界面聚合法合成聚邻苯二胺及其表征

邻苯二胺电聚合膜己广泛用于生物活性物质固定、电催化、腐蚀防护和电色材料研究,近期也用于制备分子印迹型化学/生物传感器[1,2]。人们已经研究了聚邻苯二胺的结构特性、性能及应用前景[3,4,5]。目前聚合物基纳米复合材料的制备方法主要有:分子自组装法、微乳液聚合法、电化学     

界面聚合法合成聚吡咯甲烷微球及其影响因素研究

采用吡咯和对二甲氨基苯甲醛通过酸催化静态界面聚合的方法得到了聚[吡咯-2,5-二(对二甲氨基苯甲烷)]微球。通过扫描电镜分析．研究了酸催化剂种类、浓度和反应温度对成球的影响。红外光谱分析表明得到的聚合物具有类似开环卟啉的结构。     

界面聚合自组装合成三维多孔网络状聚邻甲基苯胺

采用界面聚合法在植酸的辅助作用下自组装合成具有连续三维多孔网络结构的聚邻甲基苯胺(POT)。采用扫描电镜(SEM)、氮气吸附和接触角测定的手段,研究了POT的微观结构、比表面积和亲水性。结果表明:当植酸浓度为0.3mol/L,聚合温度为10℃时,POT呈现三维多孔网络状形貌,开孔尺寸为0.2~1μm,且网络上附着粒径不足200nm的聚合物颗粒。该POT具有相对较高的电导率(7.52×10-3 S/cm)和比表面积(37.5 m2/g)以及较好的亲水性(接触角为34°)。在聚合过程中,多官能团的植酸既是掺杂剂又是交联剂,其与聚合物链的相互作用是该自组装行为的驱动力。     

空心聚合物纳米球研究进展

本文介绍空心聚合物纳米球的发展现状,着重阐述空心聚合物纳米球的化学制备方法,对各种制备方法进行了比较,并介绍了空心聚合物纳米球的表征、性能检测技术以及应用现状和前景。     

纳米粒子的界面自组装

近年来,随着纳米技术的发展及Pickering乳液在食品、化妆品、医药等领域中的应用,纳米粒子的界面自组装现象引起了人们的广泛关注。界面能的降低是纳米粒子液液界面自组装的主要驱动力。通过改变纳米粒子的尺寸和表面配体的化学性质,可控制纳米粒子的界面自组装行为。本文综述了不同类型纳米粒子实现界面自组装的研究工作,包括均质纳米粒子、Janus纳米粒子、棒状纳米粒子以及生物纳米粒子。最后,对纳米粒子的界面组装这一领域的可能发展做了展望。     

聚吡咯纳米颗粒的静态法合成及表征

在无模板、无表面活性剂条件下,采用静态化学氧化聚合法合成了高聚合产率(93%)聚吡咯纳米颗粒.以红外光谱、广角X射线衍射、四探针仪、扫描电子电镜和透射电子显微镜对聚吡咯的结构、电性能和形貌进行了表征.并研究了搅拌条件、氧化剂种类、过硫酸铵/吡咯摩尔比、聚合反应温度和反应介质对聚吡咯纳米颗粒的粒径、形貌的影响.结果发现,聚吡咯纳米颗粒的尺寸随聚合反应条件的变化而改变.在静态条件下,以过硫酸铵为氧化剂、过硫酸铵/吡咯摩尔比为0.25,于0℃冰水浴中有利于获得聚吡咯纳米颗粒.透射电子显微镜的结果表明以过硫酸铵/吡咯摩尔比为0.25,于0℃下1.0mol/LHCl水溶液介质中可以聚合得到直径为43nm、颗粒大小均匀的球形聚吡咯纳米颗粒.盐酸掺杂聚吡咯纳米颗粒的室温电导率可达5.5S/cm.     

溶剂热法合成ZnSe纳米球

以乙酸锌和Se粉为原料,环己酮为溶剂,于180 ℃反应24 h制得黄色纳米球ZnSe,其结构和性能经XRD,SEM及TEM表征.     

