JPH0725877B2 - Epoxy resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermosetting resin. More specifically, it relates to a novel thermosetting resin having an epoxy group at the molecular end.

Epoxy resin has curability, heat resistance, mechanical properties, adhesion,
It has excellent adhesiveness and is widely used. However, in recent years, in sealing material applications or composite material applications,
The required properties have become more sophisticated, and in addition to the conventional properties, low stress or toughness is required. The epoxy resin currently used for encapsulation material application is 0-cresol novolac type epoxy, while the epoxy resin used for composite material application is tetraglycidyl diaminodiphenylmethane or triglycidiaminophenol type epoxy. However, all of them have low stress or insufficient toughness.

From the above, the present inventors have diligently studied an epoxy resin that retains the properties of a conventional epoxy resin and additionally has excellent low stress and toughness, and the following epoxy resin is The present invention has been completed by finding that the above object is satisfied.

That is, the present invention has the following structural formula (1) [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group, an aralkyl group, an alkoxy group or Halogen atom, A is structural formula (In the formula, R ₄ and R ₅ are each independently a hydrogen atom and a carbon number of 1 to 1.
5 alkyl group, aryl group, aralkyl group, alkoxy group or halogen atom, X is a linear or branched alkylene group having 1 to 10 carbon atoms, -O-, -S-, (Wherein R ₆ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). ), And m and n each represent an integer of 0 to 100 in which at least one of them is not 0. ] The epoxy resin represented by this is provided.

As an example of the method for producing an epoxy resin of the present invention, a terminal hydroxyl group-containing compound represented by the following structural formula (2) is used as an intermediate, and this hydroxyl group is converted into epichlorohydrin, epipromohydrin, β-methylepichloro. Hirorin, β-
There is a method of dehydrohalogenating with an alkali after halohydrin etherification using epihalohydrin such as methylepipromohydrin.

[In the formula, R ₂ , R ₃ , A, m, and n are the same as described above. More specifically, as the catalyst in the halohydrin etherification reaction, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, lithium chloride, lithium hydroxide, triethylamine, tri-n-butylamine, triphenyl are used. Amine, quaternary amine such as dimethylbenzylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetraethylammonium Quaternary ammonium salt such as iodide,
Examples thereof include thioethers such as diethyl sulfide, dibenzyl sulfide, thiodiglycol, β-hydroxyethylene sulfide, and boron trifluoride, and one or more of these are used.

The halohydrin etherification reaction is preferably 80 to 180 ° C.
Can be performed at temperatures of. Usually, an excess of epihalohydrin can be used also as a reaction solvent, but other solvent can be used in combination if necessary.

Examples of the alkali used in the subsequent dehydrohalogenation reaction include sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium methoxide, potassium methoxide. , Potassium acetate,
Sodium acetate, sodium formate, calcium hydroxide,
Examples thereof include barium hydroxide, strontium hydroxide, trimethylamine, and triethylamine. These may be used alone or in combination of two or more, and the amount used may be equivalent or more. The reaction temperature of dehydrohalogenation is preferably 30 to 180 degrees, and the reaction solvent is not particularly limited.

The glycidyl etherification can also be carried out by a method in which halohydrin etherification and dehydrohalogenation are carried out simultaneously. Alternatively, it can also be carried out by a method in which after allyl etherification with allyl chloride, allyl bromide, etc., epoxidation with hydrogen peroxide, peracetic acid, etc.

As an example of the method for producing the intermediate represented by the formula (2), the general formula And bisphenols represented by HO-A-OH (wherein R ₂ , R ₃ , and A are the same as described above) by oxidative polymerization.

As a method of oxidation, there is a method of directly using oxygen gas or air, and on the other hand, there is a method of electrode oxidation, but the method is not limited thereto.

As a catalyst for oxidative polymerization using oxygen gas or air, one of CuCl, CuBr, Cu ₂ SO ₄ , CuCl ₂ , MuCl ₂ , Ag ₂ O, etc.
Or two or more of them are used, and in addition to the above catalyst, pyridine, methylpyridine, N, N-dimethyl-4-
Aminopyridine, poly-4-vinylpyridine, piperidine, morpholine, triethanolamine, n-butylamine, octylamine, dibutylamine, N, N-dimethyl-n-hexylamine, N, N-dimethyl-n-butylamine, tritetylamine , (N, N'-di-tert-butyl) ethylenediamine, 2-aminoethanetol, 2-
Methicapto-1-ethanol, 1,2-dimercapto-4
It is common to use one kind or two kinds or more of -methylbenzene etc. in combination, but it is not limited to these.

