JPH082886B2 - New epoxy compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is a novel raw material of a novel epoxy resin having excellent heat resistance, chemical resistance, mechanical properties, dimensional stability, electrical properties and the like. The present invention relates to an epoxy compound and a method for producing the same.

(Prior Art) Epoxy resins have hitherto been used in a wide range of fields such as paints, electric insulating materials, civil engineering and construction materials, adhesives, and composite materials using fibers as a reinforcing material because of various excellent properties. Among these epoxy resins, as a method for producing a heat resistant epoxy resin, 1) tetraglycidyl methylene dianiline and diaminodiphenyl sulfone are cured, 2) polyglycidyl ether of phenol novolac is cured with diaminodiphenyl sulfone, and 3) ) It is well known that dicyandiamide is used as a curing agent instead of the above diaminodiphenyl sulfone.

However, with the recent progress in technology, the performance required for epoxy resins has become more sophisticated, and the heat resistance of conventional heat-resistant epoxy resins has become insufficient.

(Object of the Invention) A first object of the present invention is to provide a novel epoxy compound which gives an epoxy resin having particularly excellent heat resistance, and the other object is to efficiently and economically produce the epoxy compound. To provide a way to do.

(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 formula (I).

(2) at least one aldehyde represented by the following formula (II-1) At least one aldehyde represented by the following formula (II-2) At least one aromatic hydroxy compound represented by the following formula (III) Ar- (OH) m (III) And are reacted in the presence of an acidic catalyst to form a polyol compound represented by the following formula (IV), This is achieved by a method for producing an epoxy compound according to the above (1), which comprises hydrolyzing the compound if necessary and then reacting this with epihalohydrin and / or β-methylepihalohydrin.

 Hereinafter, the present invention will be described in detail.

The novel epoxy compound according to the present invention has the above formula (I).
It has a novel chemical structure represented by. Of X in the above formula The structure represented by 15 to 70 mol%, preferably 20
˜65 mol%, particularly preferably 25 to 60 mol%. Also out of X The structure represented by 85 to 30 mol%, preferably 80
˜35 mol%, particularly preferably 75-40 mol%.

G in formula (I) is Or And the three Gs in formula (I) do not necessarily have to be the same group.

R ^{1 in} the formula is the above G and / or 10 carbon atoms.
The following hydrocarbon groups are represented. Examples of the hydrocarbon group having 10 or less carbon atoms include an aliphatic hydrocarbon group such as methyl, ethyl and propyl, an alicyclic hydrocarbon group such as cyclohexyl, and an aromatic hydrocarbon group such as phenyl, benzyl and naphthyl. can do.

Preferred examples of R ¹ are the above G and / or aliphatic hydrocarbon groups such as methyl, ethyl, propyl and the like, and particularly preferably the group represented by the above G. The two in the formula
R ¹ does not necessarily have to be the same group.

Examples of the group Y containing G include glycidyloxyphenyl and N, N-diglycidylaminophenyl.

In the above formula, n is 0 or an integer of 1 to 20, preferably 0 or an integer of 1 to 10, particularly preferably 0, 1 or 2. When n is too large, the viscosity of the obtained epoxy compound increases and the moldability deteriorates.

The epoxy compound of the present invention generally has a molecular weight distribution, and the molecular weight of the epoxy compound means its average.

In the formula, m represents an integer of 1 to 3, preferably 1 or 2. It should be noted that the three m's in the equation are not necessarily the same number.

In the formula, Ar is an aromatic hydrocarbon group having 20 or less carbon atoms, which may be substituted with a halogen atom. And as is clear from the formula (I), two of Ar are (1 + m)
The remaining one is a (2 + m) -valent group. Specific examples of skeleton names when Ar is unsubstituted are benzene, toluene, xylene, naphthalene, chlorobenzene, dichlorobenzene, chlorotoluene, chloronaphthalene, trichlorobenzene, bromobenzene, dibromobenzene, and tribromobenzene. Benzene, tetrabromobenzene, bromonaphthalene, 2,2-diphenylpropane, diphenyl, diphenylmethane, diphenylether, diphenylsulfide, 2,2-bis (3-chlorophenyl) propane, 2,2-bis (3,5-dichlorophenyl) propane ,
2,2-bis (3-bromophenyl) propane and 2,2-bis (3,5-dibromophenyl) propane. Of these, preferred are benzene, toluene, naphthalene, chlorobenzene, dichlorobenzene, bromobenzene, and dibromobenzene, and particularly preferred are benzene, toluene, naphthalene, and dibromobenzene.
These Ar may contain the above-mentioned plural forms in one molecule. That is, the three Ar skeletons in formula (I) do not necessarily have to be the same.

