JPH0456834B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for preparing N-glycidyl compounds, more particularly aromatic N-glycidyl amines, especially compounds which are epoxide resins having one or more glycidyl groups per molecule on average, and N-glycidyl compounds prepared by this method. - Concerning glycidylamine. Epoxide resins are used in industry as adhesives, paints, castings, insulators, and in reinforced composite materials, and a variety of epoxy resins with different chemical properties are commercially available. Such resins are usually glycidyl ethers or esters derived from epichlorohydrin and bisphenols or dicarboxylic acids, but aromatic The use of materials having a glycidyl group attached to a group amine nitrogen atom is often preferred. Such materials contain aromatic amines with approximately the same ratio of epichlorohydrin to amino hydrogen atoms.
It can be produced by reacting with 0.8 to 10 equivalents, followed by conventional dehydrochlorination using an alkali. This reaction may be carried out without a catalyst or in the presence of an acid catalyst as described in GB 2111977. Despite their useful properties, N-glycidylamines as prepared by conventional methods leave room for improvement in two respects. First, the epoxide content of the resulting products approaches the theoretical value for complete glycidylation, i.e., the value that would be observed if all amino hydrogen atoms were replaced by glycidyl groups. This is rare. The actual epoxide group content will vary depending on the nature of the amine and the presence or absence of other substituents in the molecule.
For example, the epoxide equivalent for commercially available glycidylated bis(4-aminophenyl)methane is given by Kirk-Othmer's Encyclopedia of Chemical Technology, 3rd edition, Vol. 9, p. 277. 117 to 133.
This corresponds to 79 to 90% of the theoretically possible epoxide content. The properties of the cured resin vary according to the epoxide content of the uncured resin: the greater the epoxide content, the greater the degree of crosslinking will be, and as a result the greater the strength of the cured resin. Will.
It is therefore clear that a higher epoxide content in the resin would be advantageous. A second disadvantage of N-glycidylamines as prepared by conventional methods is believed to be due to side reactions (coupling reactions occurring) occurring during the synthesis that exceed the desired glycidylation. is often very viscous. This also explains why such coupling or low epoxide contents are obtained. Viscous resins have more difficulties for use, especially in the production of fiber-reinforced composites or cast articles, so the use of reactive or inert diluents is often necessary to reduce this viscosity. be. Mixing diluents is generally considered undesirable.
A reactive diluent is one that reacts with the curing agent and remains in the cured resin. These tend to have an adverse effect on the properties of the resin being cured. Inert diluents are removed by evaporation before curing, and these often pose a flammable or toxic hazard. Furthermore, if they are not completely removed from the resin, they also have an adverse effect on the properties of the cured resin. The present inventors have demonstrated that N-glycidylation of aromatic amines can be performed using divalent or more polyvalent metal salts of inorganic oxygen acids.
