苯胺在十二烷基苯磺酸/水体系中的乳液聚合过程研究

利用光学显微镜和扫描电镜,对以水为介质、十二烷基苯磺酸(DBSA)为乳化剂的苯胺乳液聚合过程进行监测,发现苯胺在水体系中与DBSA反应形成DBSA-苯胺盐的棒状聚集结构,讨论了DBSA、苯胺、氧化剂的配比及浓度对聚合过程中棒状聚集结构的长度和数量及生成聚苯胺的电导率的影响,提出苯胺在DBSA/水体系中的乳液聚合反应是在胶束表面进行的,而棒状聚集结构中的DBSA-苯胺盐单体经水相扩散到乳胶粒子中,形成颗粒状的聚苯胺.     

阳离子表面活性剂作用下制备一维纳米结构聚苯胺

在十六烷基三甲基溴化铵(CTAB)存在下, 以盐酸为质子酸, 过硫酸铵为氧化剂, 制备了平均直径为115 nm、具有分叉结构的聚苯胺纳米纤维和平均直径为75 nm的卷曲聚苯胺纳米线, 两者的结构产率高达90%和100%, 电导率分别为1.6×10-2和9.3×10-2 S/cm. 研究发现, 聚苯胺的一维纳米结构受盐酸浓度和苯胺与CTAB摩尔比的协同影响. 用TEM, SEM和FTIR对产物的形貌和化学结构进行了表征. 利用pH监测反应并结合SEM结果研究了聚苯胺纳米线的形成过程, 结果表明, CTAB阳离子与过硫酸根形成的絮状物的诱导作用是聚苯胺纳米纤维和纳米线形成的关键因素.     

聚苯胺纳米粒子的反胶束法合成及自组装

聚苯胺纳米粒子的反胶束法合成及自组装;聚苯胺;纳米粒子;反胶束;自组装     

聚苯胺/纳米二氧化锰复合材料Ⅱ.形貌表征

通过先用过硫酸铵引发苯胺的聚合,然后再将纳米二氧化锰(nm-MnO2)加入过硫酸铵和苯胺的反应体系中。原住制备了导电聚苯胺／纳米二氧化锰复合材料(PANL／nm-MnO2),并有效地避免了nm-MnO2在苯胺氧化聚合中的消耗。扫描电镜和透射电镜显示复合材料中nm-MnO2为聚苯胺所包裹。X射线衍射研究表明,在复合材料制备过程中nm-MnO2的晶型未发生变化,在复合材料中聚苯胺为非晶相结构。     

苯胺齐聚物对聚苯胺微纳米形貌形成的影响

聚苯胺是一种具有优异性能的导电高分子材料,在传感器、防腐、电容器、生物等领域有着广泛的应用前景。化学氧化聚合法是制备聚苯胺的常用方法。苯胺齐聚化是苯胺化学氧化聚合过程中的重要一步,不同条件下生成的齐聚物化学结构及其自组装方式的差异会导致最终聚苯胺的形貌迥异。本文结合目前人们较为认同的聚苯胺微纳米结构形成机理,基于产物形貌分类,综述了在化学氧化过程中的苯胺齐聚化反应和苯胺齐聚物自组装引导聚苯胺微纳米结构的形成,讨论了目前研究中的存在的问题并对今后研究方向进行了展望。     

无模板法聚苯胺纳米管的制备及表征

以过硫酸铵(APS)为氧化剂,在无模板,无掺杂酸条件下,利用超声辅助合成了聚苯胺纳米管.通过透射电子显微镜、傅里叶红外光谱、紫外-可见光谱、X-射线衍射对产物的形貌、结构和性能进行了表征.研究表明,形成的聚苯胺纳米管内径约为10 nm,外径约为80 nm,长度约为26μm,且管径均匀.苯胺单体浓度越高,聚合速率越快.但是,聚苯胺的形貌与苯胺单体的浓度无关,而与苯胺和过硫酸铵的摩尔比有关.超声在纳米管的形成中起主要作用,它阻止球状胶束无规则团聚,使得在较高的苯胺浓度下(0.2 mol/L)也可形成纳米管.合成的聚苯胺电导率为5×10-3S·cm-1,结晶度不高.     

