高分子LB膜

概述了高分子Langmuir-Blogett膜,并依其成膜方式分别介绍了可聚合LB膜、聚合物的LB膜及其它几种LB膜。     

聚合物的LB膜

简要介绍了聚合物LB(Langmuir -Blodgett)膜的制备装置和制备过程。同时对聚合物LB膜这一门学科最新的进展和应用前景做了较为详尽的介绍和论述。目前 ,随着对LB膜的研究深入 ,在对小分子LB膜、可聚合LB膜、聚合物LB膜的成膜研究中引入了将几种方法优点综合起来的新的成膜方法 ,并已成为研究热点     

有机金属聚合物/多酸纳米杂化LB膜的制备与光电性质研究

以含有共轭大π键的有机金属聚合物(OMP)作有机组分, 以Keggin结构和Dawson结构钨(钼)磷杂多酸作无机组分, 以十八胺为辅助成膜剂, 用LB技术制备了3种新型有机金属聚合物/十八铵/杂多阴离子OMP/ODA/HPA (HPA＝PMo₁₂, PW₁₂, P₂Mo₁₈)杂化LB膜. 用π-A曲线﹑UV-vis吸收光谱﹑荧光光谱﹑原子力显微镜(AFM)﹑扫描隧道显微镜(STM)和表面光电压谱(SPS)对标题LB膜的成膜性能及光电性质进行了研究, 结果表明标题杂化LB膜的崩溃压为26.8 mN/m, 在可见光区有较强的光电压响应, 并有好的发光性质. 当电压为±8.0 V时, 隧道电流是－0.1～－2.3 nA.     

电化学方法对两性接枝星形聚合物LB膜屏蔽效应的研究

本文将自制Y式玻碳电极拉上两性接枝星形聚合物(GPSMA)的LB膜,用循环伏安法研究谈膜的屏蔽效应,讨论了接枝量、成膜条件等对膜缺陷的影响,并提出了减少缺陷的办法。     

扩散致相转化法制备结晶性聚合物多孔膜

介绍了扩散致相转化法制备结晶性聚合物多孔膜的研究现状。其三元等温成膜体系的相图包含液-液分相和固-液分相两种相分离方式,是理解成膜过程的重要工具,总结了成膜机理和膜的结构形貌：单纯S-L相分离生成粒子状对称膜结构;单纯L-L相分离生成蜂窝状非对称膜结构;两种相分离方式竞争发生将生成多样的混合膜结构。铸膜液浓度、非溶剂种类、铸膜溶剂组成、凝胶浴组成、制膜温度是影响膜结构形貌的主要因素。     

新型LB成膜材料—两亲性侧链取代酞菁锌的合成

本文合成了一种新型的两亲性硬脂酸侧链取代的酞菁化合物。利用LB膜技术制备了致菁化合物与正十六烷混合的单层和多层LB膜,LB膜内酞菁分子大环与基片大体平行,表明该分子具有良好的成膜性能。     

导电聚合物超薄膜的制备及性能表征

采用修饰LB膜法制备了导电聚合物聚-3,4-乙烯二氧噻吩/硬脂酸(PEDOT/SA)复合超薄膜. 将硬脂酸(SA)/FeCl3 LB膜暴露于EDOT单体气氛中, EDOT 单体在多层膜中聚合, 制备了PEDOT/SA多层复合LB膜. 紫外-可见光-近红外(UV-Vis-NIR)吸收光谱和X射线光电子能谱(XPS)分析表明EDOT单体在多层膜中发生聚合并生成PEDOT导电聚合物. 扫描电子显微镜(SEM)分析显示生成的PEDOT导电聚合物颗粒分散于硬脂酸LB膜中, 被LB 膜所包裹. 二次离子质谱(SIMS)及XPS分析还发现S元素含量随LB 膜的深度变化而变化, 表明PEDOT 较好地分散于多层膜中. 采用四探针电导率仪对复合多层膜的电导率进行了测试, 结果显示60 层复合LB 膜的电导率为2.6 S·cm-1, 比普通PEDOT薄膜的电导率高一个数量级, 且表现出较好的掺杂/脱掺杂能力. 研究还发现复合膜电导率与薄膜在EDOT 单体中处理时间有关, 处理时间至120 min 后电导率达到最大值并趋于稳定, 氧化剂浓度较低可能影响EDOT在LB膜中的聚合反应速率. 对复合LB 膜的气敏特性进行了分析, 发现在较低气体浓度范围(φ<30×10^-6), PEDOT 复合LB 膜有较快的反应速率, 气敏性与气体浓度呈非线性. 在较高浓度范围(φ=(30-120)×10^-6), 气敏性与浓度呈较好的线性关系. PEDOT复合LB膜对HCl气体表现出较好的响应恢复特性. 同时对PEDOT 复合膜相关的导电机理及气体敏感机理进行了分析.     

