JPS58210050A - Preparation of polyfunctional amine compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a curing agent of an epoxy resin having excellent corrosion resistance, by reacting N,N,N',N'-tetraglycidyldiaminodiphenylmethane, etc. with a polyalkylene-polyamine. CONSTITUTION:The objective compound is prepared by reacting (A) the compound of formula I (X is H, halogen, alkyl or alkenyl), its derivative, N,N,N',N'- tetraglycidyl-m-xylenediamine of formula II or its derivative with (B) triglycidyl m-aminophenol of formula III or its derivative and (C) a polyalkylene-polyamine (e.g. ethylenediamine, diethylenetriamine, etc.) at 80-120 deg.C. An epoxy resin compounded with the compound is useful as an ultra-heavy-duty corrosion protecting paint having excellent chemical resistance, solvent resistance, boiling water resistance, adhesivity, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful method for producing polyfunctional amine compounds.

In particular, the present invention provides a new and useful method for producing amine compounds useful as curing agents for epoxy resins.

Curing agents for amine-based epoxy resins such as polyamide, polyamide adduct) or amine adduct are used as curing agents for room-temperature curing resins for locations exposed to harsh conditions such as ships, bridges, and offshore structures. It is widely used for so-called heavy-duty anti-corrosion paints.

When such heavy-duty anti-corrosion paints are used as tank interior paints for product carrier ships, which particularly require chemical resistance, the paint systems that can be used are amine-curing epoxy resins, or inorganic or organic zinc-curing paints. Exclusively limited to rich paints, contamination and chemical resistance of cargo (
Although amine-curing epoxy resin paints, which are superior in terms of (alkali and acid resistance) The reality is that there are limits in terms of chemical resistance, product resistance, etc., and therefore there is a desire to further improve these various performances.

Among these, as a means to improve chemical resistance, it is effective to use novolak type epoxy resin instead of using general-purpose bisphenol A diglycidyl ether thread epoxy resin as the main resin, The type or composition of the curing agent to be used is limited, and furthermore, poor adhesion of the cured coating film to the base metal and deterioration of impact resistance are major drawbacks.

On the other hand, chemical resistance can also be improved by modifying amines with phenol/formalin, but this inevitably reduces the adhesion of the cured coating to the base metal, and furthermore, formalin remains. There are problems such as it is not good from a safety and health standpoint.

However, in view of the current situation as described above, the present inventors have developed an amine-based epoxy resin curing agent that is less toxic (and also has excellent anticorrosive properties such as boiling water resistance, chemical resistance, lfi layer property, and impact resistance). (As a result of intensive research, we have completed the present invention.)

That is, in the present invention, [A] has the general formula and represents an alkyl group or an alkenyl group. N, N, N', N'-tetraglycidyldiaminodiphenylmethane or its derivative represented by J (a-1
), general formula [However, X in the formula shall be as described above. ] N, N, N', N-tetraglycidyl-m-xylene diamine or its derivative (a-2
), and the general formula [however, X in the formula shall be as described above3]
A corrosion-preventing agent useful as a curing agent for room-temperature curable epoxy resins, consisting of reacting triglycidyl (a-3) of m-aminophenol or its derivative represented by (B) with a polyalkylene polyamine. The present invention provides a method for producing a polyfunctional amine compound with excellent performance.

On the other hand, the above-mentioned polyalkylene polyamine (B) has the general formula % () [However, n in the formula is an integer from 1 to 7.

] The compounds shown are typical.

Since the polyalkylene polyamine has a high vapor pressure and is highly irritating to the skin, it is preferable to remove unreacted polyalkylene polyamine after the reaction. is suitable.

The method of the present invention is carried out by a commonly used method, and the reaction temperature is approximately 80 to 120°C.
This range is common.

The polyfunctional amine compound thus obtained can be used as a curing agent for room-temperature curable epoxy resins, or can be used as it is. It may be used after being diluted with a solvent.

Therefore, the polyfunctional amine compound, which is the object of the present invention, is blended with an epoxy resin and applied by a known and commonly used coating method such as brush coating or spray coating to achieve gloss and adhesion without blooming or brushing. It can provide an excellent coating film, especially for products.
In the field of super-heavy-duty anticorrosion coatings such as carrier ship tank interior coatings, it exhibits excellent physical properties such as chemical resistance, solvent resistance, boiling water resistance, and adhesion.

Depending on the size and use, it may be used in combination with other curing agents for epoxy resins, and catalysts, fillers, fine materials, and other additives may also be added.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Example 1 11 Into a four-eye flask, add 268 g of diethylenetriamine.
1 part and 280 parts of pheasant were charged, and the temperature was raised to 60'C with stirring. Then, the epoxy equivalent is 1197
．． 268 parts of N, N, N', N'-tetraglycidyldiaminodiphenylmethane were charged in portions and reacted at 100°C for 4 hours over a period of about 50 minutes, and then heated to 160°C. The quidylol and excess diethylenetriamine were removed under reduced pressure.

