Aqueous fluorine-containing acrylate modified polyurethane coating, preparation method and application thereof

A polyurethane coating and acrylate technology, applied in the coating and other directions, can solve the problems of no obvious improvement in the hydrophobicity of the film, no obvious improvement in the water resistance of the polyurethane film, and the long fluorocarbon chain is harmful, and achieves improved mechanical properties, Excellent surface properties, good stability

Active Publication Date: 2012-12-12
BOMEX CHEM SHANGHAI
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  • Summary
  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

[0004] (1) Preparation and performance of fluorine-containing polyurethane-acrylate core-shell emulsion, Journal of Functional Polymers, 2010, 23(2): 120-124, reported that water-based PU was capped with hydroxyethyl methacrylate (HEMA) as The macromer is free radically polymerized with methyl methacrylate (MMA) and perfluoroalkylethyl methacrylate in the emulsion to prepare a water-based fluorine-containing polyurethane-acrylate emulsion with a core-shell structure; The effect of the content of fluorine monomer on the properties of latex film was studied. The results showed that with the introduction of fluorine monomer and the increase of the amount, the surface properties and mechanical properties of the material were improved, but the water resistance of the modified polyurethane film was not. Significant improvement;
[0005] (2) Synthesis of waterborne fluorine-containing polyurethane and research on its film properties, Printing and Dyeing Auxiliaries, 2007,24(10):24-27, reported Hydroxyethyl acrylate (HEMA) was used to prepare water-based polyurethane containing carbon-carbon double bonds, and then free-radically copolymerized with octafluoropentyl acrylate (OFBA) to prepare fluorine-containing water-based polyurethane emulsion; the effects of different fluorine contents on water-based polyurethane The impact of water dispersibility, surface free energy and mechanical properties of the film, the reduction of surface energy is relatively high, but the long fluorocarbon chain is more harmful to the environment and human body;
[0006] (3) Synthesis and characterization of anionic fluorinated aqueous polyurethane emulsion, Polyurethane Industry, 2010,25(1):20-23, reported the use of isophorone Anionic fluorinated aqueous polyurethane emulsion (FWPU) was synthesized from diisocyanate (IPDI), polytetrahydrofuran ether (PTMG), perfluoroalcohol (Rf-OH), dimethylolpropionic acid (DMPA), etc., and the Rf- The effects of OH content, DMPA content, R value (NCO to OH molar ratio), etc. on the storage stability of FWPU emulsion and the water resistance of the latex film, the results show that the thermal stability has been improved, and the surface properties of the latex film have been improved, but The hydrophobicity of the membrane was not significantly improved

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] In a 500mL four-neck flask equipped with a stirrer, reflux condenser, thermometer and feeding device, add 9.975g of polyether polyol (NJ-330), 0.9907g of dimethylolpropionic acid (DMPA) and 15g of N-methylpyrrolidone (NMP) solvent, heat the system to 60°C, add 5.55g of isophorone diisocyanate (IPDI), dropwise add 0.075g of catalyst dibutyltin dilaurate (T-12), and stir for 30min Finally, raise the temperature of the system to 70°C (if the viscosity of the system is too high, add a certain amount of acetone), continue the reaction for 3 hours, then lower the temperature to 60°C, add 3.25g of hydroxyethyl methacrylate (HEMA), and react for 4 hours Afterwards, the temperature was lowered to 30°C, 0.9810g of triethylamine was added, reacted for 0.5h, and 58.3248g of deionized water was added dropwise for dispersion. After 0.5h, 4.5g of reactive diluent butyl hexafluoroacrylate ( FA), after 30min, the temperature was raised to 40°C, 0.2g thermal initiator azobisisobutyronitr...

