含芴功能材料的研究与应用

从芴的结构特点出发,讨论了芴的基本性质,包括化学结构特征、酸性与反应活性、热稳定性、光谱特征;综述了含芴结构的重要有机中间体,如芴酮、芴甲醇的化学特性与应用;综述了含芴结构的高分子材料改性单体,如双酚芴、9,9-双(3-氨基-4-羟苯基)芴等,以及它们在各种材料改性中的应用;介绍了含芴结构化合物在感光与光导材料领域的应用,如9,9-二烷基芴、芴-三苯胺结构化合物、芴-偶氮结构化合物;介绍了含芴结构的电致发光材料,如聚烷基芴、芴-噻吩共聚物、芴-噁二唑共聚物等;还介绍了含芴结构的医药与农药,如苯芴醇和含芴结构的植物生长激素;另外还介绍了用于催化剂领域的含芴功能化合物。     

Synthesis and studies of blue light emitting polymers containing triphenylamine‐substituted fluorene and diphenylanthracene moiety

Photoluminescent (PL) polymers containing triphenylamine‐substituted fluorene and diphenylanthracene (DPA) units were synthesized by aromatic nucleophilic substitution reaction. The light emitting polymers (LEPs) contains hole‐transporting triphenylamine (TPA) groups at the C‐9 position of fluorene and DPA‐emitting segments in the main chain. The obtained polymers were soluble in various organic solvents and thermally stable. The synthesized polymers were successfully characterized by elemental analyses, FTIR and, ¹H NMR spectroscopy. The electrochemical measurements and optical properties of the polymers were also studied. The obtained polymers showed significant blue emission. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚丙烯催化剂内给电子体9,9-双(苯甲酸甲酯基)芴的合成与表征

以自制的9,9-双羟甲基芴(BHMF)和苯甲酰氯为原料,以三乙胺为吸收剂合成了9,9-双(苯甲酸甲酯基)芴,采用了红外光谱和核磁共振氢谱等分析测试手段对产品进行了结构表征并逐一归属。考察了原料配比、反应时间、反应温度及吸收剂用量等因素对9,9-双(苯甲酸甲酯基)芴收率的影响。实验结果表明,最佳工艺条件为:0.1 mol BHMF,n(BHMF)∶n(苯甲酰氯)=1.0∶3.0,三乙胺吸收剂为60 mL,反应温度10℃,反应时间4.0 h,在此条件下9,9-双(苯甲酸甲酯基)芴收率可达85.4%。     

芴环结构对聚碳酸酯热性能的改进

对聚碳酸酯结构与其热性能的关系进行分析介绍,并对采用非双酚A类聚合单体,特别是具有Cardo环结构的双酚类化合物参与进行聚碳酸酯合成的方法及其对聚碳酸酯热性能的改进研究,进行了系统的分析归纳,采用上述单体聚合得到的聚碳酸酯热性能具有明显的提高.     

Facile synthesis of 5,8‐linked quinoline‐based copolymers

Coupling quinoline at its 5,8‐positions provides a facile way to copolymerize quinoline with other conjugated moieties without breaking conjugation. Model compounds containing quinoline units, either at the periphery or in the core, were synthesized and one of them was characterized by X‐ray diffraction. Copolymers of quinoline and 9,9‐dialkylfluorene (R = n‐octyl or 2‐ethylhexyl) were synthesized in good yield by palladium‐catalysed Suzuki cross‐coupling. The copolymers are highly soluble in common organic solvents and gel permeation chromatography measurements against polystyrene standards showed the number‐average molecular weight to be in the range (1.02–2.06) × 10⁴ g mol^?1. Both copolymers emit in the blue region with an emission maximum centred at 435 nm. Copyright © 2012 Society of Chemical Industry     

Experimental Study on the Fluorene Removal From Fluorene-Acenaphthene-Dibenzofuran Mixtures of Wash Oil

The azeotrope mixtures in wash oil usually could not use conventional distillation to separate. The objective of this work is to separate and obtain fluorenone from fluorene-acenaphthene-dibenzofuran mixtures which were extracted from wash oil via chemical transformation and azeotropic distillation. We prepared fluorenone-acenaphthene-dibenzofuran mixtures from fluorene-acenaphthene-dibenzofuran mixtures by liquid-phase catalytic oxidation employing air. The effects of catalyst loading, type, and amount of solvent have been investigated. The result showed that fluorene was transformated into fluorenone while other substances were not oxidized. Then we used azeotropic distillation to isolate fluorenone from fluorenone-acenaphthene-dibenzofuran mixtures. And ethylene glycol was found to be the better entrainer than diethylene glycol. The purity and recovery rate of fluorenone was more than 96% and 95%, respectively.     

苯胺盐酸盐催化合成双胺芴

改进了苯胺盐酸盐催化合成双胺芴的方法,利用甲苯除水促进了反应速度,降低了反应温度,提高了反应产率;并探讨了不同酸苯胺盐的催化效果及催化剂用量、苯胺用量、反应温度、反应时间等因素对双胺芴合成产率的影响.实验结果表明,当n(苯胺)n∶(PhNH2·HCl)n∶(芴酮)=101∶.51∶,温度130℃,反应6 h时,双胺芴的产率达88.2%.并且过量苯胺得到回收,减少了对环境的污染,有利于双胺芴工业化生产.     

芴类衍生物有机电致发光器件中的激基复合物

利用紫外-可见光吸收光谱和荧光发光(PL)光谱,研究了新型芴类小分子材料2,3-bis(9,9-dihexyl-9H-flu-oren-2-yl)-6,7-difluoroquinoxaline(F2Py)的本征光谱特性,并制备了基于F2Py的有机电致发光器件(OLEDs),讨论了器件的电致发光(EL)光谱。结果表明,F2Py在溶液状态下的本征PL峰值位于452 nm,在薄膜状态下的本征PL峰值位于448 nm,而F2Py与NPB的混合物的PL发光峰在544 nm。在器件的EL光谱中,观察到了位于530~550 nm范围的激基复合物发光峰,以及来自F2Py与NPB激子发光的共同作用形成的位于430nm左右的肩峰。当F2Py层厚度为50 nm时,器件的启亮电压为17 V,最高亮度为58 cd/m2;而当F2Py厚度为20 nm并加入了Alq3(10 nm)做电子传输层(ETL)时,器件启亮电压为8 V,最高亮度为5030 cd/m2,EL性能大大提高。     

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.