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Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof

A technology of polyurethane acrylate and water-based resin, applied in the direction of coating, etc., can solve problems such as skin irritation, insufficient hardness and rigidity, and environmental pollution, and achieve reduced toxicity and irritation, good wear resistance and hardness, and excellent comprehensive performance Effect

Inactive Publication Date: 2016-07-13
SHENZHEN POLYTECHNIC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] It is often necessary to add more low-molecular-weight diluents to light-curing coatings, but this can also cause the following problems: some diluents are harmful to the human body, and even harmless diluents form mist droplets during the spraying process that will pollute the environment , to irritate people's skin; when using light-cured coatings on some porous substrates, such as wood, cement, and paper, the diluent is easy to diffuse into the pores and cannot be cured, so that the object to be coated has a long-term odor; the diluent will be strong. Affect the properties of the cured film
[0006] It is easier to introduce hydrophilic groups into urethane acrylates, so water-based urethane acrylate photocurable resins are the most researched, but one problem is that urethane acrylates are mostly flexible chain segments, and the film formed after curing Good wear resistance, but insufficient hardness and rigidity. Generally, the hardness of water-based polyurethane acrylate light-curing resin tested is below B after curing, so it is difficult to use alone. Generally, it needs to be used in combination with other resins.

Method used

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  • Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof
  • Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof
  • Polyurethane acrylate modified ultraviolet light cured water-dilutable resin and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0042] A kind of urethane acrylate modified UV-curable water-based resin, the structure of the urethane acrylate-modified UV-cured water-based resin is as shown in formula (1):

[0043]

[0044] Among them, R1 and R2 are CH 2 CH 3 .

[0045] It is prepared by the following steps:

[0046] Step S1: Synthesis of partial esterification of acrylic acid and epoxy;

[0047] Add 500g of tetrabromobisphenol A epoxy resin into a 1000mL three-necked flask, heat the oil bath to 100°C, and stir; in addition, add the catalyst tetrakis(acetylacetonate)zirconium complex and p-hydroxyanisole to the metered acrylic acid, and add it dropwise In the epoxy resin, wherein, the molar ratio of the epoxy group to the acrylic acid is 2:1, the mass percent of the catalyst tetrakis(acetylacetonate) zirconium complex is 0.7%, and the p-hydroxyanisole The mass percentage accounted for is 0.5%. After reacting for 4 hours, the acid value of the system is less than 3mgKOH / g by alkali titration, that i...

Embodiment 2

[0056] A urethane acrylate modified UV-curable water-based resin, the structure of the urethane acrylate-modified UV-curable water-based resin is as shown in formula (1), wherein R1 and R2 are CH 2 CH 2 CH 3 .

[0057] It is prepared by the following steps:

[0058] Step S1: Add 450g of bisphenol A epoxy (epoxy E44) into a 1000mL three-necked flask, heat the oil bath to 110°C, stir, add the catalyst triphenylphosphine and p-hydroxyanisole to the other metered acrylic acid, add dropwise to the ring In epoxy resin, wherein, the molar ratio of epoxy group and acrylic acid is 2:1, the mass percent that described catalyst triphenylphosphine accounts for is 0.5%, and the mass percent that described p-hydroxyanisole accounts for is 0.3 %, the system acid value is less than 3mgKOH / g after reacting for 3.5h, promptly obtains the epoxy acrylate monoester of formula (2) structure;

[0059] Step S2: Add 2 mol of diphenylmethane diisocyanate (MDI) to a three-necked flask and heat to 70...

Embodiment 3

[0064] A urethane acrylate modified UV-curable water-based resin, the structure of the urethane acrylate-modified UV-curable water-based resin is as shown in formula (1), wherein R1 and R2 are CH 2 CH 2 Oh.

[0065] It is prepared by the following steps:

[0066] Step S1: Add 220g novolac epoxy resin into a 500mL three-necked flask, heat the oil bath to 115°C, and stir; add the catalyst triethanolamine and p-hydroxyanisole to the other metered acrylic acid, and add them dropwise to the epoxy resin, wherein, The molar ratio of epoxy group to acrylic acid is 2:1, the mass percentage of the catalyst triethanolamine is 0.8%, and the mass percentage of p-hydroxyanisole is 0.8%, and after 3 hours of reaction, the alkali Titrate until the acid value of the system is less than 3mgKOH / g, to obtain the epoxy acrylate monoester of formula (2);

[0067] Step S2: Add 2 mol of isophorone diisocyanate (IPDI) to a 1000 mL three-necked flask, and heat to 80° C.; add dibutyltin dilaurate to ...

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Abstract

The invention provides polyurethane acrylate modified ultraviolet light cured water-dilutable resin and a preparation method thereof.The structure of the polyurethane acrylate modified ultraviolet light cured water-dilutable resin is shown in the formula (1), wherein R1 represents CH3 or CH2CH3 or CH2CH2OH or CH2CH2CH3 or CH2CH2CH2CH3, and R2 represents CH3 or CH2CH3 or CH2CH2OH or CH2CH2CH3 or CH2CH2CH2CH3.According to the technical scheme, the resin structure is provided with a polyurethane flexible chain segment and an epoxy rigid chain segment, a cured film has good abrasion resistance and hardness, and the after-curing hardness is H or above; meanwhile, curing can be conducted by means of ultraviolet light, and use is more convenient; water can serve as a diluent, and the toxicity and irritation of a system are reduced.

Description

technical field [0001] The invention belongs to the technical field of organic polymer synthesis, and in particular relates to a polyurethane acrylate-modified ultraviolet-curable water-based resin and a preparation method thereof. Background technique [0002] Ultraviolet (UV) curing technology is a green and environmentally friendly technology that does not use solvents. It has fast curing speed (0.1-10s), less environmental pollution, low energy consumption, automatic production, and is suitable for use on heat-sensitive substrates. Etc. According to its use, there are mainly UV-curable coatings, adhesives, inks, etc. Among them, UV-curable coatings are widely used and produced the most varieties. UV-curable coatings can be divided into UV-curable coatings for wood, UV-curable coatings for plastics, UV-curable coatings for metals, UV-curable coatings for paper, UV-curable coatings for optical fibers, etc. according to their application fields. [0003] Most UV-curable ...

Claims

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Application Information

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IPC IPC(8): C08G81/00C08G59/17C08G18/67C08G18/32C08G18/48C09D187/00
CPCC08G81/00C08G18/3206C08G18/4825C08G18/4833C08G18/672C08G59/1466C09D187/005C08G18/48
Inventor 刘红波张武英林峰
Owner SHENZHEN POLYTECHNIC
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