The phase structure,chain diffusion motion and local reorientation motion: C Solid-state NMR study on the highly-crystalline solid polymer electrolytes

In our previous paper, we investigated the influence of the phase structure on the polymeric chain diffusion in the complexed crystals of solid polymer electrolytes of PEO:LiAsF₆ and PEO:LiCF₃SO₃. We observed that with the increase of the crystallinity, the chain diffusion rate decreases dramatically. In this work, by employing the ¹³C CODEX NMR spectroscopy, we demonstrate that opposite to the behavior of the chain diffusion motion, the local reorientation motion of polymeric chains within the complexed crystals are greatly increased with the increase of the crystallinity, which is accompanied by the change of the phase structure. The relationship between the different molecular motions within the complexed crystals and the phase structure are discussed therefore.     

On-off switching properties of one-dimensional photonic crystals consisting of azo-functionalized polymer liquid crystals having different methylene spacers and polyvinyl alcohol

In this paper, photoresponsive behavior of multi-bilayered films having precisely controlled layer thickness prepared by stacking an azo-functionalized polymer liquid crystal, PMAzXAc, and polyvinyl alcohol alternatively, PVA, is described. The multi-bilayered films were found to reflect a light of specific wavelength depending on the layer thickness and refractive index, and showed the reversible change in the reflection intensity by irradiation with visible and UV lights. The change in the reflection intensity was brought about by change in the molecular orientation of PMAzXAc between an out-of-plane orientation and a photo-induced isotropic state, and was strongly dependent on the number of methylene spacer of PMAzXAc linking the azobenzene side group with the acrylate polymer main chain. PMAz6Ac with hexa-methylene spacer showed the largest change in the reflection intensity, while smaller change in the reflection intensity was observed for PMAzXAc having shorter or longer methylene spacer than 6. The effect of the methylene spacers on the photochemical change in the molecular orientation of azobenzene chromophores in the multi-bilayered films will be discussed.     

Nanostructured poly(3-hexylthiophene-2,5-diyl) films with tunable dimensions through self-assembly with polystyrene

Poly(3-hexylthiophene-2,5-diyl) is among the most widely used conjugated polymers for opto-electronic applications. To enhance its properties, researchers have attempted to nanostructure this polymer using various processes including breath figure arrays, nanolithography and elaborated organic synthesis. We here demonstrate a simple process to nanostructure the conjugated polymer using self-assembly with polystyrene and selective removal of one of the phases. The influence of the molecular weight of each polymer on the thin film morphology was systematically studied by atomic force microscopy. Using this approach, we observe two types of nanostructure, namely, nanoporous and nanoisland structures, of which the dimensions can be tuned by modifying the molecular weight of each polymer in the blend. This simple process introduces a cost-effective alternative to produce thin films of conjugated polymer with average nano-features from 100 nm up to 500 nm which could be used in a wide range of applications.     

Influence of polyimide precursor synthesis route and ortho-position functional group on thermally rearranged (TR) polymer properties: Conversion and free volume

Thermal rearrangement of polyimides with ortho-position groups to polybenzoxazoles and related structures has been of recent interest for producing gas separation membranes. This study explores the influence of synthesis route and ortho-position functional group on the thermal rearrangement process and the fractional free volume of thermally rearranged (TR) polymers produced from polyimides derived from 3,3′-dihydroxy-4,4′-diamino-biphenyl and 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (HAB–6FDA). Acetate, propanoate, and pivalate ortho-position functional groups were considered. Thermogravimetric analysis (TGA) was used to study thermal rearrangement at temperatures between 350 and 450 °C, and evolved gases from TGA were analyzed via mass spectrometry to characterize the byproducts of thermal rearrangement and thermal degradation. CO₂ was the major byproduct of thermal rearrangement for all samples, and its evolution began well before the onset of thermal degradation. When non-hydroxyl ortho-position groups were present in the polymers, several byproducts other than CO₂ were also observed due to the loss of these ortho-position groups before thermal rearrangement. Free volume generally increased with increasing extent of thermal rearrangement, but precise values of free volume could not be accurately determined for polymers with propanoate and pivalate ortho-position functional groups due to uncertainties in the chemical structure of partially converted materials. For polymers with acetate and hydroxyl ortho-position groups, free volume could be determined within the uncertainty of density measurements. Thermal rearrangement behavior and free volume results for acetate containing polymers synthesized via different routes were very similar. Based on these results, the chemical structure of the ortho-position functional group has a larger impact on TR polymer properties than the polyimide precursor synthesis route.     

