JPS5890572A - polyepoxy compound - Google Patents

Abstract

NEW MATERIAL:A polyepoxy compound expressed by formulaI(R1 and R2 are H or methyl). USE:A raw material for epoxy resins, capable of giving cured epoxy resin articles having more improved heat resistance, and obtainable economically from inexpensive raw materials. PROCESS:Isophthalaldehyde is reacted with a monohydric phenol, e.g. phenol or cresol, in the presence of an acidic catalyst, e.g. hydrochloric acid or sulfuric acid, at 40-200 deg.C to give a compound expresed by formula II, which is then reacted with an epihalohydrin or beta-methylepihalohydrin in the presence of a quaternary ammonium salt or an alkali to afford the compound expressed by formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel tetrafunctional epoxy compound which is useful by itself or in combination with other epoxy compounds to provide an epoxy resin exhibiting excellent cured properties. It is.

Epoxy resin is a thermosetting resin that can be coated, laminated, painted,
Widely used in various fields such as adhesion, sealing, and molding, various epoxy compounds such as glycidyl needle type and glycidyl ester type are known as polyfunctional epoxy compounds for epoxy resins. There is.

However, the types and physical properties of known polyfunctional epoxy compounds are not necessarily sufficient to satisfy all of the many different resin applications in terms of properties such as curing properties and curing speed.

For example, a bifunctional engineered poxy compound obtained by reacting bisphenol A and epichlorohydrin in the presence of an aqueous solution of caustic soda has a low heat distortion temperature, and also has the drawback of decreasing bending strength and large weight loss when kept at high temperatures for a long time. has.

In addition, Shell Chemical's Eviny) 103 shown by the following formula
No. 1 is intended to improve the drawbacks of the above-mentioned difunctional engineered poxy compounds, but it has not been reprinted at present.

CH-CH The present inventors have noticed that a polyfunctional epoxy compound or an epoxidized metal having a large number of aromatic rings provides a cured epoxy resin with excellent heat resistance. , investigated various phenolic compounds as raw materials for epoxy compounds, and by reacting a -valent phenol compound with terephthalaldehyde, a compound containing many aromatic rings and four heptenolic hydroxyl groups in the molecule was found. Para-(a, tx, d, d-tetrakis(glycidyloxyaryl))xylene produced by obtaining a polyhydric phenol compound, reacting it with shrimp halohydrin, and completing the ring-closing reaction with caustic soda is then treated with a curing agent. He discovered that a cured product with excellent heat resistance could be obtained, and filed an application earlier (Japanese Unexamined Patent Publication No. 1983-1999).
No. 139373).

However, since terephthalaldehyde is expensive as a raw material, para-[α, α
, α', α'-tetrakis(glycidyloxyaryl)]quixin must also be expensive.

The present inventors have discovered that inphthalaldehyde, which is obtained by treating meta-xylene diamine with hexamethylenetetramine, concentrated hydrochloric acid, and aqueous acetic acid, can be produced at a production cost approximately 30% lower than that of terephthalaldehyde, and that it is derived from isophthalaldehyde. Meta-[α, α
, α′, α′-tetrakis(glycidyloxyaryl)]quixin is converted to para-[α, a, α′, α
'-Tet2kis(glycidyloxyaryl)] It was discovered that a cured product with no color loss was obtained compared to the cured product of chixin, and the present invention was completed. [In the formula, R1 and R3 represent a hydrogen atom or a methyl group] This provides a meta-[a, a, g', a'-tetrakis(glycidyloxyaryl)]quixin represented by ) The tetrafunctional glycidyl compound represented by the formula is
In advance, as described above, iso7taldehyde and a monovalent phenol compound, that is, phenol or cresol, are subjected to a dehydration reaction to form a tetravalent phenol compound represented by the following general formula (R1'' R2 (seal) [Formula wherein R2 represents a hydrogen atom or a methyl group] and then reacting this with shrimp halohydrin or β-methyl shrimp halohydrin in the presence of a quaternary ammonium salt or an alkali.

Isophthalaldehyde is produced by reacting a mixture of metaxylene diamine, hexamethylenetetramine, concentrated hydrochloric acid, and acetic acid aqueous solution under reflux (approximately 105°C) for 3 hours as described above, and hydroxylating the reactant. After that, it is economical to leave the precipitated acicular crystals at a temperature of 5°C for a day and night, separate the precipitated needle crystals, and dry them.
It can also be obtained by dissolving xylene in a mixture of acetic anhydride and acetic acid and oxidizing it with a sulfuric acid solution of chromium oxide.

