JP2781268B2 - Production method of new epoxy compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing an epoxy compound.

(Prior Art) Conventionally, epoxy resins have been used in a wide variety of fields such as paints, electric insulating materials, civil engineering and building materials, adhesives, and composite materials used as fiber reinforcing materials because of their excellent properties. Among these epoxy resins, methods for producing a heat-resistant epoxy resin include: 1) curing tetraglycidylmethylenedianiline and diaminodiphenylsulfone; 2) curing polyglycidylether of phenol novolak with diaminodiphenylsulfone; Methods such as using dicyandiamide as a curing agent instead of dianodiphenylsulfone are well known.

However, with the recent technological advances, the performance required for epoxy resins has become more sophisticated, and the heat resistance of conventional heat-resistant epoxy resins has not always been sufficient.

(Object of the Invention) An object of the present invention is to provide a method for efficiently and economically producing a novel epoxy compound which gives an epoxy resin having excellent heat resistance.

(Constitution of the Invention) The object of the present invention as described above is to provide at least one aldehyde represented by the following formula (I): At least one aromatic hydroxy compound represented by the following formula (II): Is subjected to a dehydration condensation reaction in the presence of an acidic catalyst, and the obtained reaction mixture is subjected to a hydrolysis reaction in the presence of a basic compound, and the obtained hydrolysis reaction mixture is selected from epihalohydrin and β-methyl epihalohydrin. At least one halohydrin, and reacting the hydrolysis product in the mixture with the halohydrin to produce an epoxy compound of the following formula (III): Achieved by

 Hereinafter, the present invention will be described in detail.

The epoxy compound produced by the method of the present invention has a novel chemical structure represented by the above formula (III).

In the above formula, n is a number of 1 to 20, preferably 0 or 1.
It is a number of 1010, particularly preferably 0, 1 or 2. If 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 indicates its average.

In the formula, m represents a number of 1 to 3, preferably 1 or 2
It is. Note that the three m's in the equation are not always the same. G in the formula (III) is And the three Gs in the formula (III) are not necessarily the same group.

R in the formula (III) represents the above G and / or a hydrocarbon group having 10 or less carbon atoms. Examples of the hydrocarbon group having 10 or less carbon atoms include alicyclic hydrocarbon groups (cycloalkyl groups) such as methyl, ethyl and propyl, phenyl,
Benzyl. An aromatic hydrocarbon group (allyl group) such as naphthyl can be exemplified.

Preferred examples of R are the above-mentioned G and / or an aliphatic hydrocarbon group (alkyl group) having about 1 to 5 carbon atoms such as methyl, ethyl, propyl and the like.
Is a group represented by The two Rs in the formula need not all be the same group.

In the formula (III), Ar represents a total of 20 carbon atoms which may be substituted with a halogen atom or a lower alkyl group having 1 to 5 carbon atoms.
These are the following aromatic hydrocarbon groups. As a specific example, benzene skeleton, naphthalene skeleton or (Wherein, X is a direct bond, -O -, - S -, - SO 2 -, - C
O- or an alkylidene group having 1 to 3 carbon atoms), specifically, benzene, toluene, xylene, naphthalene,
Chlorobenzene, dichlorobenzene, chlorotoluene,
Chlornaphthalene, bromobenzene, dibromobenzene, tribromobenzene, 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, 2,2-bis (3,5-
Dibromaphenyl) propane. Of these, preferred are benzene, toluene, naphthalene, chlorobenzene, dichlorobenzene, grombenzene, and dibromobenzene, and particularly preferred are benzene, toluene, naphthalene, and dibromobenzene.

As is clear from the above formula (III), two of Ar are (m + 1) -valent groups, and the other one is (m + 2) -valent group. These Ars may have a plurality of the above-mentioned forms in one molecule. That is, the three Ars in the formula (III) do not necessarily have to have the same skeleton.

The novel epoxy compound according to the present invention contains at least 60% or more, preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more of the structure represented by the general formula (III). In addition to the above, examples of the structure that can be included in the compound include non-glycidylated alcohols and / or carboxylic acids, and halohydrin ethers in which the epoxy group remains open.

Next, a method for producing an epoxy compound according to the present invention will be described.