In the novel epoxy compound according to the present invention, the structure represented by the general formula (I) is 60% or more, preferably 70% or more.
The above content, particularly preferably 80% or more, is contained. Other than the above, examples of the structure that can be contained in the compound include an alcohol and / or a carboxylic acid which is not glycidylated, and a halohydrin ether in which an epoxy group remains ring-opened.

Next, a preferable method for producing the novel epoxy compound of the present invention will be described.

The novel epoxy compound of the present invention comprises a first aldehyde component represented by the above formula (II-1), a second aldehyde component represented by the above formula (II-2), and an aroma represented by the above formula (III). A group hydroxy compound (phenolic compound) is reacted in the presence of an acidic catalyst to form a polyol represented by the above formula (IV), and the compound is hydrolyzed, if necessary, and then epihalohydrin or β- It can be produced efficiently and economically by reacting with methyl epihalohydrin.

In the present invention, as the first aldehyde component which is one component of the raw material, those represented by the following formula (II-1) are mainly used.

Specific examples of R ² include hydrogen, an aliphatic hydrocarbon group such as methyl, ethyl, propyl, pentyl, hexyl and octyl, an alicyclic hydrocarbon group such as cyclohexyl and methylcyclohexyl, phenyl, benzyl, chlorophenyl and bromine. Examples thereof include aromatic hydrocarbon groups such as phenyl and naphthyl. Specific examples of preferable R ² include aliphatic hydrocarbon groups such as hydrogen, methyl, ethyl and propyl.
Representative aldehyde components (II
-1) is P-formylbenzoic acid, methyl P-formylbenzoate. These aldehyde components (II-1) may be used alone or in admixture of two or more.

As the second aldehyde component which is another raw material in the present invention, a compound represented by the following formula (II-2) is mainly used.

Represented by formula (II-2), which is preferably used in the present invention,
Typical aldehyde components are m- or p-hydroxybenzaldehyde and p-aminobenzaldehyde, and these aldehyde components (II-2) are used alone or in combination of two or more.

Further, as the above-mentioned aldehyde component (II-2), other glyoxal, glutaraldehyde, terephthalaldehyde, etc. may be used as the (II-2) component from the viewpoint of improving the resin properties.
It is also possible to add 30 mol% or less, preferably 20 mol% or less.

In the following, the above-mentioned first aldehyde component (II-1) and second aldehyde component (II-2) are combined to form a total aldehyde component (I
Although referred to collectively as I), the preferred use ratio of the first component (II-1) and the second component (II-2) in the total aldehyde component (II) is 15 to 70 mol% with respect to the total aldehyde component (II). , 85-30 mol%, preferably 20-65 mol%, 80-
35 mol%, particularly preferably 25-60 mol%, 75-40
Mol%.

When the molar ratio of the components (II-1) and (II-2) is selected within the above range as in the present invention, an epoxy compound which becomes an epoxy resin having particularly excellent heat resistance can be obtained. That is, heat resistance can be significantly improved without impairing workability of the epoxy resin by introducing a specific group having a phenyl group nuclear-substituted with Y into the epoxy compound at a constant ratio.

As the aromatic hydroxy compound component which is another raw material in the present invention, a compound represented by the following formula (III) is mainly used.

Ar- (OH) m ... (III) Specific examples of the aromatic hydroxy compound include phenol, cresol, xylenol, α-naphthol, β-naphthol, bromophenol, and m = 1 in the above formula (III). Aromatic monohydroxy compounds such as chlorophenol, dibromophenol, dichlorophenol, tribromophenol, trichlorophenol, etc., resorcinol with m = 2, dihydroxynaphthalene, bromoresorcinol, chlorresorcinol, dibromoresorcinol, dichlororesorcinol, tribromoresorcinol , Trichlororesorcinol, hydroquinone, chlorohydroquinone, bromohydrtoquinone, 2,5-dichlorohydroquinone, t-butylhydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) pu Bread, 4,4'-dihydroxydiphenyl, 4,4'
Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylmethane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4 -Hydroxyphenyl) propane, 2,2-bis (3-chloro-4-
Hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2
An aromatic dihydroxy compound such as -bis (3,5-dibromo-4-hydroxyphenyl) propane, m = 3
Aromatic trihydroxy compounds such as 1,3,5-trihydroxybenzene, pyrogallol and the like are mentioned, among which,
Phenol, cresol, α-naphthol, β-naphthol, bromophenol, 2,6-dibromophenol and resorcinol are preferable. These aromatic hydroxy compounds (III) are used alone or as a mixture of two or more kinds.

