邻位取代苝酰亚胺衍生物的合成及其电子迁移率

以N,N'-二(3-戊胺)苝酰亚胺为底物,分别经过Ir催化剂直接催化邻位C—H的硼酸酯化和取代反应得到了2,5,8,11位含氯和含溴的苝酰亚胺衍生物Ⅲ和Ⅳ,利用1HNMR、13CNMR和HRMS对产物进行了表征。通过在苝酰亚胺的邻位引入卤原子后,相对于化合物Ⅰ,化合物Ⅲ和Ⅳ吸收光谱和荧光光谱均发生了蓝移;LUMO能级明显降低,分别为-4.18 eV和-4.16 eV。邻位引入卤原子后化合物Ⅲ和Ⅳ仍然具有良好的热稳定性,其失重5%时的温度(T d)均大于370℃。利用空间电荷限制电流(SCLC)法测试了它们的电子迁移率,发现卤原子的引入使分子间排列更加有序,其中化合物Ⅲ的迁移率最高,可以达到3.05×10-4cm2·V-1·s-1。     

两种不对称苝酰亚胺小分子的合成及光伏应用研究

以3,4,9,10-苝四酸二酐为原料,通过在分子两端芳香环（bay位）分别连接2-甲氧基乙氧基和硝基,合成了两个不对称苝酰亚胺小分子N, N’-二(2-乙基己基)-1-(2-甲氧基乙氧基)-7-硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅲ)和N, N’-二(2-乙基己基)-1-(2-甲氧基乙氧基)-6,7-二硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅳ),利用1H NMR, 13C NMR和MS对其结构进行了表征。通过密度泛函理论计算优化了分子空间立体构象、扭曲结构和电子云分布;紫外-可见吸收光谱(UV-Vis)结果表明,与无取代基的苝酰亚胺相比,Ⅲ和Ⅳ的最大吸收峰红移至559 nm和572 nm。半峰宽变宽为104 nm和112 nm;经循环伏安(CV)测试估算分子Ⅲ和Ⅳ的HOMO、LUMO能级分别为−5.85 eV、−3.55 eV和−5.87 eV、−3.62 eV;在相对湿度为50%的在大气环境中,构建了有机太阳能电池器件,Ⅲ和Ⅳ分别与苯并二噻吩联噻吩并噻吩类聚合物（PTB7-Th）共混时器件性能分别提高到短路电流密度JSC= 3.6 mA/cm2,开路电压VOC=0.30V,填充因子FF= 0.40,光电转换效率PCE= 0.42%和JSC= 4.00 mA/cm2,VOC= 0.25 V,FF= 0.41,PCE= 0.40%。     

吸电子基对苝酰亚胺微纳米结构传感性能的影响

在苝四酸酐的苝湾(1,7位或1,6,7,12位)位置引入—Cl或—CN,分别制备了两种苝酰亚胺衍生物N,N-双(七氟丁基)-1,6,7,12-四氯-3,4:9,10-苝二酰亚胺(PTCDI-ClF7)和N,N-双(七氟丁基)-1,7-二氰基-3,4:9,10-苝二酰亚胺(PTCDI-CNF7),探索了其在氯仿/甲醇混合溶液中的超分子自组装并测定其微/纳米结构的气敏传感性能。研究显示,两种化合物在苯肼氛围中的灵敏度变化不同,PTCDI-ClF7气敏传感器电阻下降比PTCDI-CNF7高出近2个数量级,其原因是两者占据的最低未占分子轨道(LUMO)能级值相差较大。结果表明:湾位吸电子取代基的不同对苝酰亚胺衍生物微/纳米结构的气敏传感性能影响显著。     

