阅读说明：本技术 一种碳纳米管环氧水性涂料及其制备方法 (Carbon nano tube epoxy water-based paint and preparation method thereof ) 是由 王凯 于 2021-02-24 设计创作，主要内容包括：本发明公开了一种碳纳米管环氧水性涂料,它是由下述重量份的原料组成的：碳纳米管改性酯分散液200-240、环氧树脂E41 50-60、二亚乙基三胺3-4、聚甲基丙烯酸甲酯10-14、二甲基硅油2-3,本发明碳纳米管改性酯分散液通过加入松香改性的酯溶液,不仅有效的改善了碳纳米管的表面活性,还提高了成品涂料的粘结强度,本发明的涂料表面强度高,韧性好,附着力强,综合性能优越。(The invention discloses a carbon nano tube epoxy water-based paint which is prepared from the following raw materials in parts by weight: 200-240 parts of carbon nano tube modified ester dispersion liquid, 4150-60 parts of epoxy resin E, 3-4 parts of diethylenetriamine, 10-14 parts of polymethyl methacrylate and 2-3 parts of dimethyl silicone oil.)

1. the carbon nanotube epoxy water-based paint is characterized by being prepared from the following raw materials in parts by weight:

200-240 parts of carbon nano tube modified ester dispersion liquid, 4150-60 parts of epoxy resin E, 3-4 parts of diethylenetriamine, 10-14 parts of polymethyl methacrylate and 2-3 parts of dimethyl silicone oil.

2. The carbon nanotube epoxy water-based paint as claimed in claim 1, wherein the carbon nanotube modified ester dispersion comprises the following raw materials in parts by weight:

6-9 parts of rosin, 20-30 parts of dichloroethane, 30-40 parts of carbamate, 1-2 parts of aluminum trichloride, 4-7 parts of carbon nano tube, 10-20 parts of chloroform, 3-4 parts of acrylic acid, 40-50 parts of methyl methacrylate, 1-2 parts of dicumyl peroxide, 1-2 parts of essential oil and 1-2 parts of dispersing agent.

3. The carbon nanotube epoxy water-based paint as claimed in claim 2, wherein the preparation method of the carbon nanotube modified ester dispersion comprises the following steps:

(1) adding rosin into dichloroethane, and uniformly stirring to obtain a rosin solution;

(2) soaking carbon nanotube in 97-98% nitric acid solution for 10-12 hr, discharging, drying, mixing with acrylic acid, adding into chloroform, maintaining at 40-50 deg.C for 3-5 hr, filtering, and drying to obtain pretreated carbon nanotube;

(3) adding carbamate into the rosin solution, uniformly stirring, adding aluminum trichloride, feeding into a reaction kettle, adjusting the temperature of the reaction kettle to be 120-140 ℃, carrying out heat preservation reaction for 1-2 hours, adding essential oil, reducing the temperature to be 60-65 ℃, carrying out heat preservation reaction for 30-40 minutes, discharging and cooling to obtain a pretreated ester dispersion liquid;

(4) adding dicumyl peroxide into absolute ethyl alcohol with the weight 10-20 times of that of the dicumyl peroxide, and uniformly stirring to obtain an initiator solution;

(5) adding methyl methacrylate into the pretreated ester dispersion liquid, uniformly stirring, feeding into a reaction kettle, adding the pretreated carbon nano tube, introducing nitrogen under the stirring condition, adjusting the temperature of the reaction kettle to be 70-75 ℃, adding an initiator solution, carrying out heat preservation reaction for 4-5 hours, discharging, adding a dispersing agent, uniformly stirring, removing a solvent, adding water until the solid content is 20-25%, and emulsifying to obtain the carbon nano tube modified ester dispersion liquid.

4. The carbon nanotube epoxy water-based paint as claimed in claim 2, wherein the essential oil is one of lavender and thyme essential oil.

5. The carbon nanotube epoxy water-based paint as claimed in claim 2, wherein the dispersant is one of polyethylene glycol 200 or 400.

6. The carbon nanotube epoxy water-based paint as claimed in claim 3, wherein the 2 times of drying in the step (2) are performed, the first drying temperature is 180-200 ℃, and the second drying temperature is 70-90 ℃.