Specific examples of epihalohydrin and β-methylepihalohydrin used in the reaction with the polyol compound (IV) or a hydrolyzate thereof in the present invention include epichlorohydrin, epibromhydrin, β-methylepichlorohydrin, β-methylepibrohydrin. Etc. Particularly preferred are epichlorohydrin and β-methylepicrylhydrin.

These may be used alone or in combination of two or more.

Each of the above raw materials can be manufactured at a low cost, and the fact that such raw materials can be used is one of the advantages of the present invention.

According to the production method of the present invention, first, an aldehyde component and an aromatic hydroxy compound are reacted in the presence of an acidic catalyst to produce a polyol compound. In this reaction. The charging ratio of the total aldehyde component represented by the above formula (II) and the aromatic hydroxy compound represented by the above formula (III) is adjusted by the degree of polymerization of the desired epoxy compound, but the total aldehyde component (II) is generally used. The aromatic hydroxy compound (III) is used in an amount of 0.5 to 2.0 mol per mol.

Further, as the acidic catalyst used in the reaction, specifically, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acid and other protic acids, boron trifluoride, boron trifluoride ether complex, chloride Lewis acids such as aluminum, tin chloride, zinc chloride, iron chloride and titanium chloride, oxalic acid and the like can be used.

Among these, it is preferable to use a protonic acid, and particularly hydrochloric acid, boric acid, methanesulfonic acid, toluenesulfonic acid and the like are preferably used.

The amount of these catalysts used is the total aldehyde component (II) of the raw material.
To 0.001 to 0.05 mol times. However, when the aldehyde component contains an amino group, it is selected in the range of 0.8 to 1.2 mole times. The above catalysts are used in one kind or a mixture of two or more kinds.

In the present invention, the reaction of the aromatic hydroxy compound (III) with the aldehyde component (II) in the presence of an acidic catalyst is usually carried out at 80 to 250 ° C.

The reaction temperature is 80 to 150 ° C. in the initial stage, and the reaction temperature is further raised if necessary. The reaction time can be selected in the range of 1 hour to 24 hours.

The above reaction of the present invention is carried out by the aromatic hydroxy compound (II
I) can be used in excess and used as a solvent, which can prevent the viscosity of the reaction system from increasing with the increase in the degree of polymerization.

When the aromatic hydroxy compound (III) is used as a solvent, the ratio of the aldehyde component (II) and the aromatic hydroxy compound component (III) used is not limited to the above range.

In the above reaction, aromatic hydrocarbons such as toluene, chlorobenzene, dichlorobenzene, nitrobenzene and diphenyl ether, ethers such as ethylene glycol, diethylene glycol, tetrahydrofuran and dioxane and water can be used as a solvent.

Also, when the aldehyde component contains an amino group, the amino group forms a salt with the acid used as the catalyst, and thus the amino group can be liberated by subjecting this to alkali decomposition.

Thus, the polyol compound of the above formula (IV) is obtained. When R ² is not hydrogen, this compound (IV) can be hydrolyzed to hydrogenate R ² if necessary.

The method of hydrolysis is in the presence of water according to a known method,
It can be carried out using acid and alkali catalysts.

Next, the polyol compound (I
V) or its hydrolyzate and epihalohydrin, β
The novel epoxy compounds of the present invention are obtained by reacting with at least one of -methyl epihalohydrin.
This reaction is carried out by a method of reacting the polyol compound (IV) or a hydrolyzate thereof with epihalohydrin or β-methylepihalohydrin in the presence of a quaternary ammonium salt and / or a base as a catalyst, preferably the reaction A method is also employed in which unreacted epihalohydrin and β-methylepihalohydrin are separated from the mixture and then the reaction product is further reacted with a base.

