JP2732082B2 - Composition comprising epoxy resin, phenol and promoted catalyst - Google Patents

Description

The present invention relates to an epoxy resin, a mononuclear or polynuclear phenol having at least two phenolic hydroxyl groups, and a phosphonium or alkylenephosphorane halide and certain phenols. A composition comprising a promoted catalyst which is a combination of the above nitrogen heterocyclic compounds, and an improved method for promoting the reaction between an epoxy resin and phenol by using the promoted catalyst.

(Prior art) Conventionally, polyhydroxyether is a product of an accelerated reaction between an epoxy resin and phenol. Generally, a dihydric phenol and epichlorohydrin are reacted in the presence of an alkali to produce a low-molecular-weight epoxy resin, Subsequently, the epoxy resin is treated with a predetermined aqueous solution to remove soluble inorganic substances, and then added to the treated low molecular weight epoxy resin in an additional amount with a dihydric phenol and a catalyst, and then subjected to a promoting reaction. ing.

Various methods are known for promoting epoxy resins with phenol using various promoting catalysts.

U.S. Pat. No. 3,634,323 describes the reaction of an epoxy resin with a dihydric phenol in the presence of imidazoles, benzimidazoles, imidazolines, dihydropyrimidines, tetrahydropyrimidines or dihydroquinazolines as catalysts.

Phosphonium halide salts as catalysts for accelerated reactions are disclosed, for example, in U.S. Pat. No. 3,477,990.

The reaction of an epoxy resin with a phenolic compound in the presence of a catalyst selected from the group consisting of phosphonium salts of organic and inorganic acids, imidazoles, imidazolines and quaternary ammonium compounds is disclosed in U.S. Pat.
No., published in Japanese Unexamined Patent Publication No. No use or combination of the above catalysts is disclosed or proposed.

GB 1,398,197 discloses the use of alkylene phosphoranes as catalysts for the promotion of epoxy resins with dihydric and polyhydric phenols.

U.S. Pat. No. 4,389,520 discloses the use of formylmethylenetriphenylphosphorane and formylmethyltriphenylphosphonium halide as catalysts for accelerated reactions.

Japanese Unexamined Patent Publication No. 60-144324 discloses a polyepoxide and a polynuclear diamine characterized by using 0.1-5% by weight of a phosphonium salt and 0.001-1% by weight of an alkali metal hydroxide or an alkaline earth metal hydroxide as a catalyst. A catalytic reaction of a polyhydric phenol is described.

(Problems to be Solved by the Invention) When an epoxy resin is used, for example, as a paint for cans, especially a paint used for food sanitary cans, the extraction of the components of the inner wall coating film into the contents of the can is minimized. It is requested that From this viewpoint, it is desired to reduce the low molecular weight fraction of the polyhydroxy ether used in the paint for cans and to improve the processability of the polyhydroxy ether, and thus to obtain a polyhydroxy ether having a high molecular weight. Was rare. In addition, it was also desirable to achieve as narrow a molecular weight distribution as possible of a polyhydroxyether as a precursor to promote the transformation of the high molecular weight polyhydroxyether and to increase its solubility in solvents.

Of the above catalysts, those other than phosphines or phosphonium salts not only catalyze the desired reaction of epoxide groups with phenolic hydroxyl groups, but also undesired competitive side reactions such as the reaction of epoxide groups with phenolic hydroxyl groups. Hydroxyl group generated by Reaction with epoxide group, homogeneous polymerization reaction of epoxide group,
And also catalyze other similar reactions. The result is a mixture of different polymer resins of different molecular weights and having different side chains and terminal functional groups. Such diversity reduces the quality and utility of the product and is therefore disadvantageous.

As a method for producing a polyhydroxyether having a well-defined molecular weight distribution, a method using a phosphonium halide has already been proposed. However, although this method suppresses the above side reactions, it is disadvantageous in that the reaction takes a long time, thereby reducing the productivity, and that it is difficult to obtain a polymer resin having a sufficiently high molecular weight by this method. It is. Polyhydroxyethers having a sufficiently high molecular weight can only be obtained in this way by using large amounts of catalyst. However, when a large amount of catalyst is used, the catalyst itself is extracted as a low molecular weight impurity, and the quality of the product is reduced. Furthermore, the use of such large amounts of catalyst is economically disadvantageous.

Generally, high molecular weight resins are formed by solution polymerization.
Solution polymerization is advantageous in that a linear polymer can be obtained without the formation of a gel since the reaction proceeds at a relatively low temperature, even if phosphonium halide is used as a catalyst, it is more promoted. On the other hand, solution polymerization is disadvantageous in that the reaction inevitably requires a very long time.

The present invention has been made in view of the above. An object of the present invention is to provide an improved method for producing a high molecular weight polyhydroxyether having a sharp molecular weight distribution in a very short time and with high efficiency.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, a high-molecular-weight polyhydroxyether having a sharp molecular weight distribution can be obtained by converting a polyepoxide and a mononuclear or polynuclear phenol into a phosphonium halide or an alkylenephosphorane. It has been found that when reacted in the presence of an effective amount of a combined catalyst consisting of and a certain nitrogen heterocyclic compound, a small amount of catalyst can be formed within a short reaction time.