7. The preparation method of the carbon nanotube epoxy water-based paint as claimed in claim 1, which comprises the following steps:

adding diethylenetriamine into the carbon nano tube modified ester dispersion liquid, stirring uniformly, sequentially adding epoxy resin E41 and polymethyl methacrylate, stirring at 1000-.

Technical Field

The invention belongs to the field of coatings, and particularly relates to a carbon nanotube epoxy water-based coating.

Background

At present, the epoxy resin is mainly applied to the coating industry and the electronic industry, covers a plurality of civil and military fields such as automobiles, ships, traffic, electric power, energy, food and the like, and the market demand at home and abroad is continuously expanded, and particularly the epoxy coating has great development potential. However, epoxy resin is difficult to dissolve in water, and the traditional epoxy coating is usually accompanied with the use of organic solvents such as alcohols, ketones or aromatic hydrocarbons, and the emission of volatile organic compounds causes pollution to the environment and also poses a threat to the health of people. In recent years, relevant environmental protection laws and execution standards in China and China are increasingly strict, low-carbon, energy-saving and environment-friendly effects are more and more emphasized, development of environment-friendly water-based epoxy coating becomes a mainstream trend of the epoxy coating industry, and the prospect is very bright;

the solvent type epoxy coating has good physical and chemical properties, excellent bonding strength to the surface of a metal material and excellent anti-corrosion performance. Therefore, the epoxy coating anticorrosive system is the coating system which is recognized to be the best in anticorrosive performance and the widest in application range at present, and has very large demand on epoxy coatings in marine corrosion prevention and industrial corrosion prevention. However, the content of volatile organic compounds in the paint is limited at home and abroad, and the water-based anticorrosive paint is widely concerned and applied.

The contradiction between the storage stability of the aqueous dispersion of the water-based anticorrosive paint and the water resistance and corrosion resistance of a dispersion coating is a bottleneck for restricting the development of the water-based epoxy resin anticorrosive paint. Therefore, research and development of water-based anticorrosive paint which has good storage stability, excellent coating water-bank water resistance and excellent corrosion resistance are urgent, and considerable economic and social benefits are achieved.

Disclosure of Invention

The invention aims to provide.

In order to achieve the purpose, the invention adopts the following technical scheme:

a carbon nano tube epoxy water-based paint is composed of the following raw materials in parts by weight:

200-240 parts of carbon nano tube modified ester dispersion liquid, 4150-60 parts of epoxy resin E, 3-4 parts of diethylenetriamine, 10-14 parts of polymethyl methacrylate and 2-3 parts of dimethyl silicone oil.

The carbon nano tube modified ester dispersion liquid comprises the following raw materials in parts by weight:

6-9 parts of rosin, 20-30 parts of dichloroethane, 30-40 parts of carbamate, 1-2 parts of aluminum trichloride, 4-7 parts of carbon nano tube, 10-20 parts of chloroform, 3-4 parts of acrylic acid, 40-50 parts of methyl methacrylate, 1-2 parts of dicumyl peroxide, 1-2 parts of essential oil and 1-2 parts of dispersing agent.

The preparation method of the carbon nano tube modified ester dispersion liquid comprises the following steps:

(1) adding rosin into dichloroethane, and uniformly stirring to obtain a rosin solution;

(2) soaking carbon nanotube in 97-98% nitric acid solution for 10-12 hr, discharging, drying, mixing with acrylic acid, adding into chloroform, maintaining at 40-50 deg.C for 3-5 hr, filtering, and drying to obtain pretreated carbon nanotube;

(3) adding carbamate into the rosin solution, uniformly stirring, adding aluminum trichloride, feeding into a reaction kettle, adjusting the temperature of the reaction kettle to be 120-140 ℃, carrying out heat preservation reaction for 1-2 hours, adding essential oil, reducing the temperature to be 60-65 ℃, carrying out heat preservation reaction for 30-40 minutes, discharging and cooling to obtain a pretreated ester dispersion liquid;

(4) adding dicumyl peroxide into absolute ethyl alcohol with the weight 10-20 times of that of the dicumyl peroxide, and uniformly stirring to obtain an initiator solution;

(5) adding methyl methacrylate into the pretreated ester dispersion liquid, uniformly stirring, feeding into a reaction kettle, adding the pretreated carbon nano tube, introducing nitrogen under the stirring condition, adjusting the temperature of the reaction kettle to be 70-75 ℃, adding an initiator solution, carrying out heat preservation reaction for 4-5 hours, discharging, adding a dispersing agent, uniformly stirring, removing a solvent, adding water until the solid content is 20-25%, and emulsifying to obtain the carbon nano tube modified ester dispersion liquid.

