基于铜尾矿/聚磷酸铵的阻燃硬质聚氨酯泡沫复合材料制备及性能  

Preparation and properties of flame-retardant rigid polyurethane foam composite based on copper tailings/ammonium polyphosphate

作　　者：刘秀玉[1] 王国栋 都一达 王学庆[1] 吴胜华 戴康 管梦凡 唐刚[1] LIU Xiuyu;WANG Guodong;DU Yida;WANG Xueqing;WU Shenghua;DAI Kang;GUAN Mengfan;TANG Gang(School of Civil Engineering and Architecture,Anhui University of Technology,Maanshan 243002,China;Department of Scientific Research,Anhui University of Technology Maanshan 243002,China;School of Environmental Science and Engineering,Guangdong University of Technology,Guangzhou 510006,China)

机构地区：[1]安徽工业大学建筑工程学院,马鞍山243002 [2]安徽工业大学科研处,马鞍山243002 [3]广东工业大学环境科学与工程学院,广州510006

出　　处：《中国有色金属学报》2025年第2期654-670,共17页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(22075053);安徽省自然科学基金资助项目(2108085ME178);国家级大学生创新创业训练计划资助项目(202310360048)。

摘　　要：采用铜尾矿(CTS)酸解上清液通过阳离子置换对聚磷酸铵(APP)进行表面改性,制备改性APP(APP-M),并将其与铜尾矿复配加入硬质聚氨酯泡沫(RPUF)中,制备硬质聚氨酯泡沫/铜尾矿/改性聚磷酸铵(RPUF/CTS/APP-M)复合材料,并对其进行了扫描电子显微镜(SEM)、热重-红外联用分析(TG-FTIR)、极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热(CCT)、拉曼(Raman)光谱、导热系数的测试和表征,系统研究复合材料各项物性,并在此基础上,提出RPUF/CTS/APP-M复合材料气相-凝聚相协同阻燃机理。结果表明:RPUF-1的LOI值达到24.3%(体积分数),燃烧时无熔融滴落,UL-94垂直燃烧测试达到V-0等级,RPUF/CTS/APP-M复合材料阻燃性能明显提高。RPUF-5的pHRR和THR较纯样下降幅度最大,分别为234.4 kW/m^(2)、23.3 MJ/m^(2),相对于纯RPUF分别下降22.0%、41.8%,RPUF/CTS/APP-M复合材料火灾安全性能提高。RPUF/CTS/APP-M复合材料在燃烧过程中形成高度石墨化致密炭层,APP-M和CTS通过气相-凝聚相协同阻燃有效提升了RPUF复合材料的阻燃性能。该研究为铜尾矿的高价值利用和阻燃RPUF复合材料的研制提供新的思路。Ammonium polyphohate(APP)was modified by acid hydrolysis supernatant of copper tailings(CTS)through cation substitution,and modified APP(APP-M)was prepared,which was mixed with copper tailings and added to rigid polyurethane foam(RPUF)to fabricate the rigid polyurethane foam/copper tailings/modified ammonium polyphosphate(RPUF/CTS/APP-M)composite.Scanning electron microscopy(SEM),thermogravimetric infrared analysis(TG-FTIR),limiting oxygen index(LOI),vertical combustion(UL-94),cone calorimetry(CCT),Raman spectroscopy,and thermal conductivity of the composite were tested and characterized to systematically study the physical properties of the composite.The vapor-condensed phase synergistic flame retardant mechanism of RPUF/CTS/APP-M composites was proposed.The results show that the LOI value of RPUF-1 reaches 24.3%(volume fraction),there is no melting dripping during combustion,the vertical combustion test of UL-94 reaches V-0 grade,and the flame retardancy of RPUF/CTS/APP-M composite is significantly improved.Compared with pure sample,the pHRR and THR of RPUF-5 decrease the most,which are 234.4 kW/m^(2) and 23.3 MJ/m^(2),respectively.Compared with pure RPUF,the pHRR and THR decrease by 22.0%and 41.8%,respectively,and the fire safety performance of RPUF/CTS/APP-M composite is improved.The highly graphitized dense carbon layer is formed in the combustion process of RPUF/CTS/APP-M composites,and the flame retardant properties of RPUF composites are effectively improved by the synergistic flame retardant of APP-M and CTS through the gascondensed phase.This study provides a new idea for the high value utilization of copper tailings and the development of flame retardant RPUF composites.

关 键 词：铜尾矿 硬质聚氨酯泡沫 聚磷酸铵 阻燃剂 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]