表面功能化聚苯乙烯纳米微球的制备及自组装

用乳液聚合的方法合成了表面富含羧基的聚苯乙烯纳米微球，采用热分析、红外、透射电镜和X射线粉末衍射仪等对其进行了结构和性能表征;并用自组装的方法将其在玻璃表面组装成膜.考察了制备条件，通过对自组装薄膜原子力显微镜形貌图的分析，确立了最佳组装方案.     

纳米团簇-牛血清白蛋白复合物界面自组装

当表面电荷密度降低时, 纳米粒子-蛋白质复合物可在水包油(O/W)乳液界面自组装. 相对于纳米粒子, 粒度较小的纳米团簇(约2 nm)与蛋白质之间有更强的亲和力, 因此纳米团簇-蛋白质复合物可表现出不同的自组装特性. 为深入了解该特性, 对纳米团簇-牛血清白蛋白(BSA)在乳液界面自组装进行研究, 用Huckel方程计算自组装所需电荷密度范围, 用光学和电子显微镜研究纳米团簇与BSA的交联. 结果表明, 纳米团簇-BSA在乳液界面的自组装驱动力同样为表面电荷密度降低, 但纳米团簇与BSA的交联可造成无序自组装, 要实现有序自组装, 除需降低表面电荷密度外, 还需控制纳米团簇与BSA的结合率.     

界面聚合法合成手性掺杂剂诱导螺旋形聚苯胺纳米纤维

以手性试剂D-樟脑磺酸(D-CSA)和L-樟脑磺酸(L-CSA)为掺杂剂和构象诱导剂,采用界面聚合法合成了螺旋形聚苯胺纳米纤维。通过FESEM、TEM、FTIR和UV-Vis吸收光谱等测试技术对螺旋形聚苯胺纳米纤维结构进行了表征。结果表明,所得聚苯胺纤维具有螺旋形构象,形貌均一,平均直径约为50nm,长度为300～600nm,具有较高的长径比(6:1～12:1)。在水溶液中,聚苯胺纳米纤维以伸展的螺旋形分子链构象存在,调节溶液的pH值,螺旋形聚苯胺纳米纤维表现出可逆的掺杂和脱掺杂性质。循环伏安(CV)测试表明,螺旋形聚苯胺纳米纤维在0.5mol/LHCl溶液中表现出良好的电化学活性。     

Preparation of Thick PZT Ceramic Film by an Interfacial Polymerization

The formation of a PZT film of 10–20 m in thickness via an interfacial polymerization of metal-organic precursors has been studied. A commercially available PZT precursor solution developed for dip- or spin-coating was diluted with hexane containing acetylacetone as chelating agent. The solution was poured on water contained in a teflon reaction container of 88 mm inside diameter. A translucent gel film was formed at the interface of the two immiscible liquids. While floating on water it shrank as the evaporation of solvent proceeded until its diameter decreased to about 45% of its initial value. The dried gel film was almost pore free and its thickness was estimated to be about 10 m.     

Preparation of Composite Charge-mosaic Hollow Fiber Membrane by Interfacial Polymerization

The preparation of composite charge-mosaic membrane included spinning of hollow fiber as the supporting membrane, preparing a selective layer on the inside surface of the fiber by interracial polymerization. The charge-mosaic membranes show a high salt permeability while retaining sucrose. The charge-mosaic membrane can be effectively used to separate multivalent salts with organic matter of molecular weight great than 300g/mol in industry.     

中空SiO_2纳米微球的制备与表征

在乙醇/氨水介质中,将SiO2包覆在聚乙烯吡咯烷酮(PVP)功能化的聚苯乙烯(PS)微粒表面,利用一步法得到了中空纳米二氧化硅微球;研究了影响中空纳米二氧化硅微球形成的主要因素,并探讨了中空纳米SiO2微球的可能形成机理.结果表明,在一定的反应时间下,当氨水用量为0.6 mL、温度为70℃时,可以获得空心结构的SiO2纳米微球;通过控制四乙基原硅酸盐(TEOS)的量可以调节微球的包覆层厚度.     