Embodiment 2

[0030] In a 500mL four-neck flask equipped with a stirrer, reflux condenser, thermometer and feeding device, add 12.03g of polyether polyol (NJ-330), 0.8864g of dimethylolpropionic acid (DMPA) and 15g of N-methylpyrrolidone (NMP) solvent, heat the system to 60 ° C, add 5.55 g of isophorone diisocyanate (IPDI), drop 0.05 g of catalyst dibutyltin dilaurate (T-12), After stirring for 30 minutes, raise the temperature of the system to 70°C (if the viscosity of the system is too high, add a certain amount of acetone), continue the reaction for 3 hours, then lower the temperature to 60°C, and add 3.25g of hydroxyethyl methacrylate (HEMA) After 4 hours of reaction, lower the temperature to 30°C, add 0.8776g of triethylamine, react for 0.5h, add 64.2695g of deionized water dropwise for dispersion, and after 0.5h, add 1.125g of reactive diluent six to the prepolymer Fluorobutyl acrylate (FA), after 30 minutes, the temperature was raised to 40 °C, 0.2 g of thermal initiator azobisisobut...

Embodiment 3

[0032]In a 500mL four-neck flask equipped with a stirrer, reflux condenser, thermometer and feeding device, add 12.03g of polyether polyol (NJ-330), 0.8864g of dimethylolpropionic acid (DMPA) and 15g of N-methylpyrrolidone (NMP) solvent, heat the system to 60 ° C, add 5.55 g of isophorone diisocyanate (IPDI), drop 0.05 g of catalyst dibutyltin dilaurate (T-12), After stirring for 30 minutes, raise the temperature of the system to 70°C (if the viscosity of the system is too high, add a certain amount of acetone), continue the reaction for 3 hours, then lower the temperature to 60°C, and add 3.25g of hydroxyethyl methacrylate (HEMA) After 4 hours of reaction, lower the temperature to 30°C, add 0.8776g of triethylamine, react for 0.5h, add 64.2695g of deionized water dropwise for dispersion, and add 2.25g of reactive diluent hexafluoro to the prepolymer after 0.5h Butyl acrylate (FA), after 30min, the temperature was raised to 40°C, 0.2g of thermal initiator azobisisobutyronitril...

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Abstract

The present invention belongs to the field of polymer material synthesis, relates to aqueous polyurethane acrylate emulsion modification, and especially to an aqueous fluorine-containing acrylate modified polyurethane coating, a preparation method and an application thereof. The preparation method comprises: dissolving polyether polyol in an N-methyl pyrrolidone solution of dimethylol propionic acid; adding diisocyanate in a dropwise manner; adopting dibutyltin dilaurate as a catalyst, and adding hydroxyethyl methacrylate to carry out end capping; adding triethylamine to form a salt, then adding deionized water to prepare an aqueous polyurethane acrylate prepolymer emulsion; and finally adding hexafluorobutyl acrylate and azodiisobutyronitrile to prepare the aqueous fluorine-containing acrylate modified polyurethane coating. The synthesized emulsion of the present invention has the following advantages that: dispersion is uniform; stability is good; water resistance and mechanical property of the cured film are substantially improved; elasticity and mechanical property of polyurethane are provided; ultraviolet resistance, nuclear radiation resistance, flexibility, excellent surface properties, water resistance and corrosion resistance of the fluorine-containing material are provided; and the coating can be adopted as coatings for building and furniture.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, and relates to a water-based polyurethane acrylate emulsion modification, in particular to a water-based fluorine-containing acrylate modified polyurethane coating and a preparation method and application thereof. Background technique [0002] Water-based polyurethane (WPU) is a polyurethane (PU) emulsion with water as the dispersion medium. Compared with solvent-based polyurethane (PU), it has the characteristics of environmental protection, energy saving, safety and excellent performance. It is a rapidly developing green environmental protection material and It is used in various industries, because hydrophilic groups such as -COOH and -OH are introduced in the preparation process, making its water resistance much worse than that of solvent-based polyurethane (PU) resin; and it has low film-forming gloss and long film-forming time , poor water resistance, solvent resistance and chemic...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F290/06C09D151/08C08G18/67
Inventor 邱凤仙王莹莹汪青杨冬亚徐吉成
Owner BOMEX CHEM SHANGHAI
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