more particularly by metal nitrates or metal perchlorates, or by divalent or more polyvalent salts of carboxylic or sulfonic acids containing halogen atoms, and even more especially for carboxylic or sulfonic acid groups. When catalyzed by salts of acids such as those substituted by one or more halogen atoms on the carbon atoms in This is what we have discovered that can be achieved. A further surprising advantage of the process of the invention is that aromatic amines whose amino groups are sterically hindered by other groups on the molecule can be N-glycidylated relatively easily, and thus epoxide resins can be produced. The aim is to widen the range of aromatic amines available. As described in the above-mentioned GB 2111977, as a description of the disadvantages of the process for the preparation of N-glycidylamine using known catalysts,
In N-glycidylation using trifluoromethanesulfonic acid as a catalyst, the yield of N-glycidylamine with low epoxide content and high viscosity is relatively low. The use of metal salts of inorganic oxygen acids as accelerators for the curing of epoxide resins with amines is known. GB 1464045 describes (a) an epoxide resin, (b) an aromatic or cycloaliphatic polyamine, and (c) magnesium, calcium, zinc,
Curable compositions comprising perchlorates of manganese, cobalt or nickel are disclosed. British Patent No. 1521356 describes (a) an epoxide resin;
(b) an aromatic amino compound; and (c) a curable composition comprising magnesium or a nitrate of a divalent or higher valent metal of group b, b, B, B, B, B or groups of the periodic table. There is. It is known to use metal salts of halogenated carboxylic and sulfonic acids as accelerators for curing epoxide resins with amines. GB 1498542 discloses that at least two halogen atoms selected from a) in particular polyamines or polyaminoamides, b) fluorine and chlorine atoms, or salts thereof, are added on the carbon atom adjacent to the carboxyl group. aliphatic or araliphatic having 2 to 8 carbon atoms;
Compositions suitable for use as curing agents for epoxide resins comprising monocarboxylic acids are disclosed. Preferred metals for metal salts used in compositions containing aromatic amines are lithium, sodium, calcium and magnesium. British Patent No. 1500206 discloses that a) aromatic,
A composition is disclosed that is suitable for use as a curing agent for an epoxide resin comprising a heterocyclic or cycloaliphatic polyamine, and b) a salt of trifluoromethanesulfonic acid. Preferred salts are lithium, calcium, zinc, cadmium, cobalt, nickel, manganese and magnesium salts. Despite their use as accelerators for the curing of epoxide resins, so far inorganic oxyacids or metal salts of halogenated carboxylic or sulfonic acids have failed in the production of N-glycidyl group-containing epoxy resins. It was not known that it could be used to catalyze or that the resins so produced would have superior properties. Therefore, one feature of the present invention is that (a) nitric acid or perchloric acid, or (b) fluorine, chlorine or bromine on the carbon atom alpha to the carboxylic or sulfonic acid group. with at least 0.7 equivalents of epichlorohydrin based on the amino hydrogen equivalent of the aromatic amine, and preferably from 0.8 to aromatic N consisting of heating an amine having at least one and preferably at least two aromatic amino hydrogen atoms in 1.5 equivalents and dehydrochloridizing the product.
- A method for producing glycidylamine. Another feature of the invention includes aromatic N-glycidylamines obtained by this method. The nitrates and perchlorates used as catalysts in this new process are preferably nitrates and perchlorates such as those described in Lange, Handbook of Chemistry, McGraw-Hill Publishing, 12th Edition. Nitrates and perchlorates of metals from groups A, B, B, B or groups of the periodic table. Magnesium, calcium, zinc, manganese, nickel, lanthanum, vanadium (as vanadyl),
itterbium, and uranium (as uranyl)
The nitrates and perchlorates of are particularly preferred. In the salts of halogen-substituted carboxylic and sulfonic acids used as catalysts, the anions are preferably derived from acids having at most 4 carbon atoms. Particularly preferred are the salts of trifluoroacetic acid, trifluoromethanesulfonic acid, trichloroacetic acid, 2,2-dichloropropionic acid and tribromoacetic acid. Carboxylic or sulfonic acid cations substituted by fluorine, chlorine or bromine atoms are preferably used as described in Lange's Handbook of Chemistry.