不同铁盐氧化掺杂导电聚苯胺纳米结构的合成及性能研究

在没有外加掺杂剂的条件下,以FeCl3,Fe(NO3)3,Fe2(SO4)3,FePO4等多种铁盐为氧化剂,在水溶液中采用"无模板"的方法制备了具有较高电导率的聚苯胺纳米结构.铁盐是一种强酸弱碱盐,在水溶液中发生水解释放出质子,质子可以作为掺杂剂进入聚苯胺主链,因此,在苯胺的聚合过程中,铁盐同时起到氧化剂和掺杂剂的双重功能,进一步简化了导电聚苯胺纳米结构的合成条件,降低了反应成本.FTIR,UV-Vis,XRD等结构表征证实所得的纳米结构的聚苯胺均为掺杂态.试验发现,铁盐较低的氧化/还原电位使产物具有较小的直径和较高的电导率和结晶性.不同的对阴离子对聚苯胺产物的形貌有一定的影响,但对产物的结构和性能影响不大.铁盐与苯胺单体的比例对聚苯胺的形貌和电导率均有较大的影响.     

反胶束体系中合成聚苯胺-无机物复合纳米微粒

利用阴离子型表面活性剂2-乙基己基琥珀酸钠(AOT)形成的反胶束作为微反应器合成了聚苯胺-氯化银和聚苯胺-硫酸钡复合纳米粒子;考察了搅拌因素和不同合成步骤对聚苯胺-硫酸钡尺寸及形态的影响;并利用TEM, IR, UV-vis, XRD和四探针电导率仪对产物进行了表征.研究结果表明,反胶束法可以有效地应用于有机-无机复合纳米材料的制备.     

纳米纤维聚苯胺膜在不锈钢电极表面的生长过程

研究了脉冲电流法(PGM)聚合苯胺时, 纳米纤维聚苯胺(PANI)膜在不锈钢(SS)电极表面的生长过程. 用计时电位法和扫描电子显微镜(SEM)表征了聚苯胺生长过程的电化学特征和微观形貌; 并通过循环伏安(CV)法研究了苯胺的聚合速率. 结果表明, 聚苯胺的生长经历了两个阶段, 首先是在裸不锈钢电极表面上形成颗粒状聚苯胺, 此时聚合电位约为1.10 V, 经历了30 s后, 电极表面被一层颗粒状聚苯胺膜所覆盖; 在此基础上, 聚苯胺以纳米纤维状结构继续生长, 当颗粒状聚苯胺被纳米纤维状聚苯胺膜完全覆盖时, 聚合电位降至0.75 V左右并保持稳定.     

胶束作为纳米反应器的研究进展

纳米反应器作为一种新型的制备纳米粒子及重要功能分子的手段,其技术在许多领域受到广泛重视.与常规意义上的化学反应器有所不同,纳米反应器是指反应所处的受纳米尺度调制的介观环境,如反应的介质、载体、界面等等.纳米反应器一般分成两类,一种是在分散相中能自组装的分子,形成有序聚集体,如胶束、囊泡,在聚集体的内部制备纳米粒子或材料;另一种是天然存在或合成的分子,如纳米管、树枝聚合物,利用分子特有的结构或孔隙作为纳米反应器.本文主要介绍了胶束、胶束作为纳米反应器的分类;重点讨论了分子及聚合物胶束作为纳米反应器的特点,并对其研究进展及前景进行总结和展望.     

Synthesis and electrochemical performance of sandwich-like polyaniline/graphene composite nanosheets

Sandwich-like polyaniline/graphene composite nanosheets have been synthesized by chemical oxidation polymerization of aniline monomer on the surfaces of reduced graphene oxide nanosheets in the absence of any surfactants. The influences of the mass ratios of aniline and reduced graphene oxide on the sizes and morphologies of polyaniline/graphene nanocomposites have been investigated. As the mass ratio of aniline and reduced graphene oxide is smaller than 12:1, polymerization reaction of aniline occurs on the surfaces of reduced graphene oxide by heterogeneous nucleation to form sandwich-like polyaniline/graphene composite nanosheets. However, besides sandwich-like polyaniline/graphene composite nanosheets, polyaniline nanofibers are formed by homogeneous nucleation. In comparison with reduced graphene oxide and polyaniline nanofibers, the obtained sandwich-like polyaniline/graphene composite nanosheets exhibit good electrochemical performances due to the synergistic effect between graphene and polyaniline.     

Structure – Directing Effect of Renewable Resource Based Amphiphilic Dopants on the Formation of Conducting Polyaniline-Clay Nanocomposite

Summary: The structure-directing effect of two amphiphilic dopants on the nucleation and growth mechanism during the formation of micro/ nanostructured polyaniline (PANI) and polyaniline-clay nanocomposites (PANICNs) is described. PANIs and PANICNs were prepared by in-situ intercalative emulsion polymerization of aniline using the amphiphilic dopants, 3-pentadecyl phenyl phosphoric acid (3-PDPPA) and 3-pentadecyl phenol–4-sulphonic acid (3-PDPSA), derived from cashew nut shell liquid, a renewable resource. These molecules act as intercalating agents, dopants and also as structure-directing agents. X- ray diffraction (XRD) and scanning electron microscopic (SEM) studies revealed the formation of lamellar/fibrillar – network in PANI- PDPPA and cylinder/rod morphology in PANI-PDPSA. Experimental data reveal that fibrillar morphology arises from the heterogeneous nucleation followed by an indefinite growth mechanism. On the other hand rod-like structures are formed from the self-assembled rod-like micelle guided polymerization through homonucleation followed by an anisotropic growth mechanism. Electrical conductivity measurement revealed lower conductivities for PANICNs than that of PANIs.     

