环氧/阻燃席夫碱衍生物改性蒙脱土复合涂层性能  

Properties of Epoxy/flame Retardant Schiff Base Derivative Modified Montmorillonite Composite Coatings

作　　者：唐高玉 程建军 余赵燊 许吉 朱能杰 蓝席建 TANG Gaoyu;CHENG Jianjun;YU Zhaoshen;XU Ji;ZHU Nengjie;LAN Xijian(Key Laboratory of Advanced Marine Materials,Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo 315201,China;Nano Science and Technology Institute,University of Science and Technology of China,Suzhu 215000,China;College of Chemical Engineering,Zhejiang University of Technology,Huzhou 313299,China)

机构地区：[1]中国科学院宁波材料技术与工程研究所海洋关键材料重点试验室,宁波315201 [2]中国科学技术大学纳米科学技术学院,苏州215000 [3]浙江工业大学化学工程学院,湖州313299

出　　处：《中国表面工程》2024年第6期428-439,共12页China Surface Engineering

基　　金：国家重点研发计划重点专项(2022YFC3102503);宁波市科技创新2025重大专项(2020Z192);海洋新材料船舶应用研究(2022Y0011-1)。

摘　　要：环氧树脂(EP)因其良好的综合性能,而被广泛应用于涂料、胶粘剂等领域。然而EP高度易燃,燃烧时产生熔滴,同时伴随大量有毒烟气释放,容易造成严重的人员伤亡和不可估量的经济损失;另外EP质脆的缺点限制了其在舰船领域的应用。因此提升EP的阻燃性能和韧性具有重要意义。通过一锅法以多聚甲醛(POM)、二乙醇胺(DEA)和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料,合成DOPO醇胺席夫碱衍生物(DHDOPO)。再采用离子交换法将DHDOPO插层进蒙脱土(MMT)层间制得阻燃增韧型蒙脱土(DMMT),进一步将DMMT分散到环氧体系制得环氧/阻燃席夫碱衍生物改性蒙脱土(EP/DMMT)复合涂层。通过透射电镜(TEM)、傅立叶变换红外光谱仪(FTIR)和X射线衍射仪(XRD)测试验证DHDOPO成功嵌入MMT片层中,对EP/DMMT的结构和性能进行研究。结果表明:MMT被DHDOPO成功修饰得到DMMT,片层间距由1.49 nm扩大至1.90 nm。当DMMT含量为2%时,环氧复合涂层拉伸强度从49.61 MPa提升至73.13MPa,断裂伸长率从3.06%提升至5.05%,力学性能最佳;随着DMMT含量增加,阻燃效果逐渐提升,其中DMMT加量2%以上时效果更加显著。气相产物分析及燃烧后的炭渣证明DMMT在凝聚相和气相发挥协同阻燃效果,为舰船防火增韧一体化涂料提供有益借鉴。Epoxy resins(EP) are widely used in coatings and adhesives because of their excellent comprehensive performance.However, the flammability and brittleness of EP, limit the applicability in ships. Therefore, improving the flame retardancy and toughness of EP is of great significance. An organic-inorganic hybrid 9,10-dihydro-9-oxa-10-phosphatephenanthrene-10-oxide(DOPO)-based Schiff base derivative flame retardant was prepared by designing a molecular structure to address the high flammability and brittleness of EP, thereby using it for flame retardancy and toughening of EP. The DOPO alcohol amine Schiff base derivative(DHDOPO) was synthesized from polyoxymethylene(POM), diethanolamine(DEA), and DOPO using a simple one-pot method. Subsequently, DHDOPO was intercalated between montmorillonite layers to obtain a flame-retardant and toughened montmorillonite(DMMT) through an ion exchange method. DHDOPO exerts strong flame retardancy, whereas montmorillonite is a two-dimensional layered material that can enhance and toughen the substrate by deflecting cracks. Next, DMMT was dispersed into the epoxy resin through mechanical blending, and then diaminodiphenylmethane was used as a curing agent for the epoxy to obtain epoxy/flame retardant Schiff base derivative-modified montmorillonite(EP/DMMT) composite coatings. DHDOPO was successfully embedded in MMT layers using transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), and X-ray diffraction(XRD).The structure and properties of EP/DMMT were studied. The results showed that MMT was successfully modified by DHDOPO to obtain DMMT, and the interlayer spacing increased from 1.49 nm to 1.90 nm. When the DMMT content is 2%, the tensile strength of the epoxy composite coating increased from 49.61 to 73.13 MPa;the elongation at break increased from 3.06% to 5.05%, resulting in the best mechanical properties. The main reason for the improvement in the mechanical properties of the epoxy composite materials is that DMMT is a two-dimensional layered mater

关 键 词：9 10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO) 席夫碱 蒙脱土 阻燃性 增韧 环氧树脂 复合涂层 

分 类 号：TQ630[化学工程—精细化工]