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1.
以两亲性嵌段共聚物为模板是构筑导电聚合物纳米结构并对其形貌尺寸进行调控的有效方法之一。 嵌段共聚物成核段长度的变化对其胶束化行为有显著影响,进而也会改变受限于其胶束形貌的导电聚合物的形貌尺寸。 形貌尺寸的变化必然导致导电聚合物电化学性能变化。 本文欲通过嵌段共聚物模板诱导实现对聚苯胺(PANI)形貌尺寸的调控并使其电化学性能得到优化,采用可逆加成-断裂链转移自由基聚合(RAFT)法成功合成了嵌段共聚物聚苯乙烯-b-聚丙烯酸PSx-b-PAA70(x=38、64、101)并以其胶束为“模板”制备了窄相对分子质量分布的PANI。 在成核段(PS)长度较短时,模板诱导形成的棒状PANI颗粒,直径为100~200 nm。当 x=101时PANI呈现空间网状结构,其放电比容量高于其它样品,在电流密度为1 A/g时,其放电比容量可达386.71 F/g。 相似文献
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棒杆-棒杆(rod-rod)共轭嵌段共聚物体系是近几年发展起来的一类新型共轭聚合物材料,由于其特有的电学活性以及通过自组装实现纳米尺度结构可控等特性正逐渐成为人们研究的热点.构筑单元的刚性棒状结构使得rod-rod共轭嵌段共聚物体系倾向于自组装形成囊泡或层状结构等低曲率聚集体.本文总结了近年来关于rod-rod共轭嵌段共聚物体系自组装行为的研究,分别介绍了溶液中以及薄膜状态下双刚性共轭嵌段共聚物体系的自组装行为,在此基础上进一步讨论了rod-rod共轭嵌段共聚物薄膜结构与性能的关系. 相似文献
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Mark W. Hamersky Matthew Tirrell Timothy P. Lodge 《Journal of Polymer Science.Polymer Physics》1996,34(17):2899-2909
Forced Rayleigh scattering (FRS) has been used to measure the self-diffusion coefficient, D, of a lamellar-forming polystyrene-polyisoprene diblock copolymer (MPS = 1.0 X 104, MPI = 1.3 X 104) as a function of temperature. The measurements traverse the order-disorder transition (ODT), which occurs at 160°C. There is no obvious change in either D or the temperature dependence of D at the ODT, in agreement with measurements on several other systems. Electron microscopy confirms that the sample in the ordered state is quenched, with no long-range orientation of lamellae, and a typical grain size well below 1 μm. In contrast to previous measurements on a similar styrene-isoprene diblock, these FRS signals are well-described by single exponential decays; this may be largely attributed to differences in average grain size. The temperature dependence of D is modeled with several empirical expressions, based on the known monomeric friction factors for pure polystyrene and pure polyisoprene, but without quantitative success. These results underscore the need for a greater understanding of the composition and temperature dependences of local friction in polymer mixtures. © 1996 John Wiley & Sons, Inc. 相似文献
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Yue Jun Zhu~a Ye Bang Tan~ 《中国化学快报》2008,19(3):355-358
Novel double hydrophilic block copolymers with amine pendant chains were synthesized by polymerization of 4-vinyl benzylamine hydrochloric salt using 4,4′-azo-bis[4-cyanopentanoate poly(ethylene glycol) ester] as macroazoinitiator. The structures of the copolymers were characterized by ^1H NMR, FTIR spectra and acid-base titration, GPC-MALS techniques. 相似文献
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The present investigation deals with sequential block copolymerization of styrene and 1-butene with a novel MgCl2-supported TiCl4 catalyst modified with a rare earth compound NdClx(OR)y (SN-1 catalyst), which was developed in our laboratory. The catalytic activities are 1300–2500 g/g·Ti·h. Analyses of copolymers with solvent extraction, 13C-NMR, WAXD, GPC, and DSC was performed. The results indicate that the SN-1 catalyst selectively gave crystalline diblock copolymers of isotactic polystyrene and isotactic poly(1-butene), with the styrene unit content of 30–60 mol %. © 1996 John Wiley & Sons, Inc. 相似文献
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A range of polyvinylpyrrolidone–polycaprolactone diblock copolymers with varying chain lengths were synthesized by Atom Transfer Radical Polymerisation (ATRP) using bromo-polycaprolactone as macroinitiator and copper(I) bromide/bipyridine catalytic system. The copolymers self-assembled in solution into core–shell micelles with sizes varying from 150 to 205 nm and critical micelle concentration of the order of 10−5 to 10−6 M. Front line anti-Tuberculosis drugs Rifampicin (RIF), Pyrazinamide (PZA) and Isoniazid (INH) were successfully encapsulated within the micelle hydrophobic core singly or in dual combination. The effect of length of hydrophobic and hydrophilic segments on drug loading, micelle size and drug release was investigated. Determination of binding constants showed that RIF binds more strongly to the micelle core than PZA and INH, leading to highest drug loading content. All drugs were released in vitro (PBS solution at 37 °C) in a sustained manner with zero-order kinetics and followed the order INH > PZA > RIF. 相似文献
