JPS61186375A - 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 water-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 dihydric phenolic acid of formula II (e.g. resorcylic acid, catecholic acid, etc.) with the epihalohydrin of formula III (X is Cl or Br) in the presence of a catalyst such as 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 in a liquid state with low viscosity even at room temperature, and can be used in FR applications such as casting, filament winding, and hand lay-up at room temperature.
It can be applied to the P molding method, and since it does not crystallize or self-polymerize even at low temperatures, it has good storage stability and is characterized by significantly improved workability compared to conventional heat-resistant epoxy resins. It is something to do.

[Prior Art] Epoxy resins are widely used in various fields. Among epoxy resins, diglycidyl ether of bisphenol A is the most commonly used, but its heat distortion temperature is low and it cannot be used in applications that require heat resistance.Therefore, phenol novolak type epoxy resins are used as heat-resistant epoxy resins. Resin, cresol novolac type epoxy resin, 1.
Polyfunctional glycidyl ether compounds such as tetraglycidyl ether of 1', 2'2'-tetrakis(P-hydroxyphenyl)ethane have been used, but all of them are solid at room temperature or have a curing agent with a considerably high viscosity. Mixing requires heating to melt or lower the viscosity, resulting in poor workability. Applications that require the resin used to have a low viscosity, such as casting at room temperature, filament winding, and hand lay-up molding. could not be used. In addition, polyfunctional glycidyl compounds such as N, N, N', N'-tetraglycidyldiaminodiphenylmethane, N, N', O-triglycidylaminophenol, etc., which are widely used as heat-resistant epoxy resins in the field of carbon fiber composite materials, are also used. Since amine compounds have nitrogen atoms in their molecules, they are self-polymerizable and have the drawbacks of poor storage stability and poor water resistance of cured products. In addition, although these polyfunctional glycidylamine compounds are liquid at room temperature, they have high viscosity.
It was difficult to use it for casting, filament winding, hand layup, etc.

Further, as a similar example of the compound according to the present invention, triglycidyl ether of phloroglucin ()1. lee
and K, Neville, “Handbo
OK of Epoxy Re5ins”, Mc
Graw-Hllll (1967), 4-37>
However, it was inferior in terms of short-time curability at low temperatures.

[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 following general formula (1) is obtained by using a dihydric phenolic acid such as resorcinic acid as a starting material and converting its phenolic hydroxyl group and carboxyl group into glycidyl ether and glycidyl ester. They have discovered that the above problems can be solved by using a new polyepoxy compound having the chemical structure.

R:H or CHff The novel polyepoxy compound of the present invention is synthesized by the following polyepoxy compound synthesis method. First, by reacting a dihydric phenolic acid having the following chemical structure, such as R: H or CH3, such as resorcinic acid, catecholic acid, or hydroquinonic acid, with epihalohydrin in the presence of a catalyst, the epihalohydrin of the dihydric phenol is prepared. After producing the ether ester, the epihalohydrin ether ester of the dihydric phenolic acid is reacted with an alkali metal compound to obtain the novel polyepoxy compound of the present invention represented by the general formula (1).

The epihalohydrin used in the present invention includes:
It is represented by the general formula (2): X: Cα or Br R: H or CH3 Specific examples include epichlorohydrin, shrimp bromohydrin, and β-methylepichlorohydrin. 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 spring 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 diethylphate. The amount of these catalysts used is in the range of 0.1 mol % to 50 mol % based on 1 mol of the raw material phenol compound.