The solvent used in the polymerization is not particularly limited, and the temperature is also not limited, but 0 to 50 ° C. is particularly preferable.

The thus obtained epoxy resin of the present invention exhibits excellent properties of low stress and toughness when used in combination with an ordinary epoxy curing agent. Specifically, the elastic modulus and the coefficient of thermal expansion are smaller than those of the conventional epoxy, while the breaking elongation and the breaking energy are large. The curability, heat resistance, adhesiveness, adhesiveness, etc. are equal to or higher than those of conventional epoxy resins.

Examples of the epoxy curing agent include dicyandiamide, tetramethylguanidine, phenol novolac resin, cresol novolac resin, acid anhydride, aromatic amine, and one or more kinds of various aliphatic or alicyclic amines. Also, self-curing with a Lewis acid such as boron trifluoride is possible.

Examples of the acid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylxahydrophthalic anhydride, dodecenyl succinic anhydride, nadic acid anhydride, methylnadic acid anhydride, phthalic anhydride, Pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, methylsilktohexene tetracarboxylic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1-methyl- 3,4-dicarboxy-1,2,3,4-tetrahydro-1
There is one or more than one kind of naphthalene succinic acid dianhydride.

Examples of aromatic amines are 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylporopane, 4,4'-diaminodiphenyl sulfone, 3,3'-
Diaminophenyl sulfone, 2,4-toluenediamine, 2,6-toluenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, 4,4'-diaminophenyl sulfide, 3,3'-dichloro-4,4 ′
-Diaminodiphenyl sulfone, 3,3'-dichloro-
4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl)
Propane, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 4,4'-bis (3-aminophenoxy) diphenyl sulfone, 9,9'-bis (4-aminophenyl) anthracene, 9,9 ′ -Bis (4-aminophenyl) fluorene, 3,3′-dicarboxy-4,4 ′
-Diaminodiphenylmethane, 2,4-diaminoanisole, bis (3-aminophenyl) methylphosphine oxide, 3,3'-diaminobenzophenone, 0-toluisulphone, 4,4'-methylene-bis-0-ctotoaniline, tetra Chlorodiaminodiphenylmethane, m-
Xylylenediamine, p-xylylenediamine, 4,4 '
-Diaminostilbene, 5-amino-1- (4'-aminophenyl-1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3.3-trimethylindane, 5-amino -6-Methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane, 7-amino-6-methyl-1- (3'-amino-
4'-methylphenyl) -1,3,3-trimethylindane, 6-amino-5-methyl-1- (4'-amino-
3'-methylphenyl) -1,3,3-trimethylindane, 6-amino-7-methyl-1- (4'-amino-
3'-methylphenyl) -1,3,3-trimethylindane and the like.

Epoxy resin of the present invention, within the range of not impairing its properties,
It can be used in combination with a normal epoxy resin having two or more epoxy groups in the molecule. Examples include bisphenol A, bisphenol F, hydroquinone, resorcin,
Phloroglysin, Tris- (4-hydroxyphenyl)
Glycidyl ether compounds derived from divalent or trivalent phenols such as methane and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or halogenated bisphenols such as tetrabromobisphenol A, phenol, Novolak-based epoxy resin derived from novolac resin which is a reaction product of phenols such as O-cresol and formaldehyde, aniline, p-
Aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 1,4-bis (4-
Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy)
Benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine Ein, 1,4-cyclohexane-bis (methylamine), 1,3-cyclohexane-bis (methylamine),
5-amino-1- (4'-aminophenyl) -1,3,3-
Amine-based epoxy resin derived from trimethylindan, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylidane, p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, Glycidyl ester compounds derived from aromatic carboxylic acids such as isophthalic acid, hydantoin epoxy resins derived from 5,5 dimethylhydantoin, 2,2'-bis (3,4-epoxycyclohexyl) pyropan, 2 Alicyclic epoxy resins such as 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, and 3,4-epoxycyclohexylmethyl-3,4-epoxycycloxanecarboxylate, In addition, one or more kinds of triglycidyl isocyate, 2,4,6-triglycidoxy-8-tothiazine and the like are mentioned. be able to.

If necessary, conventionally known tertiary amines, phenol compounds, imidazoles and other Lewis acids may be added as curing accelerators.