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Jing Luo Qun Zhou Jun Sun Jinqiang Jiang Xin Zhou Hongwu Zhang Xiaoya Liu 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4037-4045
A novel kind of photosensitive water‐dispersible polyaniline (PANI) nanoparticles was designed and prepared by template synthesis using a photo‐responsive vinyl‐coumarin (VM)/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) copolymer micelle containing coumarin moieties. The resulting PANI nanoparticles exhibited reversible photo‐crosslinking and photo‐decrosslinking behavior similar to coumarin moiety upon irradiation with different UV light as verified by UV–vis absorption. In addition, photoinduced size change of the PANI nanoparticles after 365 nm UV light irradiation was successfully monitored by dynamic light scattering and transmission electron microscopy measurements, further confirming the photosensitivity of the obtained PANI nanoparticles by the incorporation of VM/AMPS copolymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Tae Oan Ahn Jung Ho Kim Han Mo Jeong Sang Won Lee Lee Soon Park 《Journal of Polymer Science.Polymer Physics》1994,32(1):21-28
The compatibilizing effect of polyarylate-polystyrene (PAR-PS) block copolymer prepared from macroazo initiator was examined in polyarylate/polystyrene blends from the view-points of morphology, density, and thermal, mechanical, and rheological properties. PARPS block copolymer enhanced the mutual dissolution of the homopolymers. Reduced dispersed-domain size and increased density showed the efficiency of the block copolymer as a compatibilizing agent. Results from mechanical and rheological properties could also be explained by the compatibilizing effect of PAR-PS block copolymer in the blends. © 1994 John Wiley & Sons, Inc. 相似文献
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Ronald M. Gurge Markus Hickl Gernot Krause Paul M. Lahti Bin Hu Zhou Yang Frank E. Karasz 《先进技术聚合物》1998,9(8):504-510
An alternating block copolymer, poly(1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1,4-phenylene-1,2-ethenylene-1,4-phenylene-1,2-ethenylene-3,5-dimethoxy-1,4-phenylene), 1 , was synthesized, and characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography differential scanning calorimetry ultraviolet and elemental analysis. Light-emitting single-layer test diodes using this soluble, processible copolymer as the active layer (i.e. indium tin oxide/ 1 /Ca,Al) emit green light with a luminescent spectral maximum at 513 nm. The single-layer device had a brightness of about 80 cd/m2 at a current density of 100 mA/cm2 with an internal quantum efficiency of 0.3% photon/electron. Optimization of the light-emitting properties of 1 was achieved through variation of a key Wittig polymerization step in the synthesis, using trialkyl rather than triaryl phosphonium salts in an appropriate solvent mixture to achieve nearly regiospecific trans-olefination. This provided an improvement over earlier procedures, which require a post-Wittig isomerization to minimize the presence of electroluminescence-inhibiting cis-bonds. © 1998 John Wiley & Sons, Ltd. 相似文献
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Junlian Huang Xiaoyu Huang Wenbing Hu Wenkui Lou 《Journal of polymer science. Part A, Polymer chemistry》1996,34(7):1317-1324
