高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (12): 2615.doi: 10.7503/cjcu20190257

• 高分子化学 • 上一篇    

环三磷腈-DOPO大分子阻燃剂的合成及阻燃环氧树脂性能

江民文1,尹晨辉1,李胜2,李晓丽1,*()   

  1. 1. 东北林业大学化学化工与资源利用学院, 黑龙江省阻燃材料分子设计与制备重点实验室, 哈尔滨 150040
    2. 黑龙江省科学院石油化学研究院, 哈尔滨 150001
  • 收稿日期:2019-05-06 出版日期:2019-12-04 发布日期:2019-12-04
  • 通讯作者: 李晓丽 E-mail:lixiaoli0903@163.com
  • 基金资助:
    中央高校基本科研业务费(2572017CB27);东北林业大学国家级大学生创新训练项目(201710225044)

Synthesis of DOPO-based Cyclotriphosphazene Macromolecule Flame Retardant and Its Performance in Flame-retarded Epoxy Resin

Minwen JIANG1,Chenhui YIN1,Sheng LI2,Xiaoli LI1,*()   

  1. 1. College of Chemistry, Chemical Engineering and Resource Utilization, Heilongjiang Key Laboratory of Molecular Design and Preparation of Flame Retarded Materials, Northeast Forestry University, Harbin 150040, China
    2. Institute of Petrochemistry, Heilongjiang Academy of Sciences, Harbin 150001, China
  • Received:2019-05-06 Online:2019-12-04 Published:2019-12-04
  • Contact: Xiaoli LI E-mail:lixiaoli0903@163.com
  • Supported by:
    ? Supported by the Fundamental Research Funds for the Central Universities, China(2572017CB27);the National Innovation Training Program for College Students of Northeast Foresty University, China(201710225044)

摘要:

通过取代反应、 缩合反应和加成反应等合成了一种无机-有机杂化大分子阻燃剂 六-[4-(N-苯基氨基-DOPO-次甲基)苯氧基]环三磷腈(DOPO-PCP), 并利用傅里叶变换红外光谱、 1H和 31P核磁共振波谱对其进行结构表征. 将DOPO-PCP用于环氧树脂(DGEBA)阻燃, 得到环氧树脂阻燃固化物, 通过极限氧指数(LOI)、 垂直燃烧测试(UL-94)、 热重分析与锥形量热(Cone)测试等对阻燃环氧树脂固化物的热稳定性及燃烧性能进行分析; 利用扫描电子显微镜及Mapping观察并分析了燃烧碳层的形貌与元素分布. 研究结果表明, 产物的结构符合设计的DOPO-PCP分子结构; 当DOPO-PCP在DGEBA中添加量(质量分数)达12.2%时, 磷含量为1.3%, 制得的阻燃环氧树脂固化物垂直燃烧测试通过UL-94 V-0级, LOI值为36.2%; Cone测试结果表明, DOPO-PCP的添加有效降低了DGEBA燃烧时热量与烟气的释放, 且在高温下碳残余量显著增加. 研究表明DOPO-PCP兼具气相和凝固相阻燃机理, 对DGEBA有良好的阻燃性能.

关键词: 环三磷腈-DOPO大分子, 阻燃剂, 环氧树脂

Abstract:

A novel inorganic-organic hybrid macromolecule flame retardant, hexa-[4-(N-phenylamino-DOPO-methenyl)-phenoxyl]-cyclotriphosphazene(DOPO-PCP, DOPO=9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide) was synthesized successfully through three-step reactions including substitution, condensation and addition. The chemical structure of DOPO-PCP was characterized by Fourier transform infrared spectroscopy, 1H and 31P nuclear magnetic resonance spectroscopies. All the results conformed the functional groups of the DOPO-PCP designed. Then the thermal stability of DOPO-PCP, pure epoxy(DGEBA) and their composites was analyzed by thermogravimetric analysis, and the properties of flame-retarded cured epoxy were investigated by limited oxygen index(LOI), UL-94 vertical burning test and Cone calorimeter test. Among all the samples, P-1.3 passed UL-94 V-0 level test and its LOI value reached 36.2%, while the phosphorus content in it was only 1.3%. In cone calorimeter test, the heat release rate(HRR) and the smoke production rate(SPR) of P-1.3 went down obviously, meanwhile, its residual char mass increased significantly, demonstrating that DOPO-PCP was favored to flame-retarded DGEBA. Furthermore, the SEM images showed the excellent compatibility between the additives and DGEBA matrix, which made for the formation of the continuous char layer. The mapping photographs displayed the uniform distribution of phosphorus and nitrogen elements in intumescent char layer. As a result, DOPO-PCP was evaluated as a higher efficiency flame retardant by synergistic flame retardant mechanism in both gas phase and the solidification phase.

Key words: Cyclotriphosphazene-DOPO macromolecule(DOPO=9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide), Flame retardant, Epoxy resin

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