界面聚合法制备复合膜

本文对近年来国内外利用界面聚合法制备超薄复合膜的研究进行了综述。阐述了界面聚合成膜反应的原理,并从反应单体种类的角度进行分类,对目前由界面聚合法制备复合膜的研究现状进行了较详细的介绍和分析;对界面聚合法制备复合膜存在的问题以及研究前景进行了展望。     

Thick Silicate Film by an Interfacial Polymerization

A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO₃ or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic acids, can diffuse in.     

界面聚合及其应用进展

综述了界面聚合的发展过程及其在膜、微胶囊、纳米材料、聚酯等制备方面的应用进展.     

聚甲基丙烯酸甲酯-氯化银复合纳米微球的制备及其摩擦学性能

采用原位种子乳液聚合法合成了聚甲基丙烯酸甲酯 氯化银(PMMA AgCl)核壳结构复合纳米微球,通过透射电镜(TEM),红外光谱(IR),热分析(TG DTA)和X射线粉末衍射(XRD)等测试手段对其结构及性能进行了表征.在四球试验机上对其摩擦学行为进行了考察,研究结果表明,PMMA AgCl核壳结构复合纳米微球用作润滑油添加剂具有良好的抗磨性能,能显著提高基础油的失效负荷.     

Interfacial Mass Transfer in Nitroxide‐Mediated Miniemulsion Polymerization

A mathematical model has been developed to describe the interfacial mass transfer of TEMPO in a nitroxide‐mediated miniemulsion polymerization (NMMP) system in the absence of chemical reactions. The model is used to examine how the diffusivity of TEMPO in the aqueous and organic droplet phases, the average droplet diameter and the nitroxide partition coefficient influences the time required for the nitroxide to reach phase equilibrium under non‐steady state conditions. Our model predicts that phase equilibrium is achieved quickly (< 1 × 10⁻⁴ s) in NMMP systems under typical polymerization conditions and even at high monomer conversions when there is significant resistance to molecular diffusion. The characteristic time for reversible radical deactivation by TEMPO was found to be more than ten times greater than the predicted equilibration times, indicating that phase equilibrium will be achieved before TEMPO has an opportunity to react with active polymer radicals. However, significantly longer equilibration times are predicted, when average droplet diameters are as large as those typically found in emulsion and suspension polymerization systems, indicating that the aqueous and organic phase concentrations of nitroxide may not always be at phase equilibrium during polymerization in these systems.

Influence of droplet phase TEMPO diffusivity, D_TEMPO,drop, on the predicted organic phase concentration of TEMPO.     

界面聚合法制备复合膜中的改性研究

介绍了复合膜的结构及性能,阐述了界面聚合法的基本原理及用该法制备复合膜的优越性;同时重点综述了国内外对复合膜的性能如通量和截留率、耐氯性、热稳定性、耐溶剂性和抗污染性的研究现状及改进方法,并对界面聚合法制备复合膜存在的问题以及研究前景进行了展望。     

Preparation of PZT Thick Films by an Interfacial Polymerization Method

Pb(Zr_0.53Ti_0.47)O₃ (PZT) films of 10 to 50 m in thickness were prepared by a new sol-gel process using an interfacial polymerization technique. The interfacial polymerization process is that an alkoxide precursor solution is poured on the surface of water in a container to form a gel film at the interface between the two immiscible liquids. The precursor solution was prepared by adding PZT alkoxide solution, PZT powders coated with Pb₅Ge₃O₁₁ (PG), and a surfactant into hexane solvent. After the polymerization at the interface, the gel films were gently placed on a silicon substrate by draining the water in the container. The gel films containing PZT powders were sintered at 950°C for 10 min to obtain crystallized PZT films. The remanent polarization of a PZT thick film was 33.1 C/cm². The piezoelectric d ₃₃ constant measured with a Mach-Zehnder interferometer was 225 pm/V and was independent of frequency from 0.2 to 3 kHz.