The gist of the present invention is: (a) an epoxy resin having an average of one or more epoxy groups per molecule; (b) a mononuclear or polynuclear phenol having at least two phenolic hydroxyl groups per molecule; And (c) (c1) Formula I or Formula II Wherein X represents a halogen atom, such as a chlorine atom, a bromine atom or an iodine atom, and R ¹ , R ² and R ³ may be the same or different and are hydrocarbons containing 1 to 25 carbon atoms And R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, said hydrocarbon group optionally being a carbonyl group, a carboxylic acid ester Group and one or more groups selected from carboxamide groups, and when each of R ⁴ and R ⁵ represents a hydrocarbon group, R ⁴ and R ⁵ together form a ring And a halogenated phosphonium or alkylenephosphorane containing a carbonyl group at the β-position to the phosphorus-carbon bond, and (c2) substituted or unsubstituted imidazoles; Benzimidazoles, imidazolines, dihydropyrimidines,
A composition comprising a small but effective catalytic amount of a catalyst which is a combination of a nitrogen heterocyclic compound selected from the group consisting of tetrahydropyrimidines, dihydroquinazolines, salts thereof, and mixtures thereof.

The epoxy resin used according to the invention can be any polyepoxide as long as it has, on average, two or more 1,2-epoxy groups in one molecule. It is preferably a liquid at room temperature. It may be a saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic epoxide. If desired, it may have non-interfering substituents such as halogen atoms, hydroxyl groups, ether groups, ester groups and the like. Examples of the polyepoxide include, for example,
Epoxy novolak resin; 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane,
Polyglycidyl ethers of dihydric phenols such as bis (4-hydroxyphenyl) sulfone, resorcinol and hydroquinone; polyglycidyl ethers of trihydric alcohols such as glycerin; polyglycidyl esters such as diglycidyl phthalate and diglycidyl isophthalate; Epoxidized esters of polyethylene-type unsaturated fatty acids such as epoxidized linseed oil; epoxidized esters of unsaturated alcohols and unsaturated carboxylic acids such as 3,4-epoxycyclohexylmethyl and 3,4-epoxycyclohexylcarboxylic esters Epoxidized 2,2-bis (2
Epoxidized polyethylene-type unsaturated hydrocarbons such as -cyclohexenyl) propane, epoxidized vinylcyclohexane, epoxidized dimer of cyclopentadiene, and the like. Of these polyepoxides, polyglycidyl ethers of polyhydric phenols, and especially diglycidyl ethers of dihydric phenols are preferred. Particularly preferred as component (a) is diglycidyl ether of 22-bis (4-hydroxyphenyl) propane.

The epoxy resin component (a) preferably has an epoxy equivalent in the range of 180-200 g / equivalent.

The mononuclear or polynuclear phenol (b) used according to the invention may be any mononuclear or polynuclear phenol as long as it has at least two phenolic hydroxyl groups. It may have any number of other substituents of any kind as long as it is inert to the epoxy group. For example, the phenol to which the present invention is applied is represented by the following formula: Wherein R ′ is a hydrogen atom, a lower alkyl group having 1 to 7 carbon atoms (eg, methyl, propyl, tert-butyl), a halogen atom (eg, bromine, chlorine), an aryl group (eg, phenyl) Groups and naphthyl groups, lower alkaryl groups (the aryl part may be, for example, a phenyl group or a naphthyl group, and the alkyl part may be an alkyl group having 1 to 7 carbon atoms, for example, a methyl group, a propyl group and the like), aromatic Lower alkyl groups (where the alkyl moiety is a group having 1 to 7 carbon atoms such as methyl, propyl, tert-butyl and the like phenyl- or naphthyl-lower alkyl groups), cycloalkyl groups (for example cyclopentyl group) , Cyclohexyl group), cycloalkyl-alkyl group (C1-7 group such as methyl group, Propyl group, a cyclopentyl with tert-butyl and the like - or cyclohexyl -
An alkyl group), an alkoxy group (a group having 1 to 20 carbon atoms, preferably a group having 1 to 7 carbon atoms such as a methoxy group, a propoxy group, a 2-methoxyoctyl group and the like), and an alkenyl group (a carbon atom group). T represents 2 to 20, preferably 2 to 7 carbon atoms such as propen-1-yl, buten-2-yl and the like), and phenoxy. bond i.e. the formation of diphenyl moiety, or oxygen atoms between, sulfur atom, -NH -, - SO ₂
-Represents a linear or branched lower alkylene group having 1 to 10 carbon atoms (for example, hexylene group, methylene group and the like), a phenylmethylene group or a tolylmethylene group; Represents an integer up to 3, provided that when one of q or t is equal to 3, the other represents a number less than 2, p and s represent an integer from 0 to 2, and the sum of p and s is greater than 2. Not small. ] It is a compound represented by these.

In a preferred embodiment of the present invention, in the dihydric phenol, R 'represents a hydrogen atom, a bromine atom or a lower alkyl group, T represents a methylene group or an isopropylene group, and n, q and t each represent Represents an integer from 0 to 2, and p and s each represent 1. A preferred dihydric phenol is represented by the following formula: (Wherein T ¹ is a bond between two phenyl rings, O, S, SO ₂ ,
NH, represents a CH ₂ or C (CH _{3) 2.} ). Particularly suitable dihydric phenols in the practice of the present invention are 2,2-bis (4-hydroxyphenyl) propane, resorcin, 1,4-dihydroxynaphthalene, 2,2
-Bis (4-hydroxyphenyl) methane, bis (4-
(Hydroxyphenyl) sulfone, tetrabromo- and tetrachloro-bisphenol A, pyrocatechin, hydroquinone, bis (4-hydroxyphenyl) -methyl-
Phenyl-methane, bis (4-hydroxyphenyl)-
Tolyl-methane, 4,4'-dihydroxydiphenyl, phenolphthalein, and 4,4'-dihydroxy-3,
3 ', 5,5'-tetramethylbiphenyl is included. Particularly preferred among these are bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl) propane.