液晶聚合物的单层与Langmuir-Blodgett膜

系统研究了手性液晶聚硅氧烷和光致变色液晶聚硅氧烷两个毓的侧链液晶聚合物在空气/水界面的单层行为和Langmuir-Blodgett(LB)膜沉积特性,对LB膜结构与存在的聚集现象进行了系统的表征,并初步探讨了LB膜中液晶聚合物表现的功能性。     

浸没沉淀相转化法制备结晶性聚合物微孔膜的研究进展

综述了近期关于结晶性聚合物浸没沉淀相转化法制备微孔膜的成膜机理和实验研究工作.对制膜体系的热力学、相分离、成膜机理进行了分析和总结,并依此解析了结晶性聚合物膜中常见的结构形态,最后从热力学和动力学两个方面对影响膜结构形态的因素如聚合物的浓度、铸膜液的组成、凝固浴的组成等进行了详细的讨论.     

单臂冠醚液晶LB膜的相变研究

研究了两种单臂冠醚液晶及配合物(1, 2及1.Eu^3^+)的LB膜的成膜特性,实验发出它们均可在气-液界面形成单分子膜, 但不易转移, 化合物1在压膜过程中出现一维相变。用CPK模型对成膜分子构型和面积进行估算, 其结果与实验相一致, 并讨论了冠醚液晶结构对LB膜相变的影响。     

含偶氮生色团的“倒浮萍”聚合物LB膜及其可逆光信息存储特性

含偶氮苯功能基团的聚合物在光电子器件研制中具有诱人的应用前景．Wendorff[1]利用偶氮液晶聚合物首次实现可逆的光学信息存储后，利用偶氮苯分子的激光诱导二向色性和双折射效应实现可逆光学信息存储引起人们极大的兴趣．与传统的利用偶氮苯的顺反异构体实现信息存储的方式相比，这种信息存储方式由于偶氯苯分子始终处于热力学稳定的反式构象，因而具有突出的长期稳定性，具有更广阔的应用前景[1,2]．本工作设计合成了以含有给受体的偶氮苯分子为接枝侧链的两亲性聚合物，并研究了其成膜特性与可逆光信息存储特性．1实验部分两亲性聚合物…     

Synthesis of novel hybrid films of a layered silicate and alkylammonium cations on rough polymeric surfaces by Langmuir–Blodgett method

Hybrid films of a layered silicate and an amphiphilic alkylammonium (hexadecyltrimethylammonium) cation have been prepared by Langmuir–Blodgett (LB) method and transferred onto a polyamide surface by dip coating. This is the first time that stable LB hybrid monolayer and multilayer films have been formed on rough polymeric surfaces. The films were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and water contact angle measurements. XRD and FTIR showed that the hybrid multilayer was well-organized and the thickness of one layer was calculated to be 1.6 nm. Furthermore, the layered silicate was determined to be on the substrate side and the amphiphilic molecule layer was exposed to the air side. This provides a novel methodology for the surface modification of polymers.     

Photo-induced structural changes of azobenzene Langmuir-Blodgett films

Structural changes of the Langmuir-Blodgett (LB) films of azobenzene accompanied by photoisomerization are described. First, photoisomerization is explained in terms of 'free volume'. In the polyion complex monolayers of amphiphiles having two azobenzene units at the air-water interface, the area per molecule depends on the polycation species. The fraction of cis-azobenzene in the LB films at the photostationary state under the illumination with UV light increased with increasing area per molecule, which is consistent with the concept of free volume. Second, a counter example of the concept of free volume is presented. Three-dimensional cone-shaped structures developed with trans-to-cis photoisomerization in the polyion complex LB film of a water-soluble amphiphilic azobenzene. These structures appeared and disappeared reversibly by alternate illumination with UV and visible light. The results indicate that the two-dimensional LB film structure exerts significant modification by photoisomerization. This is against the concept of free volume because this concept does not consider the possibility that the two-dimensional LB film structures may change into three-dimensional ones. Finally, photo-induced J-aggregate formation of non-photochromic and photochromic dyes is described. Two cyanine dyes were each mixed with an amphiphilic azobenzene in the LB films. These cyanine dyes are known to form J-aggregates in single-component LB films. In the mixed LB films, the J-aggregate formation was suppressed to some extent. The alternate illumination of the films with UV and visible light caused the photoisomerization of azobenzene in the mixed LB films, which triggered the J-aggregate formation of the cyanine dyes. The J-aggregate formation was accompanied by the development of three-dimensional cone-shaped structures from the film surface. When an amphiphilic merocyanine was mixed with the azobenzene in the LB films, J-aggregate formation was also induced by the alternate illumination with UV and visible light. This J-aggregate formation was also accompanied by a large morphological change: circular domains changed into fractal-like ones. The J-aggregate formation of the dyes and the concomitant morphological change were irreversible. In these cases, the photoisomerization of azobenzene served as a trigger to induce self-organization of the dye molecules.     

