JPS6094945A - Novel aliphatic triamine compound - Google Patents

Abstract

NEW MATERIAL:1,8-Diamino-4-aminomethyl-2,4,7-trimethyloctane expressed by the formula. USE:A curing agent for epoxy resins, capable of curing the epoxy resins rapidly at ordinary temperature to give cured articles of the epoxy resins having improved heat distortion temperature as compared with cured articles cured with hexamethylenediamine or triethylenetetramine and improved chemical resistance to organic solvents, e.g. methanol or toluene. PREPARATION:2,4,7-Tricyano-4-methyloctane obtained by electrolytic reductive trimerization of methacrylonitrile is hydrogenated to afford the aimed compound expressed by the formula. The above-mentioned hydrogenation is carried out in the presence of Raney-cobalt as a catalyst at 130-170 deg.C under 40-75kg/cm<2> pressure, and the reaction solution is distilled.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel aliphatic triamine compounds.

Conventionally, the aliphatic triamine compound 9 has the following 1,8-diamino-4- obtained by hydrogenating 1,3,6-)lycyanohexane, which is a trimer of acrylonitrile.
Aminomethyloctane (hereinafter abbreviated as TA) is known [US Pat. No. 3,246,000 Specification Co., J.O.
rg, Chem, 30 (5), 1351 (
1965) :].

TA has 6 active hydrogens in one molecule, and has hexamethylenediamine (1 (MDA), diethylenetriamine (DETA),) diethylenetetramine (TETA).
It is known as a curing agent for epoxy resins (Japanese Patent Publication No. 50-29957).

The entire purpose of the present invention is to provide a novel aliphatic triamine compound whose structure is completely different from that of TA. In other words, the new aliphatic triamine compound that has achieved all of the above objectives has the following structural formula. 1,8-diamino-4-
It is aminomethyl-2,4,7-drimethyloctane (hereinafter abbreviated as MTA).

CD.

H2 The MTA of the present invention has 1. compared to the conventional TA.
The 8-diaminooctane chain is the same, but at the 2nd, 4th, and
They have six methyl substituents at the 7-position, and their carbon skeletons are completely different. If TA' (5-methylated MTAi
In order to obtain this, three methyl groups would have to be selectively introduced into the 2-, 4-, and 7-positions, but this is chemically extremely difficult. The difficulty can be inferred from the fact that no substituted TNA compounds have hitherto been known.

The manufacturing method of MTA will be described below.

MTA according to the present invention is obtained by hydrogenating 2,4,7-)lycyano-4-methyloctane obtained by total electrolytic reduction of methacrylonitrile.

2.4.7-) Dicyano-4-methyloctane is prepared by using lead as both the cathode and anode, using a container with a cathode chamber and anode chamber separated by a cation exchange membrane, and dimethyl sulfoxide of methacrylonitrile as the catholyte. For example, tetraethylammonium monoethyl sulfate [(C
2H,), N5O4C2,H,:] and a solution containing 8 to 10% by weight of water,
Current density 5-20 A/dm2, reaction temperature 40-60℃
It is obtained by carrying out electrolysis at a constant current density and completely distilling the catholyte after this electrolysis.

MTA was prepared using 2.4',7-)dicyano-4-methyloctane with Raney cobalt as a catalyst at a temperature of 130-1
It is obtained by hydrogenating at a 70C5 pressure of 40 to 75 kg/CI/l and then distilling the reaction solution.

The MTA thus obtained has a boiling point of 151-152U/
It is a liquid substance with a temperature of 5 +imHg (the instrument was calibrated), and has all the spectral data and elemental analysis values shown below.

In addition, as is clear from its structural formula, MTA has the 2nd position,
It is estimated that 94 types of isomers (8 types if each optical isomer is included) exist depending on the asymmetric carbons at the 4th and 7th positions.

The lH-NMR spectrum data shown below shows that isomers are present.

(11"H-NMR, r, vector (60R4Hz,
CD30D) δppm: 2.4 to 2.7 (Multiple NI (27C)
H,,\) 6H Note that the chemical shift of the NHt- proton varies depending on the solvent used for measurement, and in the case of CDCM, δppm: around 7.6 CD301
), δp424.6.

(2) IR spectrum (rock salt plate, liquid film method) crn-
':3360.3280.2920.2860.161
0.1460.1580.1060.960~800(
3) Elemental analysis values Element Theoretical value Actual value C66,92% 66.81% H13,57% 13,59% N 19,519! As shown in Reference Example I1j55, this MTA rapidly cures the epoxy resin at a rising temperature, and like TA, it can be used as a curing agent for epoxy resins. In addition, the epoxy resin cured product cured with MTA is TETA.

Compared to the cured epoxy resin material cured using HMDA'5, the heat distortion temperature is improved and the product's resistance to organic solvents such as methanol and toluene is also improved. Furthermore, when compared with a cured epoxy resin product cured with TA, an improvement in the Atsuki solvent resistance is also observed.

EXAMPLES Both the cathode and anode were made of lead, and a battery case was used in which a cathode chamber and an anode chamber were separated by a cation exchange membrane.

1,245 kg of methacrylonitrile as a liquid to shade 4,
Dimethyl sulfoxide 1,287 kg, tetraethylammonium monoethyl sulfate 0. t98kg,
Using a mixture of 0.27 yu of water and about 3 kg2 of a 10 wt% sulfuric acid aqueous solution as the polar liquid, the reaction temperature was 50-55.
'Cc 1t) Constant' turtle current density electrolysis was carried out at a Tb density of 15 A/dm. This electrolytic reaction was carried out 5 times in batches, and the catholyte after the reaction was collected and distilled to give 183 to 188
C/ 2.4 at 0.6 mmHg (meter not calibrated).
7-) Approximately 1 oorr of phosphorus ano-4-methyloctane was obtained.

This 2,4,7-)dicyano-4-methyloctane 40
2 and Raney cobalt 2.07, internal volume 1o o
The mixture was charged into a 5US316L autoclave equipped with a cc-4Q stirrer, and after nitrogen substitution, hydrogen substitution was carried out, and the reaction temperature was 150C1, and the hydrogen pressure was 50kg/c++! The hydrogenation reaction was carried out for 3 hours while stirring and stirring.

After the reaction, the reaction solution was filtered to remove the catalyst, and distilled under reduced pressure to obtain a fraction of 20 tkA0 at nodes 151-15' 2 c/5 mmHg (the instrument was not calibrated). This liquid'
I checked the H-NMR spectrum, IR spectrum, and elemental analysis values, and found that they were the same as above, and that fc was MT.
It was identified as A.

Reference example epoxy resin CA E R331, :! : Phoxy equivalent weight 19o.

MTA 1.8 F was added to 10 g of Asahi Kasei Industries Co., Ltd., stirred, and left to stand at 25C, which completely solidified in about 3 hours.

Agent’at water shame L

Claims (1)

[Claims] 1.8-Diamino-4-aminomethyl-2,4,7-drimethyloctane.