| 引用本文: | 唐高玉,程建军,余赵燊,许吉,朱能杰,蓝席建.环氧/阻燃席夫碱衍生物改性蒙脱土复合涂层性能[J].中国表面工程,2024,37(6):428~439 |
| TANG Gaoyu,CHENG Jianjun,YU Zhaoshen,XU Ji,ZHU Nengjie,LAN Xijian.Properties of Epoxy / flame Retardant Schiff Base Derivative Modified Montmorillonite Composite Coatings[J].China Surface Engineering,2024,37(6):428~439 |
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| 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 73.13 MPa，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。 |
| 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 |
| DOI：10.11933/j.issn.1007-9289.20240313004 |
| 分类号:TQ630 |
| 基金项目: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） |
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| Properties of Epoxy / flame Retardant Schiff Base Derivative Modified Montmorillonite Composite Coatings |
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TANG Gaoyu1，2，CHENG Jianjun1，YU Zhaoshen1，3，XU Ji1，ZHU Nengjie1，LAN Xijian1
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1.Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences, Ningbo 315201 , China ；2.Nano Science and Technology Institute, University of Science and Technology of China,Suzhou 215000 , China ；3.College of Chemical Engineering, Zhejiang University of Technology, Huzhou 313299 , China
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| Abstract: |
| 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 material. When DMMT is uniformly dispersed in the epoxy system, the coating is microscopically divided into many small intervals, blocking the propagation of cracks, causing the cracks that are about to pass through to deviate from the original growth path. The shifted cracks may expand in multiple directions, resulting in an increase in the cross-sectional roughness, cross-sectional surface area, and toughness of the composite coating. Thermogravimetric analysis showed that the addition of DMMT reduces the decomposition rate of epoxy composite materials, improves the residual carbon rate of epoxy composite materials, and significantly enhances the thermal stability of the epoxy composite materials. When the DMMT content was 2%, the peak heat release, total heat release, and residual carbon rate of the epoxy composite material increased by 6.46%, 14.92% and 114.54%, respectively, compared to those of pure epoxy. In addition, when the DMMT content was 5%, the peak heat release, total heat release, and residual carbon rate of the epoxy composite material increased by 15.12%, 17.58% and 127.63%, respectively, compared to those of pure epoxy. This indicates that with an increase in DMMT content, the flame retardancy and smoke suppression effects of DMMT on the epoxy resin gradually improve, and the effect is more significant when the DMMT content is above 2%. The morphology of the residual carbon after the cone calorimetry test showed that there is very little residual carbon after pure epoxy combustion, and that it has been burned through the insulation pad. In comparison, the residual carbon of the epoxy composite material modified by DMMT was complete and dense, protecting the bottom insulation pad and providing good fire safety. Gas-phase product analysis and post-combustion carbon residue proved that DMMT has a synergistic flame-retardancy effect in the condensed and gaseous phases. This study provides a useful reference for the integrated fire-resistant and toughening coatings of ships. |
| Key words: 9 10-dihydro-9-oxa-10-phosphatephenanthrene-10-oxide (DOPO) Schiff base montmorillonite flame retardancy toughening epoxy resin composite coating |
