苯乙烯和N-乙烯基吡咯烷酮共聚物/Ag复合微球的制备及性能研究

首先用无皂乳液聚合法制备了单分散聚苯乙烯(PSt)乳液,以此为种子乳液,使用N,N-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,进行苯乙烯和N-乙烯基吡咯烷酮(NVP)共聚合制备了以PSt为核、St和NVP共聚物为壳的具有核-壳结构的聚合物微球(P(St-NVP)).以此微球为模板通过化学沉积法得到了粒径分布均匀、单分散的P(St-NVP)/Ag复合微球.傅里叶红外光谱、X-射线衍射、扫描电镜、透射电镜、激光粒度仪和紫外-可见光谱对复合微球的结构、形貌、物相及催化性能进行了表征.结果表明,P(St-NVP)/Ag复合微球具有规则的球形结构,粒径在400～700 nm之间,随交联剂浓度或种子乳液浓度的增加,复合微球粒径减小.粒径在十几个纳米左右的银粒子均匀分布在微球表面和内部.载银复合微球在NaBH4还原4-硝基苯酚为4-氨基苯酚的模型反应中表现出较高的催化活性.     

共聚物酸掺杂接枝聚苯胺的研究

采用核壳乳液聚合方法合成了以甲基丙酸甲酯、甲基丙烯酸和丙烯酸丁酯三元共聚物酸为核,聚苯胺为壳的导电高分子复合物。复合物的电导率随着聚苯胺含量的增加而升高。用粒径分析仪、ＴＥＭ、ＦＴ－ＩＲ和ＤＳＣ对复合材料进行了表征。结果表明形成了核壳结构,由于共聚物酸起到了掺杂剂的作用,使制得的复合物能在环己酮、四氢呋喃等普通有机溶剂中有好的溶解性。     

导电聚苯胺/TiO_2微/纳米球的制备及其结构表征

采用具有八面体形貌的氧化亚铜为模板,制备了聚苯胺/TiO2(PANI/TiO2)微/纳米球,TiO2纳米粒子很均匀地分散在聚苯胺中.研究了不同TiO2/苯胺(TiO2/ANI)摩尔比对PANI/TiO2复合物的结构、形貌和电学性能的影响.实验结果表明,随着TiO2/ANI摩尔比的增加,PANI/TiO2复合物的直径逐渐减小,当TiO2/ANI摩尔比为0.16时,复合物的平均直径为373nm,而当TiO2/ANI摩尔比增加到1.6时,复合物的平均直径降到80nm.PANI/TiO2复合微/纳米球的电导率随着TiO2/ANI摩尔比的增加先升高后降低,当TiO2/ANI摩尔比达到1.6时,电导率由10-4S/cm提高到100S/cm,达到最大值.产物的形貌和结构分别采用扫描电镜、透射电镜、红外吸收光谱和X-射线衍射等手段进行了表征.     

具有核壳结构磁性复合微球的制备与表征

采用两步法制备了具有核壳结构的Fe3O4/P(MMA/DVB)(core)-P(St/GMA/DVB)(shell)磁性复合微球.首先,用改进的细乳液聚合制备了Fe3O4/P(MMA/DVB)微球;然后,加入总量不同的苯乙烯(St)、甲基丙烯酸缩水甘油酯(GMA)和二乙烯基苯(DVB),通过种子乳液聚合,制备了不同磁含量的核壳结构的磁性复合微球.分别用X-射线衍射(XRD)、高倍透射电镜(HR-TEM)、热重分析(TGA)、振动样品磁力计(VSM)等手段对磁性微球的性能进行了表征.实验结果表明,Fe3O4/P(MMA/DVB)微球的磁含量为84 wt%;通过改变加入壳层单体的量,核壳复合微球的磁含量可控在20 wt%~76 wt%之间.该微球具有超顺磁性,相应的饱和磁化强度为12~50Am2/kg.     

尺寸可控的聚苯胺复合微球的电纺制备与表征

以十二烷基苯磺酸(DBSA)掺杂的导电聚苯胺与聚乙二醇(PEG)及Fe3O4的混合氯仿溶液,采用静电纺丝(spinning technology)方法制备含Fe3O4纳米颗粒的导电聚苯胺(PANI)/PEG/Fe3O4复合微球.SEM结果表明,电纺所得的PANI/PEG/Fe3O4复合微球结构依赖于PEG聚合物浓度、静...     

