聚合后修饰法制备含脲基聚乙炔及其阴离子识别性能  

Post-Polymerization Modification Approach for Synthesis of Urea Group-Containing Polyacetylenes with Anion-Sensing Properties

作　　者：王登飞[1] 杨国兴[1] 赵兴龙[1] 张瑞[1] 何书艳[1] 任俊涛 WANG Dengfei;YANG Guoxing;ZHAO Xinglong;ZHANG Rui;HE Shuyan;REN Juntao(Daqing Petrochemical Research Center,Petrochemical Research Institute of PetroChina,Daqing 163714,China;Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116000,China)

机构地区：[1]中国石油天然气股份有限公司大庆化工研究中心,黑龙江大庆163714 [2]中国科学院大连化学物理研究所,辽宁大连116000

出　　处：《化学反应工程与工艺》2023年第6期563-568,共6页Chemical Reaction Engineering and Technology

摘　　要：官能团的引入使聚乙炔衍生物具有多种独特的物理化学性质,在不对称催化、光学材料和化学传感器等方面具有潜在的应用价值。本工作设计并合成含氨基甲酸酯支链的聚乙炔衍生物(P1),将其作为底物进行后续改性。基于氨基甲酸酯可与多种胺分子发生亲核取代反应,选取1-苯乙胺和3,5-双(三氟甲基)苯胺分别对P1进行后修饰,成功得到含脲基的P2和P3两种目标聚合物。由于脲基与阴离子间固有的氢键结合能力和聚乙炔共轭主链的协同作用,P3表现出阴离子传感特性。向P3/四氢呋喃溶液添加阴离子可导致其紫外可见吸收光谱的变化,特别是使用的阴离子为F-,Cl-,Br-和CH_(3)COO-时,新的吸收峰出现在约为450nm和480nm的可见光区域,可应用于比色传感器。Incorporation of functional groups can endow polyacetylene derivatives with unique physical and chemical properties.These polymers had potential applications in asymmetric catalysis,optical materials,and chemosensors.In this study,carbamate pendent group-containing polyacetylene(P1)was designed and synthesized as a substrate for subsequent modification.On the basis of the carbamate moiety could undergo nucleophilic substitution with various amine molecules,modification of P1 with 1-phenylethanamine and 3,5-bis(trifluoromethyl)aniline afforded the two target polymers bearing urea moieties,P2 and P3,respectively.By virtue of the synergistic effects of intrinsic capability of hydrogen bonding between urea and anion and conjugated main-chain of polyacetylene,P3 exhibited intriguing anion-sensing properties.The addition of anions to the P3/THF solution led to different adsorption peak changes in the UV-vis spectra depending on the anion type,and especially for some cases such as F-,Cl-Br-,and CH_(3)COO-,new peaks appeared around 450 nm and 480 nm at the visible area,suggesting that it can be used as a colorimetric sensor.

关 键 词：单取代聚乙炔 聚合后修饰 阴离子识别 

分 类 号：O631.11[理学—高分子化学] O641.3[理学—化学]