二茂铁基席夫碱及盐的合成与导电性能

中性条件下,以二茂铁甲醛和对苯二胺为原料,合成了二茂铁基席夫碱,考查了反应温度和时间对产率的影响,并测得其本征态室温电导率σ＝1.26×10-9 S·cm-1。利用Fe3+、Al3+、Ti3+盐对二茂铁基席夫碱进行了掺杂,探讨了掺杂量和掺杂温度对产物室温电导率的影响,研究了掺杂产物电导率与温度的变化关系,并用红外光谱、紫外光谱和电子探针对产物结构和组成进行了表征。结果表明：经金属盐掺杂后,电导率可提高4～5个数量级, 根据Arrhenius曲线得到了化合物的电活化能在0.09～1.54 eV范围内,表明了它们具有较好的半导体性能。     

两种二茂铁基席夫碱的合成及其抑菌活性

合成了两种标题化合物,产率分别为58.2%和81.3%;其结构通过元素分析、IR、1HNMR进行了表征;抑菌实验表明,两种席夫碱对大肠杆菌和金黄色葡萄球菌均有较好的抑菌活性.     

碘代二茂铁的合成

卤代二茂铁是一类重要的金属有机化学试荆,常用作二茂铁衍生物合成的中间体。其中碘代二茂铁方便易得,反应活性好,应用广泛。文献报道卤代二茂铁的合成方法可归纳为以下两类:1.通过汞化反应     

一种含二茂铁基水杨醛席夫碱的合成及性质表征

通过4-(2-二茂铁乙炔基)苯胺与水杨醛缩合反应得到一种新的含二茂铁基水杨醛席夫碱1,并研究了其对不同金属离子电化学及紫外-可见光谱的识别性质。结果表明,1对Cr3+有很好的紫外-可见光谱及电化学信号响应:其位于467nm的Fe(Ⅱ)→Cp的荷移光谱红移至502nm,同时Fe(Ⅲ)/Fe(Ⅱ)电位发生了～20mV的阳极移动。     

新型含二茂铁基席夫碱的合成与表征

以乙炔基二茂铁和对碘苯胺为原料,通过Sonogashira反应制得对二茂铁乙炔基苯胺,然后分别与苯甲醛和二茂铁甲醛进行缩合,合成了两种二茂铁基席夫碱,通过元素分析,1H NMR和13C NMR对产物进行了表征。对合成目标化合物的反应条件进行了筛选,确定了合成含二茂铁基席夫碱的最佳合成条件。     

双乙酰基二茂铁双缩二胺席夫碱的合成及结构表征

通过双乙酰基二茂铁与两种二胺化合物缩合合成了两种新型的含二茂铁席夫碱,并通过元素分析。红外光谱和核磁共振对其结构进行了确证。     

含双噻唑和二茂铁聚席夫碱及Fe2+配合物的合成和性能

合成了一种新型的含二茂铁和双噻唑结构的聚合席夫碱,采用红外光谱、核磁技术对产物进行了表征,研究了温度、时间和催化剂对产率的影响. 结果表明,在80℃下反应6 h生成的二茂铁席夫碱的产率达到87.2%;采用AlCl3为催化剂时聚合效果最好,聚二茂铁席夫碱的产率达到72.4%. 热重分析表明聚合物具有较好的热稳定性;常温下聚二茂铁夫碱配合亚铁金属离子后的电导率下降,但掺杂I2后的电导率可提高到2.14×10-3 S/cm,同时亚铁金属配合物的磁性测试发现其具有S形特征磁滞回线,磁饱和强度为0.612 emu/g,剩余磁场强度为0.0257 emu/g,矫顽力为130 Oe,表明聚合席夫碱的亚铁配合物是一种有机软铁磁体.     

两种含二苯膦基二茂铁酮亚胺席夫碱的合成与表征

以二茂铁、醋酸酐和苯甲酰氯为原料,经过傅克反应和酮胺缩合等反应,合成了标题化合物.讨论了催化剂、溶剂、反应时间和投料计量比对目标产物收率的影响.通过红外光谱、核磁共振氢谱与碳谱、质谱及元素分析对产物的结构进行了表征,并研究了其电化学性质.     