It is a cation of metals and transition metals of Group A of the Periodic Table of the Elements as described in the 12th edition published by McGraw-Hill. Particularly preferred cations are the iron, zinc, cadmium and lanthanum cations and most particularly the magnesium, vanadium (as vanadyl), manganese, cobalt and nickel cations. Certain preferred salts as catalysts in the process of the invention are magnesium perchlorate, calcium perchlorate, zinc perchlorate, nickel perchlorate, magnesium nitrate, manganese nitrate, lanthanum nitrate, ytterbium nitrate, launyl nitrate, trifluoro These are magnesium acetate, manganese trifluoroacetate, nickel trifluoroacetate, vanadyl trifluoroacetate, magnesium trifluoromethanesulfonate, cobalt trifluoromethanesulfonate, magnesium trichloroacetate, magnesium 2,2-dichloropropionate, and magnesium tribromoacetate. The amount of salt present in the reaction mixture is generally from 0.1 to 10 parts per 100 parts by weight of aromatic amine, particularly preferably from 0.4 to 2 parts per 100 parts by weight of amine. Aromatic amines glycidylated according to the present invention can be only primary amines, only secondary amines, or can have both primary and secondary amino groups attached directly to the aromatic ring. and it can also have one or more aromatic rings. Further groups which can be present in such aromatic rings are alkyl groups, especially those having 1 to 4 carbon atoms, C1 to 4 alkylene groups, sulfonyl groups, halogen atoms, hydroxyl groups, 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
to 4 alkoxy groups, and tertiary amino groups. Preferred amines used in this method have one or two primary amino groups. Aniline, aminophenyl indane and the following formula or: (In the above formulas, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and X is a valence bond, a carbon An amine represented by an alkylene group having 1 to 4 atoms, an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group is particularly preferred. Examples of particularly preferred amines include aniline,
1,3,3-trimethyl-1-(4-aminophenyl)-5-aminoindan, 1,3,3-trimethyl-1-(4-aminophenyl)-6-aminoindan, O-, m-, or p -phenylenediamine, 2,4-diethyl-6-methyl-1,3
-phenylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)-ketone, bis(4-aminophenyl) ether, bis(4-aminophenyl) sulfide, bis(3-
aminophenyl) and bis(4-aminophenyl)sulfone, 4,4'-diamino-3-ethyldiphenylmethane and bis(4-amino-3-ethylphenyl)-methane. The catalyst is an inert organic solvent such as 2-methoxyethanol, isodecanol, ethylene glycol,
diethylene glycol, N-methylpyrrolidone,
γ-Butyrolactone, benzyl alcohol, dibutyl phthalate, butane-1,4-diol, ethyl methyl ketone, benzene or toluene is best mixed into the reaction mixture. The reaction is usually carried out in an inert solvent, such as one or more of the solvents mentioned above, at elevated temperature, especially from 50 to 100°C. Epichlorohydrin and catalyst may be added simply or dropwise, if desired. When the reaction between the amine and epichlorohydrin is judged to be complete, usually within 1 to 5 hours, the dehydrochlorination is carried out by adding water, optionally together with a quaternary ammonium halide, such as benzyltrimethylammonium chloride, as a catalyst. This is carried out in a conventional manner by adding sodium oxide or potassium hydroxide.
After heating at 50 to 100°C for 2 to 10 hours, the mixture is washed with water and the organic layer is separated and washed with N.
- Obtain glycidylamine. It is used as prepared or after purification by conventional means. The N-glycidyl group-containing epoxide resin produced by the method of the present invention may be cured by conventional methods. The invention therefore includes products, such as castings or fiber-reinforced materials, made of the material obtained by curing the epoxide resin produced by the method of the invention. Suitable curing agents for epoxide resins containing N-glycidyl groups are known:
They include dicyandiamide, aromatic amines such as bis(3-aminophenyl) sulfone and bis(4-aminophenyl) sulfone and bis(4-aminophenyl) sulfone.
aminophenyl)methane (usually together with a promoter such as a _BF3 -amine complex), and polycarboxylic anhydrides such as cyclohexane 1,2-dicarboxylic anhydride, methylbicyclo[2,2,1]-hept- 5-ene-2,3-dicarboxylic anhydride,
Includes pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride. The following examples illustrate the invention in detail. All parts and percentages are by weight. Example 1 Bis(4-aminophenyl)methane (100g),
Toluene (100 ml) and 50% magnesium perchlorate (1 g) dissolved in 2-methoxyethanol are stirred and heated to 60°C. Add epichlorohydrin (203.5 g) little by little over 2 hours,
Maintain temperature between ℃ and 90℃. Once the addition is complete, the mixture is maintained at 80°C for an additional hour. The mixture was allowed to cool to 75°C, and 50% aqueous benzyltrimethylammonium chloride solution (6 g) was added.