The reaction between isophthalaldehyde and the monovalent phenol compound in the first step is carried out in the presence of an acidic catalyst such as hydrochloric acid, sulfuric acid, or para-toluenesulfonic acid at a ratio of 4 to 50 moles of the -valent phenol compound per mole of isophthalaldehyde. React for 1-12 hours at a temperature of 40-200℃.
After the reaction is complete, the excess phenol compound is distilled off under reduced pressure, and the resulting solid product is crushed, washed with a solvent such as tetrachloroethane, and heated and dried under vacuum to give a deep orange color. The above-mentioned -valent phenol compounds include phenol, ortho-cresol, meta-cresol, para-cresol, ortho-bromophenol, metabromophenol, varabromophenol, propylphenol, butylphenol,
Examples include octylphenol-nonylphenol. These may be used alone or in combination of two or more.

Next, the subsequent reaction will be explained in detail. The shrimp halohydrin or β-methyl shrimp halohydrin used is:
For example, epichlorohydrin, shrimp bromohydrin, β
-Memethiepichlorohydrin and β-methylevibromohydrin. The amount of shrimp halohydrin or β-memethyrohydrin used is 4 to 40 mol, preferably 6 to 20 mol, per 1 mol of the raw material tetravalent phenol compound. The shrimp halohydrin or β-methyl shrimp halohydrin used in excess can be recovered by distillation and reused.

The reaction method includes (1) a one-step method in which addition reaction and dehydrogenation reaction are performed at once using an alkali;
(2) Two-stage addition reaction using a catalyst such as a quaternary ammonium salt at a temperature of 50 to 150°C, followed by a dehydrohalogenation reaction with an alkali at a temperature of 35 to 80°C. However, the latter two-step method is preferred from the viewpoint of yield and product quality. Examples of the alkali used include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, etc., but sodium hydroxide or potassium hydroxide is preferably used. Examples of the catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium bromide, triethylmethylammonium chloride, tetraethylammonium iodide, cetyltriethylammonium bromide, benzyldimethylamine, triethylamine, N, N, N, , tertiary amines such as N'-tetramethylethylenediamine, triphenylethylphosphonium diethyl phosphate, and the like.

Particularly preferred is tetramethylammonium chloride or tetraethylammonium blonde. The amount of alkali used is usually 4 to 5 mol per 1 mol of the raw material tetravalent heptanol compound. The alkali is usually added to the reaction system in the form of solid particles or in the form of an aqueous solution. Further, the amount of the quaternary ammonium salt used is usually about 0.1 to 3.0 parts by weight based on the weight part of the tetravalent heptadol compound Zoo as the raw material.

The reaction temperature varies depending on the type of reactants, but is usually 4.
The temperature is 0-200°C, preferably 70-150°C. The reaction time is until the reaction is substantially completed, and varies depending on the papermaking, reaction temperature, etc., but is usually 2 to 10 hours, preferably 2 to 5 hours.
It's time.

After the reaction is completed, excess shrimp halohydrin or -monomethyl shrimp halohydrin and water are removed under reduced pressure, and the halogenated terchloride produced as a by-product is separated from P to obtain the epoxy compound of the present invention.

As is clear from the structural formula, the tetrafunctional epoxy compound of the present invention produced in this manner is a tetraglycidyl etherified product of the tetravalent phenol compound used as a raw material or a derivative thereof.

This tetrafunctional epoxy compound is rarely isolated alone, and generally glycidyl groups or V-methyl groups represented by R2 in formula (1) are 2.2', 3.3', 4, 4', 5.5
a mixture of various tetrafunctional poxy compounds at position ';
For example, when phenol is used as a raw material, meta-[α,
α, α-a′-tetrakis(p-glycidyloxyphenyl)]-xylylene is meta-[α, α, α′, α′-
Tetrakis(0-glycidyloxyphenyl)]-xylylene (though it seems to be a minor component, meta-[α, tz
, d, d-tetrakis(m-glycidyloxyphenyl)]-quixin: When m-cresol is used as a raw material, meta-("+"+α',α'-tetrakis(2-methyl-4-glycidyloxy phenyl)]-xylylene is a mixture of meta-('+"+α', α'-tetrakis(2-methyl-6-glycidyloxyphenyl)]-xylylene.

This tetrafunctional poxy compound can be used alone or in combination with other epoxy compounds for use as an epoxy resin. In other words, this tetrafunctional epoxy compound may be used alone, or it may be combined with one or two other epoxy compounds.
If these or more species are used in combination and a curing (crosslinking) reaction is carried out with an appropriate curing agent, a cured product with extremely excellent thermal properties as represented by the degree of thermal deformation m can be obtained. There are no particular restrictions on the other epoxy compounds used in combination, and various epoxy compounds may be used in combination depending on the intended use. Other epoxy compounds used in combination include polyglycidyl ethers such as bisphenol AM and bromobisphenol A, polyglycidyl esters such as phthalic acid and cyclohexanedicarboxylic acid, and polyglycidyl esters such as haaniline or toluidine. Amines, etc., styrene oxide, cyclohexene oxide, phenyl glycidyl ether, butylg,
Examples include monoepoxy compounds such as lycidyl ether, allyl glycidyl ether, and persatic acid glycyl ester, which are used in combination with the epoxy compound of the present invention in a proportion of 10 to 90% by weight.

