JPH03264571A - Epoxy-based compound, production thereof and cured resin obtained from same compound - Google Patents

Abstract

NEW MATERIAL:An epoxy based compound shown by formula I [G is group shown by formula II or formula III; R is H or <=4C hydrocarbon group; n and m are 1-4; Ar is (halogen-substituted) <=16C (n+m)-functional aromatic hydrocarbon group]. EXAMPLE:N-(3-Glycidyloxyphenyl)acrylamide. USE:A component for epoxy-based resin, having a low melting point, excellent workability, rapidly curing, curable by radical curing, ultraviolet light curing, epoxy curing, etc., useful for adhesive, casting resin, coating compound, electrical insulating material, complex material matrix resin, etc., having excellent mechanical characteristics such as heat resistance and impact resistance. PREPARATION:A compound shown by formula IV is reacted with a carboxylic acid introducing group of a compound shown by formula V [Y is halogen or -O-R' (R' is hydrocarbon group], then with an epihalohydrin and dehydrohalogenated to efficiently give a compound shown by formula I.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel epoxy compound, a method for producing the same, and mechanical properties obtained therefrom, such as dimensional stability, heat resistance, chemical resistance, electrical properties, etc. This invention relates to an excellent new epoxy resin.

[Prior Art] Conventionally, epoxy resins have been used in a wide range of fields such as paints, electrical insulation materials, civil engineering and construction materials, adhesives, and composite materials using fibers as reinforcing materials because of their various excellent properties. However, as technology advances in recent years, the performance required of epoxy resins has become more sophisticated, and there is a demand for epoxy resins that can be molded faster and have higher heat resistance.

There is an acryloyl group that cures in a shorter time than an epoxy group, and a compound having an acryloyl group is polymerized using ultraviolet light or a radical initiator to form a cured molded product. Therefore, the introduction of this acryloyl group into an epoxy compound has already been disclosed in JP-A-60-130580. This epoxy compound utilizes the fast curing property of the acryloyl group and has the property of being able to be quickly formed into a molded article.

However, this disclosed epoxy compound does not necessarily have sufficient heat resistance when used as a resin, and higher heat resistance and better mechanical properties are required.

[Object of the Invention] The first object of the present invention is to provide a novel epoxy compound that cures quickly and provides an epoxy resin with excellent heat resistance. Another object of the present invention is to provide an epoxy resin having good heat resistance and excellent mechanical properties, which is obtained by curing the epoxy compound using a curing agent. be.

[Structure of the Invention] The object of the present invention as described above is: (1) An epoxy compound mainly composed of a structure represented by the following general formula (I>), an aromatic hydrocarbon group having a valence of 1?(n+m) .

(2) The amino group of the compound represented by the following general formula (n) and (H2N+.Ar -(OH) , -(II)
A metal compound (IV) is prepared with a phosphoric acid derivative group, and then the amide compound (IV)
1. A method for producing an epoxy compound, which comprises reacting and epihalohydrin, followed by dehydrohalogenation.

(3) This is achieved using a cured epoxy resin obtained by curing the epoxy compound of formula (I> above) with an epoxy curing agent, a radical initiator, and/or an ultraviolet ray.

The present invention will be explained in detail below.

The novel epoxy compound according to the present invention has a novel chemical structure represented by the above-mentioned format (1). In the above formula (I>, R is hydrogen and/or carbon number 1-
-4 hydrocarbon groups, and examples of such hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl.

Among R, hydrogen groups and methyl groups are particularly preferred.

■ is an integer from 1 to 4, preferably 1 or 2;
m is an integer of 1 to 4, preferably 1 or 2.

G in formula (I> is CH3. In an epoxy compound containing two or more G,
Each G may be any of the above.

In addition, Ar in the same formula is a halogen atom and/or a carbon number 1
1 carbon atom optionally substituted with ~4 alkyl groups
It is an aromatic hydrocarbon group of 6 or less and has a valence of <n10m>.