The dihydric phenol reacted with the epoxy resin according to the method of the present invention may be the same or different from the dihydric phenol used to make the 1,2-epoxy resin component. For example, the diglycidyl ether of bisphenol A may be reacted with bisphenol A or resorcin.

In the present invention, the relative amounts of the polyepoxide and the mono- or polynuclear dihydric phenol can be varied as appropriate over a wide range based on the desired properties of the product, ie, on the desired degree of acceleration. Usually, they are used in such proportions that the amount of dihydric phenol is from 0.4 to 2.5 equivalents, and preferably from 0.8 to 1.25 equivalents, per equivalent of polyepoxide. Most preferably, the amounts of components (a) and (b) used in accordance with the present invention are such that the phenolic component (b) contains from 0.85 to 0.95 hydroxyl equivalents per epoxy equivalent of component (a).

Generally, the accelerated reaction according to the present invention is from about 100 to about 250
C., preferably at a temperature in the range of about 150 to about 200.degree.

Unlike other methods using inorganic bases, in the method of the present invention, there is no need to remove or deactivate the catalyst after the reaction, since the remaining catalyst does not affect the subsequent product performance.

According to the invention, the reaction of the polyepoxide with the phenol is carried out in the presence of a catalyst, in the molten state or in the presence of a solvent. When a solid reactant is used and / or when a highly viscous product is produced, the presence of an inert solvent is advantageous. Examples of inert solvents which can be used are xylene, toluene, methyl isobutyl ketone, ethylene glycol diethyl ether, cyclohexanone, dibutyl ether and butyl acetate. Mixtures of these solvents can also be used.

The catalyst component (c1) according to the invention has the formula I or II Wherein X represents a halogen atom, such as a chlorine atom, a bromine atom or an iodine atom, and R ¹ , R ² and R ³ may be the same or different and are hydrocarbons containing 1 to 25 carbon atoms And R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, said hydrocarbon group optionally being a carbonyl group, a carboxylic acid ester Group and one or more groups selected from carboxamide groups, and when each of R ⁴ and R ⁵ represents a hydrocarbon group, R ⁴ and R ⁵ together form a ring A phosphonium halide or alkylenephosphorane represented by the following formula:

R ¹ , R ² and R ³ can be the same or different and each is a monovalent hydrocarbon group, i.e. an alkyl, cycloalkyl, aryl, alkaryl or aryl group having up to 25 carbon atoms. Alkyl group, preferably 1 to
These groups having 18 carbon atoms such as phenyl groups,
Represents a butyl group, a lauryl group, a hexadecyl group or a cyclohexyl group, a benzyl group and a phenethyl group.

The groups R ¹ , R ² and R ³ are preferably identical and are 1 to 1
Represents a hydrocarbon group containing 8 carbon atoms. Most preferably, R ¹ , R ² and R ³ represent a phenyl group.

In the compounds of the formulas I or II according to the invention, the radicals R ⁴ and R ⁵ preferably independently of one another represent a hydrogen atom or a hydrocarbon radical containing 1 to 10 carbon atoms.

Phosphonium halides of the formula I and formula II
Is a compound having a carbonyl group at the β-position to the phosphorus carbon bond, and the alkylenephospholane is particularly stable.

Examples of the above-mentioned phosphorane or phosphonium salt (c1) include, among others, tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, benzyltriphenylphosphonium chloride, (o-methylbenzyl) triphenylphosphonium bromide, bromide (m -Methylbenzyl) triphenylphosphonium, (p-methylbenzyl) triphenylphosphonium bromide, (3,3-diphenylpropyl) bromide
Triphenylphosphonium, tributyl (p-methylbenzyl) phosphonium chloride, tridodecyl (aldodecylbenzyl) phosphonium chloride, triphenylpropylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide, methyl bromide Triphenylsulfonium, methyltriphenylphosphonium iodide, dodecyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, (4-methylpentyl) triphenylphenylphosphonium bromide,
Tetrabutylphosphonium iodide, tributylethylphosphonium iodide, n-amyltriphenylphosphonium bromide, formylmethylenetriphenylphosphorane, formylmethyltriphenylphosphonium chloride, benzoylmethylenetriphenylphosphorane, acetylmethylenetriphenylphosphorane, odor Phenacyltriphenylphosphonium bromide, methoxycarbonylmethylphosphonium bromide, ethyl triphenylphosphoranylideneacetate, methyl triphenylphosphoranylideneacetate, ethoxycarbonylmethylenetriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, (ethyl triacetate Phenylphosphonium-acetic acid) complexes and the like.

The most preferred component (c1) according to the invention is formylmethyltriphenylphosphonium chloride.

The catalyst component (c2) used according to the present invention is a substituted or unsubstituted imidazole compound, benzimidazole compound, dihydropyrimidine compound, tetrahydropyrimidine compound, imidazoline compound or dihydroquinazoline compound or a salt thereof, or a mixture thereof. These compounds may contain at most 4 substituents on the carbon atoms and may contain suitable substituents on the nitrogen atom, each of which may have from 1 to 20 carbon atoms. including.

