共轭微孔聚合物材料的研究进展

共轭微孔聚合物(CMPs)是一类由共价键结合的3D网络结构化合物,由于其热稳定性好,比表面积高以及结构可控等优点,作为一类具有潜在应用前景的多孔材料日益受到重视。重点介绍了CMPs的性质、制备方法和综合应用,并对CMPs在储氢方面存在的不足和未来的研究方向做出了总结和展望。     

基于二维材料膜构筑纳米流体通道的研究进展

纳米流体学涉及在纳米尺度通道内流体独特的传输行为,近年来引起了研究者们的广泛兴趣。二维（2D）材料的出现以及2D材料膜的快速发展,开创了纳米流体研究的新时代。本文综述了近年来基于二维材料膜构筑纳米流体通道的研究进展,着重介绍了二维材料膜纳米流体通道的构筑方法,包括“自上而下”策略、“自下而上”策略、人工造孔策略制备二维材料多孔膜,以及范德华组装策略、液相组装策略制备二维材料叠层膜;深入讨论了二维材料膜纳米流体通道的调控手段,包括通道尺寸、长度和形状等物理结构的精密控制,通道亲和性、电荷性等化学环境的合理设计;最后总结展望了二维材料膜纳米流体在材料开发、仿生设计、传输机理和器件应用等方面所面临的机遇与挑战。     

非对称性聚合物微孔膜研究进展

综述了近年来在微孔膜的非对称性结构控制方面的研究进展,重点介绍了添加剂种类和摩尔质量、聚合物组成和制膜工艺等对微孔膜非对称结构的影响。     

共轭聚合物膜的渗透汽化性能及应用

论述了大π键共轭聚合物膜的渗透汽化性能和应用，讨论了掺杂和去掺杂态聚苯胺膜、聚(3-甲基噻吩)和聚(N-甲基吡咯)膜对水、甲酸、乙酸、丙酸、甲醇、乙醇、异丙醇的渗透汽化性能以及它们与水的混合液的分离性能。指出掺杂态聚苯胺膜呈亲水性，有利于醇类的渗透；而去掺杂态聚苯胺膜呈疏水性，有利于有机酸类的渗透。聚丙烯酸／聚苯胺及聚酰亚胺预聚体／聚苯胺共混膜对混合液体都具有较好的分离性能，其中的大分子酸会对聚苯胺链节进行掺杂，能有效地克服盐酸小分子掺杂剂易于损失的缺点。共轭聚合物膜可望应用于醇／水混合液、有机酸/水混合液、多组分混合液的分离。     

含噻吩的共轭微孔聚合物的合成与表征

以对溴碘苯为原料,通过Sonogashira偶联反应,Suzuki偶联反应,八羰基二钴催化的三聚反应,FeCl3氧化关环反应,成功合成了一种未见文献报道的含噻吩的六苯基苯共轭微孔聚合物,该共轭微孔聚合物经XRD测试为无序结构,TG研究结果表明热稳定性良好;其最大吸收峰位于380 nm处,发射出黄色荧光,该共轭微孔聚合物较单体波长发生红移,是聚合后链长增加共轭效应增强的结果。     

聚四氟乙烯微孔膜及其过滤材料制备研究

采用三拉伸工艺制备聚四氟乙烯微孔膜,研究不同工艺对e PTFE膜的孔径及结构的影响,并通过对薄膜与不同滤料基材的复合方式研究制备高效除尘滤料。     

TEMPO功能化共轭微孔聚合物作为高效醇催化氧化剂

2,5-二溴对苯二甲酸通过酰化反应得到了2,5-二溴对苯二甲酰氯(Ⅱ)。接着,中间体Ⅱ与4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基(4-NH2-TEMPO)反应获得了侧链嫁接双2,2,6,6-四甲基哌啶氧自由基(TEMPO)的有机单体。然后,该有机单体与四(4-乙炔基苯)甲烷通过Sonogashira偶联反应,合成了高密度TEMPO自由基功能化的CMP-4-(TEMPO)₂共轭微孔聚合物。利用核磁共振谱(NMR)、扫描电子显微镜(SEM)、X射线衍射(XRD)、红外吸收光谱(FTIR)和电子顺磁共振谱(EPR)对所合成单体及CMP-4-(TEMPO)₂进行了表征。结果表明,CMP-4-(TEMPO)₂由微球和中空纳米管组成,具有较高的比表面积(486m²/g),含有微孔、介孔以及大孔复合孔,孔道含有丰富的TEMPO自由基官能团,可将各种芳香醇和杂原子醇高效、高选择性地氧化成相应的醛和酮。     