Process with. Flaked sodium hydroxide (89
g) in portions over 2 hours and then heat the mixture at 75° C. for 3 hours. Next, water (300ml)
and toluene (250 ml) with vigorous stirring and filtered. Discard the aqueous layer and remove the organic layer with 1310 ml of water.
1 part, 450 parts of sodium chloride and 9 parts of acetic acid (250 ml). The organic solution was then evaporated under reduced pressure on a rotary evaporator, redissolved in toluene (250 ml), filtered and evaporated under reduced pressure with epoxide content: 8.62 eq/Kg (91% of theory) and viscosity: A product of 46.5 Pas is obtained at 40 °C. When the experiment was repeated omitting the magnesium salt catalyst, the epoxide content of the product was 8.37 equivalents/Kg.
(88.3% of the theoretical amount), and the viscosity at 40℃ is
It is 70.7 Pas. Examples 2 to 7 Example 1 is repeated by replacing the magnesium perchlorate with another salt dissolved in 2-methoxyethanol. The epoxide content and viscosity of the product are as follows.

[Table] In Examples 2, 3 and 5 to 7, the salt was 2
Two equal parts are added, the first at the beginning of the reaction and the second at the end of the addition of epichlorohydrin. Example 8 2,4-diethyl-6-methyl-1,3-phenylenediamine (100 g) is heated to 65°C and 50% magnesium perchlorate (1 g) dissolved in methoxyethanol is added. Epichlorohydrin (207.9 g) is added in portions over 2 hours, maintaining the reaction mixture below 80°C. When the epichlorohydrin addition was complete, another 50% magnesium perchlorate (1 g) was added and the mixture was heated to 80°C.
Heat for 8 hours. Isopropanol (106 ml) is added and the mixture is adjusted to 65°C. 50% aqueous sodium hydroxide solution (187.2 g) is added in portions over 2 hours and the mixture is then heated at 65° C. for a further 2 hours. Add water (150 ml) and ethyl methyl ketone (250 ml) and discard the aqueous layer. The organic layer is washed with the brine solution described in Example 1 (250 ml), evaporated on a rotary evaporator under reduced pressure and redissolved in ethyl methyl ketone (250 ml). Filtration and evaporation give a product having an epoxide content of 7.84 equivalents/Kg (78.8% of theory) and a viscosity at 25° C. of 21.5 Pas. omit magnesium perchlorate, instead of 8 hours.
When repeating the previous example with an initial reaction time of 16 hours, the product has an epoxide content: 5.67 equivalents/Kg (57% of theory) and a viscosity at 25° C.: 581.9 Pas. Example 9 Magnesium perchlorate was replaced with 1.5 each of 33% magnesium nitrate dissolved in methoxyethanol
Example 8 is repeated using two additions of g. The product has epoxide content: 7.77 equivalents/Kg
(78.1% of theory) and viscosity at 25°C: 27.5 Pas. Example 10 Bis(4-aminophenyl)methane, 4,4'-
The amine used in Example 1 was replaced by a liquid mixture of diamino-3-aminodiphenylmethane and bis(4-amino-3-ethylphenyl)-methane, and the magnesium perchlorate was replaced by lanthanum nitrate. Example 1 is repeated with the following substitutions. At the end of the epichlorohydrin addition, the mixture is heated to 80° C. for 3 hours. The product has epoxide content: 8.23 equivalents/Kg (96.2% of theory)
and viscosity at 25°C: 17.3 Pas. If the experiment is repeated omitting the lanthanum nitrate catalyst and using an initial reaction time of 12 hours instead of 3 hours at 80°C, the epoxide content of the product is 7.64 equivalents/
Kg (89% of the theoretical amount) and the viscosity at 25℃ is
It is 50.3 Pas. Example 11 Bis(4-aminophenyl)methane (100g),
50% manganese nitrate (1 g) dissolved in toluene (150 g) and 2-methoxyethanol is heated to 60°C and reduced pressure (18665 Pa = 140 mmHg). Add epichlorohydrin (203.5 g) in portions over 1 hour. After the addition is complete, stop the vacuum and lower the temperature.