The only exact feature of the catalysts (c2) is that they belong to any of the classes of catalysts mentioned above. Accordingly, catalyst (c2) may contain suitable substituents on carbon atoms, for example, alkyl groups having 1 to 20 carbon atoms, preferably lower alkyl groups having 1 to 7 carbon atoms, such as methyl, propyl, pentyl and The like; amino groups; monoalkylamino and dialkylamino groups having 1 to 20 carbon atoms, preferably mono- and di-lower alkylamino groups having 1 to 7 carbon atoms such as ethylamino group;
Dipropylamino, hexylamino and the like; phenyl, phenoxy, carboxyl; carboalkoxy having 1 to 20 carbon atoms, preferably carbo-lower alkoxy having 1 to 7 carbon atoms, such as carbomethoxy Groups, carbobutoxy groups, carboisopropoxy groups and the like; mercapto groups; hydroxyl groups; halogen atoms such as chlorine and bromine atoms; azo groups; alkanoyl groups having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms. Lower alkanoyl groups such as acetyl, propionyl and the like; benzoyl groups;
A phenylthio group; a halophenyl group such as a p-chlorophenyl group, an o-bromophenyl group and the like; an alkylthio group having 1 to 20 carbon atoms, preferably a lower alkylthio group having 1 to 7 carbon atoms such as a methylthio group, a propylthio group, A pentylthio group and the like; a nitro group; an alkanoylamino group having 1 to 20 carbon atoms, preferably an alkanoylamino group having 1 to 7 carbon atoms such as an acetylamino group, a propionylamino group and the like; a carbamide group; C1-20 hydroxyalkyl, preferably C1-7 hydroxy lower alkyl such as hydroxymethyl, hydroxypropyl, hydroxybutyl and the like; anilino; C1-20 alkenyl Group, preferably carbon atom 2-7 lower alkenyl groups such as propen-1-yl, buten-2-yl group and the like; C7-C15 aralkyl groups, preferably C7-C12 same groups such as benzyl Phenethyl group, phenylpropyl group and the like; C7-C15 alkaryl group, preferably C7-C12 same group such as methylphenyl group, 2,4-dimethylphenyl group, propylphenyl group And the like; alkanoic acid groups having 2 to 12 carbon atoms, preferably the same groups having 2 to 7 carbon atoms such as acetic acid group, butyric acid group and the like can be used. Suitable substituents on the nitrogen atom are an alkyl group, an aryl group, an aralkyl group, an alkaryl group, a phenoxy group, an alkanoyl group, a carboxy group, an alkanoic acid group, a hydroxyalkyl group, -R-NH
₂ groups, -R-NHR group, -RN (R) ₂ group, -R-SH group. In these groups, R represents an alkyl group, a phenyl group or an aralkyl group. ｝ And the like. In these various substituents, the carbon chain is as defined above.

The following are typical catalysts (c2). :
Imidazole, 4-acetaminoimidazole, 5-acetaminoimidazole, 1-acetylimidazole,
4-aminoimidazole, 5-aminoimidazole, 2
-(2-aminoethyl) -imidazole, 5-amino-
1-methyl-imidazole, 1-benzoylimidazole, 2-benzylthioimidazole, 4,5-bis (p-
Bromo-phenyl) -imidazole, 2-chloroimidazole, 4-benzylthio-5-nitroimidazole,
5-benzylthio-4-nitroimidazole, 4-bromoimidazole, 5-bromoimidazole, 2-bromo-4,5-diphenyl-imidazole, 2-butylthio-
2-cyclohexyl-4,5-diethyl-imidazole,
1,5-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 4-methylimidazole, 1-methyl-4-phenylimidazole, 1-methyl -4-nitroimidazole, 5-nitroimidazole, 1-phenylimidazole, 2-phenylimidazole, 1-methylimidazole, imidazole-4-acetic acid, 1-vinyl-2-methylimidazole,
Imidazole-1-acetic acid, imidazole-1-aniline, 5-butylamidoimidazole, 4-carboxamidoimidazole, 4-carboxyimidazole, 2-carboxyl-1-benzyl-imidazole, 4,5-dicarboxamido-imidazole, 4,5 -Dicarboxyimidazole, imidazole-1-ethanol, 2-thioimidazole, 2-acetoamino-1-benzylbenzimidazole, 1-acetylbenzimidazole, 2-aminobenz-imidazole, 2- (1-aminobutyl)
-4-amino-6-ethoxybenzimidazole, 2-
Amino-1-ethylbenzimidazole, 2-amino-
1-methylbenzimidazole, 1-benzylbenzimidazole, 2-benzylaminobenzimidazole,
1-benzyl-2-chlorobenzimidazole, 2-benzyl-5-nitrobenzimidazole, 2-p-bromobenzylbenzimidazole, 2-butylthiobenz-imidazole, 5-chlorobenzimidazole, 6-
Chlorobenzimidazole, 6-chloro-1,2-dimethylbenzimidazole, 5,6-dichlorobenzimidazole, 5,6-dimethylbenzimidazole, 5,6-dinitrobenzimidazole, 2-ethyl-5-nitrobenzimidazole , 1-methylbenzimidazole, 6-
Methyl-2-phenylbenzimidazole, 6-phenylbenzimidazole, 2-acetamino-N-methylbenzimidazole, benzimidazole-2-acetic acid, 2-carboxamidobenzimidazole, 2-carboxy-benzimidazole, 2-carboxy-5 -Bromobenzimidazole, 2,4-dimethylimidazoline, 2-methylimidazoline, 1-vinyl-2-methylimidazoline, 2-ethyl-4-methylimidazoline,
2-chloromethyl-2-imidazoline, 2-methylimidazoline phenate, imidazole lactate, imidazole acetate, 3,4-dihydro-4-phenylpyrimidine, 4-methyl-1,4,5,6-tetrahydropyrimidine, 3, 4-dihydroquinazoline, 2-benzyl-2-imidazoline-4-carboxylic acid, 2- (1-naphthylmethyl) -2-imidazoline and 2-chloromethyl-2-
Imidazoline.