Furthermore, in the epoxy resin using the epoxy compound of the present invention, various curing agents similar to those applicable to known epoxy resins can be used. For example, aliphatic amines, aromatic amines, heterocyclic amines, Lewis acids such as boron trifluoride and their salts, organic acids, organic acid anhydrides,
Examples include urea or derivatives thereof, and polymercaptans. Specific examples include diaminodiphenylmethane, diaminodiphenyl sulfone,
2. Aromatic amines such as 4-diamino-m-xylene: 2
-Imidazole or imidazole substitutes such as methylimidazole, 2,4.5-triphenylimidazole, l-cyanoethyl-2-methylimidazole, or salts of these with organic acids; fumaric acid, trimellitic acid, hexahydrophthalic acid Organic carboxylic acids such as; phthalic anhydride,
organic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, dicyandiamide,
urea derivatives such as triethylenetetramine, diethylenetriamine, xylylene triamine, inphorondiamine, etc.; and their epoxy compounds such as ethylene oxide and propylene oxide, or acrylic compounds such as acrylonitrile and acrylic acid. Adducts with compounds etc. can be used.

Furthermore, in addition to a curing agent, the epoxy resin using the epoxy compound of the present invention may optionally contain a plasticizer, an organic solvent, a reactive diluent, an extender, a filler, a reinforcing agent, a pigment, and a flame retardant. A variety of additives such as thickeners, thickeners, and flexibility imparters can be blended.The cured epoxy resin using the epoxy compound of the present invention has a higher viscosity compared to conventional general-purpose bisphenol-based epoxy resins. Thermal properties such as thermal deformation fIi degree are extremely excellent, and the mechanical properties are the same or higher. Therefore, this epoxy compound can be advantageously used in various fields such as molding, adhesion, painting, and lamination similar to those for conventional epoxy resins.A more specific explanation will be given below with examples. However, these examples are merely illustrative, and the present invention is not limited by the examples.Isophthalaldehyde is usually prepared in a 2-t four-bottle flask equipped with a thermometer, a stirrer, and a cooling tube, and a meta-xylylene microwave is used. Amine 108.8f, hexamethylenetetramine 4GOf, 50% acetic acid aqueous solution 1.2
8 t of concentrated hydrochloric acid and 192 d of concentrated hydrochloric acid were charged, and after the reaction was completed, 1.54 t of a 7.7% aqueous sodium hydroxide solution was added to the reactant while stirring slowly.

After standing at a temperature of 5° C. for a day and night, nine needle-shaped crystals precipitated were separated by F, washed with a large amount of water, and dried to obtain pale yellow isophthalaldehyde. The yield was 70%, and the melting point was 88-90°C.

Production example of tetrahydric phenol compound Production example 1 K in a four-hole flask equipped with a temperature needle, a stirrer, and a cooler,
20F of isophthalaldehyde and 224.42 of phenol were charged.◎The mixture was kept at 50-60°C, 2-3 drops of concentrated hydrochloric acid was added, and stirring was started. Subsequently, the system temperature was maintained at 100° C. and stirred for 4 hours to complete the dehydration reaction.

After the reaction, unreacted phenol was distilled off under reduced pressure (30-Hg) using an evaporator, and the residue was poured into an aluminum dish and cooled to solidify. After pulverizing this, it was pulverized two to three times with tetrachloroethane. Washed and dried to melting point 107-1
15°C, red powder with hydroxyl equivalent of 120 68.6 f
I got it.

It was confirmed by infrared absorption spectrum (Figure 1) and nuclear magnetic resonance spectrum (Figure 2) that this powder was meta-C"+α,l,α'-tetrakis(hydroxyphenyl)]-quixin.

Production Example 2 Phenol 673.2F, isophthalate^7hf) in a 1 ton three-bottle flask equipped with a temperature needle, stirrer, and condenser.
After the reaction was completed, the catalyst was dissolved in 700 parts of methyl isobutyl ketone, washed twice with 500 parts of water, and the catalyst was removed. Methyl isobutyl ketone and residual phenol were removed using a rotary evaporator under reduced pressure (40 to 1 μHg, 60
~180°C).

