多功能聚对亚苯基乙烯类光电材料的制备与性能研究

【作者】 杨燕；

【导师】 牛海军；

【作者基本信息】 黑龙江大学 ， 高分子化学与物理， 2021， 硕士

【摘要】 PPV类材料以其高效的发光能力与结构可裁剪性广受科学家的青睐。而氰基改性的PPV（CN-PPV）以其优异的吸电子特性得到了不断的开发与应用。三苯胺作为典型的空穴输送材料,并具有优异的电致变色功能;同时,三芳胺可作为电子给体,应用于荧光检测与忆阻器等材料上。本文首先对PPV材料、三苯胺等功能材料进行了进展评述。其次利用对氟苯腈与苯胺类材料合成了新型的5种二腈基三芳胺,并利用二异丁基氢化铝还原还原腈基,得到了二醛基芳胺。利用两种含烷氧基链的二乙腈苯与合成的二醛基单体反应生成了6种三芳胺键入主链型的CN-PPV。利用核磁与红外对合成的单体和聚合物进行了表征。该种聚合物不仅具有良好的溶解性,还呈现溶致荧光特性。随溶剂极性的增大,聚合物的荧光发射峰会发生红移,紫外吸收峰会发生轻微的蓝移。这些共聚物具有优良的热稳定性,在400℃左右只失重10%,当温度上升至800℃大部分聚合物仍然保持60%以上的残余量。对这些共聚物进行循环伏安测试（CV）,它们表现出可逆氧化还原峰,随着电压的升高,薄膜表现出从浅黄色到浅蓝色、深蓝色的转变。通过CV曲线计算了这些聚合物的最高占据轨道HOMO、最低未占据轨道LUMO能级以及带隙值E_g,与量子化学理论计算值的变化趋势较为符合。对这些固态聚合物进行了电控荧光的测试,这些共聚物随着施加电压的升高其荧光不断下降。这些聚合物可以进行检测2,4,6-三硝基甲苯（TNT）,2,4,6-三硝基苯酚（TNP）,且最低检出限（DL）均在10^-5mol/L（M）以上。这系列的CN-PPVs还可以用于HCl气体检测,响应时间10秒（s）左右,当再接触NH₃气时,荧光可以快速回复。这些聚合物具有电阻记忆效应,开关比在10⁵以上。这一系列的多功能的聚合物材料的成功制备为多功能材料的开发提供了理论基础与物质模型。更多还原

【Abstract】 PPV materials have attracted scientists because of their good stability,efficient luminous ability and designability.PPV modified with cyano group（CN-PPV）has become a research hotspot due to its superior solubility and film-forming properties,and has been continuously developed and applied.As a typical electrochromic material,triphenylamine has an excellent multi-color conversion function.Inserting it into the polymer chain can make the polymer obtain color-changing properties.Triphenylamine can be used as an electron donor for fluorescent detection materials.This article first summarizes the PPV materials,triphenylamine and functional materials.Secondly,five kinds of dinitrile triarylamines were synthesized using p-fluorobenzonitrile and aniline materials,and the nitrile group was reduced by diisobutylaluminum hydride reduction method to obtain dialdehyde arylamine.Six kinds of triarylamines were formed into the main chain CN-PPV by the reaction of two diacetonitrile benzenes containing alkoxy chain and the dialdehyde monomers designed and synthesized.Using NMR and infrared,the synthesized monomers and polymers were characterized to determine their structure.This kind of polymer not only has good solubility,but also shows different fluorescence in different solvents.As the polarity of the solvent increases,the polymer’s fluorescence emission peak will undergo a relatively large red shift,the polymer’s UV absorption peak will undergo a slight blue shift.These copolymers also have excellent thermal stability,at around 400 ^oC 10%weight loss.When the temperature rises to 800 ^oC,most of the polymer still retains more than 60%of the residual amount.These copolymers were subjected to cyclic voltammetry（CV）tests of positive and negative potentials,and these polymers showed relatively symmetric redox peaks at positive and negative potentials,respectively.With the increase upon applied voltage,the polymer film showed a transition from light yellow to light blue to dark blue.The highest occupied orbit HOMO,the lowest unoccupied orbit LUMO and the band gap value Eg of these polymers were calculated by the CV curve,which are in line with the change trend of the calculated value of Gaussian quantum chemistry theory.The fluorescence of these copolymers will continue to decline as the applied voltage increases,but their fluorescence will no longer recover after the reverse voltage is applied.The potential of these polymers as fluorescent detection materials was studied,and it was found that these polymers can be used to detect2,4,6-trinitrotoluene（TNT）and 2,4,6-trinitrophenol（TNP）,and the lowest The detection limit（DL）is above 10^-5mol/L（M）.Not only that,this series of CN-PPVs can also be used for the rapid response of hydrochloric acid（HCl）gas,the response time is only about 10 seconds（s）,the polymer fluorescence after exposure to HCl gas weakens,or even basically quenches,for several minutes It will not recover,and after exposure to ammonia gas（NH3）,the fluorescence can be recovered quickly,and the fluorescence can be used again for the response of HCl gas after recovery.Therefore,these polymers can be used repeatedly for HCl gas detection.These polymers have been tested for resistance memory effect,with a switching ratio of more than 10⁵,showing good characteristics.The successful preparation of this series of multi-functional polymer materials provides some useful theory and material basis for the development of multi-functional material.更多还原