In a preferred embodiment of the invention, the catalyst (c2) is an imidazole, benzimidazole, dihydropyrimidine, tetrahydropyrimidine, dihydroquinazoline having 0 to 2 substituents and in particular having 0 or 1 substituent. And imidazolines. Preferred substituents are lower alkyl, aryl-lower alkyl, lower alkaryl, aryl, lower alkenyl, and lower alkoxy, among which methyl,
Ethyl, phenyl and vinyl groups are particularly preferred.

In a most preferred embodiment of the present invention, the catalyst (c2) is selected from imidazoles and imidazolines. Particularly preferred catalysts (c2) are imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4
-Methylimidazole, 2,4-dimethylimidazole,
2-phenylimidazole, 1-vinyl-2-methylimidazole, 2-methylimidazoline, 2-ethyl-4
-Methylimidazoline, 2,4-dimethylimidazoline and imidazole lactate. Most preferred catalysts (c2) are 1-methylimidazole and 2-phenylimidazole.

Particularly preferred compositions of the present invention are those wherein component (a) is the diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane and component (b) is 2,2-bis (4-hydroxyphenyl) propane. Wherein component (c1) is formylmethyltriphenylphosphonium chloride and component (c2) is 1-methylimidazole or 2-phenylimidazole.

In the composition according to the invention, the amount of component (b) is preferably from 0.4 to 2.5, in particular from 0.8 to 1.0, per equivalent of component (a).
To 1.25, most preferably 0.85 to 0.95 equivalents, and based on the total weight of the epoxy resin (a) and phenol (b), respectively, the amount of component (c1) is preferably from 0,1 to 0,25.
005 to 5, especially 0.01 to 0.1% by weight of the component (c
The amount of 2) is from 0.0001 to 0.1, in particular from 0.0002 to 0.04% by weight.

Another aspect of the present invention is a precatalyst comprising an epoxy resin having an average of one or more epoxy groups per molecule and a small but effective catalytic amount of a combined catalyst comprising components (c1) and (c2) according to the present invention. The added epoxy resin composition.

Another aspect of the present invention is to promote the reaction of an average of one or more epoxy resins per molecule with a mononuclear or polynuclear phenol having at least two phenolic hydroxyl groups per molecule at about 50 ° C. In a process for producing a solid, substantially linear resin at a temperature of from about 225 ° C to about 225 ° C, the improvement is the reaction of (c1) a phosphonium halide or alkylenephosphorane and (c2) a substituted or unsubstituted imidazole. A small but effective catalytic amount of a combination of a nitrogen heterocyclic compound selected from the group consisting of, benzimidazoles, imidazolines, dihydropyrimidines, tetrahydropyrimidines, dihydroquinazolines, salts thereof and mixtures thereof An improved method for accelerating an epoxy resin, characterized in that the method is carried out in the presence of:

A particularly preferred method of the present invention is a method wherein the catalyst is a combination of formylmethyltriphenylphosphonium chloride and 1-methyl-imidazole or 2-phenylimidazole.

In carrying out the process of the present invention, other known promoting catalysts such as alkali metal or alkaline earth metal hydroxide may be added to the combined catalyst comprising components (c1) and (c2) of the present invention and added as a catalyst. it can.

Accelerated epoxy resins made according to the present invention can react with a curing agent to produce hard, insoluble, infusible products. Any known curing agent for epoxy resin,
It can be used to obtain crosslinked products by known methods.

The curing of the epoxy resin produced by the method of the present invention is within the knowledge of the art. Cure from room temperature
The reaction is carried out at a temperature of from 120 to 300 ° C. for a suitable time in the presence of a curing agent. The curing agent is used in a stoichiometric amount ± 50% with respect to the epoxy resin.

Curing agents that can be used are, for example, aromatic polyamines containing at least three amino hydrogen atoms, such as p-phenylenediamine, m-phenylenediamine, bis (4-aminophenyl) methane, bis (4-aminophenyl) Ether, bis (4-aminophenyl) ketone, aniline-
Formaldehyde resin, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone and 2,
4'-diamino-diphenyl sulfone; polycarboxylic anhydrides such as maleic anhydride, succinic anhydride, dodecenyl succinic anhydride, polyazeleic anhydride, sebacic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, hexachloroendmethylenetetrahydrophthalic anhydride and pyromellitic dianhydride; and catalytic hardeners such as dicyanodiamide, semicarbazide and polyhydrazines such as isophthalyl dihydrazide, sebacyl dihydrazide and adipyl dihydrazide.

Curing at elevated temperatures results in a network of high crosslink density. Thus, as used herein, the expression "curing" refers to obtaining a shaped article such as a cast, pressed or laminated article, or providing a two-dimensional structure such as a paint, enamel or adhesive. Of the adduct and the epoxide material and the insoluble / infusible cross-linked product together with the shaping for forming.

The polyhydroxyethers obtained according to the invention can be used in various applications, for example as metal primers, if appropriate by adding solvents, diluents, tars, fillers, pigments and the like to the polyhydroxyethers. Can be used for the production of insulating varnishes. Furthermore, the combined use of polyhydroxyether and other resins enables the production of a coated film having excellent processability. In addition, special emulsions can be made by reacting polyhydroxyethers with methacrylic acid, styrene, ethyl acrylate and the like.