Thereafter, the temperature was lowered to 100°C, and 127 parts of doluol and 64 parts of n-butanol were added to reduce the nonvolatile content to 70.3 parts.
Viscosity in % (measured at 25°C by Gardner-Holdt method;
A transparent solution named V-W (the same applies hereinafter) was obtained, which is a mixture mainly consisting of a compound represented by the following structural formula.

Example 2 684 parts of ethylenediamine and 240 parts of triol were charged into a 11-piece four-eye flask, and while stirring, N,N
.

680 parts of N',N'-tetraglycidyldiaminodiphenylmethane was charged and reacted at 100'C for 4 hours, then the temperature was raised to 160C and doluol and excess ethylenediamine were removed under reduced pressure. After that, 10
Ib'4 to 0'C? = 164 parts of doluol and 82 parts of n-butanol were added to give a non-volatile content of 72.1%.
A transparent solution with a viscosity of S -T was obtained, which is a mixture mainly composed of a compound represented by the following structural formula.

Comparative Example 1 [380 parts of Ebikuron 1050-1 (epoxy resin manufactured by Inu Nippon Ingi Chemical Industry ■; t=475 per Ebogishi), 120 parts of diethylenetriamine, and 160 parts of Kijirol
After reacting at 120° C. for 1 hour, the temperature was raised to 180° C., and quijirole and excess diethylenetriamine were removed under reduced pressure.

This was then added with 250 parts of pheasant roll and 250 parts of n.
-Addition of butanol, non-volatile content 50.2%, viscosity U-
A clear solution of amine adduct V was obtained.

Example 6 412 parts of diethylene triamine and 100 parts of doluol were charged into a four-eye flask of 11, and the temperature was raised to 80°C, and N, N, N' with an epoxy white value of 102 were added.
, 204 parts of N'-tetraglycidyl-m-xylene diamine were charged in portions over about 60 minutes.

Hereinafter, 118 parts of doluol and 58 parts of n-butanol
The same procedure as in Example 1 was carried out except that the non-volatile content was 764% and the viscosity was 2.5%. A transparent solution was obtained, which is a mixture mainly consisting of a compound represented by the following structural formula.

Example 4 240 parts of ethylenediamine was used instead of diethylenetriamine, the amount of doluol was changed to 200 parts, and the amount of doluol and n-butanol to be added after the reaction was 92 parts and 4 parts, respectively.
A transparent solution with a non-volatile content of 74.6% and a viscosity of R-8 was obtained in the same manner as in Example 6, except that the amount was changed to 6 parts. It is a mixture of

Example 5 371 parts of diethylenetriamine and 147 parts of doluol were charged into a four-eye flask of 1j, and the temperature was raised to 80°C while stirring, and then 2
16 parts of triglycidyl m-aminophenol to about 3
After charging in portions for 0 minutes and reacting at 100°C for 4 hours, the temperature was raised to 160°C and doluol and excess diethylenetriamine were removed under reduced pressure.
87 parts of pheasant roll and 87 parts of n-butanol were added to give a nonvolatile content of 72.3%, viscosity, and Q-R.
A clear solution was obtained, which is a mixture mainly consisting of the compound represented by the following structural formula.

Example 6 216 parts of ethylenediamine was used instead of diethylenetriamine, and 200 parts of KK
Example 5 was repeated, except that 72 parts of doluol and 56 parts of n-butanol were used as the solvents added after the reaction was completed, and the non-volatile content was 77. 2%, a transparent liquid with a viscosity of R-8 was obtained, which is a mixture mainly consisting of a compound having the following structure.

The polyfunctional amine thread compounds and amine adducts obtained in the following ten examples and comparative examples were mixed with epoxy resin (
Here, [Evicron 1050-75XJ
Table 1 summarizes the results of coating film properties and chemical immersion tests of clear paints using the method of the present invention as a curing agent for conventional amine adduct curing. It exhibited excellent anticorrosive properties such as boiling water resistance, salt water resistance, alkali resistance, and acid resistance compared to other agents.

Claims (1)

[Scope of Claims] (N N, N, N', N'-tetraglycidyldiaminodiphenylmethane or its derivative (a-1) represented by the general formula
General formula [However, X in the formula shall be as described above. ] N, N, N', N'-tetraglycidyl-m-
Xylene diamine or its derivative (a-2), or the general formula [However, X in the formula shall be as described above. A method for producing a polyfunctional amine compound, which comprises reacting triglycidyl (a-5) of m-amine phenol or its derivative represented by (B) with a polyalkylene polyamine.