阅读说明：本技术 水性环氧树脂固化剂及其制备方法 (Water-based epoxy resin curing agent and preparation method thereof ) 是由 沈岳 伍宽平 吕宏飞 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种水性环氧树脂固化剂及其制备方法,该方法包括以下步骤：将间苯二甲胺、乙二胺、1-甲基吡咯烷-3-羧酸、N-甲基吡咯烷酮、苯基缩水甘油醚、三羟甲基丙烷三缩水甘油醚混合均匀,60-80℃反应4h以上,将环氧树脂滴加混合物中,于60-100℃反应5-9h,然后于100℃加入去离子水,即可。1-甲基吡咯烷-3-羧酸引入羧基,使环氧树脂上枝接羧基,提高了本发明对光照的不耐性,延长了本发明的使用寿命。(The invention discloses a waterborne epoxy resin curing agent and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 5-9h, and then adding deionized water at 100 ℃ to obtain the aqueous solution. Carboxyl is introduced into the 1-methylpyrrolidine-3-carboxylic acid, so that the carboxyl is grafted on the epoxy resin, the intolerance to illumination is improved, and the service life of the epoxy resin is prolonged.)

1. The waterborne epoxy resin curing agent is characterized by comprising the following raw materials in parts by weight: 40-60 parts of m-xylylenediamine, 20-30 parts of trimethylolpropane triglycidyl ether, 10-40 parts of phenyl glycidyl ether, 10-20 parts of epoxy resin, 20-30 parts of ethylenediamine, 80-100 parts of deionized water, 10-12 parts of N-methylpyrrolidone and 3-10 parts of 1-methylpyrrolidine-3-carboxylic acid.

2. The waterborne epoxy resin curing agent of claim 1, comprising the following raw materials in parts by weight: 50 parts of m-xylylenediamine, 25 parts of trimethylolpropane triglycidyl ether, 30 parts of phenyl glycidyl ether, 15 parts of epoxy resin, 25 parts of ethylenediamine, 90 parts of deionized water, 11 parts of N-methylpyrrolidone and 7 parts of 1-methylpyrrolidine-3-carboxylic acid.

3. The waterborne epoxy resin curing agent of claim 1, comprising the following raw materials in parts by weight: 40 parts of m-xylylenediamine, 20 parts of trimethylolpropane triglycidyl ether, 10 parts of phenyl glycidyl ether, 10 parts of epoxy resin, 20 parts of ethylenediamine, 80 parts of deionized water, 10 parts of N-methylpyrrolidone and 3 parts of 1-methylpyrrolidine-3-carboxylic acid.

4. The waterborne epoxy resin curing agent of claim 1, comprising the following raw materials in parts by weight: 60 parts of m-xylylenediamine, 30 parts of trimethylolpropane triglycidyl ether, 40 parts of phenyl glycidyl ether, 20 parts of epoxy resin, 30 parts of ethylenediamine, 100 parts of deionized water, 12 parts of N-methylpyrrolidone and 10 parts of 1-methylpyrrolidine-3-carboxylic acid.

5. The waterborne epoxy resin curing agent of claim 1, comprising the following raw materials in parts by weight: 55 parts of m-xylylenediamine, 24 parts of trimethylolpropane triglycidyl ether, 15 parts of phenyl glycidyl ether, 16 parts of epoxy resin, 27 parts of ethylenediamine, 86 parts of deionized water, 10 parts of N-methylpyrrolidone and 4 parts of 1-methylpyrrolidine-3-carboxylic acid.

6. The preparation method of the water-based epoxy resin curing agent according to claim 1, comprising the steps of: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 5-9h, and then adding deionized water at 100 ℃ to obtain the aqueous solution.

Technical Field

The invention belongs to the field of curing agents, and particularly relates to a water-based epoxy resin curing agent and a preparation method thereof.

Background

The epoxy resin curing agent is an additive which reacts with epoxy resin to form a reticular three-dimensional polymer, and the composite material aggregate is enveloped in a reticular body to change linear resin into tough body-type solid.

Chinese patent application No. CN201510254044.1 discloses a high-flexibility epoxy resin curing agent. Firstly, mixing phenol and aliphatic polyamine, firstly, slowly adding formaldehyde aqueous solution or paraformaldehyde at 60-100 ℃ for reaction, dehydrating in the reaction process, dropwise adding acrylonitrile after dehydration, reacting at 60-90 ℃ until the amine value is stable, stopping the reaction, cooling, and discharging to obtain the product. Although the toughness is improved to some extent, the resistance to light is general.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a water-based epoxy resin curing agent and a preparation method thereof, which are resistant to illumination corrosion and long in service life.

In order to solve the technical problems, the invention adopts the following technical scheme: the waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 40-60 parts of m-xylylenediamine, 20-30 parts of trimethylolpropane triglycidyl ether, 10-40 parts of phenyl glycidyl ether, 10-20 parts of epoxy resin, 20-30 parts of ethylenediamine, 80-100 parts of deionized water, 10-12 parts of N-methylpyrrolidone and 3-10 parts of 1-methylpyrrolidine-3-carboxylic acid.