两种不对称苝酰亚胺小分子的合成及光伏应用

以3,4,9,10-苝四酸二酐为原料,通过在分子两端芳香环(bay位)分别连接2-甲氧基乙氧基和硝基,合成了两个不对称苝酰亚胺小分子N,N'-二(2-乙基己基)-1-(2-甲氧基乙氧基)-7-硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅲ)和N,N'-二(2-乙基己基)-1-(2-甲氧基乙氧基)-6,7-二硝基-3,4,9,10-苝四羧酸二酰亚胺(Ⅳ)。利用1HNMR,13CNMR和MS对其结构进行了表征。通过密度泛函理论计算优化了分子空间立体构象、扭曲结构和电子云分布;紫外-可见吸收光谱结果表明,Ⅲ和Ⅳ的最大吸收峰红移至559和572 nm,半峰宽变宽,为104和112 nm;经循环伏安(CV)测试估算,分子Ⅲ和Ⅳ的HOMO、LUMO能级分别为-5.85、-3.55 e V和-5.87、-3.62 e V;在相对湿度为50%的大气环境中,Ⅲ和Ⅳ分别与窄带隙聚合物(PTB7-Th)共混构建了有机太阳能电池器件,Ⅲ与PTB7-Th共混时对应的短路电流密度Jsc=3.6 m A/cm2,开路电压Voc=0.30 V,填充因子FF=0.40,光电转换效率η=0.42%;Ⅳ与PTB7-Th共混时对应的Jsc=4.00 m A/cm2,Voc=0.25 V,FF=0.41,η=0.40%。     

N-(6-氯-1-氧-3-吡啶甲基)邻苯二甲酰亚胺的合成

以邻苯二甲酰亚胺为起始原料,在常温条件下与氢氧化钾反应合成了邻苯二甲酰亚胺钾,其熔点352.8~353.4℃,收率95%。然后在70℃和微波辐射条件下,以邻苯二甲酰亚胺钾作为亲核试剂,与2-氯-5-氯甲基吡啶反应20 m in,制备了N-(6-氯-3-吡啶甲基)邻苯二甲酰亚胺,熔点140.3~140.5℃,收率98.5%。最后以双氧水为氧化剂,在75℃条件下,N原子氧化,合成了目标产物N-(6-氯-1-氧-3-吡啶甲基)邻苯二甲酰亚胺,熔点138.2~139.4℃,收率92%。利用红外光谱(FTIR)、核磁共振氢谱(1HNMR)、气-质联用仪(GC-MS)解析并确定了中间产物及目标化合物的结构。     

苝酰亚胺-硼氟类荧光材料的合成及性能表征

将2-甲基吡啶连接到苝酰亚胺(Perylene tetracarboxylic diimide,PDI)单元的酰亚胺N的位置,进而与BF3·OEt2反应,合成了含PDI单元和硼氟荧光体单元(Difluoroboradiazaindacene,BODIPY)的新颖荧光染料。其结构经1HNMR、13CNMR、MS、IR和元素分析所证实。该化合物具有优良的性能,最大吸收波长和最大发射波长大大红移,具有较高的荧光量子产率和强的电子接受能力,是潜在的有价值的n型有机半导体材料。     

含邻苯二甲腈基酰亚胺模型化合物的合成和固化

以间苯三酚为原料合成了含羟基芳香二胺(OHDA)和含邻苯二甲腈基团的芳香二胺(CNDA)。2种二胺单体分别与邻苯二甲酸酐反应制得2种酰亚胺模型化合物,即含羟基酰亚胺模型化合物(OHLPI)和含邻苯二甲腈基团的酰亚胺模型化合物(CNLPI)。采用FTIR、1H-NMR、TGA、DSC对2种酰亚胺模型化合物的结构和性能进行表征,并将2种模型化合物按一定物质的量比混合,用原位红外和流变分析研究了酚羟基对氰基聚合反应的催化作用。结果表明,在升温过程中,酚羟基对氰基的聚合反应催化作用显著,反应迅速,但是延长时间,效果不显著。     

苝酰亚胺衍生物的合成及光谱性能研究

以3,4:9,10-苝四酸二酐为原料,合成了两种新型的苝酰亚胺衍生物:N-(1-己基庚基)-N'-苯基-3,4:9,10-苝四酸二酰亚胺和N-(1-己基庚基)-N'-苯基-1,7-二(4-叔丁基苯氧基)-3,4:9,10-苝四酸二酰亚胺,其结构经¹H NMR和MS表征。用紫外可见吸收光谱和荧光光谱研究了它们的光学性质,研究结果表明苝核海湾区供电子基团的引入,使得苝核的最大吸收波长发生了明显的红移,Stokes位移达到了29 nm。     