The epoxy resin produced according to the present invention may be used at any stage prior to curing, with conventional modifiers such as extenders,
Fillers and reinforcing agents, pigments, dyes, organic solvents, plasticizers,
It can be further mixed with adhesives, rubbers, accelerators, diluents and the like.

 Enhancements which can be used in the curable mixtures according to the invention
Examples of fillers, reinforcing agents, fillers and pigments include:
Can be mentioned: coal tar, bitumen, moth
Lath fiber, boron fiber, carbon fiber, cellulose, polye
Tylene powder, polypropylene powder, mica, asbestos,
Various quartz powders, fused silica, silicates, silanes, charcoal
Magnesium acid and calcium carbonate, masonry, bent
Aerosil ), Lithobon, heavy crystals
Stone, titanium dioxide, carbon black, graphite,
Iron oxide, or iron powder. Also, another usual additive, for example,
Flame retardants, such as antimony trioxide, with thixotropic
Additives, flow regulators such as silicone, cellulose acetate butyrate
, Polyvinyl butyral wax, stearate and
And similar (some are also used as release agents)
Can be added to the curable mixture.

In the adhesive, for example, a rubber such as carboxyl group-terminated acrylonitrile butadiene rubber, a modifier such as triglycidyl p-aminophenol, and an accelerator such as boron trifluoride monoethylamine complex or imidazole complex may be added. It is possible.

The curable mixture can be mixed with a known mixing device (stirrer, kneader,
Rollers and the like) in a conventional manner.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but these examples should not be construed as limiting the scope of the present invention.

In the following Examples and Comparative Examples, all parts are parts by weight.

Example 1: 300 parts of glycidyl ether of bisphenol A having an epoxy equivalent of 189 g / eq was heated in a 500 ml four-necked flask equipped with a thermometer, a stirrer and a heater under a nitrogen stream, and the inside of the flask was heated. Increase temperature to 70 ° C. Subsequently, 0.0045 part of 2-phenylimidazole and 0.184 part of formylmethyltriphenylphosphonium chloride are added as a catalyst, and when the temperature is raised to 100 ° C., 161.03 parts of bisphenol A is added, and then the temperature is raised to 180 ° C. At that temperature the contents of the flask are allowed to react for 5 hours. Thus, a polyhydroxy ether is produced. 1;
The average molecular weights of the respective products after 3 and 5 hours of reaction are given below. Table 1 shows the same data for _{n w w} / _{n 1} hour 5530 15275 2.76 3 hours 6116 18165 2.97 5 hours 6978 22 981 3.29 present product epoxy equivalent weight and average molecular weight, as well as the product of Example 2 to 10 below.

Example 2: A reaction is carried out under the same conditions and procedures as in Example 1 except that 0.0028 part of 2-phenylimidazole and 0.184 part of formylmethyltriphenylphosphonium chloride are used as a catalyst to produce a polyhydroxyether.

Example 3 A reaction is carried out under the same conditions and procedures as in Example 1 except that 0.0045 parts of 2-phenylimidazole and 0.092 parts of formylmethyltriphenylphosphonium chloride are used as a catalyst to produce a polyhydroxyether.

Example 4: A reaction is carried out under the same conditions and procedures as in Example 1 except that 0.0045 part of 2-enylimidazole and 0.046 part of formylmethyltriphenylphosphonium chloride are used as a catalyst to produce a polyhydroxyether.

Example 5: 300 parts of a glycidyl ether of bisphenol A having an epoxy equivalent of 189 g / eq and 158.25 parts of bisphenol A were used as reactants, and 0.0028 part of 2-phenylimidazole and 0.183 part of formylmethyltriphenylphosphonium chloride were used as a catalyst. Otherwise, the reaction is carried out under the same conditions and procedures as in Example 1 to produce polyhydroxyether.

Example 6: 300 parts of glycidyl ether of bisphenol A having an epoxy equivalent of 189 g / eq and 164.41 parts of bisphenol A were used as reactants, and 0.0028 part of 2-phenylimidazole and 0.184 part of formylmethyltriphenylphosphonium chloride were used as a catalyst. Otherwise, the reaction is carried out under the same conditions and procedures as in Example 1 to produce polyhydroxyether.

Example 7: A reaction is carried out under the same conditions and procedures as in Example 1 except that 0.0028 parts of 1-methylimidazole and 0.184 parts of formylmethyltriphenylphosphonium chloride are used as a catalyst to produce a polyhydroxyether.

Example 8: A reaction is carried out under the same conditions and procedures as in Example 1 except that 0.00445 part of 1-methylimidazole and 0.184 part of formylmethyltriphenylphosphonium chloride are used as a catalyst to produce a polyhydroxyether.

Example 9: 500 m equipped with a thermometer, a stirrer, a reflux device and a heater
l In a four-necked flask, 200 parts of glycidyl ether of bisphenol A having an epoxy equivalent of 189 g / eq, 113.67 parts of bisphenol A, 16.5 parts of methyl isobutyl ketone as a solvent, and 2-phenylimidazole as a catalyst
0.003 parts and 0.25 parts of formylmethyltriphenylphosphonium chloride are added. After raising the temperature to 160 ° C. and at that temperature the contents of the flask are reacted for 5 hours.
Thus, a polyhydroxy ether is produced.