Spectroscopic studies on the effect of doping with iodine on metal chloride-treated poly(vinyl alcohol)

The ultraviolet and infrared spectra of films of PVA treated with Co(11), Ni(11), and Cu(11) and then doped with iodine were studied. The spectra of the films preheated in air at temperatures from 25 to 180°C for 2 h were investigated. The obtained data revealed that treatment of PVA with different concentrations of each of the mentioned metal salts causes profound spectral changes. The analysis of UV spectra showed that the intensity of the band at 280 nm decreases with increasing metal concentration. It was also found that doping with iodine results in an appearance of an additional peak at about 360 nm. Careful examination of the infrared spectra indicated that the crystallinity of the samples depends on the concentration of metals and is affected by temperature treatment.     

合成润滑油基础油茂金属聚-α烯烃合成研究进展

介绍了茂金属聚α-烯烃(mPAO)的性能和优点,重点评述了mPAO的合成催化剂和合成工艺的研究进展.讨论了以茂金属为催化剂,甲基铝氧烷(MAO)为助催化剂合成mPAO的工艺中尚存的问题,并认为降低MAO用量,研发出具有较高催化活性的茂金属催化剂和工艺是今后mPAO的研究向之一.     

Simultaneous synthesis and doping of poly(1,6-heptadiyne-co-dipropargyl ether) using ionic initiators

Cyclocopolymerization of 1,6-heptadiyne with dipropargyl ether was carried out under nitrogen atmosphere using KSCN, KBr and KI as initiators in N,N-dimethyl formamide. The course of polymerization was monitored through UV-Vis spectroscopy. The rate of cyclocopolymerization was determined at different polymerization conditions and the relative efficiency of different initiators was evaluated. KSCN was found to be particularly an effective initiator for the copolymerization. The resulting dark brown colour polymer exhibits good solubility in common organic solvents. ¹H-NMR, FTIR and UV-Vis spectra of poly(1,6-heptadiyne-co-dipropargyl ether) revealed that the copolymer possesses cyclic polyene units in the back bone. Doped nature of the polymer was evident from UV-Vis and FTIR spectroscopy. Thermal characteristics, conductivity and electroactivity of the copolymer were also explored.     

Electrochemical synthesis and corrosion performance of poly(pyrrole-co-o-anisidine)

The electrochemical synthesis of poly(o-anisidine) homopolymer and its copolymerization with pyrrole have been investigated on mild steel. The copolymer films have been synthesized from aqueous oxalic acid solutions containing different ratios of monomer concentrations: pyrrole:o-anisidine, 9:1, 8:2, 6:4, 1:1. The characterization of polymer films were achieved with FT-IR, UV–visible spectroscopy and cyclic voltammetry techniques. The electrochemical synthesis of homogeneous-stable poly(o-anisidine) film with desired thickness was very difficult on steel surface. Therefore its copolymer with pyrrole has been studied to obtain a polymer film, which could be synthesized easily and posses the good physical–chemical properties of anisidine. The kinetics and rate of copolymer film growth were strongly related to monomer feed ratio. The introduction of pyrrole unit into synthesis solution increased the rate of polymerization and the substrate surface became covered with polymer film soon, while this process required longer periods in single o-anisidine containing solution. The protective behavior of coatings has been investigated against steel corrosion in 3.5% NaCl solution. For this aim electrochemical impedance spectroscopy (EIS) and anodic polarization curves were utilized. The synthesized poly(o-anisidine) coating exhibited significant protection efficiency against mild steel corrosion. It was shown that 6:4 ratio of pyrrole and anisidine solution gave the most stable and corrosion protective copolymer coating.     

Kinetics of isomerization and doping of poly(t-butyl-acetylene)

Summary The kinetics of doping with I₂and isomerization of poly(t-butylacetylene) has been studied. A first-order reaction in polymer and iodine was observed during the doping process, as was found for unsubstituted polyacetylene. However, for the isomerization process, a reaction order of 0.5 in iodine and no simple order in poly(t-butylacetylene) were determined. These results can be explained using a free radical mechanism where the free radicals catalyze the isomerization. In contrast to unsubstituted polyacetylene, the isomerization and doping processes are not related; isomerization occurs first, within about 30 min, and it is followed by doping at much later times.     