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 10°C.
It is carried out in a substantially anhydrous state at a temperature range of 0° 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 to be used is 0.000 to 1 mole of phenolic hydroxyl group of the raw material phenol compound.
It ranges from 8 to 1.2 moles. 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 reacted by azeotroping with shrimp halohydrin. It is preferable to proceed with the reaction while removing it from the system, and it is further preferable to proceed with the reaction under reduced pressure in order to 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 diethylenetriamino, triethylenetetramine, and isophoronediamine, and adducts of these with epoxy compounds such as ethylene oxide and propylene oxide, or acrylic compounds such as acrylonitrile and acrylic acid, and diaminoethylated diethylenetriamine. modified aliphatic polyamines, such as
Polyamide amines such as dimer acid/diethylenetriamine condensates, aromatic polyamines such as methylene dianiline, m-phenylene diamine, and diaminodiphenylsulfone, adducts of these with epoxy compounds, Lewis acids such as boron trifluoride, and these salts and complexes, polymercaptan compounds such as polysulfide resins,
Imidazole compounds such as 2-ethyl-4-methylimidazole, salts of these with organic acids, acid anhydrides such as hexahydrophthalic anhydride and methylnadic anhydride, and phenolic water II such as phenol novolac. Examples include compounds having dicyandiamide, urea, and derivatives thereof.

The novel polyepoxy compound of the present invention may be used alone 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.

In addition to a curing agent, the epoxy resin composition using the novel polyepoxy compound of the present invention may optionally contain fillers, flame retardants, heat stabilizers, antioxidants, thickeners, and flexibility imparting agents. , lubricants, curing accelerators, and various other additives 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 trifunctional, 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. Water resistance is also good. In addition, the most important feature of the new polyepoxy compound of the present invention is that it is a liquid with low viscosity at room temperature and does not crystallize even at low temperatures, and has significantly improved workability, so it can be used in a wide variety of applications. be able to. 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.

Triglycidyl ether of phloroglucin can be mentioned as a similar example to the present invention, but the novel polyepoxy compound of the present invention is useful in that it cures at a lower temperature and in a shorter time.

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

Example 1 46.2 g of resorcinic acid (0.3 mOl ＞ and epichlorohydrin 416°3CI (4.5 mol) were heated and dissolved at 50°C in an oil bath, and then benzyltrimethylammonium chloride 3.33Cl (0
,018m.

1) was added, and the mixture was heated and stirred at 50°C for 24 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 distilled water 'room+,
It was added dropwise over an hour. The pressure of the reaction system was reduced to 100 mmHg, and the reaction proceeded while removing water in the system by azeotropy with epichlorohydrin. 1 in the same state after the completion of dripping
After continued heating for hr, the produced NaCf1 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 obtain 90 g of a brown liquid product. Ta.

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 20°C was 140 poise, and the epoxy equivalent measured by the hydrochloric acid-dioxane method was 128 (theoretical value 107°3).

Example 2 An epoxy resin composition prepared by blending 4BQ of diaminodiphenylsulfone to 100 l of the epoxy compound obtained in Example 1 was heated to uniformly dissolve it, and then vacuum defoamed.
Pour into a 120mm x 120mm x 2mm silicone mold and heat in an oven at 150°C x 1hr', 190'C.
It was cured under the conditions of x4 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 boiling for 2Qhr 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-828 (liquid bisphenol A type epoxy resin; manufactured by Yuka Shell Epoxy Co., Ltd.) as an epoxy compound
A cast plate was prepared in exactly the same manner as in Example 2, except that an epoxy resin composition containing 100 g of diaminodiphenylsulfone and 22 g of diaminodiphenylsulfone as a curing agent was used, and its physical properties were measured. The results are shown in Table 1.

Comparative example 2 ELM-12o (N, N.

A casting plate was prepared in exactly the same manner as in Example 2, except that an epoxy resin composition containing 100 g of 〇-triglycidyl-m-amine phenol (manufactured by Sumitomo Chemical Co., Ltd.) and 52 g of diaminodiphenylsulfone as a hardening agent was used, and the physical properties were determined. was 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 VJT polyepoxy compound of the present invention is trifunctional and has excellent heat resistance.Since it does not contain nitrogen atoms in the molecule, it is not self-polymerizable and has excellent storage stability. Water resistance is also good.

[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