有机硅改性环氧树脂防腐蚀涂层的研究进展  

Advances in Silicone-modified Epoxy-resin Anticorrosive Coatings

作　　者：邓付国 龚兴厚[1,2,3] 罗锋[3] 杨叶华[3] 胡涛[1,2,3] 吴崇刚[1,2,3] 

机构地区：[1]湖北工业大学绿色轻工材料湖北省重点实验室,武汉430068 [2]绿色轻质材料与加工湖北工业大学协同创新中心,武汉430068 [3]湖北工业大学材料与化学工程学院,武汉430068

出　　处：《高分子通报》2017年第4期19-32,共14页Polymer Bulletin

基　　金：湖北省自然科学基金(2014CFA094);人社部留学人员科技活动项目择优资助基金(人社厅函[2013]277号);湖北工业大学博士科研启动基金(BSQD14007)

摘　　要：环氧树脂(EPRs)因其良好的耐蚀性、耐化学品性、黏附性及低固化收缩率而广泛应用于防腐蚀涂层。由有机硅烷或线性聚硅氧烷出发,经前者的水解、缩合及两者与EPR的加成等反应,将疏水性良好的有机硅树脂(SR)凝胶或链段作为(EPR-填料)偶联层、(金属基底)底漆、(分散或互穿聚合物网络)相、或(共聚)组分引入到EPR固化涂层体系中,可以通过疏水阻隔及凝胶相或交联点(链段)缓蚀的机理提高改性EPR涂层的防腐蚀性能;SR的体积分数效应亦改善了涂层的耐老化性与耐热性。在无水催化条件下,经有机硅烷的烷氧基与EPR的羟基之间的醇解(缩合)反应,生成硅烷小分子接枝改性EPR固化涂层;亦能通过体系中未反应的烷氧基的水消化(水解)阻隔改良涂层的防腐蚀性能。当向SR改性EPR涂层中加入陶瓷(纳米氧化物、粘土、碳材料)填料时,适中的含量可能导致独特的树脂-陶瓷两相形态而产生结构性疏水;当引入无机酸盐(铬酸盐、磷酸盐、硅酸盐、稀土铈盐、钼酸盐、高锰酸盐)或有机化合物(8-羟基喹啉、四氯代苯对醌)转化膜或颗粒时,可能在涂层-金属界面处发生转化保护型电化学防护;而当填充低电位活性金属(Mg、Zn)粉末时,则可能在金属基底表面形成阴极保护型电化学防护;同时,所有三种填料的加入均可能进一步增强涂层的缓蚀效应。在调控与优化EPR-SR体系结构与形态的同时,辅以各种改性填料的协同耦合使用,成为实现SR改性EPR涂层防腐蚀性能最佳化的必经途径之一。Owing to their good corrosion performance,chemical resistance and adhesion to metallic substrates,as well as low shrinkage upon cure,epoxy resins （EPRs） have found an extensive application in anticorrosive coatings.Siliconeresin （SR） gels or chain-segments of good hydrophobicity have been introduced to cured EPR coating systems as EPR-filler coupling layers,primers of metallic substrates,dispersed or interpenetrating-polymer-network phases,copolymerizing component,etc.,via hydrolysis and condensation of organosilanes and/or addition-reaction to the EPRs of linear polysiloxanes or the organosilanes,to improve the corrosion performance of the modified EPR coatings through both the hydrophobic barrier and the gel-phase or cross-link （i.e.,cross-linking chain-segment） corrosion-inhibition mechanisms;the SR volume fraction also effects both enhancements of the aging and heat resistance of the coatings.The anticorrosive performance of cured EPR coatings is increased as well upon grafting,prior to cure,of organosilane small-molecules onto the EPR backbones via alcoholysis （i.e.,condensation） reaction under anhydrous catalysis between the alkoxyls of the former and the hydroxyls of the latter,due to the presence of water-digestion barrier during the service time of the coatings through hydrolysis of the unreacted alkoxy groups of the organosilane grafts.For SR-modified EPR coatings,a moderate content of ceramic （nano-oxide,clay,carbon,etc.） fillers added may result in unique resin-ceramic two-phase morphology that produces structural hydrophobicity,inorganic-acid-salt （chromate,phosphate,silicate,rare-earth-cerium-salt,molybdate,permanganate,etc.） or organic-compound （8-hydroxyquinoline,chloranil,etc.） conversion-coatings or-particles incorporated may function at resin coating-metal interfaces as electrochemical convertive protection,and lowerelectrode-potential,active metal （Mg,Zn,etc.） powders loaded may serve at metallic-substrate surfaces as electrochemical cathodic protection;meanwhil

关 键 词：环氧树脂 有机硅 防腐蚀涂层 阻隔 电化学防护 

分 类 号：TG174.46[金属学及工艺—金属表面处理]