Synthesis and characterization of soluble poly(ether imide)s containing fluorenyl cardo groups

Two series of poly(ether imide)s (PEIs) containing fluorenyl cardo groups in the main chains were synthesized, which are derived from the polycondensation of 9,9′‐bis(4‐aminophenoxyphenyl)fluorene (BAOFL) or 9,9′‐bis(3‐trifluoromethyl,4‐aminophenoxyphenyl)fluorene (6F‐BAOFL) with four kinds of dianhydrides (3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalicanhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bisphenol‐A dianhydride), respectively. The PEI films and PEI powder were prepared by thermal and chemical imidization, respectively. The PEIs were characterized by FTIR, ¹H‐NMR, differential scanning calorimetry, thermogravimetric analysis, and UV–vis were performed on inherent viscosity, solubility, and tensile tests. The effects of fluorenyl cardo groups and ether linkages on the solubility, tensile properties, thermal stability, and optical properties were investigated in detail. It was found that the PEIs had good solubility in common organic solvents and good optical transparency in visible light region. In addition, the PEI films exhibited excellent tensile and thermal properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

一种绿色高效的溴代硝基芴酮的制备方法

以芴为原料,通过氧化、溴代、硝化反应,制得2-溴-7-硝基芴酮及2,7-二溴-4-硝基芴酮,对硝化反应条件进行了优化。2-溴-7-硝基芴酮最佳合成条件为:水作溶剂,质量分数65%的硝酸和质量分数96%的硫酸混合酸为硝化试剂,回流反应3h,其中n(HNO3)∶n(H2SO4)∶n(2-溴芴酮)=29∶36∶1,m(2-溴芴酮)∶m(H2O)=1∶7.7,所得2-溴-7-硝基芴酮的产率为92.8%,质量分数高于98.0%;2,7-二溴-4-硝基芴酮最佳合成条件为:水作溶剂,质量分数85%的硝酸和质量分数95%的硫酸混合酸为硝化试剂,回流反应4h,其中n(HNO3)∶n(H2SO4)∶n(2,7-二溴芴酮)=40∶36∶1,m(2,7-二溴芴酮)∶m(H2O)=1∶5.9,所得2,7-二溴-4-硝基芴酮的产率为90.9%,质量分数高于98.0%。产品结构经红外、核磁共振波谱确证。     

2,7-二溴-9-二烷硫基亚叉芴的合成及表征

以芴为起始原料,合成了2,7-二溴-9-二甲硫基亚叉芴、2,7-二溴-9-二十二烷硫基亚叉芴、2,7-二溴-9-二苄硫基亚叉芴和2,7-二溴-9-二硫代乙烯撑亚叉芴4种新的芴衍生物.所得产物的结构经IR,NMR表征.     

空间结构聚芴的设计及光电性能

用一种简单的缩合方法合成了具有新颖空间结构的聚芴材料,并用DSC、TGA、循环伏安法、荧光测试等技术对聚芴材料进行了表征。结果表明:该聚芴材料具有很高的Tg(164℃或234℃)和热分解温度、稳定的电化学性能和较高的荧光性能。该材料在真空100℃热处理24 h后,保持了稳定的荧光性能。     

含芴共聚聚酰亚胺胶黏剂的合成与性能研究

以3,3’,4,4’-二苯甲醚四甲酸酐(ODPA)为二酐单体,采用等摩尔分数的9,9’-二(4-氨基苯基)芴(BAFL)和3,4’-二氨基二苯醚(3,4’-ODA)、4,4’-二氨基二苯醚(4,4-’ODA)、1,3-双(4-氨基苯氧基)苯(1,3,4-APB)或1,4-二(4’-氨基苯氧基)苯(1,4,4-’APB)分别共聚制备含芴共聚聚酰亚胺(CPI)薄膜。对CPI薄膜进行FT-IR,DMTA,TGA和拉伸性能的测试。采用部分酰亚胺化的CPI薄膜与不锈钢黏结,制备单搭接黏结件,测试其室温及高温拉伸剪切强度,进而比较其黏结性能。结果表明,含芴CPI薄膜具有较好的力学性能和热性能。BAFL,3,4’-ODA与ODPA共聚所得CPI薄膜的黏结性能最好,室温拉伸剪切强度达到19.2MPa,250℃仍然可达13.4MPa。     