The obtained phenol compound had a yield of 104.2 f, a red transparent solid, a softening temperature of 105 to 112°C, and a hydroxyl equivalent of 119.

Production example 3 Metacresol 2 instead of phenol 24i, 4t
53.1 Production Example 1 except that f is used Island = similarly red transparent meta-Ca, α, α', a'-tetrakis ()
1 idroxytrile)]-]xylene approx. 75.5ft
-4 The melting point of this product is 104-112℃, and the hydroxyl equivalent is 13
It was 3.

Example 1 The N-hydric phenol compound obtained in Production Example 1 was placed in a three-bottle flask equipped with a temperature needle, a stirrer, and a condenser with 60 t1 of ebichlor ε-drine, 187.6 F, and 0.6 f of tetraethylammonium chloride. Prepare
The mixture was heated to 117° C. in an oil bath and reacted under reflux for 2 hours.

Next, it was cooled to 60°C and a water separator was attached. Add 21.2 f of sodium hydroxide (1.05 equivalents per hydroxyl group) and reduce the pressure to 40-100-Hz.

The reaction was carried out while controlling the reaction system so that the temperature was 50 to 70°C. A reaction produces. Water was removed by azeotropy with epichlorohydrin, and epichlorohydrin was continuously returned to the system for reaction for 2 hours.To the obtained epichlorohydrin solution of the epoxy compound, 500f of toluene was added and washed three times with 500f of water. The generated common salt and excess sodium hydroxide were completely removed. Epichlorohydrin and toluene were removed using a rotary evaporator under reduced pressure (100 to 1 μHg, 160 to 150°C) to obtain a yellow transparent solid 86F.

The softening temperature of this material is 65-70℃, the epoxy equivalent is 19
It was 5.

The infrared absorption spectrum and nuclear magnetic resonance spectrum of this polyepoxy compound were as shown in FIGS. 3 and 4, respectively.

Actual Example 2 The same procedure as in Example 1 was made except that the tetrahydric phenol compound 66f obtained in Production Example 2 was used instead of the tetrahydric phenol compound 60F obtained in Production Example 1, and the product was orange and transparent, with a melting point of 61 to 67°C.
, a solid 91.9 F having an epoxy content of 203 was obtained.

Application Examples 1 to 2 To 100 parts by weight of the epoxy resin obtained in each example, 90 parts by weight of methylnadic acid anhydride manufactured by Nippon Kayaku ■ was added as a curing agent.
The heat distortion temperature (A・S
TM-D-648) was measured.

The results are shown in Table 1.

Application Comparative Example 1 ~ As an epoxy resin, para-[α, α, ff', ff'
- Tetrakis (glycidyloxyphenyl)] - xylene, phenol novolac epoxy resin 1 Epicoat 154 (trade name) manufactured by Yuka Shell Epoxy ■, Nippon Kayaku ■
Ortho-cresol novolac epoxy resin “EOCN”
A cured product was obtained in the same manner as in Application Example 1 except that IO4S (trade name)'# was used, and its heat distortion temperature was measured.

The results are shown in Table 1.

(Left below) Application Examples 3 to 4, Comparative Application Examples 4 to 6 The polyepoxy compound obtained in Example 1.2, para-(a,
a, α', α'-tetrakis (glycidyloxyphenyl)] xylene, orthocresol novolac epoxy resin, tetraglycidyl methylaniline manufactured by Tobu Kasei ■
Using YH434 (trade name) # as an epoxy resin, 100 parts by weight of these, 25 parts by weight of diaminodiphenylmethane as a hardening agent, and 200 parts by weight of fused silica as a filler were mixed with a roll to 70~b, and then a pulverizer was used. This was granulated using a heating press at 160°C for 1'0 minutes at a pressure of 100 lc.
Compression molded under f/cd conditions, length 12.7am, width 1
．． A molded product having a thickness of 27 aw and a thickness of 0.6451 was obtained.

Table 2 shows the physical properties of the molded product obtained.

From the results obtained, it can be seen that the epoxy compounds of the present invention all have high heat resistance at a relatively low temperature of 160°C for 10 minutes for a short time and excellent mechanical strength retention at high temperatures.

[Brief explanation of drawings]

Figures 1 and 2 are the infrared absorption spectrum (EngR) and nuclear magnetic resonance spectrum (NMR) of the tetrahydric phenol compound obtained in Production Example 1, respectively, and Figures 3 and 4 are
The figures are IR and NMR of the 94-functional epoxy compound obtained in Example 1. Patent applicant: Mitsubishi Yuka Co., Ltd.

Claims (1)

[Scope of Claims] A polyepoxy compound represented by the general formula: [wherein Ro and R2 represent a hydrogen atom or a methyl group].