Synthesis and Investigation of Monoesters of Polymaleic Acids with Azo Group

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Modulated Fluorescence in LB Films Based on DADQs—A Potential Sensing Surface?

Novel fluorescent Langmuir-Blodgett (LB) films have been constructed from three different amphiphilic dicynaoquinodimethanes (DADQs). The DADQs varied in functional group structure, which had an impact on the LB film structure and the fluorescence properties. As the fluorescence of DADQs competes with non-radiative decay (conformational change), the packing and/or free volume in the LB film will influence the average fluorescence lifetime and integrated intensity. The pristine (blank) LB films were then exposed to a selection of non-fluorescent target analytes (some with environmental relevance) and the fluorescence was measured and analyzed relative to the pristine LB film. Exposure of the LB films to selected target analytes results in a modulation of the fluorescence, both with respect to average fluorescence lifetime and integrated intensity. The modulation of the fluorescence is different for different DADQ LB films and can be attributed to restricted non-radiative decays or charge transfer reactions between target analyte and DADQ LB film. The response from the DADQ LB films shows that these systems can be developed into sensing surfaces based on fluorescence measurements.     

Synthesis of polymeric 1‐iminopyridinium ylides as photoreactive polymers

Two synthetic routes to polymeric 1‐imino pyridinium ylides as new photoreactive polymeric architectures were investigated. In the first approach, polymerization of newly synthesized 1‐imino pyridinium ylide containing monomers yielding their polymeric analogues was achieved by free radical polymerization. Alternatively, reactive precursor polymers were synthesized and converted into the respective 1‐imino pyridinium ylide polymers by polymer analogous reactions on reactive precursor polymers. Quantitative conversion of the reactive groups was achieved with pentafluorophenyl ester containing polymers and newly synthesized photoreactive amines as well as by the reaction of poly(4‐vinylbenzoyl azide) with a photoreactive alcohol. The polymers obtained by both routes were examined regarding their photoreaction products and kinetics in solution as well as in thin polymer films. Contact angle measurements of water on the polymer films before and after irradiation showed dramatic changes in the hydrophilicity of the polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 832–844, 2010     

Precursor method for polymeric LB films

First, the general concept of the “Precursor Method” for the preparation of polymeric Langmuir-Blodgett (LB) films that possess no long alkyl chain between film layers, and the preparation of polybenzothiazole 7 LB film are described. The preparation of 7 LB film was carried out by the same procedure as that used to make polyimide LB films via precursor LB films of polyamides that contain β-carboxyethylthio alkylamine salts 6. Precursor 6 LB film had a Y type structure with monolayer thickness of 2.8 nm, while polybenzothiazole 7 LB film had 0.34 nm. The nonlinear susceptibility χ⁽³⁾ of polybenzothiazole 7 LB film in parallel to the dipping direction was 3.8 × 10⁻¹¹ esu, whereas the susceptibility in the perpendicular direction was about one fifth of that of the parallel direction.     

Effects of surface water on gas sorption capacities of gravimetric sensing layers analyzed by molecular descriptors of organic adsorbates

The gas sorption capacities of sputtered carbonaceous films are evaluated with quartz crystal resonators. These films are sensitive to 20 ppm organic vapors and exhibit structure-dependent responses. Films derived from synthetic polymers are hydrophobic, whereas films derived from biomaterials are amphiphilic or hydrophilic. Polyethylene (PE) film has an extremely high sorption capacity for a wide range of vapors. Transient sorption responses are investigated using a humidified carrier by employing carboxylic acid esters, whose aliphatic groups are systematically changed. Small esters with a higher affinity to water induce negative U-shaped responses from amphiphilic films derived from biomaterials. On the other hand, polymeric films exhibit positive exponential response curves. Even if the concentrations are decreased, the response intensities are enhanced with the incremental expansion of carbon chains of aliphatic groups. Only fluoropolymer film shows the opposite tendency. The modeling of quantitative structure property relationships has indicated that the sorption capacities of the PE film to the carboxylic acid esters are fundamentally governed by electrostatic interactions. The intermolecular attractive forces are basically attributable to interactions between the positively polarized sites in esters and the negatively polarized/charged sites in PE film.     

Molecular Arrangement of a Bolaamphiphilic Anthrancene Derivative in Langmuir-Blodgett Film

Langmuir monolayer at the air/water interface is the basis to understand the molecular arrangement and to fabricate the organized molecular films1. Bolaamphiphiles describes the molecules in which two head functional groups are linked by one or two hydrophobic chains2,3. In comparison with the one-headed amphiphile, abundant configurations of Langmuir monolayer are expected in bolaamphiphiles. Generally, three kinds of configurations of the Langmuir monolayers of bolaamphiphile at the air/w…