Increase to 80℃. Furthermore, add catalyst solution (1 g),
The mixture is maintained at 80°C for 5 hours. Add 50% benzyltrimethylammonium chloride (1.5g),
Adjust temperature to 75°C. Sodium hydroxide (97.1
g) in 10 equal parts at 10 minute intervals. At the end of the addition, the mixture is kept at 75° C. for 1 hour and then treated with water (310 mls). Discard the water layer,
The organic layer was washed with the brine solution described in Example 1 and then evaporated under reduced pressure to give epoxide content: 8.48.
Equivalent weight/Kg (89.6% of theory) and viscosity at 50°C:
A product with 8.6 Pas is obtained. When the experiment was repeated omitting the manganese nitrate catalyst, the product had an epoxide content of 7.98 equivalents/Kg.
(84.3% of theory) and viscosity at 50°C: 9.8 Pas. Example 12 Aniline (100g), toluene (150g) and 2
-Heat 50% lanthanum nitrate (1g) dissolved in methoxyethanol to 60℃ and reduce the pressure (18665Pa=140
mmHg). Epichlorohydrin (216.6
g) in portions over 1 hour, after which the vacuum is stopped and the temperature is increased to 80°C. Further catalyst solution (1 g) is added and the mixture is maintained at 80°C for 4 hours, followed by the addition of 50% aqueous benzyltrimethylammonium chloride solution (1.5g) and the temperature is adjusted to 75°C. Sodium hydroxide (103.2g)
was added in 10 equal parts at 10 minute intervals, the mixture was subsequently maintained at 75°C for 1 hour, and then water (350 ml)
Process with. The aqueous layer was discarded and the organic layer was washed with the brine solution described in Example 1 (250 ml) and then evaporated under reduced pressure to give an epoxide content of 9.19 eq/Kg (94.4% of theory) and a viscosity at 25°C. : A product with 0.09 Pas is obtained. The experiment was repeated omitting the lanthanum nitrate catalyst solution to obtain an epoxide content of 3.17 equivalents/Kg (theoretical amount).
32.5%) and a viscosity at 25° C. of 51.1 Pas. Example 13 Bis(3-aminophenyl)sulfone (50g),
Toluene (50 g) and 50% lanthanum nitrate (5 g) dissolved in 2-methoxyethanol are heated to 60°C and reduced pressure (18665 Pa = 140 mmHg). Epichlorohydrin (81.3 g) is added in portions over 1 hour, then the vacuum is stopped and the temperature is increased to 80°C. Further catalyst solution (5 g) is added and the mixture is maintained at 80° C. for 6 hours. The temperature is adjusted to 75°C and the mixture is treated with 50% aqueous benzyltrimethylammonium chloride solution (0.75g). Sodium hydroxide (38.7 g) is added in 10 equal parts at 10 minute intervals, then the mixture is heated at 75° C. for 1 hour and then treated with water (150 ml). Discard the water layer;
The organic layer was soaked in the brine solution described in Example 1 (125
ml) and evaporated under reduced pressure. Epoxide content:
A product is obtained with 7.40 equivalents/Kg (87.4% of theory) and a viscosity at 50° C.: 456.1 Pas. When the experiment was repeated omitting the catalyst solution, the temperature was 80°C.