The novel epoxy compound according to the present invention has the above formula (I)
A reaction mixture obtained by reacting an aldehyde component represented by the formula (II) with an aromatic hydroxy compound (phenolic compound) represented by the above formula (II) in the presence of an acidic catalyst,
A hydrolysis reaction is carried out using a basic compound in the presence of water according to a known method, and a halohydrin selected from epihalohydrin and β-methylepihalohydrin is added to the resulting hydrolysis reaction mixture, and the hydrolysis reaction in the mixture is performed. By reacting the decomposition reaction product with halohydrin, it can be produced efficiently and economically.

In the present invention, as the aldehyde component as one component of the raw material, one represented by the following formula (I) is mainly used.

Specific examples of R include aliphatic hydrocarbon groups (alkyl groups) such as methyl, ethyl, propyl, pentyl, hexyl, and octyl; alicyclic hydrocarbon groups (cycloalkyl groups) such as cyclohexyl and methylcyclohexyl;
And aromatic hydrocarbon groups (allyl groups) such as benzyl, chlorophenyl, bromophenyl and naphthyl. Preferred specific examples of R include an aliphatic hydrocarbon group having 1 to 5 carbon atoms (alkyl group) such as methyl, ethyl and propyl.
Is raised. A representative aldehyde component that is particularly preferably used in the present invention is methyl P-formylbenzoate. These aldehyde components (I) may be used alone or
Used as a mixture of more than one species. As the aldehyde component, from the viewpoint of improving the physical properties and handling properties, in addition to the aldehyde of the above (I), formaldehyde, acetaldehyde, benzaldehyde, butyraldehyde, n-hexylaldehyde, n-octylaldehyde, P-hydrexibenaldehyde, Other aldehydes such as hexahydrobenzaldehyde, glyoxal, curtalaldehyde, m-hydroxybenzaldehyde, terephthalaldehyde, P-aminobenzaldehyde and ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diisopropyl ketone, acetophenone, benzophenone, etc. 30 mol% or less, preferably 20 mol%
It is also possible to add up to mol%.

As the aromatic hydroxy compound component serving as another raw material in the present invention, an aromatic hydroxy compound represented by the following formula (II) is mainly used.

Ar- (OH) _m (II) [However, Ar and m in the formula (II) are the same as above] As a specific example of the aromatic hydroxy compound, in the above formula (II), m = 1. Phenol, cresol, xylenol, α-naphthol, β-naphthol,
Aromatic monohydroxy compounds such as bromophenol, chlorophenol, chlorocresol, chloronaphthol, dibromophenol, dichlorophenol, tribromophenol, tetrabromophenol, bromonaphthol and trichlorophenol; resorcinol, dihydroxynaphthalene having m = 2; Bromoresorcinol, chlororesordinol, dibromoresorcinol,
Dichlororesorcinol, tribromoresorcinol,
Trichlororesorcinol, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,5 dichlorohydroquinone, t-butylhydroquinone, catechol, 2,2-bis (4
-Hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether,
4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylmethane, 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, 2,2bis (3,5-dimethyl-4hydroxyphenyl) 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-bis (3,5-dibromo-4-hydroxyphenyl) Aromatic dihydroxy compounds such as propane; and aromatic trihydroxy compounds such as 1,3,5 trihydroxybenzene and pyrogallol where m = 3, among which phenol, cresol, α-naphthol, β-naphthol, bromo Phenol, 2,6-dibromophenol and resorcinol are preferred. These aromatic hydroxy compounds (II) are used alone or as a mixture of two or more.

Specific examples of epihalohydrin and β-methyl epihalohydrin used in the method of the present invention include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, and the like. Particularly preferred are epichlorohydrin and β-methylepichlorohydrin.

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

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

According to the production method of the present invention, first, an aldehyde component and an aromatic hydroxy compound are subjected to a dehydration condensation reaction in the presence of an acidic catalyst. The charging ratio of the aldehyde component represented by the above formula (I) and the aromatic hydroxy compound represented by the above formula (II) is controlled by the degree of polymerization of the target epoxy compound. To the aromatic hydroxy compound (I
I) is used in the range from 0.5 to 2.0 mol.