Poly(ester)s and poly(amide)s with fluorene and diphenyl-silane units in the main chain: Effects of iodine doping on the structure and electrical conductivity

Intramolecular charge transfer interaction between the electron donor and electro acceptor units within the polymeric structure and its optoelectronic properties were studied. The monomer, 9H-fluorene-2,7-dicarboxylic acid, was prepared from 9H-fluorene-2,7-dicarbonitrile using CuCN/N,N-dimethylformamide followed by the decomposition of the complex with FeCl₃x6H₂O in HCl and KOH/H₂O. The formation of two new classes of polymers was reported at different reaction times. The poly(ester) (PEF) was synthesized by the reaction of the diacid monomer with bis(4-hydroxiphenyl)diphenylsilane using tosyl chloride/pyridine/dimethylformamide system as condensing agent. Alternatively, the poly(amide) (PAF) was synthesized by the direct polycondensation of the diacid monomer and bis(4-aminophenyl)diphenylsilane in N-methyl-2-pyrrolidine solution containing dissolved calcium chloride. The resulting new polymers were obtained in good yields and were characterized by FTIR, NMR (¹H, ¹³C, and ²⁹Si), ESI, Raman, UV (optical gap) and fluorescence spectroscopy. The thermal properties were characterized by DSC and TGA. The electrical conductivity of the polymers was measured before and after exposure to iodine vapor, utilizing films of different thickness. Ellipsometric studies were used for the determination of the film thickness. Morphological differentiation was carried out by SEM-EDX analysis. Oxidation of the polymer films of low thickness decreased their conductivities, mainly due to the small structural changes. For a polymeric sample with a higher thickness, the doping process slightly increased the conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrical conductivity of plasma-treated poly(p-phenylene sulfide) doped with iodine

Plasma treatment of poly(p-phenylene sulfide) (PPS) doped with I₂ is found to increase both the electrical conductivity and the stability of the material. The average conductivity of plasma-treated samples reaches an apparently saturated value of 1.7 × 10^?3s cm^?1, which is about six orders of magnitude higher than that of the same material without plasma treatment, and this conductivity remains practically unchanged under exposure to ambient environment for 10 days. Infrared and secondary ion mass spectra of the samples before and after plasma treatment suggest that the charge-transfer complexes are formed in PPS doped with I₂ after plasma treatment. This is also consistent with the temperature dependence of conductivity results which show that the activation energy for electrical conduction decreases from 2.0 eV for pure PPS to 0.2 eV for plasma-treated I₂-doped PPS. Using isothermal potential and current decay techniques, we have also measured the trap density distribution. Plasma treatment, on the one hand, does create more traps in PPS, but, on the other hand, it enhances conductivity. The mechanism of electrical conduction is briefly discussed.     

Electrochemical synthesis of poly(3,4-ethylenedioxythiophene) on stainless steel and its corrosion inhibition performance

Poly(3,4-ethylenedioxythiophene) (PEDOT) coatings have been electrochemically prepared on stainless steel (SS) in acetonitrile and aqueous media, respectively, by the cyclic voltammetry technique. The corrosion behavior of the coated SS was evaluated in 3.5 wt% NaCl solution using anodic polarization and electrochemical impedance spectroscopy, which demonstrate that the polymer coatings are able to mitigate the corrosion of the SS substrate in chloride solution. PEDOT works as the electron exchange medium to passivate the SS underneath and reduce the oxygen on the surface. By comparing the performances, it was clear that PEDOT electrodeposited from an aqueous solution can afford better corrosion inhibition capability.     

一种曼尼希碱的合成及缓蚀性能研究

根据炼油厂常减压塔顶冷凝系统存在的腐蚀原因和机理,研制出了以甲醛、苯乙酮、环己胺为原料合成的曼尼希碱为主剂的新型缓蚀剂。采用静态失重法,在模拟炼厂常减压装置中HCl-H2S-H2O型腐蚀的环境下进行缓蚀性能评价,结果表明：具有优良的缓蚀性能。当曼尼希碱的加入量为85μL／L时,向腐蚀介质溶液中加入曼尼希碱6h后,腐蚀环境温度在90℃左右时曼尼希碱展现出良好的缓蚀性能,缓蚀率达90％以上。说明合成的产物适用于炼厂低温腐蚀环境。     

Electrochemical properties of complexes of iodine with cyclized poly(acrylonitrile) and 2-poly(vinylpyridine)

Electrochemical and conductivity measurements have been performed on the iodine complexes of cyclized poly(acrylonitrile) and 2-poly(vinylpyridine). The thermodynamic activity of iodine as a function of iodine content was determined using cells of the type $\text{polymer(I}{}_2\text{)}{}_{\mathrm{x}}\text{¦}\text{AgI}\text{¦}\text{Ag}$. The results indicate that chemical bonding between iodine and polymer is relatively weak. The conductivity data show a strong dependence of conductivity on the iodine content of the complex.