Very little reaction occurs after 6 hours of heating at . Example 14 A mixture of 1,3,3-trimethyl-1-(4-aminophenyl)5-aminoindan and 1,3,3-trimethyl-1-(4-aminophenyl)6-aminoindan (100 g), toluene ( 150g)
and 50% lanthanum nitrate (1 g) dissolved in 2-methoxyethanol was heated to 60℃ and reduced pressure (18665Pa
= 140mmHg). Epichlorohydrin (151.5
g) in portions over 1 hour, then stop the vacuum and increase the temperature to 80°C. Further catalyst solution (1 g) is added and the mixture is maintained at 80° C. for 5 hours. The temperature was adjusted to 75°C and the mixture was diluted with 50% aqueous benzyltrimethylammonium chloride solution (1.5
g). Sodium hydroxide (72.3g)
Add in 10 equal parts at 10 minute intervals, then maintain the reaction at 75° C. for about 1 hour, then treat with water (250 ml). The aqueous layer was discarded and the organic layer was washed with the brine solution (250 ml) described in Example 1 and evaporated under reduced pressure to give an epoxide content of 7.87 eq/Kg (theoretical amount).
96.6%) and a viscosity at 50° C.: 121.7 Pas. The experiment was repeated omitting the lanthanum nitrate catalyst.
Epoxide content: 6.06 equivalents/Kg (theoretical 74.4
%) and a viscosity at 50° C.: 220 Pas is obtained. Example 15 Bis(4-aminophenyl)methane (100g),
Toluene (100ml) and 50% magnesium trifluoromethanesulfonate (1g) dissolved in 2-methoxyethanol are mixed and heated to 60°C. Epichlorohydrin (203.5 g) was added in portions over 2 hours, maintaining the temperature between 60°C and 80°C, and when the addition was complete, the mixture was
Heat at 80℃ for another hour. Then cool to 75℃,
Add 50% aqueous benzyltrimethylammonium chloride solution (6 g). The mixture is treated with sodium hydroxide (89 g) added in portions over 2 hours. When the addition is complete, heat the mixture to 75°C.
Heat for 3 hours, add water (300ml) and toluene (250ml)
ml) with vigorous stirring. Then strain the mixture and discard the aqueous layer. The organic layer is washed with a solution (250 ml) containing 1310 parts of water, 450 parts of sodium chloride and 9 parts of acetic acid and then evaporated on a rotary evaporator under reduced pressure.
The residue was redissolved in toluene (250 ml), filtered and then evaporated under reduced pressure to give an epoxide content of 8.87.
Equivalent weight/Kg (93.% of theory) and viscosity at 40℃:
A product with 16.2 Pas is obtained. When the reaction was repeated omitting the magnesium salt catalyst, the product had an epoxide content of 8.37 equivalents/Kg.
(88.3% of theory) and viscosity at 40°C: 70.7 Pas. Examples 16 to 19 Example 15 is repeated, replacing 1 g of magnesium trifluoromethanesulfonate by 2 g of another salt dissolved as a 50% solution in methoxyethanol. This salt addition takes place in two stages:
Half is added before the addition of epichlorohydrin and the rest is added at the end of the addition of epichlorohydrin. The details of the salt and the nature of the product are shown below:

[Table] Example 20 2,4-diethyl-6-methyl-1,3-phenylenediamine (100 g) is heated to 65°C and 50% magnesium trifluoromethanesulfonate (1 g) dissolved in methoxyethanol is added. Epichlorohydrin (207.9 g) is added in portions over 2 hours, maintaining the reaction mixture below 80°C. At the end of the addition of epichlorohydrin, further
50% magnesium trifluoromethanesulfonate (1 g) is added and the mixture is heated at 80° C. for 4 hours. Isopropanol (106 ml) is added and the mixture is adjusted to 65°C. 50% aqueous sodium hydroxide solution (187.2 g) is added in portions over 2 hours, after which the mixture is heated at 65° C. for a further 2 hours. Water (1150ml) and ethyl methyl ketone (250ml)
ml) and discard the aqueous layer. The organic layer is washed with the brine solution described in Example 1 (250 ml), evaporated on a rotary evaporator under reduced pressure and redissolved in ethyl methyl ketone (250 ml). By filtration and evaporation, epoxide content: 7.90
Equivalent weight/Kg (79.4% of theory) and viscosity at 25°C:
A product with 20.0 Pas is obtained. When the experiment was repeated omitting the magnesium salt and using an initial reaction time of 16 hours instead of 4 hours, the product had an epoxide content of 5.67 equivalents/Kg (theoretical amount).
