JPS6228948B2 - - Google Patents

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. Amine-based epoxy resin curing agents such as polyamide, polyamide adduct, or amine adduct are used as curing agents for cold-curing epoxy resins in so-called heavy-duty applications such as ships, bridges, and offshore structures that are exposed to harsh conditions. It is widely used as an anticorrosion paint. When such heavy-duty anti-corrosion paints are used as tank interior paints for product carrier ships, which particularly require chemical resistance, the coating systems that can be used are amine-curing epoxy resins, or inorganic or organic zinc coatings.・Limited to rich paints, in particular, amine-curing epoxy resin paints, which are relatively superior in terms of cargo staining and chemical resistance (alkali resistance or acid resistance), are often used. There is. However, with existing room temperature curable epoxy resin paints,
The reality is that there are limits to achieving a comprehensive balance of boiling water resistance, chemical resistance, product resistance, etc., and therefore there is a desire to further improve these various properties. For example, as a means to improve chemical resistance, there is a method of using a novolak type epoxy resin instead of using a general-purpose bisphenol A/diglycidyl ether type epoxy resin as the main resin. Although the effect of improving properties is achieved, the type or composition of the curing agent to be combined is limited, and furthermore, poor adhesion of the cured coating to the base metal and deterioration of impact resistance are major drawbacks. . On the other hand, amines were modified with phenol/formalin.
Although chemical resistance can be improved by aging, it is inevitable that the adhesion of the cured coating film to the base metal will deteriorate, and furthermore, formalin may remain, causing problems from a health and safety perspective. There are some problems that are said to be undesirable. However, in view of the current situation as described above, the present inventors have developed an amine-based epoxy resin curing agent that is particularly useful as an amine-based epoxy resin curing agent that is low in toxicity and has excellent anticorrosive properties such as boiling water resistance, chemical resistance, adhesion, and impact resistance. As a result of intensive research to obtain a polyfunctional amine compound, the present invention was completed. That is, the present invention is based on the following formula [] N,N,N',N'-tetraglycidyldiaminodiphenylmethane (a-1) represented by the following formula [] N,N,N',N'-tetraglycidyl-m-xylene diamine (a-2) shown by, or the following formula Trigcidyl (a-3) of m-aminophenol represented by (B) the following general formula [However, n in the formula shall be an integer from 1 to 7. ] The following general formula consists of reacting a polyalkylene polyamine represented by [However, n in the formula shall be an integer from 1 to 7. ] 〓〓〓〓〓
[However, n in the formula shall be an integer from 1 to 7. 〕 or [However, n in the formula shall be an integer from 1 to 7. ] The present invention provides a method for producing a polyfunctional amine-based compound having excellent anticorrosion performance, which is particularly useful as a curing agent for room-temperature curable epoxy resins, and is based on the compound shown below. 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, but the reaction temperature is approximately
A range of 80 to 120°C is common. The polyfunctional amine compound thus obtained may be used as it is, especially as a curing agent for room temperature curable epoxy resins, or it may be diluted with various solvents that are usually classified as solvents for epoxy resins. Good too. 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. Especially in the field of super-heavy-duty anticorrosion coatings such as tank interior coatings for product carrier ships, it has excellent chemical resistance, solvent resistance, boiling water resistance, and adhesion. It indicates physical properties. At that time, depending on the application, it can be used in combination with other epoxy resin curing agents, if necessary.
Catalysts, fillers, pigments and other additives can 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 1 238 parts of diethylenetriamine and 280 parts of xylene were charged into a four-necked flask, and the temperature was raised to 60°C while stirring. Next, 238 parts of "Sumi Epoxy ELM434"(N,N,N',N'-tetraglycidyldiaminodiphenylmethane manufactured by Sumitomo Chemical Co., Ltd.) with an epoxy equivalent of 119 was divided over about 50 minutes. The mixture was charged and reacted at 100°C for 4 hours, then the temperature was raised to 160°C and xylene and excess diethylenetriamine were removed under reduced pressure. After that, the temperature was lowered to 100℃, and 127 parts of toluene and 64 parts of n-butanol were added to remove nonvolatile components.
