JPH04330041A - Modified aromatic diamine composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying an aromatic diamine having a primary amino group into a corresponding secondary amine, and a modification composition.

0002

BACKGROUND OF THE INVENTION Aromatic diamines having a secondary amino group are known to be useful as raw materials for polyurea RIMs, elastomers, and other materials, and as raw materials for plastics such as epoxy resins. Aromatic diamines having a secondary amino group have superior characteristics in terms of reactivity with polyisocyanates and physical properties of the resulting polyurea, as compared to the corresponding primary amines.

One of the known methods for producing aromatic diamines having a secondary amino group is disclosed in, for example, JP-A-2-31
1116, this is a method in which an aromatic diamine having a primary amino group is alkylated or aralkylated with an alkyl halide, an aralkyl halide, etc., and the primary amino group is secondaryized. In this method, since a solvent such as dioxane is used, a removal operation after the reaction is necessary, and a part of the raw material primary amine itself is consumed due to the binding of by-product hydrogen halide. Alternatively, an acid binder such as alkali hydroxide must be used separately, but the conversion rate of all primary amino groups to secondary amines is still relatively low and the alkylating agent is relatively expensive. have Therefore, an aromatic diamine in which only one of the amino groups is converted to a secondary amino group is used.

0004

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of the known methods described above, and further provides a method in which the second substituent of the secondary amino group is different from known secondary amino group aromatic diamines. The present invention aims to provide a novel aromatic diamine composition.

[0005]

[Means to solve the problem]

Summary of the Invention The present invention provides that at least a portion of the amino groups of an aromatic diamine are a primary amino group and a compound of the formula CH2=CH-Y (wherein, Y
means an electron-withdrawing group. Provided is a modified aromatic diamine composition for producing plastics, which is secondaryized by a Michael addition reaction with an unsaturated compound.

[0006] In addition, in terms of the method, the present invention is characterized in that an aromatic diamine and a compound of the formula CH2=CH-Y (the symbols in the formula have the same meanings as above) are subjected to a Michael addition reaction. A method for modifying aromatic diamines is provided.

The Michael addition reaction of the present invention can be represented by the following formula. -NH2 +CH2 =CH-Y → -NHCH
2-CH2-Y

In prior art secondary amino aromatic diamines, the second substituent on the secondary amino group is generally a non-functional hydrocarbon group, and therefore the modified compositions of the present invention have a structurally Contains novel compounds.

The primary aromatic diamines used in the present invention include meta-phenylene diamine, para-phenylene diamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1-methyl-3,5-diethyl-2, 4-diaminobenzene, 1-methyl-3,5-diethyl-2,6
-diaminobenzene, 3-isopropyl-2,6-diaminotoluene, 5-isopropyl-2,4-diaminotoluene, 5-t-butyl-2,4-diaminotoluene,
3-t-butyl-2,6-diaminotoluene, 3,5-
Diethylthio-2,4-diaminotoluene, 3,5-diethylthio-2,6-diaminotoluene, 1,3,5-
Triethyl-2,6-diaminobenzene, 4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3
',5,5'-tetrapropyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 5
, 7-diamino-1,1-dimethylindane, 4,6-
Diamino-1,1-dimethylindane, 4,7-diamino-1,1-dimethylindane, 5,7-diamino-1
, 1,4,6-tetramethylindane and mixtures thereof.

Various aromatic diamines are commercially available, such as 1-methyl-3,5-diethyl-2,4-
Diaminobenzene and 1-methyl-3,5-diethyl-2
, 6-diaminobenzene as a mixture of etacure 1
00 (manufactured by Asano Chemicals Co., Ltd.), tolylenediamine (manufactured by Mitsui Toatsu Chemical Co., Ltd.) as 2,4-diaminotoluene, and MDA as 4,4'-diaminodiphenylmethane.
-220 (manufactured by Mitsui Toatsu Chemical Co., Ltd.), and any of these can be conveniently used in the present invention.

The other raw material compound has the formula CH2=CH
-Y (wherein Y means an electron-withdrawing group such as an ester residue, a ketone residue, a cyano group, an unsubstituted or substituted amide residue, a sulfone residue, or a sulfonic acid ester residue).
Examples of unsaturated compounds include acrylic esters (n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,
methyl acrylate, lauryl acrylate, stearyl acrylate, propyl acrylate, etc.), acrylonitrile, acrylamide, N,N-dimethylacrylamide, methyl vinyl ketone, ethyl vinyl ketone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl vinyl sulfonate, ethyl Examples include vinyl sulfonate. Any of these may be advantageously used in the present invention.

The Michael addition reaction according to the invention is facilitated by using neutral or acidic catalysts commonly used in esterification reactions as catalysts for the reaction. Such catalysts are practically necessary to obtain high conversion rates.

Examples of such esterification catalysts include:
Commonly used as acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, propionic acid, formic acid, acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, p-toluenesulfonic acid, etc.), monoatomic metals as solid acids Oxides (aluminum oxide, silicon oxide, niobium oxide, etc.), composite metal oxides (SiO2 -Al2O3, TiO2
-SiO2, SiO2 -La2O3, TiO
2-Al2O3, etc.), sulfides (zinc sulfide, etc.)
, metal sulfates (nickel sulfate, copper sulfate, etc.), metal phosphates (aluminum phosphate, titanium phosphate, etc.), chlorides (aluminum chloride, copper chloride, etc.), clay minerals (acid clay, montmorillonite, kaolin, etc.) , solidified acids (solidified phosphoric acid, solidified sulfuric acid, solidified boric acid, etc.), resins (ion exchange resins, etc.), zeolites, organotin compounds (dibutyltin oxide, dibutyltin, etc.) as organometallic compounds. dilaurate, etc.), organoaluminum compounds (trialkoxy, chelate, acylate) (
Aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum ethylate, aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate),
aluminum bisethyl acetoacetate monoacetylacetonate, etc.), organic titanium compounds (tetraalkoxy, chelates, acylates) (tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis-
2-Ethylhexoxytitanium, tetrastearoxytitanium, di-iso-propoxy bis(acetylacetonato)titanium, iso-propoxy(2-ethylhexanediolate)titanium, di-n-butoxybis(triethanolate) (minato) titanium, hydroxy bis(lactato) titanium, etc. These are also advantageously used in the present invention.