用于二次电池中电极材料的π共轭导电聚合物

简要地介绍了以导电聚乙炔ＰＡ为主的用于二次电池中电极材料的π共轭导电聚合物的合成方法。     

TEMPO功能化共轭微孔聚合物催化氧化醇性能

将2,2,6,6-四甲基哌啶氧自由基(TEMPO)嫁接到2,5-二溴苯甲酸侧链,并与1,3,5-三乙炔苯(Ⅰ)通过Sonogashira偶联反应,合成出TEMPO自由基功能化共轭微孔聚合物CMP-3-TEMPO。利用SEM、XRD、FTIR和EPR等测试了CMP-3-TEMPO的形貌和结构组成。催化性能测试结果表明:CMP-3-TEMPO在氧气氛围、较温和条件下(80℃,常压),可将各种一级醇、二级醇以及杂原子醇氧化成相应的醛或酮化合物,转化率为70%～100%。CMP-3-TEMPO经过3次循环利用后,催化性能有所降低,可能的原因是反应过程中CMP-3-TEMPO存在局部解体,导致催化活性位点降低。     

三嗪基富氮共轭微孔聚合物的可控合成

本文以N2,N4,N6-三(4-溴苯基)-1,3,5-三嗪-2,4,6-三胺为中心建构模块,通过Buchwald-Hartwig(BH)偶联反应成功制备了三种三嗪基富氮共轭微孔聚合物(TBTT-CMP@1,TBTT-CMP@2,和TBTT-CMP@3),研究表明该类聚合物不仅具有大的比表面积,且骨架具有丰富的π电子。因此,其在吸附、催化等领域有潜在的应用价值。     

Post-synthetic modification of conjugated microporous polymers

Control over the surface functionality and microporosity in conjugated microporous polymers (CMPs) has been achieved by the post-synthetic modification of amines into amides of with different alkyl chains, one of which was chiral. The surface areas, pore volumes, carbon dioxide uptakes and isosteric heat of adsorption for carbon dioxide can be rationally tuned.     

Symmetry-dependent photocatalysis of conjugated microporous polymers based on pyrene for oxygenation of sulfides with O2

To date, conjugated microporous polymers (CMPs) have been developed into multifaceted photocatalysts. Here, two CMPs based on pyrene with the linkages of thiazolo[5,4-d]thiazole (TzTz) are prepared for visible light photocatalysis. The dimension of the molecular building block’s symmetry on the property and activity of CMPs is systematically investigated. Py(4)-TzTz-CMP with a pyrene building block of D_2h symmetry gives rise to better optoelectronic property than Py(2)-TzTz-CMP with a pyrene building block of C₂ symmetry. Therefore, Py(4)-TzTz-CMP photocatalyst is endowed with superior conversions for the green light-promoted oxygenation of sulfides with O₂. Intriguingly, mechanistic explorations disclose that both superoxide and singlet oxygen are responsible for the production of the target sulfoxides. This work gives insight into the rational design of highly active CMP photocatalysts for selective chemical transformations.     

Design,preparation and application of conjugated microporous polymers

Conjugated microporous polymers (CMPs) are of great interest because these types of materials have high specific surface area and pore diameters less than 2 nm. CMPs have found applications in the fields of hydrogen storage, heterogeneous catalysts, gas‐permeable membranes and light‐emitting organics. A large number of recent reports have demonstrated that CMPs can be prepared using several approaches like noble metal‐mediated ethynyl, Sonogashira–Hagihara coupling, Suzuki coupling and Yamamoto coupling reactions. In this review, the synthetic routes, functionalization and potential applications of CMPs are systematically introduced. © 2013 Society of Chemical Industry     