The epoxy compound of the present invention may be used in combination with a filler, a filler, a reinforcing agent, a pigment or the like, if necessary. For example, silica, calcium carbonate, antimony trioxide, kaolin,
One or more of titanium dioxide, zinc oxide, mica, barite, carbon black, polyethylene powder, polypropylene powder, aluminum powder, iron powder, copper powder, glass fiber, carbon fiber, alumina fiber, asbestos fiber, etc. are used. To be It can be used for molding, lamination, adhesives, composite materials, etc.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 <Preparation of Intermediate> stirrer, thermometer, chloroform with a flask air inlet tube 112g, CuCl ₂ 0.276g (2.79 mmol) 4-dimethylaminopyridine 0.498 g (4.08 mmol) 25 ° C.
Bubbled air at 20 l / hr for 15 minutes. After that, 2,6-xylenol 1 dissolved in 201 g of chloroform in advance was used.
0.5 g (86.0 mmol), 2,2'-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane 6.15 g (21.6 mmol) were added, and while bubbling 20 l / hr of air, 25 The temperature was kept at 3 ° C for 3 hours. After keeping the temperature, 20 l / hr of nitrogen gas was bubbled for 10 minutes, washed twice with 75 g of 15% hydrochloric acid aqueous solution, neutralized with 5% NaHCO ₃ aqueous solution, and further washed with water several times for post-treatment. Then, chloroform was distilled off under the final conditions of 160 ° C. and 2 mmHg to obtain an intermediate.

This product had a hydroxyl equivalent of 427 g / eq, a number average molecular weight of 950 determined from VPO, and a melting point of about 110 ° C.

<Production method of epoxidized product> Agitator, thermometer, cooling liquid separator, dropping funnel, intermediate 17,17 g (0.04 equivalent per hydroxyl group) obtained above in a flask equipped with a decompression device, epichlorohydrin 185 g ( 2 mol)
Was charged and the temperature was raised to 60 ° C. to dissolve. Then 150mmHg
The pressure was reduced to, and while water was distilled off azeotropically, 3.67 g (0.044 mol) of a 48% sodium hydroxide aqueous solution was added for 1 hour. The temperature during the dropwise addition was about 60 ° C., and after the dropwise addition, the temperature was kept for 30 minutes to complete the water distillation. After that, the remaining epichlorohydrin was distilled off under the conditions of final 140 ° C. and 5 mmHg, the obtained resin product was dissolved in 198 g of toluene, the generated salt was removed by filtration, and the impurities were removed by further washing with water. . After that, toluene was distilled off under final conditions of 150 ° C. and 2 mmHg to obtain an epoxidized product.

This product had an epoxy equivalent of 594 g / eq and a melting point of about 90 ° C.

Example 2 <Production Method of Intermediate> 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane of Example 1 was converted into 2,2-bis- (3,5-dimethyl-).
4-hydroxyphenyl) methane 25.4 g (208 mmol)
Instead, the same operations as in Example 1 were carried out except that the reaction and post-treatment were carried out. After chloroform was distilled off, the residue was dissolved in 48 g of tetrahydrofuran and precipitated in water. After the precipitation, washing with water was repeated several times and drying under reduced pressure to obtain an intermediate.

This compound had a hydroxyl equivalent of 780 kg / eq, a number average molecular weight of 1620 determined from VPO, and a melting point of about 150 ° C.

<Production method of epoxidized product> The amount of the above-mentioned intermediate used was 31.2 g (0.04 equivalent), the distillation temperature of residual epichlorohydrin was changed to 160 ° C, and the distillation temperature of toluene was changed to 170 ° C. The same operation as in 1 was performed to obtain an epoxidized product.

This product had an epoxy equivalent of 995 g / eq and a melting point of about 135 ° C.

Claims (1)

[Claims] 1. The following structural formula [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an aryl group, an aralkyl group, an alkoxy group or Halogen atom, A is structural formula (In the formula, R ₄ and R ₅ are each independently a hydrogen atom and a carbon number of 1 to 1.
5 alkyl group, aryl group, aralkyl group, alkoxy group or halogen atom, X is a linear or branched alkylene group having 1 to 10 carbon atoms, -O-, -S-, (Wherein R ₆ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). ), And m and n each represent an integer of 0 to 100 in which at least one of them is not 0. ] The epoxy resin represented by.