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Low-surface-energy high-water-solubility ultraviolet curing water-based resin and preparation method thereof

A technology with high water solubility and low surface energy, which is applied in the direction of antifouling/underwater coatings, coatings, paints containing biocides, etc., can solve the problem of reducing the cured film of epoxy acrylic resin, so as to reduce the friction coefficient and high Water solubility, effect of improving wear resistance

Active Publication Date: 2019-08-02
SHENZHEN POLYTECHNIC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The resin has high water solubility and can be formulated into water-based UV-curable products, avoiding the problems caused by the large use of low-molecular-weight reactive diluents in existing UV-curable products. At the same time, the introduction of amino silicone oil segments can make the cured film It has a hydrophobic surface, and its surface contact angle is above 96°. The introduction of flexible polyurethane segments can reduce the brittleness of the epoxy-acrylic resin cured film, improve the flexibility and wear resistance of the cured film, and improve the resin structure and performance. Find a reasonable balance point between them, so that the comprehensive performance of the resin has more practical value

Method used

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  • Low-surface-energy high-water-solubility ultraviolet curing water-based resin and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] In the first step, add 260g of bisphenol A epoxy (epoxy E51) into a 500mL three-necked flask, heat the oil bath to 110°C, stir, and add acrylic acid (the molar ratio of epoxy group to acrylic acid is 1:1) Add total mass 0.5% catalyst tetrakis (acetylacetonate) zirconium complex and 0.3% p-hydroxyanisole, add dropwise in the epoxy resin, the system acid value is less than 3mgKOH / g after reacting 4h, namely the epoxy acrylate I; In the second step, add 2mol of toluene diisocyanate (TDI) in a three-necked flask, heat to 60°C, dibutyltin dilaurate is added to 1mol of polyethylene glycol (molecular weight 400) by 0.2% of the total mass, drop Add to toluene diisocyanate (TDI) solution, continue to react for 3 hours after dripping, add 0.2% p-hydroxyanisole to 1mol of hydroxyethyl acrylate, add the above reaction system, raise the temperature to 100°C and react for 2.5 hours to obtain There is also polyurethane acrylic acid II with -NCO group at one end; the third step is to a...

Embodiment 2

[0038] In the first step, add 210g novolac epoxy resin to a 500mL three-necked flask, heat the oil bath to 115°C, stir, and add 0.8% of the total mass to the measured acrylic acid (the molar ratio of epoxy group to acrylic acid is 1:1). The catalyst triethanolamine and 0.8% p-hydroxyanisole are added dropwise into the epoxy resin, and the acid value of the system after 3 hours of reaction is less than 3mgKOH / g, that is, epoxy acrylate I; in the second step, add 2mol of isophorone diisocyanate (IPDI), heated to 80 ° C, dibutyltin dilaurate is added to 1mol of polyether diol by 0.6% of the total mass, and isophorone diisocyanate (IPDI) is added dropwise ) solution, continue to react for 2 hours after dripping, add 0.8% p-hydroxyanisole to 1mol of hydroxypropyl methacrylate, add the above reaction system, raise the temperature to 107°C for 3 hours, and obtain -NCO at one end The urethane acrylate II of the group; the third step, add a certain amount of epoxy acrylate I in the thr...

Embodiment 3

[0041] In the first step, add 420g of bisphenol A epoxy (epoxy E44) into a 1000mL three-necked flask, heat the oil bath to 100°C, stir, and add acrylic acid (the molar ratio of epoxy group to acrylic acid is 1:1) Add total mass 0.6% catalyst tetrabutylammonium bromide and 0.3% p-hydroxyanisole, add dropwise in the epoxy resin, after reacting for 3.5h, the acid value of the system is less than 3mgKOH / g, that is, the epoxy acrylate I; In the second step, add 2mol of diphenylmethane diisocyanate (MDI) in a three-necked flask, heat to 70°C, and dibutyltin dilaurate is added to 1mol of polyethylene glycol (molecular weight 600% by 0.4% of the total mass) ), added dropwise in the diphenylmethane diisocyanate (MDI) solution, continued to react for 2h after the drop, added 0.3% p-hydroxyanisole in 1mol of hydroxyethyl methacrylate, added the above reaction system, and heated up to React at 95°C for 2.5h to obtain urethane acrylate II with —NCO group at one end; in the third step, add ...

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Abstract

The invention discloses a low-surface-energy high-water-solubility ultraviolet curing water-based resin and a preparation method thereof. The preparation method comprises the following steps: synthesizing epoxy acrylic resin at first; then reacting dihydric alcohol, diisocyanate and hydroxyl acrylate to prepare polyurethane acrylate with an -NCO functional group at one end, reacting the two resinstogether to prepare polyurethane acrylate modified epoxy acrylate, adding amino silicone oil into the resin, and grafting onto the polyurethane acrylate modified epoxy acrylate through Michael addition reaction; and then reacting diisocyanate with dihydroxy carboxylic acid to form a prepolymer, grafting the prepolymer onto an epoxy acrylate main chain, and adding the grafted resin into a concentrated alkaline solution to prepare the low-surface-energy high-water-solubility ultraviolet curing water-based resin. The cured film of the water-based resin disclosed by the invention has the outstanding advantages of low surface energy, good water solubility and the like while having good hardness, flexibility, cured gel rate and wear resistance.

Description

technical field [0001] The invention relates to the technical field of organic polymers; in particular, it relates to a low-surface-energy, high-water-soluble, ultraviolet-curable water-based resin and a preparation method thereof. Background technique [0002] China is in a period of rapid development of the national economy, and the subsequent pressure on environmental protection has also increased sharply. It has become an inevitable trend to reduce the use of volatile organic solvents in coatings, inks, and adhesives. is one of the best measures to solve this problem. Ultraviolet (UV) curing technology is an environmentally friendly curing technology developed in the 1940s. After being irradiated by ultraviolet light, it undergoes a photochemical reaction, which causes polymerization and crosslinking, making the liquid coating instantly become a solid film. , it has the advantages of fast, no solvent pollution, suitable for assembly line production, etc., and has been d...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G81/00C09D187/00C09D5/16
CPCC08G81/00C09D5/1675C09D187/005
Inventor 刘红波张霞张武英隗晶晶林峰肖望东
Owner SHENZHEN POLYTECHNIC
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