In the method of the present invention, a quaternary ammonium salt and / or a base is used as a catalyst.
Tetraalkyl type or benzyltrialkyl type such as tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride and benzyltrimethylammonium acetate are preferable. The amount of the quaternary ammonium salt used is appropriately in the range of 0.001 to 0.1 mole times the total of the hydroxyl group and the carboxyl group in the polyol compound (IV) or its hydrolyzate. Examples of the base include alkali metals such as sodium and potassium and / or weak acid salts such as hydroxides and carbonates thereof, and sodium hydroxide is particularly preferable. When the hydroxyl group, carboxy group and aldehyde component in the polyol compound (IV) or its hydrolyzate contain an amino group, the amount of the base used is 0.8 equivalent or more, preferably 0.9 to 3.5, based on the total active hydrogen of the amino group. An equivalent amount, particularly preferably 1.0 to 3 equivalents, is suitable.

In the case where a method of reacting the polyol compound (IV) or its hydrolyzate with excess epihalohydrin or β-methylepihalohydrin, removing unreacted epihalohydrin or β-methylepihalohydrin from the reaction system, and then further reacting The preferred amount of the base is less than or equal to the total amount of active hydrogen of the amine when the hydroxyl group, the carboxyl group and the aldehyde component of the polyol compound (IV) or its hydrolyzate contain an amino group, and more preferably less than or equal to 0.6 equivalent. , Particularly preferably 0.2 to 0.5 equivalent.

The amount of epihalohydrin or β-methylepihalohydrin used is at least twice the molar amount of active hydrogen of the amine when the hydroxyl group, carboxyl group and aldehyde component in the polyol compound (IV) or its hydrolyzate contain an amino group. It is preferably used in an amount of 3 times or more, more preferably 5 times or more.

Unreacted epihalohydrin or β-methylepihalohydrin can be easily recovered after the reaction and used again in the reaction.

The reaction temperature is generally 30 to 150 ° C, preferably 50 to 130 ° C, particularly preferably 60 to 120 ° C.

This reaction is carried out for 1 to 20 hours. Since the epoxy compound obtained by the above-mentioned reaction contains water-soluble inorganic substances such as quaternary ammonium salt and / or base in addition to unreacted epihalohydrin or β-methylepihalohydrin as described above, it is usually unreacted from the reaction mixture. Alternatively, after removing β-methylepihalohydrin by distillation, if necessary, it is dissolved in a solvent such as toluene or benzene that is not easily compatible with water, and the water-soluble inorganic substance is extracted with water.
It can be removed by another method or the like to obtain a high-quality polyglycidyl ether suitable for producing an epoxy resin.

Thus, the epoxy compound of the present invention represented by the following formula (I) is obtained.

The epoxy compound obtained here may be further heat-treated with a base, for example, at 60 to 100 ° C. for 1 to 20 hours to reduce the halogen content in the epoxy compound. In this case, the epoxy compound is preferably dissolved in an organic solvent such as methyl ethyl ketone, benzene or toluene.

The epoxy compound of the present invention has a low melting point as a heat resistant epoxy compound and is excellent in handleability.

This epoxy compound can be identified by measuring epoxy equivalent, molecular weight, infrared analysis (IR) and nuclear magnetic resonance analysis (NMR).

The novel epoxy compound of the present invention can be cured with a conventionally known epoxy-based curing agent, and can be a cured epoxy resin having good heat resistance.

Examples of the curing agent include amines, acid anhydrides, polyamide resins, polysulfide resins, boron trifluoride amine complex, novolac resins, dicyandiamide, and the like.

(Effects of the Invention) With the novel epoxy compound according to the present invention, for example, a cured product obtained by curing with the above-mentioned curing agent becomes a resin molded product having excellent heat resistance, mechanical properties and the like. Therefore, this resin is
In addition to casting resins, paints, electrical insulating materials such as printed circuit boards and sealants, matrix resins for composite materials using carbon fibers, glass fibers, thermoplastic fibers, etc., it can be used for various purposes. Further, according to the production method of the present invention, the above novel epoxy compound can be produced efficiently and inexpensively.

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

In the examples, “part” means “part by weight” unless otherwise specified.

Further, the analysis methods of infrared absorption spectrum analysis (IR) and nuclear magnetic resonance spectrum analysis (NMR) used for identifying the epoxy compounds obtained in each example are as follows.

a) Infrared absorption spectrum analysis (IR) A neat epoxy compound was cast on a KBr plate and measured by a conventional method.

b) Nuclear magnetic resonance spectrum analysis (NMR) It measured using deuterated chloroform as a solvent and tetramethylsilane as a standard sample.