Preferably, the waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 50 parts of m-xylylenediamine, 25 parts of trimethylolpropane triglycidyl ether, 30 parts of phenyl glycidyl ether, 15 parts of epoxy resin, 25 parts of ethylenediamine, 90 parts of deionized water, 11 parts of N-methylpyrrolidone and 7 parts of 1-methylpyrrolidine-3-carboxylic acid.

Preferably, the waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 40 parts of m-xylylenediamine, 20 parts of trimethylolpropane triglycidyl ether, 10 parts of phenyl glycidyl ether, 10 parts of epoxy resin, 20 parts of ethylenediamine, 80 parts of deionized water, 10 parts of N-methylpyrrolidone and 3 parts of 1-methylpyrrolidine-3-carboxylic acid.

Preferably, the waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 60 parts of m-xylylenediamine, 30 parts of trimethylolpropane triglycidyl ether, 40 parts of phenyl glycidyl ether, 20 parts of epoxy resin, 30 parts of ethylenediamine, 100 parts of deionized water, 12 parts of N-methylpyrrolidone and 10 parts of 1-methylpyrrolidine-3-carboxylic acid.

Preferably, the waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 55 parts of m-xylylenediamine, 24 parts of trimethylolpropane triglycidyl ether, 15 parts of phenyl glycidyl ether, 16 parts of epoxy resin, 27 parts of ethylenediamine, 86 parts of deionized water, 10 parts of N-methylpyrrolidone and 4 parts of 1-methylpyrrolidine-3-carboxylic acid.

The preparation method of the water-based epoxy resin curing agent comprises the following steps: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 5-9h, and then adding deionized water at 100 ℃ to obtain the aqueous solution.

The invention has the following beneficial effects: carboxyl is introduced into the 1-methylpyrrolidine-3-carboxylic acid, so that the carboxyl is grafted on the epoxy resin, the intolerance to illumination is improved, and the service life of the epoxy resin is prolonged.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

Example 1

The waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 50 parts of m-xylylenediamine, 25 parts of trimethylolpropane triglycidyl ether, 30 parts of phenyl glycidyl ether, 15 parts of epoxy resin, 25 parts of ethylenediamine, 90 parts of deionized water, 11 parts of N-methylpyrrolidone and 7 parts of 1-methylpyrrolidine-3-carboxylic acid.

The preparation method of the water-based epoxy resin curing agent comprises the following steps: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 7h, and then adding deionized water at 100 ℃ to obtain the epoxy resin modified epoxy resin.

Example 2

The waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 40 parts of m-xylylenediamine, 20 parts of trimethylolpropane triglycidyl ether, 10 parts of phenyl glycidyl ether, 10 parts of epoxy resin, 20 parts of ethylenediamine, 80 parts of deionized water, 10 parts of N-methylpyrrolidone and 3 parts of 1-methylpyrrolidine-3-carboxylic acid.

The preparation method of the water-based epoxy resin curing agent comprises the following steps: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 5h, and then adding deionized water at 100 ℃ to obtain the epoxy resin.

Example 3

The waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 60 parts of m-xylylenediamine, 30 parts of trimethylolpropane triglycidyl ether, 40 parts of phenyl glycidyl ether, 20 parts of epoxy resin, 30 parts of ethylenediamine, 100 parts of deionized water, 12 parts of N-methylpyrrolidone and 10 parts of 1-methylpyrrolidine-3-carboxylic acid.

The preparation method of the water-based epoxy resin curing agent comprises the following steps: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 9h, and then adding deionized water at 100 ℃ to obtain the epoxy resin modified epoxy resin.

Example 4

The waterborne epoxy resin curing agent comprises the following raw materials in parts by weight: 55 parts of m-xylylenediamine, 24 parts of trimethylolpropane triglycidyl ether, 15 parts of phenyl glycidyl ether, 16 parts of epoxy resin, 27 parts of ethylenediamine, 86 parts of deionized water, 10 parts of N-methylpyrrolidone and 4 parts of 1-methylpyrrolidine-3-carboxylic acid.

The preparation method of the water-based epoxy resin curing agent comprises the following steps: uniformly mixing m-xylylenediamine, ethylenediamine, 1-methylpyrrolidine-3-carboxylic acid, N-methylpyrrolidone, phenyl glycidyl ether and trimethylolpropane triglycidyl ether, reacting at 60-80 ℃ for more than 4h, dripping epoxy resin into the mixture, reacting at 60-100 ℃ for 8h, and then adding deionized water at 100 ℃ to obtain the epoxy resin modified epoxy resin.

Comparative example 1

The difference from example 1 is that: 1-methylpyrrolidine-3-carboxylic acid was not added.

And (3) performance testing: the light transmittance of the cured product is reduced to below 70% under the condition of 400 nm.

As can be seen from the table, 1-methylpyrrolidine-3-carboxylic acid can improve uv coloration resistance of the present invention because it introduces carboxyl groups to graft carboxyl groups on the epoxy resin, which improves light intolerance of the present invention and prolongs the service life of the present invention.

The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.