Viscosity at 70.3% (at 25°C by Gardner-Holt method)
A transparent solution of V-W was obtained, which is a reaction mixture mainly composed of a compound represented by the following structural formula. Example 2 Into the four-necked flask from Step 1, add 384 parts of ethylenedi
Amine and 240 parts of triol were charged, and while stirring, 380 parts of "Smith Epoxy ELN434" was charged and reacted at 100°C for 4 hours.Then, the temperature was raised to 160°C, and toluol and excess ethylenediamine were combined under reduced pressure. Removed. Thereafter, the temperature was lowered to 100°C, and 164 parts of toluene and 82 parts of n-butanol were added to obtain a transparent solution with a nonvolatile content of 72.1% and a viscosity of ST, which is shown by the following structural formula. This reaction mixture is mainly composed of compounds that Comparative example 1 “Epicron 1050” (Dainippon Ink Chemical Co., Ltd.)
380 parts of epoxy resin; epoxy equivalent = 475), 120 parts of diethylenetriamine and 160 parts of xylol
After reacting at 120°C for 1 hour, the temperature was raised to 180°C, and xylene and excess diethylenetriamine were removed under reduced pressure. This was then added with 250 parts of xylol and 250 parts of n.
- Adding butanol, non-volatile content 50.2%, viscosity U
A clear solution of the amine adduct named -V was obtained. Example 3 412 parts of diethylenetriamine and 100 parts of toluene were charged into the four-necked flask of 1.
"TETRAD-X" (manufactured by Mitsubishi Kosikagaku Co., Ltd., N, N,
204 parts of N',N'-tetraglycidyl-m-xylene diamine] were charged in portions over about 30 minutes. Thereafter, a transparent solution with a nonvolatile content of 76.4% and a viscosity of Z ₅ was obtained in the same manner as in Example 1, except that 118 parts of toluene and 58 parts of n-butanol were added. This is a reaction mixture mainly consisting of a compound represented by the structural formula. Example 4 240 parts of ethylenediamine was used instead of diethylenetriamine, and the amount of toluene was changed.
The non-volatile content was 74.3% and the viscosity R was the same as in Example 3, except that the amount of betoluol and n-butanol added after the reaction was changed to 92 parts and 46 parts, respectively. -S
A transparent solution was obtained, which is a reaction mixture mainly consisting of a compound represented by the following structural formula. 〓〓〓〓〓
Example 5 371 parts of diethylenetriamine and 147 parts of toluene were charged into the four-necked flask of 1.
The temperature was raised to 80°C while stirring, and then 216 parts of "Sumi Epoxy ELM120" (m-aminophenol triglycidyl manufactured by Sumitomo Chemical Co., Ltd.) with an epoxy equivalent of 120 was charged in portions over about 30 minutes. ,
After reacting at 100°C for 4 hours, the temperature was raised to 160°C, toluol and excess diethylenetriamine were removed under reduced pressure, the temperature was lowered to 100°C, and 87 parts of xylene and 87 parts of n-butanol were added. A transparent solution with a non-volatile content of 72.3% and a viscosity of QR was obtained, which was a reaction mixture mainly consisting of a compound represented by the following structural formula. Example 6 Using 216 parts of ethylenediamine instead of diethylenetriamine, and changing the amount of toluene
The non-volatile content was 77.2 parts in the same manner as in Example 5, except that 72 parts of toluene and 36 parts of n-butanol were used as the solvents to be added after the reaction was completed. %in,
A transparent solution having a viscosity of RS was obtained, which was a reaction mixture mainly consisting of a compound represented by the following structure. Using the polyfunctional amine compounds and amine adducts obtained in each of the above Examples and Comparative Examples as a curing agent for an epoxy resin (here, "Epiclon 1050-75X" was used as the main resin),
The physical properties of the clear paint film and the results of the chemical immersion test are summarized in Table 1. The results obtained by the method of the present invention show superior boiling resistance compared to conventional amine adduct hardeners. Water-based, salt water resistant,
It exhibited excellent anticorrosive properties such as alkali resistance and acid resistance.

[Table] 〓〓〓〓〓

[Table] 〓〓〓〓〓

Claims (1)

[Claims] 1 (A) The following formula [] N,N,N',N'-tetraglycidyldiaminodiphenylmethane (a-1) represented by the following formula [] N,N,N',N'-tetraglycidyl-m-xylene diamine (a-2) shown by, or the following formula [] Trigcidyl (a-3) of m-aminophenol, represented by (B) the following general formula [] [However, n in the formula shall be an integer from 1 to 7. 〓〓〓〓〓〓〓〓〓〓〓〓〓〓〓〓〓〓
[However, n in the formula shall be an integer from 1 to 7. ] [However, n in the formula shall be an integer from 1 to 7. 〕 or [However, n in the formula shall be an integer from 1 to 7. ] A method for producing a polyfunctional amine compound based on the compound shown below.