多层核-壳结构P(AM-co-MAA)/W/UF复合微球制备研究

以反相悬浮聚合技术合成的丙烯酰胺(acrylamide,AM)和甲基丙烯酸(methacrylic acid,MAA)共聚高分子微凝胶P(AM-co-MAA)为模板,通过离心沉积法将微米级钨粉沉积于高分子微凝胶表面,得到具有核-壳结构的P(AM-co-MAA)/W复合微球材料;再以P(AM-co-MAA)/W复合微球为模板,通过控制甲醛和尿素的缩聚反应在模板与油/水相界面进行,制备得到了具有多层核-壳结构的高分子/钨/脲醛树脂[P(AM-co-MAA)/W/Urea-formaldehyde resin]复合微球材料.利用扫描电子显微镜(SEM)、红外(FT-IR)、X射线衍射(XRD)和热分析(TGA)等手段对复合微球进行了表征.实验结果表明,外壳层脲醛树脂的包覆量、复合微球的表面形貌可通过改变甲醛和尿素溶液的浓度、甲醛和尿素的物质的量之比等因素进行控制.复合微球的导电性测试结果表明,P(AM-co-MAA)/W复合微球表面壳层脲醛树脂包覆前后,其电导率由1.9×10-3降低为0.9×10-8S·m-1.该研究获得的三层核-壳复合微球材料其外层脲醛树脂的包覆较为完整、致密,其导电性接近于绝缘材料,为含钨复合微球作为电子元件的抗辐射涂层材料打下了基础.     

聚苯乙烯微球表面接枝丙烯腈的研究

采用分散聚合法制备出平均粒径为3.85 μm的窄分布聚苯乙烯微球， 并在此基础上引入第二单体丙烯腈进行共聚反应， 制备出平均粒径为4.02 μm的窄分布苯乙烯-丙烯腈共聚物微球. 对聚苯乙烯微球和苯乙烯-丙烯腈共聚物微球进行了形貌及粒径、红外光谱、差示扫描量热法(DSC)分析， 结果表明丙烯腈基团均匀分布在聚苯乙烯微球表面， 提高了聚苯乙烯微球表面的极性.     

温敏性P(St-NIPAM)/PNIPAM-Ag复合微凝胶制备及性能研究

通过无皂乳液聚合和种子乳液聚合两步法合成苯乙烯与N-异丙基丙烯酰胺共聚物/聚N-异丙基丙烯酰胺[P(St-NIPAM)/PNIPAM]核-壳结构复合微凝胶, 再以其为模板在硝酸银水溶液中充分溶胀, 并以乙醇为还原剂, 在NH₃气氛条件下还原, 制备得到高分子微凝胶负载纳米银P(St-NIPAM)/PNIPAM-Ag的复合微凝胶材料. 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)、热分析(TGA)、紫外-可见分光光度计(UV-vis)、激光粒度分析等手段对复合微凝胶进行结构、组成和性质表征. 研究结果表明, 复合纳米银后的P(St-NIPAM)/PNIPAM-Ag复合微凝胶仍具有温敏性, 且其温度敏感性随壳层中复合纳米银含量的增加而减弱. P(St-NIPAM)/PNIPAM-Ag复合微凝胶对对硝基苯酚的还原反应具有良好的催化活性, 在45 min内基本将对硝基苯酚催化还原为对氨基苯酚.     

无规-类接枝共聚物自组装制备交联纳米微球

无规-类接枝共聚物(SFG)由大分子单体-己内酯改性丙烯酸酯(FA)、亲油性单体苯乙烯和甲基丙烯酸缩水甘油酯(GMA)共聚所得，SFG与聚苯乙烯在甲醇溶液中进行自组装，形成核壳结构纳米胶束，进一步对PGMA壳进行化学交联。最终得到具有核壳结构的纳米微球。动态激光光散射和透射电子显微镜表征结果显示SFG自组装形成了窄分布的纳米微球，微球粒径在100～200nm之间。     

分散共聚法制备特殊形态高分子微球的研究

以聚乙二醇 (PEG)大分子单体为反应性稳定剂 ,在丙烯腈的分散共聚反应中添加少量苯乙烯以形成疏水性核 ,制备得到了亚微米级高分子微球 .透射电子显微镜研究表明 ,该高分子微球具有特异的形态结构 .同时研究了分散共聚体系中各种反应因素对微球形态和直径的影响 ,结果表明 ,苯乙烯单体的添加量、PEG大分子单体的浓度及分子量、混合溶剂的组成对微球直径和形态均有明显的影响 .X 射线光电子能谱 (XPS)研究结果表明 ,微球表面聚集有亲水性PEG链 ,核为疏水的聚 (丙烯腈 苯乙烯 ) ,即形成的特异形态的PEG接枝高分子微球亦为复合型结构     