Example 1 Phenol 316 parts and p-toluenesulfonic acid monohydrate
0.6 part was dissolved in 280 parts toluene and p was added to the solution heated to 95 ° C.
A solution of 55 parts of methyl formyl benzoate and 27 parts of a predetermined amount of P-hydroxybenzaldehyde dissolved or uniformly dispersed in 400 parts of toluene was added dropwise under stirring in a nitrogen stream over 1.5 hours. The water that came out during the reaction was distilled off to the outside of the system and reacted for an additional 1 hour, followed by reacting at 100 ° C. for 1 hour, adding 6 parts of concentrated hydrochloric acid thereto and reacting for another 2 hours
This was reacted at 115 ° C. for 2 hours. To the reaction mixture obtained here, 600 parts of a 5% aqueous sodium hydroxide solution was added to obtain 2
After heating for 3 hours under reflux, hydrolysis is performed, the toluene layer is separated and removed, the aqueous layer is acidified with a 10% aqueous hydrochloric acid solution, and the obtained solid is washed 3 times with 300 parts of water, and then distilled under reduced pressure and steam. Unreacted phenolic compound was removed by flushing to obtain hydroxycarboxylic acid. Obtained hydroxycarboxylic acid
100 parts and 3 parts of benzyltriethylammonium chloride were added to 2000 parts of epichlorohydrin and heated under reflux for 5
The reaction was carried out with stirring for a time. After the reaction mixture was heated to 95 ° C., 100 parts of a 50% aqueous solution of sodium hydroxide was added dropwise at 160 mmHg under stirring for 1.5 hours. At this time, water coming out of the system was distilled out of the system. The obtained reaction mixture was purified by the following method. That is, after completion of the reaction, epichlorohydrin was recovered by vacuum distillation, and 5000 parts of toluene was added to the residue,
1000 parts of this water, then 1000 parts of dilute phosphoric acid aqueous solution
It was washed 5 times with 1000 parts to remove excess sodium hydroxide and precipitated sodium chloride. Toluene was distilled off from the toluene layer to obtain a purified epoxy compound. The yield of this epoxy compound was 120 parts, the melting point was 40 to 69 ° C., the epoxy equivalent was 180 g / eq, the result of elemental analysis, and the structure of the compound confirmed by NMR and IR were as shown below. C (%): 71.
88, H (%) 5.79.

X: 60 mol% X: 40 mol% However, Average value of n in formula (I) = 0.1 Example 2 210 parts of p-formylbenzoic acid, 169 parts of p-aminobenzaldehyde and 130 parts of hydrochloric acid were added to 788 parts of phenol, and the mixture was reacted at 60 ° C. for 1 hour and then 100 ° C. After reacting for 5 hours, water was distilled off, and phenol was removed by vacuum distillation and steam flushing. After adding 556 parts of 10% sodium hydroxide aqueous solution to the obtained reaction mixture and stirring for 2 hours, water was distilled off and the obtained solid was crushed and washed with water to obtain 300 parts of hydroxycarboxylic acid.

100 parts of the obtained hydroxycarboxylic acid and 3 parts of benzyltriethylammonium chloride were added to 2000 parts of epichlorohydrin, and they were reacted with heating under reflux for 5 hours with stirring. After the reaction mixture was heated to 95 ° C., 100 parts of a 50% aqueous solution of sodium hydroxide was added dropwise at 160 mmHg under stirring for 1.5 hours. At this time, water coming out of the system was distilled out of the system. The obtained reaction mixture was purified in the same manner as in Example 1.

The obtained epoxy compound was 115 parts and had a melting point of 42-65.
Epoxy equivalent at ℃ 168g / eq, elemental analysis result is C
(%): 70.8, H (%): 5.89, N (%) 1.39.

It was confirmed by IR, NMR and elemental analysis that the following compound was obtained.

X: 50 mol% X: 50 mol% However Average value of n in formula (I) = 0.1 Using this epoxy compound, a cured resin molded article was produced by a known method with an amine curing agent, and a molded article having extremely excellent heat resistance was obtained.

Claims (2)

[Claims] 1. An epoxy compound mainly composed of a structure represented by the following formula (I). 2. At least one aldehyde represented by the following formula (II-1): At least one aldehyde represented by the following formula (II-2) At least one aromatic hydroxy compound represented by the following formula (III) Ar- (OH) m (III) And are reacted in the presence of an acidic catalyst to form a polyol compound represented by the following formula (IV), The method for producing an epoxy compound according to claim (1), wherein the compound is hydrolyzed as necessary and then reacted with epihalohydrin and / or β-methylepihalohydrin.