Synthesis and properties of carbazole-based hyperbranched conjugated polymers

Carbazole-based novel hyperbranched conjugated polymers linked with triphenylamine and benzene moieties were synthesized by Sonogashira coupling polycondensation of N-octadecyl- and N-octyl-3,6-diethynylcarbazoles with tris(4-iodophenyl)amine and 1,3,5-tribromobenzene. Solvent-soluble polymers with number-average molecular weights in the range of 3500-21,000 were obtained in 48-66% yields. The UV-vis absorption bands of the polymers were red-shifted compared to that of carbazole, indicating the extension of conjugation length. The polymers emitted blue-green fluorescence with high quantum yields up to 67% in CHCl₃. Poly(1/3) containing triphenylamine units emits visible light and shows unique solvatochromism. The polymers were electrochemically redox-active.     

Synthesis of a soluble conjugated copolymer based on dialkyl-substituted dithienothiophene and its application in photovoltaic cells

A soluble conjugated alternating 3,5-didecanyldithieno[3,2-b:2′,3′-d]thiophene-thiophene copolymer was synthesized by palladium(0)-catalyzed Stille coupling reaction. The thermal, absorption, emission, electrochemical, and photovoltaic properties of the polymer were examined. A weight-average molecular weight around 6.2 × 10⁴ and a polydispersity index of 1.8 was estimated for the polymer using gel permeation chromatography. The polymer exhibits good thermal stability with decomposition temperature of 340 °C and glass-transition temperature of 136 °C. The polymer shows strong absorption peaked at 505 nm in diluted solution and 518 nm in thin film with an optical band gap 2.0 eV. The polymer exhibits intense emission located at 550 nm in solution and 603 nm in film. The HOMO and LUMO energies of the polymer were estimated to be −5.4 and −3.4 eV, respectively, by cyclic voltammetry. Polymer solar cells were fabricated based on the blend of the polymer and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM). The power conversion efficiency of 0.7% was achieved under AM 1.5, 100 mW/cm² using polymer:PCBM (1:4, w/w) as active layer.     

Synthesis and properties of novel fully conjugated polymers containing bithiazole rings

Two novel fully conjugated polymers containing bithiazole rings (PDDBTz and PDABTz) were first synthesized by polycondensation of 2,7-dimethyl-2,4,6-octatriene-1,8-dial with 2,2′-bis(diethylphosphinatyl methyl)-4,4′-bithizole or 2,2′-diamino-4,4′-bithiazole (DABT). The structure of the polymers was determined by IR, ¹H NMR and elemental analysis. PDDBTz is soluble in trifluoroacetic acid and DMSO, whereas PDABTz is soluble in common solvent such as THF, DMSO, DMF. Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions. Their lanthanide metal complexes were prepared. The magnetic behavior of these polymeric complexes was measured as a function of magnetic field strength (0-60 kOe) at 4 K and as a function of temperature (4-300 K) at magnetic field strength of 30 kOe. The results show that they all exhibit features of soft ferromagnet.     

有机单体空间构型对共轭微孔聚合物催化性能的影响

以TEMPO自由基功能化2,5-二溴-N-(2,2,6,6-四甲基哌啶)苯甲酰胺为有机单体,与平面三角构型(D3h对称性)的1,3,5-三乙炔苯和四面体构型(Td对称性)的四(4-乙炔基苯)甲烷分别通过Sonogashira-Hagihara偶联反应获得CMP-3-TEMPO和CMP-4-TEMPO。扫描电子显微镜照片(SEM)显示两种TEMPO功能化CMPs形貌上有显著差异,CMP-3-TEMPO为不规则的棒状和块状微米聚合物,CMP-4-TEMPO为尺寸较均一的微米球聚合物。固态电子顺磁共振谱(EPR)证明了CMP-3-TEMPO和CMP-4-TEMPO均含有TEMPO自由基。两种CMPs催化剂均可将5-羟甲基糠醛(5-HMF)选择性催化氧化成2,5-二甲酰基呋喃(2,5-DFF),但在催化效率和循环利用率方面存在显著差异。有机配体的空间立体构型对CMPs的形貌和催化性能有重要影响,选择具有空间立体构型的有机单体,所合成的CMP-4-TEMPO具有更稳定的结构,催化循环性能更优异。