目的 采用传统方法制备丙烯酸树脂时通常需要使用引发剂引发单体进行聚合反应,偶氮二异丁腈是常用的引发剂之一。然而,偶氮二异丁腈在采用电合成方法制备丙烯酸树脂涂层时能否发挥引发剂的作用仍有待研究。方法 在热场和电场协同作用的条件下,探索了电解液中引发剂（偶氮二异丁腈）与电解质（硝酸铈铵）的含量对电合成制备含铈硅丙烯酸树脂涂层的影响。结果 结果表明,当电解液中偶氮二异丁腈的质量分数从0%提升至1.2%时,所制备涂层的防护效率从86.4%降低至68.4%,涂层的水接触角从98.5°降低至65.0°。当电解液中硝酸铈铵的含量从2 g/L提升至6 g/L时,所制备涂层的防护效率从84.9%提高至96.9%,涂层的水接触角从84.9°提高至109.9°。结论 电解液加入偶氮二异丁腈并没有起到提升涂层疏水性能以及涂层耐蚀性能的作用。如果将电解液中的硝酸铈铵换成硝酸钠等导电盐,则无法成功制备涂层,说明铈盐在电解液中不仅起到导电作用,同时也发挥了引发剂的作用。当电解液中硝酸铈铵的含量为6 g/L时所制备的涂层最为致密均匀,可有效提高涂层的防护性能。
Abstract
When acrylic resin is prepared by traditional methods, initiators are required to initiate monomer polymerization reactions. Azodiisobutyronitrile is one of the commonly used initiators. However, whether azodiisobutyronitrile can play the role of an initiator in the preparation of acrylic resin coating by electrosynthesis remains to be studied. In this study, the effects of the contents of the initiator (azodiisobutyronitrile) and the electrolyte (ammonium ceric nitrate) on the preparation of cerium containing silicone acrylate coatings by electrosynthesis are explored under the synergistic effect of thermal fields and electric fields.
Q235 low-carbon steel is cut into 10 mm × 30 mm × 0.3 mm rectangular blocks to serve as the substrate. The Q235 low-carbon steel substrate is polished step by step with 500, 700, 1 000 and 2 000 mesh metallographic sandpaper, and then polished with a diamond polishing agent with a particle size of 2.5 μm on a metallographic polishing machine. The polished substrate is placed in an acetone solution for ultrasonic cleaning for 15 minutes, followed by rinsing with ethanol and deionized water. It is then blown dry with nitrogen for later use. The electrolytic cell is placed in a heat-collecting constant-temperature heating magnetic stirrer for the experiment. The acrylic resin coating is prepared by galvanostatic method with a current density of -0.4 mA/cm2. The working electrode is Q235 low carbon steel (with a working area of 1.0 cm2). The reference electrode is Ag|Ag+ electrode (0.01M silver nitrate, with CH3CN as the solvent). The counter electrode is a platinum sheet electrode (30 mm× 30 mm× 0.2 mm). An electrochemical workstation (CHI-440E) is used as the power supply for coating preparation. An atomic force microscope (AFM), a scanning electron microscope (SEM), an energy dispersive spectrometer (EDS) and an X-ray photoelectron spectrometer (XPS) are used to analyze the surface morphology and chemical composition of the samples. The hydrophobicity of the coatings is characterized by water contact angle (WCA). The electrodeposition behavior and corrosion resistance of the coating materials are analyzed by electrochemical test. According to the ASTMD3359-09 standard, the adhesion of the coating is graded with a grid knife.
The results show that when the mass fraction of azodiisobutyronitrile in the electrolyte is increased from 0wt.% to 1.2wt.%, the protective efficiency of the coating decreases from 86.4% to 68.4%, and the water contact angle of the coating decreases from 98.5° to 65.0°. When the content of ammonium ceric nitrate in the electrolyte is increased from 2 g/L to 6 g/L, the protective efficiency of the coating increases from 84.9% to 96.9%, and the water contact angle of the coating increases from 84.9° to 109.9°. The addition of azodiisobutyronitrile to the electrolyte did not improve the hydrophobic properties and corrosion resistance of the coating. Furthermore, the coating could not be successfully prepared when ammonium ceric nitrate in the electrolyte is replaced with other conductive salts such as sodium nitrate, indicating that cerium salt not only serves as a conductive agent in the electrolyte but also acts as an initiator. When the content of ammonium ceric nitrate in the electrolyte is 6 g/L, the coating is the densest and most uniform, effectively improving the protective performance of the coating.
关键词
电化学合成 /
丙烯酸树脂 /
偶氮二异丁腈 /
硝酸铈铵 /
防腐性能
Key words
electrosynthesis method /
acrylic resin /
azodiisobutyronitrile /
ammonium ceric nitrate /
anticorrosive performance
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基金
国家自然科学基金（52001300）; 杭州市重点科研计划项目（2023SZD0052）
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