N~1-(4-氨基丁基)-N~4-(9-蒽甲基)-1,4-丁二胺的合成

以N-叔丁氧羰基-1,4-丁二胺和N-(4-溴丁基)邻苯二甲酰亚胺为原料,经取代及保护两步反应合成N1-(4-邻苯二甲酰亚胺)丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅳ),然后肼解得N1-氨基丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅴ),3步反应总收率38%;Ⅴ与9-蒽甲醛缩合后用NaBH4还原,产物提纯后脱保护得目标产物N1-(4-氨基丁基)-N4-(9-蒽甲基)-1,4-丁二胺盐酸盐(Ⅶ),3步反应总收率约7 5%。化合物Ⅳ~Ⅶ的结构经13CNMR,1HNMR和ESI-MS确证,并对反应条件进行了初步优化。     

四取代全氟辛基金属酞菁的合成

以邻苯二甲酰亚胺为起始原料,在30%的发烟硫酸条件下经碘化得到3-碘邻苯二甲酰亚胺,氨解、脱水得到3-碘邻苯二甲腈,并与全氟辛基碘在铜粉催化作用下,生成3-全氟辛基邻苯二甲腈,选用DBU合成法得到了标题化合物。对3-碘邻苯二甲酰亚胺的合成条件进行考察,得到了最佳反应条件:反应温度为60℃,n(邻苯二甲酰亚胺)∶n(单质碘)=1∶1,反应时间为12 h。目标产物结构经1HNMR和HRMS确认。     

Synthesis of dysprosium/Mn–Cu ferrite binary nanocomposite: Analysis of structural,morphological, dielectric,and optomagnetic properties

Manganese–copper ferrite (MCFO) and dysprosium (Dy)-doped manganese–copper ferrite nanocomposites (Mn_0.5Cu_0.5Dy_xFe_2−xO₄) (x = 0, 0.05, 0.10, and 0.15) were synthesized by sonochemical method. Crystal structure and the structural parameters of the MCFO were analyzed based on the doping concentration of Dy ion. It was observed that the average crystalline size of the synthesized nanocomposite decreases when the concentration of Dy increases. The existing spherical surface morphology of the MCFO and Dy-doped MCFO nanocomposites were obtained through scanning electron microscopy. In the UV spectrum, the pristine MCFO sample showed an absorbance peak at 743 nm whereas the absorbance values of Dy-doped ferrite nanocomposite considerably shifted (blue) toward a lower wavelength (231–222 nm). The dielectric parameters of all ferrite nanocomposites were studied in the frequency range of 100 Hz to 5 MHz. The dielectric spectrum revealed that dielectric constant and loss tangent decreased with increased doping concentration of Dy ion. The saturation magnetization also changed with Dy doping in MCFO. The impact of Dy on manganese–copper ferrite changed the optical, dielectric and magnetic properties of the prepared binary ferrite nanocomposite, which can be used for microwave-absorbing material applications.     

Mechanical Properties of Compression Molded Banana Pseudo-stem Filled Unplasticized Polyvinyl Chloride (UPVC) Composites

Mechanical strengths of a banana pseudo-stem (BPS) fiber and unplasticized polyvinyl chloride (UPVC) composite were evaluated to assess the possibility of using it as a new material in engineering applications. Samples were fabricated by the compression molding process with reference to the effect of filler loading. The samples were submitted to mechanical tests to measure tensile, flexural, and impact properties of the composites. The nature of adhesion between the matrix and the reinforcement and information relating the structure of mechanical properties can be obtained by scanning electron microscopy (SEM) assessment of the composite fracture surface. The mechanical properties show that the composites did not have good adhesion between filler and matrix; on the other hand, the filler insertion improved the flexural modulus and the material rigidity.     