The essential oil is one of lavender and thyme essential oil.

The dispersant is one of polyethylene glycol 200 or 400.

And (3) drying for 2 times in the step (2), wherein the first drying temperature is 180-200 ℃, and the second drying temperature is 70-90 ℃.

A preparation method of a carbon nanotube epoxy water-based paint comprises the following steps:

adding diethylenetriamine into the carbon nano tube modified ester dispersion liquid, stirring uniformly, sequentially adding epoxy resin E41 and polymethyl methacrylate, stirring at 1000-.

The invention has the advantages that:

the preparation method has the beneficial effects that rosin is used as a tackifier and is dispersed into an inert solvent, then carbamate is used as a raw material, thermal decomposition reaction is carried out in the rosin solution to obtain a modified ester solution, the modified ester solution is then blended with methyl methacrylate monomers, and the carbon nano tube is doped and polymerized under the action of an initiator to obtain a carbon nano tube modified ester dispersion liquid.

Detailed Description

Example 1

A carbon nano tube epoxy water-based paint is composed of the following raw materials in parts by weight:

carbon nanotube modified ester dispersion 200, epoxy resin E4150, diethylenetriamine 3, polymethyl methacrylate 10, and dimethylsilicone oil 2.

The carbon nano tube modified ester dispersion liquid comprises the following raw materials in parts by weight:

rosin 6, dichloroethane 20, carbamate 30, aluminum trichloride 1, carbon nanotube 7, chloroform 10, acrylic acid 3, methyl methacrylate 40, dicumyl peroxide 1, essential oil 1 and dispersing agent 1.

The preparation method of the carbon nano tube modified ester dispersion liquid comprises the following steps:

(1) adding rosin into dichloroethane, and uniformly stirring to obtain a rosin solution;

(2) soaking carbon nanotube in 97% nitric acid solution for 10 hr, discharging, drying, mixing with acrylic acid, adding into chloroform, holding at 40 deg.C for 3 hr, filtering, and drying to obtain pretreated carbon nanotube;

(3) adding carbamate into the rosin solution, stirring uniformly, adding aluminum trichloride, feeding into a reaction kettle, adjusting the temperature of the reaction kettle to 120 ℃, carrying out heat preservation reaction for 1 hour, adding essential oil, reducing the temperature to 65 ℃, carrying out heat preservation reaction for 30 minutes, discharging and cooling to obtain a pretreated ester dispersion liquid;

(4) adding dicumyl peroxide into 10 times of absolute ethyl alcohol by weight, and uniformly stirring to obtain an initiator solution;

(5) adding methyl methacrylate into the pretreated ester dispersion liquid, stirring uniformly, feeding into a reaction kettle, adding the pretreated carbon nano tube, introducing nitrogen under the stirring condition, adjusting the temperature of the reaction kettle to be 70 ℃, adding an initiator solution, carrying out heat preservation reaction for 4 hours, discharging, adding a dispersing agent, stirring uniformly, removing a solvent, adding water until the solid content is 20%, and emulsifying to obtain the carbon nano tube modified ester dispersion liquid.

The essential oil is lavender

The dispersant is polyethylene glycol 200.

And (3) drying for 2 times in the step (2), wherein the first drying temperature is 180 ℃, and the second drying temperature is 70 ℃.

A preparation method of a carbon nanotube epoxy water-based paint comprises the following steps:

and (3) adding diethylenetriamine into the carbon nano tube modified ester dispersion liquid, stirring uniformly, sequentially adding epoxy resin E41 and polymethyl methacrylate, stirring at 1000 rpm for 1 hour, adding dimethyl silicone oil, and stirring uniformly to obtain the epoxy resin modified ester dispersion liquid.

Example 2

A carbon nano tube epoxy water-based paint is composed of the following raw materials in parts by weight:

carbon nanotube-modified ester dispersion 240, epoxy resin E4160, diethylenetriamine 4, polymethyl methacrylate 14, and dimethylsilicone oil 3.