A bifunctional initiator with the characteristics of anionic and charge transfer polymerization using p-aminophenol as parent compound is useful for synthesis of block copolymers. A block copolymer of ethylene oxide and acrylonitrile (PEO-b-PAN) is prepared by this method. In the first step, p-aminophenol potassium with protected amine group initiated polymerization of ethylene oxide (EO) to yield polyethylene oxide (PEO) with Schiffs base end groups. The charge transfer complexes (CTC) consisted of the PEO prepolymers with aniline group, which is formed by acidolysis of Schiffs base, and benzophenone (BP) initiated the polymerization of acrylonitrile under UV irradiation. Successful blocking has been confirmed by a strong change in the molecular weight of the prepolymer PEO and the block copolymer as well as IR, DSC, and NMR. The block copolymerization are strongly dependent on the polarity of the solvents. The effect of length of PAN block on glass transition temperature of PAN and the crystallinity of PEO block were discussed. © 1996 John Wiley & Sons, Inc. 相似文献
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Polybenzidine (PBz) particles were formed by the chemical polymerization in micelles of block copolymer by using Poly (ethylene oxide)-b-Polystyrene [PEO113-b-PSx (x = 50, 58 and 100)] as templates. The samples were characterized by IR, UV-vis absorption spectroscopy, transmission electron microscopy, cyclic voltammetry, constant current charge-discharge and electrochemical impedance to determine their morphologies and electrochemical properties. The results show that the prepared PBz is submicron to nanometer rod-like conducting particles with uniform sizes. Removing the templates did not affect the morphology but slightly reduced the size of the PBz particles. The size and morphology of PBz particles can be tuned by adjusting the amount of monomer. The PBz submicrorods showed 412 F·g?1 specific capacitance in 0.3 mol·L?1HClO4 at the current density of 1 A·g?1, indicating its better electrochemical activity. The specific capacitance of the PBz particles reduced less than 10% after 500 charge-discharge cycles at the current density of 3 A·g?1, indicating its good cycling stability. 相似文献
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ZHANG Yu XIAO ChunSheng LI MingQiang DING JianXun YANG ChenGuang ZHUANG XiuLi& CHEN XueSi 《中国科学:化学(英文版)》2014,57(4):624-632
A series of well-defined amphiphilic linear-dendritic block copolymers (telodendrimers, MPEG-b-PAMAM-cholesterol) with 1,2,4 or 8 cholesteryl groups (named as P1, P2, P4, P8, respectively) were synthesized. Their chemical structures were characterized with 1H NMR and mass spectrum (MALDI-TOF MS). The telodendrimers could self-assemble into micelles in aqueous solution, and encapsulate chemotherapeutic drug doxorubicin (DOX) and paclitaxel (PTX) for combination therapy. All the telodendrimers could encapsulate DOX with similar capability. However, their drug-loading capability of PTX is increased with the increasing number of cholesteryl groups. P8 exhibited much higher PTX loading efficiency than its counterparts. Thus, P8 was selected for further application of drug delivery in the paper. The drug-loading micellar nanoparticles (NPs) of P8 were spherical in shape and their diameters were less than 150 nm which were determined by dynamic light scattering measurements (DLS) and transmission electron microscope (TEM). In vitro drug release experiment demonstrated that P8 exhibited a controlled release manner for both DOX and PTX, and the two drugs were released simultaneously. In vitro cytotoxicity experiment further demonstrated that the co-delivery of DOX and PTX in P8 exhibited better anti-cancer efficiency than the delivery systems encapsulated with single drug (DOX or PTX). This indicates a synergistic effect. The co-delivery system showed potential in future anti-cancer treatment. 相似文献
