure represented by the following general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) R: H or CH_3