The synthesis of Ag-polypyrrole nanocomposite coated latex particles and their application as a fluorescent quenching agent

 Submicron-sized Ag-polypyrrole/poly(styrene-co-methacrylic acid) (Ag-PPy/P(St-co-MAA)) composite particles were fabricated via a redox reaction between pyrrole and AgNO₃ in the presence of P(St-co-MAA) soap-free latex. The products are characterized by transmission electron microscopy (TEM), electron diffraction spectra (EDS), Raman spectra, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The results showed that Ag-PPy nanocomposites were in situ deposited onto the surface of P(St-co-MAA) latex particles tailored by carboxylic-acid groups. The nanocomposites of Ag-PPy distributed on the surface of polymer particles transformed from discretely dots to continuously coating as the reaction temperature increased from 15℃ to 60℃. Strawberry-like composite particles were obtained at the reaction temperature of 60℃. The TGA characterization confirmed that the Ag-PPy nanocomposites loading onto the P(St-co-MAA) particles were systematically controlled over a range of 6 wt%-42 wt% by changing the reaction temperatures. The fluorescence quenching effect of the Ag-PPy/P(St-co-MAA) composite particles was explored on Rhodamine B as a model molecule with the Stern-Völmer quenching constant K_SV of 5.9×10⁴ (g/mL)^-1. It is suggested that the fluorescence quenching effect is caused by the resonance energy transfer mechanism.     

Study of a nanocomposite based on a conducting polymer: polyaniline

A simple way to obtain a conducting nanocomposite is described, and the conducting particles are characterized. Core-shell particles [polystyrene-polyaniline (PANI)] have been obtained by the dispersion process from three types of polystyrene latexes: a no-cross-linked core stabilized by a nonylphenolethoxylate (NP40) and two cross-linked cores stabilized by NP40 and a mixture NP40/Surfamid (a surfactant bearing an amide group). The surface of these particles has been extensively characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and scanning electron microscopy. A maximum coverage of 94% was obtained for the high PANI content as revealed by XPS analysis. A better coverage was obtained for the cross-linked polystyrene latex stabilized by the Surfamid. The amide group of this surfactant allows the H-bonding formation with the PANI backbone and, thus, improves the conductivity. It was shown that a uniform coverage of the core particles was not required to ensure a good conductivity.     

聚苯胺钡铁氧体纳米复合材料的制备、表征及性能

采用原位掺杂聚合法, 将聚苯胺(PANI)对粒径在60~80 nm的M型钡铁氧体颗粒(BaFe12O19)进行了包覆, 得到了具有棒状结构的复合材料. 通过X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等测试手段对材料的形貌和结构进行了表征. 结果表明, PANI链段与BaFe12O19颗粒之间存在作用力. 使用振动磁强计和四探针法测定了复合材料的磁性能与电性能后发现, 饱和磁化强度与矫顽力均随聚苯胺含量的增加呈规律性下降趋势, 而电导率呈上升趋势. 复合材料的吸收特性测试结果表明, 该材料反射率小于-20 dB时, 带宽可以达到15.07 GHz. 同时详细地讨论了纳米复合材料的聚合机理及相互作用.     

Preparation and characterization of conducting polyaniline layered magnetic nano composite polymer particles

Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe₃O₄ core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe₃O₄ core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM) composite seed particles to obtain Fe₃O₄/PMMA/PANI and Fe₃O₄/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe₃O₄ core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and characterization of biotinylated and enzyme‐immobilized heterobifunctional latex particles as nanobio devices

A novel biotinylated and enzyme‐immobilized nanobio device was prepared with heterobifunctional composite latex particles. Hemispherical poly(glycidyl methacrylate‐co‐divinylbenzene)/polystyrene [P(GMA‐DVB)/PSt] particles with epoxy and hydroxyl groups were prepared by soap‐free seeded emulsion polymerization with P(GMA‐DVB) seed particles. Hydroxyl groups were introduced to PSt chain terminals in the seeded stage by adding 2‐mercaptoethanol as a chain‐transfer agent. To obtain the desired hemispherical structure particles, we studied the effects of the preswelling process, the type and amount of solvents added in the seeded polymerization step, the weight ratio of the secondary monomer (styrene) to the seed particle (M/P), and the type of initiators. Under suitable conditions, heterobifunctional P(GMA‐DVB)/PSt was obtained, which was confirmed by observing the binding of streptavidin–colloidal gold with transmission electron microscopy (TEM). To obtain biotinylated and enzyme‐immobilized particles, 5‐(N‐succinimidyloxycarbonyl)pentyl D‐biotinamide was first reacted with the hydroxyl group on the PSt domain of the particle. Pyruvate kinase (PK) was then directly immobilized to the biotinylated particles through a reaction with the epoxy group in the PGMA domain. The monolayer of PK on the latex particle surface was considered to be formed by covalent binding. The activity of immobilized PK was almost conserved, even after being stored at 4 °C for 48 days. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 562–574, 2005     