The stabilization of charged states at phenazine-like units in polyaniline under p-doping: an in situ ATR-FTIR spectroelectrochemical study

The structure and stabilization of charged states during p-doping of polyaniline (PANI) were studied by in situ ATR-FTIR spectroelectrochemistry. The role of phenazine-like units in several copolymers of aniline and a phenazine derivative (3,7-diamino-5-phenylphenazinium chloride, phenosafranine) was investigated by spectroelectrochemistry. PANI and three copolymers with different aniline to phenosafranine ratio were electrochemically prepared. FTIR spectra of as-prepared polymers as well as in situ FTIR spectra during the oxidation of the polymers give evidence of the presence of phenazine-like units in the structure of electrochemically prepared PANI, as shown by vibrations of the phenazine rings. New bands corresponding to the in-plane and out-of-plane C-H vibration of 1,2,4-trisubstituted benzene nuclei in the phenazine skeleton are found at 1033, 957, 880, 766 and 681 cm(-1). The potential dependence of IR bands observed during oxidation of the polymers was compared to that of the ESR intensity and the absorption data and points to the diamagnetic species like π-dimers formed at higher oxidation level of PANI. This charged state is shown to be fixed at the link of the phenazine-like units with the linear segments of PANI.     

FORMATION OF FLOWER-LIKE AGGREGATES FROM SELF-ASSEMBLING OF MICELLES WITH PEO SHELLS AND CROSS-LINKED POLYACRYLAMIDE CORES

Amphiphilic block copolymers,poly(ethylene oxide)-b-poly(N-acryloxysuccinimide) (PEO-b-PNAS) with various molecular weights have been successfully synthesized by atom transfer radical polymerization (ATRP) of NAS using functionalized PEO (PEO-Br) as ATRP macroinitiator.The self-assembling of the block copolymers in water,which is a good solvent for PEO and a non-solvent for PNAS.yielded spherical core-shell micelles with PNAS as core and PEO as shell.The cross-linked reaction of oxysuccinimide in PNAS ch...     

Poly(tetrafluoroethylene) composite membranes coated with urchin-like polyaniline hiberarchy: Preparation and properties

Spiny polyaniline (PANI) spheres (urchin-like) were coated on a poly(tetrafluoroethylene) (PTFE) membrane via a counter-diffuse interfacial oxidation polymerization of aniline in an aqueous medium. The produced composite membrane has both unexpected superhydrophilicity and conductivity. The microstructure and morphology of the composite membrane were characterized by FTIR, UV-vis, XRD, TGA, and SEM. Effects of reagent concentrations and polymerization time on the membrane morphology and properties were studied systematically. A possible formation mechanism of the urchin-like polyaniline nanospheres on PTFE surface has been briefly discussed. The co-effect of both spherical micelles formed by Nafion and nanofibrous micelles formed by aniline/p-toluenesulfonic acid was considered to be a reason to produce the urchin-like PANI nanospheres. The PTFE/Nafion/PANI composite membrane showed a convertible hydrophilic/hydrophobic feature via adjusting acidity/alkalinity of an aqueous medium and also was able to adsorb heavy metal-ions from the medium.     

Conducting polystyrene/polyaniline blend through template-assisted emulsion polymerization

Electrically conducting polystyrene (PS)/polyaniline blends have been prepared through a one-step “anilinium-surfactant template”-assisted emulsion polymerization at room temperature. The self-assembled cylindrical An⁺PDPSA^? micelle formed inside the PS matrix can act as a structure directing template cum dopant. Morphological observation under scanning electron microscopic studies revealed that during the progress of polymerization, the initially formed nanostructured conducting polyaniline was changed into cubic/hexagonal/lamellar particles and finally transformed into a percolated structure inside the PS matrix. Blend was further characterized by UV-Vis spectroscopy, FTIR spectroscopy, X-ray diffraction, electrical conductivity, thermal stability, dielectric property, rheological property, and electromagnetic shielding efficiency. The key finding of this work is that the conductive blend prepared through micelle-guided polymerization exhibited superior electrical conductivity (9.6 S/m) with low percolation threshold concentration (5 wt%), excellent thermal stability, electromagnetic interference (EMI) SE of 1–10 dB which makes it a promising candidate for EMI shielding and antistatic discharge matrix for the encapsulation of microelectronic devices.     