Examples of the acidic catalyst used at the time of the reaction include protonic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, and toluenesulfonic acid, boron trifluoride, boron trifluoride ether complex, and aluminum chloride. , Tin chloride,
Lewis acids such as zinc chloride, iron chloride and titanium chloride, and oxalic acid can be used.

Of these, protonic acids are preferably used, and hydrochloric acid, boric acid, methanesulfonic acid, toluenesulfonic acid and the like are particularly preferably used.

The amount of these catalysts used is selected between 0.001 and 0.05 mole times the aldehyde component (II) as the raw material. The above catalysts are used in one kind or in a mixture of two or more kinds.

In the present invention, the reaction between the aromatic hydroxy compound (II) and the aldehyde component (I) in the presence of an acidic catalyst is as follows:
Usually, it is carried out at 80 to 250 ° C.

In addition, the reaction temperature is initially between 80 and 150 ° C., and the reaction temperature is further increased as necessary. The reaction time can be selected within the range of 1 hour to 24 hours.

In the above-mentioned reaction of the present invention, the aromatic hydroxy compound (II) can be used as a solvent by using an excess amount thereof, thereby preventing an increase in the viscosity of the reaction system due to an increase in the degree of polymerization.

As described above, when the aromatic hydroxy compound (II) is used as a solvent, the use ratio of the aldehyde component (I) and the aromatic hydroxy compound component (II) is not limited to the above range.

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

Examples of the basic compound used in the subsequent hydrolysis reaction include alkali metals such as sodium and potassium and / or a weak acid salt such as a hydroxide or carbonate thereof, and particularly preferred is sodium hydroxide. The amount of the basic compound used in the hydrolysis is 0.8 equivalents or more, preferably 0.9 to 3.5 equivalents, particularly preferably 1.0 equivalent to the total of the carboxyl groups and the aromatic hydroxyl groups contained in the reaction system.
~ 3 equivalents is suitable. The reaction temperature of the hydrolysis reaction is 30 ~
150 ° C, preferably 50 to 130 ° C, particularly preferably 60 to 120 ° C
C., usually for 30 minutes to 20 hours.

The aldehyde or aromatic hydroxy compound that has not been reacted in the dehydration condensation reaction is preferably distilled off under reduced pressure before the hydrolysis reaction, in which case a base is used to eliminate the activity of the acidic substance as a catalyst. It is also preferable to add a small amount.

The amount of epihalohydrin or β-methylepihalohydrin used in the reaction of the hydrolysis reaction mixture obtained as described above with halohydrin is based on the total amount of carboxyl groups and aromatic hydroxyl groups that can be recognized before the hydrolysis reaction. It is used in an amount of at least 2 moles, preferably at least 3 moles, particularly preferably at least 5 moles. Unreacted epihalohydrin or β-methyl epihalohydrin can be easily recovered after the completion of the reaction and used again in the reaction. The reaction temperature is usually 30 to 150 ° C, preferably 40 to 130 ° C, particularly preferably 50 to 120 ° C.

The time required for this reaction depends on the temperature and the state of stirring, but is usually in the range of 1 hour to 48 hours. Since this reaction becomes a heterogeneous system of an aqueous layer and an epichlorohydrin layer, it is also preferable to use the above-described phase transfer catalyst such as a quaternary ammonium salt or uraun ether.

The epoxy compound obtained by the above reaction contains a water-soluble inorganic substance such as a quaternary ammonium salt and / or a base in addition to the unreacted epihalohydrin or β-methyl epihalohydrin as described above. Alternatively, after β-methyl epihalohydrin is removed by distillation, it is dissolved in a water-immiscible solvent such as toluene or benzene, if necessary, and the water-soluble inorganic substance is extracted with water and removed by another method to produce an epoxy resin. High-quality polyglycidyl ether suitable for

Thus, a novel epoxy compound represented by the following formula (III) is obtained.

[However, G, R, Ar, m, n are the same as above. If necessary, the epoxy compound obtained here can be further heat-treated with a basic compound at, for example, 60 to 100 ° C. for 1 to 20 hours to reduce the halogen content in the epoxy compound. In this case, the epoxy compound may be dissolved in an organic solvent such as methyl butyl ketone, benzene, and toluene.