In this case, the primary aromatic diamine and the unsaturated compound have an equivalent ratio of amino group to unsaturated bond of 1/0.
．． The reaction is carried out at a ratio of 0.01 to 1/100, preferably 1/1 to 1/10. Therefore, residual unreacted primary aromatic diamine and excess unsaturated compounds are allowed in the resulting aromatic diamine composition. Further, the esterification catalyst is usually used in an amount of 0.1 equivalent % or less based on the amino group.

[0015] Although the reaction conditions depend on the type and amount of the esterification catalyst, the reaction is generally carried out at a reaction temperature of from room temperature to 150°C.

Although no specific post-treatment is required after the reaction is complete,
If necessary, the remaining unsaturated compound may be polymerized by adding a suitable polymerization initiator, or may be treated to remove the acid. The present invention will be explained below with reference to Examples.

Example 1 91.5 g of tolylene diamine (difunctional, amine equivalent weight 61, molecular weight 122) and para-toluenesulfonic acid (PTS)
) 14.3g, stirring blade, condenser, dropping funnel,
The mixture was placed in a 500 ml glass five-necked flask equipped with a thermometer and a nitrogen inlet tube, and after the temperature was raised to 120°C, 192 g of n-butyl acrylate was added dropwise over 2 hours. Thereafter, the reaction was further carried out for 12 hours to obtain a tolylene diamine mixture. The formation of secondary amino groups was confirmed and the conversion rate to secondary amines was measured by FT-IR, LC, and 13C-NMR measurements. The results are shown in Table-1.

Example 2 In Example 1, instead of n-butyl acrylate,
The reaction was carried out under the same conditions as in Example 1 except that 276 g of 2-ethylhexyl acrylate was used. The results are shown in Table-1.

Example 3 In Example 1, Etacure 100 (difunctional, amine equivalent weight 89, molecular weight 1) was used instead of tolylene diamine.
78) The reaction was carried out under the same conditions as in Example 1, except that 133.5 g was used and the reaction time was changed to 24 hours. The results are shown in Table-1.

Example 4 In Example 1, MD was used instead of tolylene diamine.
A-220 (bifunctional, amine equivalent weight 99, molecular weight 198
) The reaction was carried out under the same conditions as in Example 1, except that 148.5 g was used. The results are shown in Table-1.

Example 5 A reaction was carried out under the same conditions as in Example 1, except that 4.5 g of acetic acid was used instead of para-toluenesulfonic acid. The results are shown in Table-1.

Example 6 In Example 1, solidified phosphoric acid (E48A1) (manufactured by Nikki Kagaku Co., Ltd.) 2 was used instead of para-toluenesulfonic acid.
The reaction was carried out under the same conditions as in Example 1 except that 0 g was used. The results are shown in Table-1.

Comparative Example In Example 1, p-toluenesulfonic acid was not used,
The reaction was carried out under the same conditions as in Example 1 except that the reaction time was changed to 24 hours. The results are shown in Table-1.

[0024]

[Table 1]

TDA: Tolylenediamine (manufactured by Mitsui Toatsu Chemical Co., Ltd.) E-100: Etacure 100 (diethyltoluenediamine) (manufactured by Asano Chemicals Co., Ltd.) MDA-220: Diaminodiphenylmethane (manufactured by Mitsui Toatsu Chemical Co., Ltd.) ) nBA: n-butyl acrylate EHA: 2-ethylhexyl acrylate PTS: para-toluenesulfonic acid Solidified phosphoric acid: E48A1 (manufactured by Nikki Chemical Co., Ltd.) *: T
DA/nBA/E48A1=91.5/192/20(
g)

Claims (5)

[Claims] Claim 1: At least a portion of the amino groups of the aromatic diamine are a primary amino group and a compound of the formula CH2=CH-Y (wherein,
Y means an electron-withdrawing group. ) A modified aromatic diamine composition for producing plastics, which is secondaryized by a Michael addition reaction with an unsaturated compound. 2. The electron-withdrawing group Y of the unsaturated compound according to claim 1, wherein the electron-withdrawing group Y is an ester residue, a ketone residue, a cyano group, an unsubstituted or substituted amide residue, a sulfone residue, or a sulfonic acid ester residue. Modified aromatic diamine composition. Claim 3: An aromatic diamine and a formula CH2=CH-Y
(In the formula, Y means an electron-withdrawing group.) A method for modifying an aromatic diamine, which comprises subjecting it to a Michael addition reaction with an unsaturated compound. 4. The electron-withdrawing group Y of the unsaturated compound according to claim 3, wherein the electron-withdrawing group Y is an ester residue, a ketone residue, a cyano group, an unsubstituted or substituted amide residue, a sulfone residue, or a sulfonic acid ester residue. Denaturation method. 5. The modification method according to claim 3 or 4, wherein the Michael addition reaction is carried out in the presence of a neutral or acidic esterification catalyst.