层层自组装原位聚合聚苯胺复合膜成膜机理研究

从苯胺单体出发, 通过原位聚合、现场掺杂以及基于静电力的层层自组装制备了聚苯胺复合膜. 通过苯胺活性溶液的温度及颜色变化跟踪聚合反应进程, 同时考察不同聚合反应阶段所得聚苯胺复合膜的紫外-可见吸收, 并进一步探讨聚苯胺复合膜的成膜机理. 研究表明, 成膜机制是由聚合反应初始阶段的苯胺阳离子或苯胺阳离子自由基通过静电作用快速吸附到负电性的基片表面, 形成均匀的聚合中心, 链增长生成聚苯胺; 该聚苯胺在酸性条件下经现场掺杂显电正性, 可吸附电负性的聚苯乙烯磺酸钠(PSS), 以此循环层层组装得到多层聚苯胺复合膜.     

Self‐assembled anionic micellar template for polypyrrole,polyaniline, and their random copolymer nanomaterials

We report an anionic surfactant approach for size and shape control in polyaniline, polypyrrole, and their polyaniline‐co‐polypyrrole random copolymer nanomaterials. A renewable resource azobenzenesulfonic acid anionic surfactant was developed for template‐assisted synthesis of these classes of nanomaterials. The surfactant exists as 4.3 nm micelle in water and self‐organizes with pyrrole to produce spherical aggregates. The sizes of the spherical aggregates were controlled by water dilution and subsequent oxidation of these templates, produced polypyrrole nanospheres of 0.5 μM to 50 nm dimensions. The anionic surfactant interacts differently with aniline and forms cylindrical aggregates, which exclusively produce nanofibers of ∼180 nm in diameter with length up to 3–5 μM. The template selectivity of surfactant toward aniline and pyrrole was used to tune the nanostructure of the aniline‐pyrrole random copolymers from nanofiber‐to‐nanorod‐to‐nanospheres. Dynamic light scattering technique and electron microscopes were used to study the mechanistic aspects of the template‐assisted polymerization. The four probe conductivity of the copolymers showed a nonlinear trend and the conductivity passes through minimum at 60–80% of pyrrole in the feed. The amphiphilic dopant effectively penetrates into the crystal lattices of the polymer chain and induces high solid state ordering in the homopolymer nanomaterials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 830–846, 2009     

Coating of multiwalled carbon nanotubes with polymer nanospheres through microemulsion polymerization

We report a simple and noncovalent method for coating multiwalled carbon nanotubes (MWCNTs) with polyaniline (PANI) nanospheres using a microemulsion polymerization method. In this method, aniline polymerization is performed with MWCNTs in the presence of sodium dodecyl sulfate (SDS), which serves as both a surfactant and a dopant. Morphological, structural, thermal, and electrical properties of MWCNT–PANI nanocomposites were analyzed. The TEM results of the nanocomposites prepared with surfactant reveal that 30–50-nm-diameter PANI nanospheres were coated on the surface of the MWCNTs. Composites prepared without surfactant were found to be in core–sheath-type cable structures. The conductivities of the nanocomposites synthesized through microemulsion polymerization were found to be one order of magnitude higher than both the conductivities of pure PANI and the composites prepared via in situ chemical polymerization without an assisting SDS surfactant. The mechanism for the formation of nanostructured composites is presented.     

On the origin of colloidal particles in the dispersion polymerization of aniline

When aniline is oxidized in an aqueous medium in the presence of a steric stabilizer, colloidal polyaniline (PANI) dispersions are obtained. The generally accepted model of the stabilization assumes that the macromolecules of the water-soluble steric stabilizer are adsorbed at the polymer, precipitating during the dispersion polymerization, and provide steric protection against further aggregation. An alternative mechanism of conducting-polymer particle formation is proposed in the present study. We suggest that the steric stabilizer provides a site for adsorption of oligoaniline initiation centers; subsequent polymerization from anchored centers yields particle nuclei that grow to produce colloidal PANI particles. This hypothesis is based on the observation that the colloidal particles are obtained only in the case where the steric stabilizer is introduced in the early stages of polymerization when aniline oligomers are present in the reaction mixture. If the stabilizer had been added during the growth of PANI chains, colloidal dispersions would not have been produced. The process of particle growth is completely analogous to the formation of conducting PANI films on the surface of microparticles and various materials. There, the polymerization of aniline at the surfaces is preferred to the same process proceeding in the bulk of the reaction mixture. While the films grow at the interfaces with the reaction mixture, the dispersion particles similarly emanate from the stabilizer chains. The particle size, the formation of nonspherical morphologies, the importance of the chemical nature of the stabilizer chains, and the general relation between the conducting-polymer film and particle growth are discussed in the light of the proposed model.