Carbon nanotube–polyaniline composites

The last decade has seen a growing interest in hybrid electrically conducting nanocomposites. This article aims to provide a detailed overview of the present status of research in carbon nanotube–polyaniline (CNT/PANI) composites, from processing to structural and property evaluations. CNT/PANI are synthesized by electrochemical and chemical processing. When chemical methods are used, the main challenge is to obtain processable CNT/PANI in the emeraldine salt (ES) form composites. Stable dispersions of ES–CNT in organic media are prepared using the post doping method, inverse emulsion polymerization, or ex situ polymerizations. On the contrary, stable water dispersions of CNT/ES are prepared using hydrophilization of a preformed CNT/ES composite, direct synthesis of micelle–CNT hybrid templates, interfacial polymerization, covalent functionalization of CNT with a water soluble polymer, or using electrostatic interactions between two oppositely charged ES and CNT aqueous colloids. Moreover, the strategies for the synthesis of ternary CNT/PANI composites incorporating noble metal nanoparticles, metal oxide, or graphene sheets are also presented and analyzed in depth. Finally, we give a review of potential applications, including chemical sensors, capacitors, fuel cells and electronic devices.     

Application of stimuli responsive polymers for sustainable ion exchange chromatography

Ion exchange processes are widely used in the food, bioprocessing and related industries for the isolation of proteins and other ionic species. Traditional ion exchange resins require salts, acids or bases for releasing adsorbed molecules creating a strong saline waste stream with negative environmental and economic impact. Stimuli responsive polymers (SRPs) with ion exchange functional groups can be used to selectively capture and release charged molecules from a complex mixture using physical stimuli to trigger conformational transitions in the polymer. The structural change of the polymers in response to a stimulus may lead to reduced ligand–target molecule interaction resulting in the release of the captured molecule without the use of chemical reagents, thereby reducing the environmental burden associated with ion exchange processes. The use of temperature responsive polymers has already been demonstrated for such applications at analytical scale. However, little progress has been made to extend these discoveries to the development of materials and methods amenable to industrial scale processing. So far, other SRPs such as, electric, magnetic and light responsive polymers remain largely unexplored for such application. This article discusses the potential of temperature responsive and other SRPs for developing sustainable ion exchange processes. It also highlights the material science and engineering challenges that need to be overcome to bring such processes to industrial application.     

驱油用聚表剂乳化性能评价方法

目前,对于聚表剂多采用瓶试法来表征其乳化性能,本研究讨论了聚表剂水溶液原油乳液的制备方法,在瓶试法研究的基础上,通过油砂吸附前后粘度及析水率评价,乳液稳定性评价,乳液微观结构观测等方法评价了驱油用聚表剂的乳化性能,丰富了聚表剂乳化性能表征手段。     

燃料电池用碱性阴离子交换膜的研究进展

碱性阴离子交换膜(AAEM)是碱性阴离子交换膜燃料电池(AAEMFC)的核心部件,起到阻隔阴阳两极和传导OH-的双重作用,其性能好坏直接影响到AAEMFC的性能和使用寿命。从膜的结构和制备方法分类,综述了碱性阴离子交换膜燃料电池用有机-无机杂化膜、掺杂型膜及均相膜的特性和研究现状。     

高分子材料学辅助有机化学教学——培养与增进学生学习的浓厚兴趣

摘有机化学是面向工科专业开设的一门基础课程,因授课教师的知识背景不同,所以在教学过程中应因地适宜考虑教学方案,提高教学质量。文章根据作者在有机化学授课上的教学实践与经验,浅议高分子材料学在有机化学教学中提高学生兴趣与课堂效率的作用。     

糠醇聚合物的制备研究

文章对糠醇(FA)聚合物的制备进行了研究。研究结果表明:糠醇的聚合反应受到反应时间、温度和催化剂量的较大影响。延长反应时间、提高反应温度或增大催化剂用量,均可增大糠醇聚合物的分子量,使其粘度增大。同时,对甲苯磺酸对糠醇(FA)聚合物具有较好的固化效果。