The novel epoxy compound obtained by the method of the present invention is
It has a melting point of 25 ° C or less and is excellent in handleability. The epoxy compound can be identified by measuring epoxy equivalent, molecular weight, infrared analysis (IR) and nuclear magnetic resonance analysis (NMR).

This epoxy compound can be cured by a conventionally known epoxy-based curing agent, and can be a cured epoxy resin having good heat resistance.

(Effects of the Invention) According to the production method of the present invention, when the above-mentioned heat-resistant epoxy compound is synthesized from an ester aldehyde, the isolation and purification steps after the hydrolysis reaction can be omitted, so that the production is efficient and inexpensive. can do.

(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, “parts” means “parts by weight” unless otherwise specified.

The analysis methods of infrared absorption spectrum analysis (IR) and nuclear magnetic resonance spectrum (NMR) used for identification of the epoxy compound 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) The measurement was performed using deuterated chloroform as a solvent and tetramethylsilane as a standard sample.

Example 1 632 parts of phenol and 4 parts of hydrochloric acid. 1.2 parts of P-toluenesulfonic acid monohydrate was heated in a 100 ° C. oil bath in advance in a nitrogen stream while stirring under a nitrogen stream.
Eight parts were added to 368 parts of toluene, and a solution uniformly dissolved at 40 ° C. was added dropwise over 2 hours. After continuing the reaction for 1 hour, the bath temperature was increased to 11
After raising the temperature to 0 ° C. and continuing for 1 hour, 12 parts of concentrated hydrochloric acid was added, and the reaction was further performed for 1 hour. Thereafter, the bath temperature was raised to 140 ° C., and the reaction was continued for another 1 hour and 30 minutes. At this time, water generated as a result of the reaction was distilled out of the reaction system. To the above reaction mixture, 5 parts of a 50% aqueous sodium hydroxide solution was added, and the mixture was stirred for 15 minutes, and then reduced in pressure. 3000 parts of a 10% aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was reacted under heating and refluxing for 5 hours.

After cooling the obtained hydrolysis reaction mixture to 70 ° C.,
The mixture was added to 4500 parts of epichlorohydrin and reacted in a nitrogen stream with stirring for 5 hours. After separating the epichlorohydrin layer with a separating funnel, the mixture was washed five times with 1000 parts of water, then with 1,000 parts of a diluted phosphoric acid aqueous solution and then with 1,000 parts of water to remove excess sodium hydroxide and precipitated sodium chloride. Subsequently, epichlorohydrin was distilled off under reduced pressure, and phenylglycidyl ether by-produced partially at 150 ° C. under reduced pressure was distilled off, and the epoxy equivalent
821 parts of an epoxy compound having a melting point of 40 ° C. or lower and 210 g / eq were obtained.
Molecular weight determined by freezing point depression method using dioxane is 524
Met.

Example 2 and Comparative Example 30 parts of the epoxy compound of Example 1 and 4,4'-diaminodiphenylsulfone were added so that the epoxy group and the active hydrogen atom of 4,4'-diaminodiphenylsulfone became equimolar. The mixture was heated to 150 ° C. to be uniformly dissolved, and cured for 1 hour in a mold preheated to 200 ° C. 22
Carrier was carried out at 230 ° C for 2 hours at 5 ° C.

Table 1 shows the results of measuring the bending properties of the obtained molded plate according to ASTM-D790.

As a comparative example, Table 1 shows the results of the same experiment using tetraglycidylmethyleneaniline instead of the above epoxy.

Comparing the two, it is understood that those using the epoxy compound according to the method of the present invention have excellent bending properties at high temperatures.

Claims (1)

(57) [Claims] (1) at least one aldehyde represented by the following formula (I): At least one aromatic hydroxy compound represented by the following formula (II): Is subjected to a dehydration condensation reaction in the presence of an acidic catalyst, the obtained reaction mixture is subjected to a hydrolysis reaction in the presence of a basic compound, and the obtained hydrolysis reaction mixture is selected from epihalohydrin and β-methyl epihalohydrin. At least 1
A method for producing an epoxy compound of the following formula (III), characterized by reacting the above-mentioned halohydrin with a hydrolysis reaction product in the above-mentioned mixture by adding a kind of halohydrin.