上海大学学报(自然科学版) ›› 2024, Vol. 30 ›› Issue (3): 373-389.doi: 10.12066/j.issn.1007-2861.2404

• •    下一篇

磷-锡环保复合协效阻燃剂制备及其在PVC 中的应用

陈立全1, 洪建婷1, 宁立新1, 彭雨晴1, 李爱军1, 马殿普2, 王金合3, 刘立起1   

  1. 1. 上海大学 材料科学与工程学院, 上海 200444; 2. 云南锡业集团(控股) 有限责任公司研发中心, 云南 昆明 650200; 3. 上海大学 理学院, 上海 200444
  • 收稿日期:2022-03-29 出版日期:2024-06-30 发布日期:2024-07-03
  • 通讯作者: 刘立起 (1981—), 男, 副教授, 博士, 研究方向为碳纤维复合材料. E-mail:llq@shu.edu.cn
  • 基金资助:
    云南省重大科技专项资助项目 (202002AB080001-2)

Ecofriendly phosphorus-tin composite synergistic flame retardant: preparation and application in polyvinyl chloride

CHEN Liquan1, HONG Jianting1, NING Lixin1, PENG Yuqing1, LI Aijun1, MA Dianpu2, WANG Jinhe3, LIU Liqi1   

  1. 1. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China; 2. R&D Center, Yunnan Tin Industry Group (Holding) Co. Ltd., Kunming 650200, Yunnan, China; 3. College of Sciences, Shanghai University, Shanghai 200444, China
  • Received:2022-03-29 Online:2024-06-30 Published:2024-07-03

摘要: 通过沉淀包覆法制备不同包覆比例的植酸锡包覆羟基锡酸锌 (tin phytate coated zinc hydroxystannate, ZHS@Sn-Phyt) 复合协效阻燃剂, 并应用在软质聚氯乙烯 (polyvinyl chloride, PVC) 中. 采用 X 射线衍射 (X-ray diffraction, XRD)、扫描电子显微镜 (scanning electron microscope, SEM)、傅里叶变换红外光谱(Fourier transform infrared spectroscopy, FTIR)、X 射线光电子能谱 (X-ray photoelectron spectroscopy, XPS) 和热重分析 (thermo-gravimetric analysis, TGA) 对包覆结构进行分析表征, 同时对 PVC 复合材料进行极限氧指数 (limiting oxygen indexand, LOI)、锥形量热 (cone calorimetry, CONE) 和力学性能测试. 结果表明: 在羟基锡酸锌 (zinc hydroxystannate, ZHS) 表面和植酸锡 (tin phytate, Sn-Phyt) 包覆层之间以 Sn—O—P—O—Zn 离子键的形式形成稳定的包覆结构; 当复合阻燃剂中 Sn-Phyt∶ZHS 质量比为 1∶9 时, 对 PVC 的阻燃效果最佳, 表现出较好的协同阻燃作用, LOI 比加入相同份数ZHS 的PVC 样品增加了1.6%, 热释放速率峰值和热释放总量分别降低了18.9% 和31.7%, 残炭率提高了6.1%, 烟释放总量相差不大, 拉伸强度和断裂伸长率分别为26.79 MPa 和 296.5%, 也均优于后者. 因此, 制备了一种高效绿色阻燃剂用以阻燃 PVC, 所制备的磷-锡协效阻燃剂具有绿色环保和工艺简单的优点.

关键词: 植酸锡, 羟基锡酸锌, 聚氯乙烯, 阻燃, 环保

Abstract: This article presents a synthetic method for tin phytate-coated zinc hydrox-ystannate (ZHS@Sn-Phyt) particles with different ratios, which were incorporated into soft polyvinyl chloride (PVC) as a composite synergistic flame retardant. The synthe-sized ZHS@Sn-Phyt particles were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The results revealed that a stable coating structure was formed in the form of Sn—O—P—O—Zn ionic bonds at the interface between the zinc hydroxystannate (ZHS) surface and the tin phytate (Sn-Phyt) coating layer. The PVC composites were evaluated through limiting oxygen index (LOI), cone calorimetry, and mechanical studies. When the mass ratio of ZHS@Sn-Phyt in the flame retardant was 1∶9, the best flame retardant properties of PVC were achieved, indicating that combining phosphorus and tin results in a better synergistic flame retardant effect. The LOI of the PVC/ZHS@Sn-Phyt composite was 1.6% higher than that of the PVC composite with only ZHS (without the Sn-Phyt coating). Moreover, the peak heat release rate and total heat release decreased by 18.9% and 31.7%, respectively. In addition, the carbon residue rate increased by 6.1% and the total smoke release of PVC/ZHS@Sn-Phyt and PVC/ZHS were similar. Both the tensile strength and the elongation at break of PVC/ZHS@Sn-Phyt were also better than those of PVC/ZHS at 26.79 MPa and 296.5%, respectively. Thus, this study provides a method for preparing efficient and green flame retardants for PVC. The phosphorus/tin-based synergistic flame retardant prepared by our method has the advan-tageous characteristics of ecofriendliness and simplicity of the preparation process.

Key words: tin phytate, zinc hydroxystannate, polyvinyl chloride, ?ame retardant, environmentally friendly

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