Example 10: A reaction is carried out under the same conditions and procedures as in Example 9 except that 0.021 part of 2-phenylimidazole and 0.165 part of formylmethyltriphenylphosphonium chloride are used as a catalyst to produce a polyhydroxyether.

Comparative Example 1: Instead of a combination of two catalyst compounds, formylmethyltriphenylphosphonium chloride 0.18 as a single catalyst
The reaction is carried out under the same conditions and procedures as in Example 1 except that 4 parts are used to produce a polyhydroxyether.

Table 2 shows the epoxy equivalents and average molecular weights of the products of Comparative Examples 1 to 11.

Comparative Example 2: Instead of a combination of two catalyst compounds, formylmethyltriphenylphosphonium chloride 0.092 as a sole catalyst
The reaction was carried out under the same conditions and procedures as in Example 1 except for using the above-mentioned parts to produce polyhydroxyether.

Comparative Example 3: Instead of a combination of two catalyst compounds, formylmethyltriphenylphosphonium chloride 0.04 as a sole catalyst
The reaction is carried out under the same conditions and procedures as in Example 1 except that 6 parts are used to produce polyhydroxyether.

Comparative Example 4: Instead of the combination of the two catalyst compounds, 0.184 parts of amyltriphenylphosphonium bromide was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 1 except that polyhydroxyether was used. Generated.

Comparative Example 5: Instead of a combination of two catalyst compounds, 0.0115 parts of sodium hydroxide was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 1 to produce a polyhydroxyether.

Comparative Example 6: Instead of a combination of two catalyst compounds, 0.045 parts of 2-phenylimidazole was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 1 to produce a polyhydroxyether. I do.

Comparative Example 7: Instead of a combination of two catalyst compounds, 0.023 parts of 2-phenylimidazole was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 1 except for producing polyhydroxyether. I do.

Comparative Example 8: Instead of a combination of two catalyst compounds, 0.0314 parts of 2-phenylimidazole was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 9 except for producing polyhydroxyether. I do.

Comparative Example 9: Instead of a combination of two catalyst compounds, 0.0627 parts of 1-methylimidazole was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 9 to produce polyhydroxyether. I do.

Comparative Example 10: Instead of a combination of two catalyst compounds, 0.0314 parts of 1-methylimidazole was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 9 except for producing polyhydroxyether. I do.

Comparative Example 11: Instead of a combination of two catalyst compounds, 0.0045 parts of 2-phenylimidazole was used as a single catalyst, and the reaction was carried out under the same conditions and procedures as in Example 1 except for that,
Produces polyhydroxyether.

Test After heating the reaction mixtures of the above Examples and Comparative Examples to a predetermined reaction temperature (180 ° C. or 160 ° C.), the epoxy equivalent of the polyhydroxyether product was measured for 1 hour and 3 hours according to the potassium iodide-hydrochloric acid method. And after a reaction time of 5 hours. The experimental data obtained as well as the desired (theoretical) epoxy equivalent for each row are shown in the table below. The desired, ie, theoretical, epoxy equivalent represents the epoxy equivalent relative to the relative amounts of epoxy resin and phenol used in the accelerated reaction. Methods for calculating the phenol dose based on the epoxy resin dose, the starting epoxy value and the desired epoxy value for the product are described in, for example, Encyclopedia of Polymer Scienc.
e and Engineering, 2nd.Ed., Vol. 6, page 328, Wiley Int
erscience, New York 1986.

The average molecular weights _n and _w are determined by gel permeation chromatography and the polydispersity is calculated from M _w / M _n . The results are summarized in Tables 1 and 2.

Based on the data presented in the table above, the following conclusions can be made.

The molecular weight of the polyhydroxyethers prepared in the examples of the invention is higher than that of the product of the comparative example and the reaction according to the invention proceeds faster. The desired epoxy equivalent (predetermined by the relative ratio of epoxy resin and phenol used) can be easily achieved in a short time by the process according to the invention, but not in the case of the comparative reaction. is not. Furthermore, the degree of polydispersity, as evidenced by the _w / _n ratio of the accelerating resin of constant molecular weight, is significantly lower for the resin produced according to the invention than for the product of the comparative example (for example after 1 hour reaction). Of the product of Example 1 with the product of Comparative Example 1 after 5 hours of reaction). The process according to the invention produced a substantially linear resin and no gel formation was observed.

In short, the process for the preparation of polyhydroxyethers according to the invention has a very high molecular weight, a product with a substantially linear molecular structure and a very narrow molecular weight distribution, i.e., which has been strongly desired, but is difficult to realize. Can be produced. The desired product can be produced economically in a very short period of time by using the above-mentioned catalysts (c1) and (c2) in combination.

Claims (19)

