荧光聚合物D-A型聚三苯胺砜/酮的合成及其在TNT检测中的应用  

Synthesis of D-A Type Triphenylamine Sulfone/Ketone Fluorescent Polymers and Their Application in TNT Detection

作　　者：何沛玉 钟迟 郑敏[1] 周明如 徐业伟[1,2,3] HE Peiyu;ZHONG Chi;ZHENG Min;ZHOU Mingru;XU Yewei(School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,Sichuan,China;Engineering Research Center of Biomass Materials,Ministry of Education,Southwest University of Science and Technology,Mianyang 621010,Sichuan,China;Sichuan Guanmusiyang New Material Technology Co.,Ltd.,Mianyang 621010,Sichuan,China)

机构地区：[1]西南科技大学材料与化学学院,四川绵阳621010 [2]西南科技大学生物质材料教育部工程研究中心,四川绵阳621010 [3]四川冠慕思杨新材料科技有限公司,四川绵阳621010

出　　处：《西南科技大学学报》2024年第4期16-23,共8页Journal of Southwest University of Science and Technology

基　　金：四川省科技创业人才项目(2022JDRC0055)。

摘　　要：为了得到一种快速且经济的三苯胺聚合物合成方法,使用廉价的商业化材料N,N’-二苯基对苯二胺和4,4’-二氟二苯砜/4,4’-二氟二苯甲酮,通过简单的C-N偶联反应一步法快速合成出D-A型三苯胺聚合物(PTPAS和PTPAK),它们以砜基/羰基为受体、三苯胺为供体,形成了独特的供-吸电子结构。两种聚合物都具有良好的热稳定性,对其光物理性质的研究发现两者均基于分子内电荷转移效应而具有荧光特性,PTPAS和PTPAK的荧光发射以第一种跃迁方式为主。研究发现两种聚合物对TNT均表现出高灵敏度,其Stern-Volmer常数分别为7.40×10^(4)L/mol和1.66×10^(5) L/mol,检测限低至0.57μmol/L和0.25μmol/L。此外,PTPAS和PTPAK对TNT的响应显示出较强的抗干扰能力,几乎不受环境中金属离子和其他硝基炸药的影响。To obtain a rapid and economical synthesis method for triphenylamine polymers,the inexpensive commercial materials N,N’-diphenyl-p-phenylenediamine and 4,4’-difluorodiphenyl sulfone/4,4’-difluorobenzophenone were employed to swiftly synthesize D-A type triphenylamine polymers(PTPAS and PTPAK)through a simple C-N one-step coupling reaction.These polymers form a unique donor-acceptor electronic structure with sulfone/carbonyl groups as acceptors and triphenylamine as donors.Both polymers exhibit excellent thermal stability,and research on their photophysical properties has found that they both possess fluorescent characteristics based on the intramolecular charge transfer effect.The fluorescence emission of PTPAS and PTPAK is mainly dominated by the first transition mode.Systematic research demonstrates that both polymers exhibit high sensitivity towards TNT,with Stern-Volmer constants of 7.40×10^(4) L/mol and 1.66×10^(5) L/mol,respectively,and detection limits as low as 0.57μmol/L and 0.25μmol/L.Additionally,PTPAS and PTPAK exhibit anti-interference ability in response to TNT,almost unaffected by metal ions and other nitro explosives in the environment.

关 键 词：三苯胺聚合物 荧光特性 TNT检测 

分 类 号：TQ32[化学工程—合成树脂塑料工业]