新型侧基含磷氮二元醇的合成及其水性聚氨酯的阻燃性能研究
详细信息 查看官网全文
- 英文论文题名：Fire Behavior and Flame-retardant Mechanism of Waterborne Polyurethane Conjugated with a Novel diol chain-extender bearing cyclic phosphoramidate lateral group
- 论文作者：章培昆 ; 范浩军 ; 陈意 ; 颜俊
- 英文论文作者：ZHANG Pei-kun ; FAN Hao-jun ; CHEN Yi ; YAN Jun ; Key Laboratory of Leather Chemistry and Engineering(Sichuan University) ; Ministry of Education ; National Engineering Laboratory for Clean Technology of Leather Manufacture ; Sichuan University
- 年：2016
- 作者机构：制革清洁技术国家工程实验室(四川大学);皮革化学与工程教育部重点实验室(四川大学);
- 论文关键词：水性聚氨酯 ; 阻燃 ; 水解性能 ; 磷氮二元醇 ; 阻燃机理
- 英文论文关键词：waterbome polyurethane ; flame retardancy ; hydrolytic resistance ; phosphoramidate ; mechanism
- 会议召开时间：2016-07-27
- 会议录名称：2016第十一届全国皮革化学品学术交流会暨中国皮革协会技术委员会第21届年会摘要集
- 英文会议录名称：Abstracts of 2016 the 11th National Conference on Leather Chemicals & 21st Annual Convention of China Leather Science and Technology Commission
- 语种：中文
- 分类号：TQ323.8
- 学会代码：ZGHG
- 会议名称：2016第十一届全国皮革化学品学术交流会暨中国皮革协会技术委员会第21届年会
- 会议地点：中国山东济南
- 主办单位：中国皮革协会技术委员会、中国皮革协会皮革化工专业委员会、中国化工学会精细化工专业委员会
- 学会名称：中国化工学会
- 页数：2
- 文件大小：87k
- 原文格式：O
- 会议级别：全国
摘要
合成了一种侧基含磷氮的二元醇(PNMPD),并将其作为扩链剂嵌段到水性聚氨酯结构中,制备出一系列不同PNMPD含量的阻燃水性聚氨酯(PNWPU)。用FT-IR、~1HNMR和~(31)PNMR表征了产物结构;并研究了PNWPU的耐水解性、热稳定性和阻燃性能。结果表明,将环状磷酰胺"悬挂"在PNWPU侧链中可保持聚氨酯优良的耐水解性能。随着PNMPD含量的增加,PNWPU的热稳定性下降,但残碳率由0.71%增至5.44%。当PNMPD引入量为12%时,PNWPU-12的LOI值为27.2%,通过UL-94V-0级测试,且胶膜的热释放速率峰值(PHRR)、总释放热(THR)、烟生成速率峰值(PSPR)和总生烟量(TSR)相比WPU分别下降了44.7%、39.0%、42.9%和36.1%。TG-FTIR、RT-FTIR、SEM和拉曼光谱等研究表明PNMPD能有效催化PNWPU在较低温度下分解,生成石墨化程度和热稳定性高的含磷膨胀型炭层,发挥凝聚相阻燃作用,从而提高PNWPU的阻燃效果。
A diol bearing cyclic phosphoramidate pendant group,namely2-(5,5-dimethyl-2-oxo-2λ~5-l,3,2-dioxaphosphinan-2-ylamino)-2-methyl-propane-1,3-diol(PNMPD) was synthesized and characterized by FTIR and NMR.Subsequently,PNMPD was applied as a flame-retardant chain extender to prepare phosphorus-nitrogen containing waterborne polyurethane(PNWPU),and the influence of PNMPD on the hydrolysis,thermal and flame-retardant properties of PNWPU was investigated.The fabricated PNMPD-based PNWPU maintains the good hydrolysis-resistance property of polyurethane.Thermal stability and flammability analysis demonstrate that though the covalent conjugation of PNMPD induces a slight thermal destabilization effect,it efficiently promotes char formation in PNWPU,as a result,a 27.2%LOIvalue and a UL-94 V-0 rating can be achieved with only 12 wt%PNMPD incorporated.Compared with WPU,the peak heat release rate(PHRR),total heat release(THR),peak smoke production rate(PSPR) and total smoke release(TSR) of PNWPU-12,evaluated with cone calorimetry,are decreased by 44.7%,39.0%,42.9%and 36.1%,respectively.In addition,the flame retarding mechanism of PNWPU was comprehensively investigated by TG-FTIR,RT-FTIR,SEM and Raman spectra,and results elucidate that these notable reductions in fire hazards were probably attributed to the formation of polyphosphoric acid-rich rugged and intumescent char in the condensed phase,which behaves as a "labyrinth effect" to effectively shield the underlying PNWPU matrix against flame.
A diol bearing cyclic phosphoramidate pendant group,namely2-(5,5-dimethyl-2-oxo-2λ~5-l,3,2-dioxaphosphinan-2-ylamino)-2-methyl-propane-1,3-diol(PNMPD) was synthesized and characterized by FTIR and NMR.Subsequently,PNMPD was applied as a flame-retardant chain extender to prepare phosphorus-nitrogen containing waterborne polyurethane(PNWPU),and the influence of PNMPD on the hydrolysis,thermal and flame-retardant properties of PNWPU was investigated.The fabricated PNMPD-based PNWPU maintains the good hydrolysis-resistance property of polyurethane.Thermal stability and flammability analysis demonstrate that though the covalent conjugation of PNMPD induces a slight thermal destabilization effect,it efficiently promotes char formation in PNWPU,as a result,a 27.2%LOIvalue and a UL-94 V-0 rating can be achieved with only 12 wt%PNMPD incorporated.Compared with WPU,the peak heat release rate(PHRR),total heat release(THR),peak smoke production rate(PSPR) and total smoke release(TSR) of PNWPU-12,evaluated with cone calorimetry,are decreased by 44.7%,39.0%,42.9%and 36.1%,respectively.In addition,the flame retarding mechanism of PNWPU was comprehensively investigated by TG-FTIR,RT-FTIR,SEM and Raman spectra,and results elucidate that these notable reductions in fire hazards were probably attributed to the formation of polyphosphoric acid-rich rugged and intumescent char in the condensed phase,which behaves as a "labyrinth effect" to effectively shield the underlying PNWPU matrix against flame.
引文