(57) [Claims] 1. An epoxy resin having an average of one or more epoxy groups per molecule, (b) a mononuclear or polynuclear phenol having at least two phenolic hydroxyl groups per molecule, and (C) (c1) Formula I or Formula II Wherein X represents a halogen atom, such as a chlorine atom, a bromine atom or an iodine atom, and R ¹ , R ² and R ³ may be the same or different and are hydrocarbons containing 1 to 25 carbon atoms And R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, said hydrocarbon group optionally being a carbonyl group, a carboxylic acid ester Group and one or more groups selected from carboxamide groups, and when each of R ⁴ and R ⁵ represents a hydrocarbon group, R ⁴ and R ⁵ together form a ring And a halogenated phosphonium or alkylenephosphorane containing a carbonyl group at the β-position to the phosphorus-carbon bond, and (c2) substituted or unsubstituted imidazoles; A small but effective catalytic amount of a catalyst which is a combination of a nitrogen heterocyclic compound selected from the group consisting of benzimidazoles, imidazolines, dihydropyrimidines, tetrahydropyrimidines, dihydroquinazolines, salts and mixtures thereof. A composition comprising: 2. A composition according to claim 1, wherein component (a) is a diglycidyl ether of a dihydric phenol. 3. A composition according to claim 2, wherein component (a) is the diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane. 4. The component (b) is represented by the following formula: (Wherein T ¹ is a bond between two phenyl rings, O, S,
Represents SO ₂ , NH, CH ₂ or C (CH ₃ ) ₂ . The composition according to claim 1, which is a bisphenol represented by the formula: 5. The composition according to claim 4, wherein component (b) is bis (4-hydroxyphenyl) methane or 2,2-bis (4-hydroxyphenyl) propane. 6. A compound according to claim 1, wherein R ¹ , R ² and R ³ are identical and represent a hydrocarbon radical containing 1 to 18 carbon atoms.
A composition as described. 7. The composition according to claim 6, wherein R ¹ , R ² and R ³ represent a phenyl group. 8. The composition according to claim 1, wherein R ⁴ and R ⁵ independently represent a hydrogen atom or a hydrocarbon group containing 1 to 10 carbon atoms. 9. The composition according to claim 1, wherein component (c1) is formylmethyltriphenylphosphonium chloride. 10. The composition according to claim 1, wherein component (c2) is unsubstituted or substituted by one to four substituents, each of which contains 1 to 20 carbon atoms. Stuff. 11. A substituent on a carbon atom includes an alkyl group, an amino group, a monoalkylamino group, a dialkylamino group,
Phenyl, phenoxy, carboxyl, carboalkoxy, mercapto, hydroxyl, halogen, azo, alkanoyl, benzoyl, phenylthio, halophenyl, alkylthio, cycloalkyl, nitro, alkanoylamino , A carboxamide group, a hydroxyalkyl group, an anilino group, an alkenyl group, an aralkyl group, an alkaryl group and an alkanoic acid, and the substituent on the nitrogen atom is an alkyl group, an aryl group, an aralkyl group, an alkaryl group. , phenoxy group, carboxy group, a hydroxyalkyl _{group, -R-NH 2, -RNHR,} -RN (R) 2 and -R-SH
(Wherein R represents an aryl group, an alkyl group or an aralkyl group).
10. The composition according to 10. 12. The composition according to claim 10, wherein the component (c2) represents an imidazole or an imidazoline. 13. Component (c2) is imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethyl-
From 4-methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, 1-vinyl-2-methylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline and imidazole lactate 13. The composition according to claim 12, wherein the composition is selected from the group consisting of: 14. The composition according to claim 13, wherein the component (c2) is 1-methylimidazole or 2-phenylimidazole. 15. Component (a) is the diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane,
Component (b) is 2,2-bis (4-hydroxyphenyl) propane, component (c1) is formylmethyltriphenylphosphonium chloride, and component (c2) is 1-methylimidazole or 2-phenylimidazole. The composition of claim 1. 16. The amount of component (b) is per equivalent of component (a).
0.4 to 2.5 equivalents and, based on the total weight of the epoxy resin (a) and the phenol (b), the amount of component (c1) is 0.005 to 5% by weight and the amount of component (c2) is 0.0001 to 0.1, respectively. The composition according to claim 1, which is in weight percent. 17. An epoxy resin having (a) an average of one or more epoxy groups per molecule, and (c) (c1) a compound of the formula I or II. Wherein X represents a halogen atom, such as a chlorine atom, a bromine atom or an iodine atom, and R ¹ , R ² and R ³ may be the same or different and are hydrocarbons containing 1 to 25 carbon atoms And R ⁴ and R ⁵ may be the same or different and represent a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, said hydrocarbon group optionally being a carbonyl group, a carboxylic acid ester Group and one or more groups selected from carboxamide groups, and when each of R ⁴ and R ⁵ represents a hydrocarbon group, R ⁴ and R ⁵ together form a ring And a halogenated phosphonium or alkylenephosphorane containing a carbonyl group at the β-position to the phosphorus-carbon bond, and (c2) substituted or unsubstituted imidazoles; A small but effective catalytic amount of a catalyst which is a combination of a nitrogen heterocyclic compound selected from the group consisting of benzimidazoles, imidazolines, dihydropyrimidines, tetrahydropyrimidines, dihydroquinazolines, salts thereof and mixtures thereof. An epoxy resin composition containing a pre-catalyst. 18. The reaction of an epoxy resin having an average of one or more epoxy groups per molecule with a mononuclear or polynuclear phenol having at least two phenolic hydroxyl groups per molecule at about 50 ° C. In a process for producing a solid, substantially linear resin at a temperature of from about 225 ° C to about 225 ° C, the improvement is that the accelerating reaction comprises: (c1) a phosphonium halide or alkylenephosphorane and (c2) a substituted or unsubstituted imidazole. , Benzimidazoles, imidazolines, dihydropyrimidines, tetrahydropyrimidines, dihydroquinazolines, salts thereof and a mixture of nitrogen heterocyclic compounds selected from the group consisting of mixtures thereof. An improved method for accelerating an epoxy resin, which is performed in the presence of a catalyst. 19. A catalyst comprising formylmethyltriphenylphosphonium chloride and 1-methylimidazole or 2-methylimidazole.
19. The method according to claim 18, which is a combination of phenylimidazole.