Carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin and cathodic polyurethane electrophoretic paint, and preparation methods thereof

A technology of hydroxyl-terminated polyurethane and carbon nanotubes, which is applied in the direction of electrophoretic coatings, conductive coatings, coatings, etc., can solve the problems of easy aggregation of carbon nanotubes, achieve environmental friendliness, reduce sedimentation, and improve mechanical properties and functionality. Effect

Active Publication Date: 2019-02-26
QINGDAO UNIV OF SCI & TECH
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  • Abstract
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  • Application Information

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Problems solved by technology

[0005] The invention proposes a carbon nanotube-grafted hydroxyl polyurethane electrophoretic resin, cathode polyurethane electrophoretic paint and a preparation method thereof. The obtained polyurethane electrophoretic resin solves the technical problem that carbon nanotubes are easy to agglomerate in a water-based polymer matrix, and improves carbon nanotube electrophoresis. The stability and uniformity of dispersion of nanotubes in water-based resins, thereby improving the mechanical properties and functionality of water-based polyurethane resins

Method used

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  • Carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin and cathodic polyurethane electrophoretic paint, and preparation methods thereof
  • Carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin and cathodic polyurethane electrophoretic paint, and preparation methods thereof
  • Carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin and cathodic polyurethane electrophoretic paint, and preparation methods thereof

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preparation example Construction

[0039] The present invention also provides a method for preparing the carbon nanotube grafted hydroxyl polyurethane electrophoretic resin as described in the above embodiments, comprising the following steps:

[0040] S1: Vacuum-dry hydroxyl carbon nanotubes at 100-120°C, then mix with toluene diisocyanate, ultrasonically react at 60-80°C, and then centrifuge at high speed to obtain oil-soluble isocyanate groups. Activated carbon nanotubes are dissolved in isophorone diisocyanate and mixed uniformly to obtain a mixture of isocyanate-modified carbon nanotubes and isophorone diisocyanate;

[0041]In this step, the hydroxyl carbon nanotubes are dried first, the main purpose is to remove the adsorbed water due to hydrogen bonding. In order to dry fully, the drying time can be 2-3 hours, which can be adjusted according to the actual situation. Then, toluene diisocyanate is used to modify the hydroxyl carbon nanotubes to prepare isocyanate group reaction-modified carbon nanotubes. ...

Embodiment 1

[0055] Take 11.1g of polycarbonate diol and 1.0g of trimethylolpropane, and dehydrate at 90°C for 1h; take 44.7g of a mixture containing 0.3g of isocyanate-modified carbon nanotubes and isophorone diisocyanate and add In the reaction of the previous step, react at 80°C for 2h; then add 13.5g of N-methyldiethanolamine in the presence of solvent 1,4-dioxane, and react at 40°C for 2h; , in the presence of 4-dioxane, add 4.8g epoxy resin and 9.8g neopentyl glycol, chain extension reaction at 80°C for 2h; finally cool down to 30°C, add 6.8g glacial acetic acid, 6g n-butanol and 12g Ethylene glycol butyl ether was neutralized for 1 hour to obtain carbon nanotube grafted hydroxyl polyurethane electrophoresis resin.

[0056] Take 48g of the above-mentioned carbon nanotube grafted hydroxyl polyurethane electrophoresis resin again, add 11.1g cationic water dispersible blocked type isocyanate and 1.4g propylene glycol phenyl ether to it, after emulsifying and shearing in water, form a fi...

Embodiment 2

[0058] Take 13.9g of polycarbonate diol and 1.2g of trimethylolpropane, and carry out dehydration treatment at 90°C for 1h; take 55.9g of a mixture containing 0.75g of isocyanate-modified carbon nanotubes and isophorone diisocyanate and add In the reaction of the previous step, react at 80°C for 2h; then add 16.9g of N-methyldiethanolamine in the presence of solvent 1,4-dioxane, and react at 40°C for 2h; , in the presence of 4-dioxane, add 6.1g epoxy resin and 12.3g neopentyl glycol, chain extension reaction at 80°C for 2h; finally cool down to 30°C, add 8.5g glacial acetic acid, 7.5g n-butanol and 15 g of ethylene glycol butyl ether was neutralized for 1 h to obtain a carbon nanotube grafted hydroxyl polyurethane electrophoresis resin.

[0059] Get 60g of the above-mentioned carbon nanotube grafted hydroxyl polyurethane electrophoretic resin again, add 14.13g cationic water dispersible blocked type isocyanate and 1.8g propylene glycol phenyl ether to it, after emulsifying and...

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Abstract

The invention provides carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin and a cathodic polyurethane electrophoretic paint, and preparation methods thereof, belongs to thetechnical field of grafting modification of carbon nanotubes, and can solve the technical problem that carbon nanotubes are easy to agglomerate in a water-based polymer matrix; the stability and dispersion uniformity of the carbon nanotubes in water-based resin are increased, and thus the mechanical properties and functionality of the water-based polyurethane resin are improved. The carbon nanotube grafted hydroxyl-terminated polyurethane electrophoretic resin is prepared by reaction of oligomer polyols, trimethylolpropane, diisocyanate, hydroxyl carbon nanotubes, epoxy resin, a hydrophilic agent, a chain extender and a neutralizing salting agent in proportion. The cathodic polyurethane electrophoretic paint can be applied to preparation of a polyurethane paint film. The obtained paint film has excellent water resistance, acid resistance, electric conductivity and high hardness. The brightness fullness of the polyurethane electrophoretic paint is greater than 90, the hardness is greater than 5 H, the acid resistance reaches 46 h, the polyurethane electrophoretic paint can resist water for 4608 h or more, and the electric conductivity of the paint film can reach 8.29*10<-3> S / cm.

Description

technical field [0001] The invention belongs to the technical field of carbon nanotube graft modification, and in particular relates to a carbon nanotube graft terminal hydroxyl polyurethane electrophoretic resin, a cathode polyurethane electrophoretic paint and a preparation method thereof. Background technique [0002] With the continuous improvement of the performance index of polyurethane electrophoretic paint in the market, people have successively carried out methods such as polyurethane internal crosslinking, external linking, two-dimensional sheet silicate particle compounding, and epoxy resin grafting to modify the structure of polyurethane resin. However, when polyurethane electrophoretic coatings with conductive functions are required, traditional polyurethane electrophoretic coatings cannot meet the application requirements. [0003] It has been reported that carbon nanotubes are particles with excellent electrical and thermal conductivity, and the preparation of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G83/00C09D187/00C09D5/44C09D5/24
CPCC08G83/001C09D5/24C09D5/4476C09D187/005
Inventor 李再峰李再胜张闯李子健李金
Owner QINGDAO UNIV OF SCI & TECH
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