Examples of such aromatic hydrocarbon groups include monoaromatic groups, specifically benzene, naphthalene, etc. when unsubstituted, or Ar'-Ar' or Ar.
' -X -Ar' (where Ar' is the above-mentioned monoaromatic group, and X is O, SO2, CH2°CH3-(,
-CH3,S, CF3-C-CF3, etc.). Specifically, the skeleton names when unsubstituted are biphenylbenzene, diphenyl ether, diphenyl meta, /, 2.2' -diphenylpropane, 2.
2'-diphenylperfluoropropane and the like. Monoaromatic groups and polyaromatic groups include chloro, bromo,
It can have substituents such as methyl, ethyl, propyl, etc.

Among these, benzene, toluene, naphthalene, chlorobenzene, dibromobenzene, 2.2'
- diphenyl isopropane, diphenyl ether, diphenyl, etc.

Specific examples of the epoxy compounds of the present invention are as follows.

o=cc=CH2 vinegar 0 　R 11 -C OH2 The melting point of such a new epoxy compound can be measured.

Identified by infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy, elemental analysis, etc.

The novel epoxy compound (I) of the present invention can be synthesized by the following route.

First, the amino group of a compound represented by the following -form (If) and (H2N+, -Ar(-OH). -(II)O OH2 to form an amide compound having a hydroxy group (IV
), then react the amide compound (IV) with 2-epihalohydrin, and then perform dehydrohalogenation with an alkali.

Specific examples of preferable compounds for the compound (II>) include the following aromatic amines.

C1(3 OH OH2 OH2 OH OH2 Oh.

C) (3 I-I OH 3 On the other hand, examples of preferred carboxylic acid 4 derivatives of the compound (III>) include acid chloride, acid bromination, phenyl ester, cresyl ester, nitrophenyl ester, etc. of acrylic acid or methacrylic acid. It is.

For the amide production reaction, conventional methods such as a solution method and an interfacial method can be applied.

Specific examples of epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichromehydrin, and β-methylepichromehydrin.
-Methyl epibromohydrin, etc. Particularly preferred are epichlorohydrin and β-methylepichromehydrin. These may be used alone or in combination of two or more. The amount of epihalohydrin used is at least equimolar, preferably at least 3 times the molar amount of the amide compound (IV) having a hydroxyl group. A non-reactive solvent may be used if necessary.

This reaction with epihalohydrin is carried out in the presence of a catalyst, and preferred catalysts include quaternary ammonium salts. 4
Preferred ammonium salts include tetraalkyl or benzyltrialkyl salts such as tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, and benzyltrimethylammonium acetate.

The amount of quaternary ammonium salt used is based on compound (IV),
A range of 0.001 to 1 mole is appropriate. The reaction temperature and reaction time are 30 to 150°C for 30 minutes to 10 hours.
Preferably, the temperature is 60 to 120°C for 1 to 5 hours.

Alkali dehydrohalogenation can be carried out subsequent to the reaction with epihalohydrin.

It is also possible - optionally after separating off the unreacted epihalohydrin from the reaction mixture, to react the reaction product further with an alkali.

Examples of the alkali used in this reaction include alkali metal salts such as sodium, potassium, and lithium, and/or weak acid salts such as their hydrides and carbonates. Among these, sodium hydride is preferred. The amount of alkali used is 0.8 mol or more, preferably 0.9 to 3.5 mol, based on compound (IV). The reaction temperature and time are room temperature to 100°C for 10 minutes to 5 hours, preferably 40 to 80°C.
30 minutes to 3 hours and 6.

Since the epoxy compound obtained by the above reaction contains water-soluble inorganic substances such as quaternary ammonium salts and/or alkalis in addition to unreacted epihalohydrin as described above, unreacted epihalohydrin is usually removed from the reaction mixture by distillation. After that, if necessary, it is dissolved in a solvent that is difficult to miscible with water, such as toluene or xylene, and the water-soluble inorganic substances are removed by extraction with water or by furnace separation. Made of quality epoxy compound.

The novel epoxy compound represented by the general formula (I) of the present invention is a viscous liquid to solid at room temperature, and is cured by a conventionally known acrylic resin curing method and/or epoxy resin curing method. It can be made into a cured resin with excellent heat resistance and good mechanical properties. Particularly in curing, a good cured resin can be obtained by using both the curing of the acrylic resin and the curing of the epoxy resin.

7. Acrylic resins are cured using commonly used radical initiators or ultraviolet irradiation. In some cases, a curing method using a Michael addition reaction using an amino group can also be used. As the radical initiator, it is preferable to use an organic peroxide from the viewpoint of handling. Examples of the radical initiator include ketone peroxide, halide peroxide, diacyl peroxide, peroxyketal, and alkyl perester. and percarbonates, specifically methyl ethyl ketone peroxide and benzoyl peroxide.

Dibutylperoxytrimethylcyclohexane.

Examples include butylperoxyethylhexanate, butylperoxyisopropyl carbonate, and the like. For further use, polymerization accelerators such as tertiary amines and metal salts such as cobalt can be added.

A hardening agent is used to harden the epoxy compound. As the curing agent, commonly used epoxy curing agents such as amines, acid anhydrides, polyamides, polysulfide resins, boron trifluoride amine complexes, novolac resins, and dicyandiamine can be used. Specifically, triethylenetriamine, inphoronediamine, xylylenediamine, phenylenediamine,
Diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, aniline-formalin resin, etc., or phthalic anhydride, methylnadic anhydride, trimellitic anhydride, ethylene glycol bistrimelitate, etc., or polysulfide resins with mercaptan groups at both ends. , aniline and boron trifluoride complexes, low molecular weight from phenol-formalin, novolak resins, dicyandiamide, etc. Further, during the curing reaction, a curing accelerator such as tertiary amines, phenols, imidazoles, etc. can be used if necessary.

Although the curing reaction of the epoxy compound of the present invention proceeds at room temperature, it is preferably carried out by heating to a temperature between 70 and 250°C. The curing time is usually 0.5 to 5 hours. Further, the heat resistance of the cured product obtained here is improved by curing preferably at a temperature of 9100°C or higher.

(Effects of the Invention) The novel epoxy compound of the present invention has a low melting point and good workability, and can be cured by radical curing, ultraviolet curing, epoxy curing, etc. The cured product has high heat resistance and excellent mechanical properties such as impact resistance. It has the advantage of retaining its mechanical properties over a long period of time, especially at high temperatures.

Therefore, this resin can be used in adhesives, casting resins, paints, electrical insulation materials, composite matrix resins, etc.
Can be used for various purposes.

(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

In addition, in each example, infrared absorption spectrum analysis (IR) was used to identify the epoxy compound.

The measurement method of nuclear magnetic resonance spectroscopy (NMR) is as follows.

a) Infrared absorption spectroscopy (IR) 0 The obtained compound and unpulverized KBr powder were mixed, press-molded, and measured using a conventional method.

b) Nuclear Magnetic Resonance Spectroscopy (NMR) Measured at room temperature using deuterated dimethyl sulfoxide as the solvent and tetramethylsilane as the standard sample.

Example 1 m-aminophenol 109.1 g (1.0 mol)
was dissolved in 500 cc of tetrahydrofuran (THF), 106 g of triethylamine was added thereto, and the mixture was placed in a water bath. Separately, prepare a solution in which 90.5 g of acrylic chloride (<1.0 mol) is dissolved in 200 cc of THF, and add it to the THF solution of m-aminophenol with stirring.

After the reaction, THF was removed under reduced pressure, ethyl acetate was added to dissolve the reactants, water was added to remove by-product salts, and the ethyl acetate layer was separated. Ethyl acetate was then removed using an evaporator and dried to yield 141 g of white powder. was gotten.

This is N-(3-hydroxyphenyl>acryl) Ruamide.