9,9′-联芴烯衍生物在有机光伏电池中的应用

由于具有独特的14π电子芳香结构和扭曲的非平面构型,9,9′-联芴烯衍生物成为近年来被广泛研究的一类新型有机光伏材料。9,9′-联芴烯衍生物含有两个刚性平面内的联苯单元,因此具有良好的热稳定性和化学稳定性;且其具有优良的光电特性,很容易接受电子,从而提升自身的最低未占分子轨道(LUMO)能级,使得其有机光伏器件的开路电压增大。此外,9,9′-联芴烯有12个不同的取代位,与富勒烯衍生物相比,其结构更具灵活性。但是,该类化合物的电子迁移率较低,使得其光伏电池的光电转化效率过低。如何通过提高该类材料的电子迁移率、拓展其光谱吸收范围和吸收强度来提高光伏器件的光电转换效率,受到越来越多的关注和研究。阐述了近年来联芴烯衍生物在有机光伏电池中的研究进展,并对其结构、性能进行了简要的分析。最后,对联芴烯类材料的发展前景进行了展望。     

芴衍生物的合成及研究进展

讨论了芴的衍生物在精细化学、高分子合成及生物化工等领域的应用及其现有的合成方法 ,简要介绍了芴酮、碱金属芴的衍生物、芴甲醇、9,9-双 (甲氧基甲基 )芴等芴的衍生物的应用的进展情况。     

新型芴-咔唑共聚物电致发光性质的研究

研究了一种新型的芴与咔唑交替共聚合物材料的电致发光(EL)特性,制备了2种不同结构的器件,分别为indium-tin-oxide(ITO)/polymer/tris-(8-hydroxyquinoline)-alumium(Alq3)/Mg:Ag和ITO/polymer/bathocuproine(BCP)/Alq3/Mg:Ag.实验结果表明;前者发射绿色光,为Alq3的本征发光,聚合物起空穴传输层(HTL)的作用;后者发射蓝色光,EL谱与聚合物材料的光致发光(PL)谱一致,说明这种共聚物除了可用做空穴传输材料外,本身亦可做为优良的OLED蓝色发光材料.     

新型电致发光聚合物的合成

根据电致发光原理,经过精妙的分子结构设计,我们合成了一种新型芴类电致发光聚合物,该聚合物既包含空穴传输性能优良三苯胺单元,又含有电子亲和性很强的氰基官能团.所以该聚合物具有较为平衡的载流子迁移率,有望成为高性能的电致发光材料用作聚合物电致发光器件的发光层.     

Synthesis and Processing of Monodisperse Oligo(fluorene‐co‐bithiophene)s into Oriented Films by Thermal and Solvent Annealing

A series of oligo(fluorene‐co‐bithiophene)s, OF2Ts , have been synthesized and characterized to investigate the effects of oligomer length and pendant aliphatic structure on glassy‐nematic mesomorphism. The OF2Ts comprising more than one repeat unit and their polymer analogue, PF2T , carrying 52 number‐average repeat units, possess the highest occupied molecular orbital energy level at ?5.3 ± 0.2 eV, but the anisotropic field‐effect mobilities increase with the oligomer length. Spin coating from high‐boiling chlorobenzene with and without subsequent exposure to saturated chlorobenzene vapor constitute solvent‐vapor annealing and quasi‐solvent annealing, respectively. Solvent‐vapor annealing yields monodomain glassy‐nematic films in which OF2Ts are aligned as well as with thermal annealing across a 2 cm diameter. Quasi‐solvent annealing, however, amounts to kinetically trapping a lower orientational order than solvent‐vapor or thermal annealing. While amenable to thermal annealing at elevated temperatures, PF2T shows no alignment at all following either strategy of solvent annealing.