57%) and viscosity at 25°C: 581.9 Pas. Example 21 Example 20 using magnesium trifluoroacetate in place of trifluoromethanesulfonate
repeat. The product has epoxide content: 8.08 equivalents/Kg (81.2% of theory) and viscosity at 25°C:
It has 31.5 Pas. Example 22 Bis(4-aminophenyl)methane, 4,4'-
Stir a liquid mixture of diamino-3-ethyldiphenylmethane and bis(4-amino-3-ethylphenyl)methane (100g), toluene (100ml), and 50% magnesium trifluoromethanesulfonate (1g) dissolved in methoxyethanol. Then heat to 60℃. Add epichlorohydrin (165.2 g) little by little over 2 hours.
The reaction mixture is maintained below 80°C. At the end of the addition of the mixture, heat the mixture at 80° C. for a further 4 hours. Cool to 75°C, add 50% aqueous benzyltrimethylammonium chloride solution (6 g), and then add sodium hydroxide (72.3 g) in portions over 2 hours. The mixture is heated at 75° C. for 3 hours and then treated with water (250 ml) and toluene (250 ml). The organic layer is separated, washed with brine (250 ml) as described in Example 1 and evaporated. The residue was dissolved in toluene (250 ml), filtered and evaporated to an epoxide content of 8.07 eq/Kg (94.4% of theory).
and a product with a viscosity at 25° C.: 33.4 Pas is obtained. When the experiment was repeated omitting the magnesium salt and using an initial reaction temperature of 80°C for 12 hours instead of 4 hours, the product had an epoxide content of 7.64 eq/Kg (89% of theory) and a viscosity at 25°C of 50.3. Has Pas. Example 23 Bis(4-aminophenyl)sulfone (100
g), toluene (100 ml), and 50% magnesium trifluoromethanesulfonate (1 g) dissolved in methoxyethanol are stirred together and heated to 65°C. Epichlorohydrin (162.5 g) is added in portions over 2 hours, maintaining the temperature of the mixture below 80°C. Furthermore, magnesium salt solution (1
g) was added and the mixture was heated at 80°C for 13 hours, by which time the epoxide content of the mixture was 0.64 equivalent/
Kg. Evaporate toluene with a rotary evaporator,
The residue is suspended in isopropanol (100ml). 50% sodium hydroxide aqueous solution (160g) 1
at 65°C over a period of time and then heat the mixture at 65°C for an additional hour. Water (300 ml) and ethyl methyl ketone (300 ml) are added, the aqueous layer is discarded and the organic layer is washed with brine (250 ml) as described in Example 1 and evaporated. The residue was dissolved in ethyl methyl ketone (250ml) and filtered.
After evaporation, the epoxide content was 6.46 equivalents/Kg (theoretical amount).
76.2%) is obtained. When the experiment was repeated omitting the magnesium salt, initial heating at 80°C for 18 hours resulted in only a slight decrease in epoxide content (5.04 to 4.40 eq/Kg).