Next, 73.5 g of this N-(3-hydroxyphenyl)acrylamide, 163.2 g of epichlorohydrin, and 1.6 g of trimethylammonium chloride are placed in a third flask and reacted for 4 hours with stirring at a bath temperature of 120°C. Next, the bath temperature was lowered to 45° C. and 112 cc of a 5N aqueous solution of caustic soda was slowly added. After the dropwise addition, the reaction is carried out at the same temperature for 1 hour, and then the reaction is completed. After repulsion, excess epichlorohydrin was distilled off, and then THF and calcium chloride 5
When % by weight of water was added and mixed well, the mixture was separated into two layers. T
The HF layer was separated and concentrated to obtain 72 g of white solid powder.

The melting point is 73-76 °C, NMR (solvent d6 DMS
From O>, H signals of epoxy group, phenyl, and amide were observed, and it was found that it was N-(3-glycidyloxyphenyl)acrylamide.

The elemental analysis value is C65.09% (calculated value 65.75
%), H6゜03% (calculated value 5.94%), H6,52
% (total 2 calculated value 6.39%). Also, the epoxy equivalent is 242
(calculated value 219).Infrared absorption spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NM
The results of R) were as shown in FIGS. 1 and 2, respectively.

Next, 10 g of this epoxy compound, 5.8 g of methylnadic anhydride, 0.07 g of benzyldimethylamine, and 0.0 g of t-butyl-peroxy-2-ethylhexanate.
Add 2g and cure at 100℃ for 30 minutes, then 150℃
It was post-cured for 10 hours at °C. It hardens in 20 minutes at 100°C.

The heat distortion temperature of the obtained cured product was 154°C, and the weight loss start temperature was 368°C, indicating high heat resistance.

Example 2 N-(4-hydroxyphenyl)methacrylamide was first synthesized from p-aminophenol and methacryl chloride in the same manner as in Example 1, and then this was epoxidized with epichlorohydrin to form N(4-glycidyloxyphenyl)methacrylamide. 3 was obtained.The melting point of this product was 94-98°C, and N
The structure was confirmed by MR. The epoxy equivalent was 261 (calculated value 233).

Next, this product was cured using the same catalyst and curing conditions as in Example 1 to obtain a cured product. The heat distortion temperature of this cured product is 162
It was ℃.

Example 3 The following compound was obtained by preparing an intermediate from 4-amino-4'-hydroxydiphenyl ether and acryl chloride in the same manner as in Example 1, and then epoxidizing this with epichlorohydrin.

The melting point of this product is 131-136℃, and elemental analysis shows C68.87% (calculated value 69.45%), H5.5
3% (calculated value 5.47%), N4.73% (calculated value 4,
50%). Also, the epoxy equivalent of this product is 3
35 (calculated value 311).

This compound was cured using a catalyst system of methylnadic anhydride, benzyl dimethylamine and dicumyl peroxide at 150°C for 1 hour and then at 170°C for 5 hours to obtain a cured product. The heat distortion temperature of this item is 169
℃, and the thermogravimetric decrease starting temperature was as high as 379℃.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the novel epoxy compound according to the present invention (described in Example 1), and FIG. 2 is a nuclear magnetic resonance spectrum diagram of the same compound.

Claims (1)

[Scope of Claims] (1) An epoxy compound mainly composed of a structure represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [However, in formula (I), G represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , R are hydrogen and/or a hydrocarbon group having 4 or less carbon atoms, and n and m are each an integer of 1 to 4. Further, Ar is an (n+m)-valent aromatic hydrocarbon group having 16 or less carbon atoms which may be substituted with a halogen atom. ] (2) The amino group of the compound represented by the general formula (II) below and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (II) [However, Ar in formula (II) is the same as the above formula (I). same. ] The carboxylic acid derivative group of the compound represented by the general formula (III) below and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (III) [However, R in formula (III) is the same Y as in formula (I) is a halogen, a hydroxyl group or -O-R', where R' is a hydrocarbon group. ] to form an amide compound having a hydroxyl group (I
A method for producing an epoxy compound, which comprises preparing amide compound (IV), then reacting the amide compound (IV) with epihalohydrin, and then dehydrohalogenating the amide compound (IV). (3) A cured epoxy resin obtained by curing the epoxy compound according to claim (1) with an epoxy curing agent, a radical initiator, and/or an ultraviolet ray.