核壳型纳米粒子合成方法及其性能的研究进展

核壳纳米粒子作为复合纳米粒子一个重要的分支,由于其光、磁和催化等方面的优异性能,近年来引起了人们广泛的关注.本文主要介绍了核壳纳米粒子的制备方法及诸多性能,并对核壳纳米粒子的发展进行了展望.     

单向玻璃纤维-铝合金层板的几种力学性能研究

本文用实验方法研究了单向玻璃纤维-铝合金层板的拉伸性能、疲劳性能和冲击性能。利用金属体积分数理论验证了这类层板的拉伸性能。通过对其疲劳性能的实验研究，发现裂纹扩展速率的大小及刚度的下降与加载的最大循环应力密切相关的规律。实验发现该层板具有比铝合金好得多的冲击性能。     

TMPTMA在硅橡胶中的应用研究

研究了助交联剂三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)对硅橡胶硫化性能、力学性能、低温性能和粘接性能的影响。结果表明,加入少量TMPTMA能改善硅橡胶的硫化特性和工艺性,提高硫化胶的硬度,降低硅橡胶的结晶温度,并有效提高硅橡胶与金属的粘接强度;但TMPTMA用量超过一定数值后,由于TMPTMA部分自聚合,在硅橡胶内形成一定的交联网络,造成两相界面粘接力变差,致使硅橡胶的拉伸强度降低。当TMPTMA用量为1份时,硅橡胶具有最佳的综合性能。     

丁腈橡胶的伏安特性与功率特性的研究

本文对乙炔碳黑填充丁腈橡胶（NBR）的伏安特性及其功率特性进行了研究,分析了丁腈橡胶在交、直流电场下的导电机理,并对环境温度变化时的丁腈橡胶的功率及功率与电压的变化规律提出了相应的关系式,同时对导电丁腈橡胶的物理机械性能进行了研究与测定。     

聚丙烯基抗菌塑料的制备与性能研究

利用熔融挤出共混技术制备了聚丙烯(PP)基抗菌塑料。研究了抗菌母料Antim-PP对PP的抗菌性能和力学性能的影响。结果表明,当抗菌母料与PP的质量比为4:100时,抗菌PP塑料对大肠杆菌的抗菌率大于99%,抗菌母料的加入使共混物的冲击性能有明显改善,其他力学性能基本不受影响。     

阻隔性PET/PEN共聚酯的性能研究

对共聚型阻隔聚酯PETNx(x为共聚酯中NDA占羧酸总质量的百分比)的热性能、流变性能和阻隔性能进行了研究。结果表明,PETNx体系属于假塑性流体。PETNx的CO2气体阻隔性优于常规PET;随着PETNx中NDA含量的增加,共聚物的玻璃化温度呈线性增高。     

Effects of support and additive on oxidation state and activity of Pt catalyst in propane combustion

The effects of support and additive on the oxidation state and catalytic activity of Pt catalyst in the low temperature propane combustion were systematically investigated on Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂–Al₂O₃. The catalytic activity varied much with both support materials and additives. The catalyst on the more acidic support showed higher activity, and the catalytic activity on every support materials increased as the electronegativity of additives increased, while some additives decreased the activity. The oxidation state of platinum, estimated by white line intensity of Pt L_III-edge XANES spectrum, also varied with the support and additives, and additives with higher electronegativity greatly prevented the platinum from its oxidation under oxidising atmosphere. Among almost all the catalysts with various supports and various additives, a clear relationship was observed between the oxidation state of platinum and the catalytic activity; the more metallic platinum showed higher activity. Thus, it was concluded that the total electrophilic/electrophobic property derived from those of the support and additive controls the oxidation state of platinum, which intensively affects the catalytic activity; i.e. higher electrophilic property provides less oxidised platinum, resulting in high catalytic activity. The mechanism of this effect was also discussed on the basis of thermochemical data, and it was proposed that the electrophobic materials promote the noble metal oxidation since the noble metal oxo-anion such as PtO^δ− is more stabilised with electrophobic cation.