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FU Yu & LIU GuoJun Research Centre for Molecular Science Engineering Northeastern University Shenyang China 《中国科学:化学》2010,(5)
A diblock copolymer poly(ethylene glycol)-block-polystyrene or PEG-b-PS with an olefinic double bond at the PEG and PS junction has been prepared by modular synthesis viaclickchemistry.This involved the synthesis of PS by atom transfer radical polymerization and the nucleophilic substitution of the terminal bromide group with azide to yield azide-terminated PS. PEG with an alkynyl terminal group was prepared from reacting carboxyl-end-functionalized PEG with 4-hydroxybut-2-enyl prop-2-ynyl succinate,which c... 相似文献
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以胆酸为引发剂,用辛酸亚锡催化丙交酯开环聚合合成星型CA-PLA。利用DCC为脱水剂,将不同分子量的端羧基化PEG与星型CA-PLA偶联,合成一系列以胆酸为核的星形两亲性嵌段共聚物,用透析法制备共聚物胶束,并用TEM和DLS研究胶束的性质。合成了分子量为6000和12000的两种CA-PLA,其分子量可以通过胆酸羟基与丙交酯的比例进行控制。将分子量2000和5000的PEG分别与两种CA-PLA偶联,合成了四种星型CA-PLA-PEG嵌段共聚物。共聚物胶束形貌为均匀的球形,粒径为20-40nm,且随共聚物中PLA链段分子量的增加而增大,随PEG链段分子量的增加而减小。临界胶束浓度(CMC)低于同等链段长度的线型PLA-PEG嵌段共聚物胶束。 相似文献
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A novel fluorinated triblock copolymer incorporating 2-ethylhexyl methacrylate (EHMA),tert-butyl methacrylate (tBMA) and 1H,1H,2H,2H-perfluorodecyl acrylate (FA) (PEHMA-b-PtBMA-b-PFA) was first synthesized using three successive reversible addition fragmentation chain transfer (RAFT) polymerization and the subsequent hydrolyzing at acidic condition.The as-fabricated triblock copolymer exhibited an interesting morphology evolution from the multi-compartment rod-like structure to spherical structure along with the addition of a selective solution.At the same time,a visible phase separation domain could be seen in the core area due to the existence of fluorocarbon segments.Furthermore,the selfassembly behavior of the triphilic copolymer at different pH was also verified by transmission electron microscopy,as well as the dynamic light scattering.These stimuli-responsive multi-compartment nanostructures may have potential applications in drug delivery. 相似文献
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Hiroshi Ohishi Toshio Nishi 《Journal of polymer science. Part A, Polymer chemistry》2000,38(2):299-309
The chain geometry of polystyrene (PS) and polyarylate (PAr) block copolymer was predicted by the simulation of the kinetics of the block‐copolymerization route. The simulation model consisted of a combination of two models. In the first model, the kinetics of the free‐radical polymerization of carboxyl‐terminated telechelic PS (COOH‐PS‐COOH) was simulated for the determination of the molecular weight distribution. In the second model, the kinetics of the PS and PAr block copolymerization with COOH‐PS‐COOH was simulated by a Monte Carlo computation, with each reacting functional group assigned by an integer. The number‐average and weight‐average molecular weights and the composition of the PS‐PAr block copolymer, as calculated by the simulation models, were in good agreement with the experimental data. From this agreement, plausible predictions for the chain geometry (i.e., the type of block copolymer and length of each segment) were obtained that were practically impossible to analyze experimentally. The simulation results showed that more than 80 wt % of the block copolymer synthesized by this method was a composite of various types of multiblock copolymers and that the length of the PAr segment was almost the same as that of the homo‐PAr obtained as a by‐product. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 299–309, 2000 相似文献