This shows that the first step of the reaction does not occur. Example 24 Example 11 is repeated replacing the manganese nitrate solution by a 50% magnesium trichloroacetate solution in isodecanol. The product has epoxide content: 9.19 equivalents/Kg (97.1% of theory) and 50
Viscosity at °C: has 4.1Pas. Example 25 Example 12 is repeated using magnesium trifluoromethanesulfonate in place of lanthanum nitrate. Product has epoxide content: 9.18 equivalent/Kg
(94.3% of theory) and viscosity at 25°C: 0.06 Pas. Example 26 Example 14 is repeated replacing lanthanum nitrate by magnesium trifluoromethanesulfonate. Epoxide content: 7.45 equivalents/Kg (theoretical amount
91.4%) and a viscosity at 50°C: 84.3 Pas. Examples 27 to 29 50% of other salts dissolved in 2-methoxyethanol
Example 24 is repeated replacing the magnesium trichloroacetate solution with % solution. The epoxide content and viscosity of the product are as follows:

【table】

Claims (1)

[Scope of Claims] 1 (a) nitric acid or perchloric acid, or (b) α to a carboxylic acid group or a sulfonic acid group
The amino hydrogen equivalent of an aromatic amine in the presence of a divalent or higher valent metal salt of a carboxylic or sulfonic acid substituted on the carbon atom in position by a fluorine, chlorine or bromine atom. with at least 0.7 equivalents of epichlorohydrin
1. A method for producing aromatic N-glycidylamine, which comprises heating an amine having two aromatic amino hydrogen atoms and dehydrochlorinating the product. 2 The salt used as a catalyst is A on the periodic table,
The claims are nitrates or perchlorates of B, B, B or group metals, or carboxylates or sulfonates substituted with fluorine, chlorine or bromine atoms of group A or transition metals. The method described in paragraph 1. 3 The salts used are magnesium, calcium,
nitrates or perchlorates of zinc, manganese, nickel, lanthanum, vanadium (as vanadyl), ytterbium, or uranium (as uranyl), or iron, zinc, cadmium, lanthanum,
Magnesium, vanadium (as vanadyl),
3. The method according to claim 2, which is a carboxylate or sulfonate substituted with a fluorine atom, chlorine atom, or bromine atom of manganese, cobalt, or nickel. 4. The salt according to claim 3, wherein the salt is magnesium perchlorate, calcium perchlorate, zinc perchlorate, nickel perchlorate, magnesium nitrate, manganese nitrate, lanthanum nitrate, ytterbium nitrate, or uranyl nitrate. Method. 5. Process according to claim 3, wherein the anion of the salt is derived from a substituted carboxylic or sulphonic acid having at most 4 carbon atoms. 6. The method of claim 5, wherein the anion is derived from trifluoroacetic acid, trifluoromethanesulfonic acid, trichloroacetic acid, 2,2-dichloropropionic acid or tribromoacetic acid. 7 The salt is magnesium trifluoroacetate, manganese trifluoroacetate, nickel trifluoroacetate, vanadyl trifluoroacetate, magnesium trifluoromethanesulfonate, cobalt trifluoromethanesulfonate, magnesium trichloroacetate, magnesium 2,2-dichloropropionate, or tribromo 7. The method of claim 6, wherein the magnesium acetate is magnesium acetate. 8. A process according to any one of claims 1 to 7, wherein the amount of salt present is from 0.1 to 10 parts per 100 parts by weight of aromatic amine. 9. A method according to any one of claims 1 to 8, wherein the catalyst is mixed into the reaction mixture dissolved in an inert organic solvent. 10. The method according to any one of claims 1 to 9, wherein the aromatic amine has one or two primary amino groups. 11 The aromatic amine is aniline, aminophenyl indane or the following formula or: (In the above formulas, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and X is a valence bond, a carbon 11. The method according to claim 10, wherein the amine is an alkylene group having 1 to 4 atoms, an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group. 12 The aromatic amine is aniline, 1,3,3-trimethyl-1-(4-aminophenyl)-5-aminoindan, 1,3,3-trimethyl-1-(4
-aminophenyl)-6-aminoindan, O-,
m-, or p-phenylenediamine, 2,4-
Diethyl-6-methyl-1,3-phenylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)-ketone, bis(4-aminophenyl)ether, bis(4-aminophenyl) sulfide, bis(3 -aminophenyl) or bis(4-aminophenyl) sulfone, 4,
Process according to claim 11, characterized in that it represents 4'-diamino-3-ethyldiphenylmethane or bis(4-amino-3-ethylphenyl)methane. 13. The method according to any one of claims 1 to 12, carried out at 50 to 100°C.