超疏水聚苯胺/聚四氟乙烯复合膜的制备及油-水乳液分离性能

以苯胺为原料, 采用原位聚合法在聚四氟乙烯(PTFE)基体上合成聚苯胺/聚四氟乙烯(PANI/PTFE)复合膜. 利用光学显微镜、 扫描电子显微镜(SEM)、 傅里叶变换红外光谱(FTIR)、 紫外-可见吸收光谱(UV-Vis)和静态水接触角测试对PANI/PTFE复合膜的形貌、 结构和浸润性进行分析, 并对其油包水乳液分离性能、 通量和循环使用性能进行了测试. 研究结果表明, PANI/PTFE复合膜仅在重力条件就能有效分离油包水乳液; 而且重复数十次过滤后, PANI/PTFE复合膜仍具有良好的抗污能力和分离性能.     

The Electrochemical Properties of Nanocomposite Films Obtained by Chemical In Situ Polymerization of Aniline and Carbon Nanostructures

Interactions between the π bonds in the aromatic rings of polyaniline (PANI) with carbon nanostructures (CNs) facilitate charge transfer between the two components. Different types of phenyleneamine‐terminated CNs, including carbon nano‐onions (CNOs) and single‐walled and multi‐walled carbon nanotubes (SWNTs and MWNTs, respectively), were prepared as templates, and the CN/PANI nanocomposites were easily prepared with uniform core–shell structures. By varying the ratio of the aniline monomers relative to the CNs in the in situ chemical polymerization process, the thickness of the PANI layers was effectively controlled. The morphological and electrical properties of the nanocomposite were determined and compared. The thickness and structure of the PANI films on the CNs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and infrared spectroscopy. TEM and SEM revealed that the composite films consisted of nanoporous networks of CNs coated with polymeric aniline. The electrochemical properties of the composites were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. These studies showed that the CN/PANI composite films had lower resistance than pure polymeric films of PANI, and the presence of CNs much improved the mechanical stability. The specific electrochemical capacitance of the CNO/PANI composite films was significantly larger than for pure PANI.     

Well-dispersed multi-walled carbon nanotube/polyaniline composite films

Multi-walled carbon nanotube (MWNT)/polyaniline (PANI) composite films with good uniformity and dispersion were prepared by electrochemical polymerization of aniline containing well-dispersed MWNTs. The results of transmission electron microscopy (TEM) show that aniline can be used to solve MWNTs via formation of donor–acceptor complexes. Scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) revealed that the well arrangement of PANI-coated MWNTs in these films facilitated improved electron and ion transfer relative to pure PANI films and this may be due to the strong interaction between MWNTs and PANI.     

碳纳米管/聚苯胺/石墨烯复合纳米碳纸及其电化学电容行为

通过真空抽滤的方法制备碳纳米管纸,并对其进行循环伏安电化学氧化处理.以该电化学氧化处理的碳纳米管(CV-CNT)纸为基体,采用电化学聚合沉积聚苯胺(PANI),随后吸附石墨烯(GR),制备具有三明治夹心结构的碳纳米管/聚苯胺/石墨烯(CV-CNT/PANI/GR)复合纳米碳纸.该结构外层为GR,内层由PANI包裹的CNT形成网络骨架,充分发挥三者各自优势构建柔性电极材料.用场发射扫描电镜(FE-SEM)、透射电子显微镜(TEM)、拉曼光谱对其形貌与结构进行表征,并测试其电化学性能.研究发现:PANI呈纳米晶须状,并均匀包裹在CV-CNT表面;该复合碳纸具有良好的电容特性、大电流充放电特性以及良好的循环稳定性能.电流密度为0.5A·g-1时,比电容可达415F·g-1;20A·g-1时仍能保持106F·g-1的比电容.由于GR的保护作用,1000次循环之后较CV-CNT/PANI保持更高的有效比电容.该CV-CNT/PANI/GR复合碳纸展现出在高性能超级电容器柔性电极材料的潜在应用价值.