The carbon nano tube modified ester dispersion liquid comprises the following raw materials in parts by weight:

9 parts of rosin, 30 parts of dichloroethane, 40 parts of carbamate, 2 parts of aluminum trichloride, 7 parts of carbon nano tubes, 20 parts of chloroform, 3-4 parts of acrylic acid, 50 parts of methyl methacrylate, 2 parts of dicumyl peroxide, 2 parts of essential oil and 2 parts of dispersing agent.

The preparation method of the carbon nano tube modified ester dispersion liquid comprises the following steps:

(1) adding rosin into dichloroethane, and uniformly stirring to obtain a rosin solution;

(2) soaking carbon nanotube in 97-98% nitric acid solution for 12 hr, discharging, drying, mixing with acrylic acid, adding into chloroform, maintaining at 40-50 deg.C for 5 hr, filtering, and drying to obtain pretreated carbon nanotube;

(3) adding carbamate into the rosin solution, stirring uniformly, adding aluminum trichloride, feeding into a reaction kettle, adjusting the temperature of the reaction kettle to 140 ℃, carrying out heat preservation reaction for 2 hours, adding essential oil, reducing the temperature to 65 ℃, carrying out heat preservation reaction for 40 minutes, discharging and cooling to obtain a pretreated ester dispersion liquid;

(4) adding dicumyl peroxide into absolute ethyl alcohol with the weight 20 times of that of the dicumyl peroxide, and uniformly stirring to obtain an initiator solution;

(5) adding methyl methacrylate into the pretreated ester dispersion liquid, uniformly stirring, feeding into a reaction kettle, adding the pretreated carbon nano tube, introducing nitrogen under the stirring condition, adjusting the temperature of the reaction kettle to be 75 ℃, adding an initiator solution, carrying out heat preservation reaction for 5 hours, discharging, adding a dispersing agent, uniformly stirring, removing a solvent, adding water until the solid content is 25%, and emulsifying to obtain the carbon nano tube modified ester dispersion liquid.

The essential oil is thyme essential oil.

The dispersant is polyethylene glycol 400.

And (3) drying for 2 times in the step (2), wherein the first drying temperature is 200 ℃, and the second drying temperature is 90 ℃.

A preparation method of a carbon nanotube epoxy water-based paint comprises the following steps:

and (3) adding diethylenetriamine into the carbon nano tube modified ester dispersion liquid, stirring uniformly, sequentially adding epoxy resin E41 and polymethyl methacrylate, stirring at 1200 rpm for 2 hours, adding dimethyl silicone oil, and stirring uniformly to obtain the epoxy resin modified ester dispersion liquid.

Comparative example 1

A carbon nano tube epoxy water-based paint is composed of the following raw materials in parts by weight:

carbon nano tube 20, epoxy resin E4160, diethylenetriamine 4, polymethyl methacrylate 14 and dimethyl silicone oil 3.

The preparation method comprises the following steps:

adding carbon nano tubes into deionized water 40-50 times of the weight of the carbon nano tubes, stirring uniformly, adding diethylenetriamine, stirring uniformly, sequentially adding epoxy resin E41 and polymethyl methacrylate, stirring at 1000-1200 rpm for 1-2 hours, adding dimethyl silicone oil, and stirring uniformly to obtain the nano-composite material.

Comparative example 2:

an epoxy waterborne coating is composed of the following raw materials in parts by weight:

epoxy resin E4160, diethylenetriamine 4, polymethyl methacrylate 14, and dimethylsilicone oil 2.

The preparation method comprises the following steps:

adding diethylenetriamine into deionized water with the weight of 100-120 times of that of the diethylenetriamine, stirring uniformly, sequentially adding epoxy resin E41 and polymethyl methacrylate, stirring at 1000 rpm for 1 hour, adding dimethyl silicone oil, and stirring uniformly to obtain the diethylenetriamine.

The coatings of examples 1-2 of the present invention and comparative examples 1-2 were tested for salt spray resistance according to GB/T1771 using a Q-FOG-CCT1100 salt spray test chamber, cathodic disbondment resistance according to GB/T7790 and immersion resistance in tap water according to GBT9286, and the test results were compared as follows: