聚(苯胺-邻六氟羟基苯胺)共聚物的合成及其性能表征

采用过硫酸铵作为引发剂,通过化学氧化聚合法制备了一系列可溶性的聚(苯胺-邻六氟羟基苯胺)(PAH)的共聚物。利用傅里叶红外光谱(FTIR)、核磁共振氟谱(19F-NMR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、紫外光谱(UV)和场发射扫描电子显微镜(FESEM)等对共聚物的化学结构和形貌等进行了表征和分析。结果表明,邻六氟羟基苯胺(HAFIP)成功导入了共聚物主链中,共聚物的数均分子量Mn介于6.51×10~4与9.04×10~4之间。HAFIP的存在抑制了共聚物的醌式结构n→π*跃迁,随着共聚物中邻六氟羟基苯胺(HAFIP)摩尔分数的增大,共聚物形貌逐渐由纳米纤维向纳米颗粒变换。与聚苯胺难于溶解于一般有机溶剂不同的是,当邻六氟羟基苯胺(HAFIP)的摩尔分数超过0.5时,共聚物可以完全溶解于四氢呋喃、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺等有机溶剂中,表明HAFIP的导入,可以大幅改善聚苯胺的溶解性能,从而扩展聚苯胺的应用范围。     

聚邻乙氧基苯胺(POEA)的研究进展

为了提高聚苯胺(PANI)的溶解性和导电性,近年来聚邻乙氧基苯胺(POEA)的合成受到越来越多的关注。POEA可由电化学方法或化学氧化法合成。本文综述了POEA的合成技术,材料表征技术、导电机理和POEA材料在导电导磁薄膜、防腐材料等领域的应用研究进展。     

聚邻甲氧基苯胺薄膜对pH的光学响应

在盐酸介质中,应用循环伏安法通过电聚合在氧化铟锡(ITO)透明导电玻璃上形成聚邻甲氧基苯胺薄膜.用紫外可见光谱方法测定了聚合物薄膜在不同pH下的特征吸收光谱,聚邻甲氧基苯胺薄膜的λmax在557～746nm之间,作出了相应的滴定曲线.结果表明,在pH为1～12范围内聚合物薄膜对pH的变化表现了极高的光学敏感性,其表观pKa约为6.4.应用聚邻甲氧基苯胺薄膜测定了不同pH的溶液,其测定结果与精密酸度计相比误差＜±4%.     

聚邻乙氧基苯胺的导电及溶致变色性研究

研究了一种聚苯胺衍生物聚邻乙氧基苯胺(POEA),以探讨取代基对聚苯胺聚合、掺杂、溶解的影响.通过化学氧化合成及重掺杂手段,制备了盐酸(HCl)、磺基水杨酸(SSA)、樟脑磺酸(CSA)、对甲苯磺酸(PTSA)等掺杂的聚邻乙氧基苯胺.以GPC、紫外、红外、XRD、四探针等测试手段,对不同掺杂态、脱掺杂态POEA进行了对比分析,同时考察了POEA在不同溶剂下的溶致变色行为.研究表明:脱掺杂态POEA数均分子量为62 834,掺杂后电导率达10-5～10-3S/cm,在常用有机溶剂中有良好的溶解性.随不同的氧化、掺杂程度,POEA溶液呈现红-蓝-绿-黄色的渐变历程,其极化子跃迁峰在494～880 nm移动.     

界面聚合法合成苯胺与邻甲氧基苯胺的樟脑磺酸掺杂共聚物及其表征

采用界面聚合法在樟脑磺酸存在的状态下合成了聚苯胺、聚邻甲氧基苯胺以及苯胺与邻甲氧基苯胺的共聚物.利用红外光谱,紫外可见吸收光谱,电子扫描微电镜,X-射线粉末衍射,循环伏安,电导率测试等手段对聚合物进行了表征,初步探讨了单体配比对共聚物形貌、结构及性能的影响.结果表明,界面聚合法合成的上述各聚合物均呈现微米级颗粒状分布,颗粒直径大多在100nm以内;共聚后聚合物的结晶性能下降;循环伏安及电导率测试结果表明,随着聚合物主链中邻甲氧基苯胺结构单元的增加,聚合物的电化学活性及电导率呈下降趋势.     

2,4,6-三溴苯胺阻燃聚甲基丙烯酰亚胺泡沫的制备及性能

通过自由基共聚合和热空气自由发泡两步法,制备阻燃聚甲基丙烯酰亚胺(PMI)泡沫,其中功能单体为甲基丙烯酸(MAA)和丙烯腈(AN)、阻燃剂为2,4,6-三溴苯胺(TBA)、引发剂为偶氮二异丁腈(AIBN)、发泡剂为甲酰胺(FA)。通过泡沫垂直燃烧和极限氧指数(LOI)研究了PMI泡沫的阻燃性能,通过锥形量热仪研究了PMI泡沫的燃烧行为,通过热重分析研究了PMI泡沫的热降解性能,通过扫描电镜对PMI泡沫的形貌进行表征,同时对阻燃PMI泡沫的拉伸、弯曲和压缩强度进行测试。结果表明,当添加8 phr TBA时,PMI50/8TBA泡沫燃烧的火焰高度明显降低,LOI高达26.3%;同时,峰值热释放速率和总热释放量相对于PMI50分别下降了25.5%,41.6%。TBA的加入,使得阻燃PMI泡沫泡孔壁变薄,从而降低了材料力学强度。     

纳米CdS/聚(苯胺-邻氨基苯甲酸)复合薄膜的荧光性能研究

以聚(苯胺-邻氨基苯甲酸)(PAOAA)为基体,采用原位生成法制备的纳米CdS/PAOAA复合薄膜中,纳米CdS粒子大小均匀,粒径分布窄.对其荧光分析表明,纳米CdS/PAOAA复合薄膜的发光由CdS纳米粒子和PAOAA共同作用产生,在430nm和520nm附近出现了两大发光峰;硫化时间为5h的薄膜表现出的CdS的荧光特征峰与硫化3h的相比,有所增强,而PAOAA的荧光特征峰减弱.     

纳米CdS／聚（苯胺-邻氨基苯甲酸）复合薄膜的制备及表征

以苯胺和邻氨基苯甲酸为单体共聚而成的聚（苯胺-邻氨基苯甲酸）（PAOAA）为基体，制备了纳米CdS／PAOAA复合薄膜。纳米CdS粒子大小均匀，粒径分布窄，较稳定地存在于基体中，且随着硫化时间的延长粒径尺寸有所增加。荧光光谱表明纳米CdS／PAOAA复合薄膜的发光由CdS纳米粒子和PAOAA共同作用产生，在430nm和520nm附近出现了两大发光峰；CdS粒径的增加导致电子-空穴对在CdS内复合增大，表现为纳米CdS的荧光特征峰增强而PAOAA的荧光特征峰减弱。     

聚邻二苄基二硫化物的合成及其性能研究

以邻二氯苄为原料,合成了新型贮能物质邻二苄基二硫化物(DBD)及其聚合物(PDBD),利用元素分析、氢谱、质谱和红外光谱来表征其组成和结构.经循环伏安法研究表明,DBD的氧化还原峰峰电位分别为-0.65V和-1.9V,相距1.3V;而PDBD的分别为0.24V和-0.14V,相距0.38V,接近DBD的1/3,表明聚苯主链对硫硫键的断键和键合过程具有电催化作用；同时,经热重分析表明聚合物的硫硫键在140℃以下是稳定的,能满足其在锂电池中的应用要求.因此,PDBD在锂电池正极材料方面具有一定的应用价值.     

聚吡咯的合成及电流变性能的研究

以有机半导体聚吡咯为分散相 ,制备了均相电流变流体 (ER流体 ) ,测试了它在电场下表观粘度、剪切应力等流变学性质的变化。结果表明 ,以 1 溴萘为分散介质的电流变流体在 3kV mm的电场中 ,剪切速率为 12s- 1 时 ,剪切应力达到最大值 10 0 0Pa。剪切应力和表观粘度随温度升高而下降 ,在 5 0℃时 ,最高剪切应力只有 36 0Pa ,而在常温同等条件下 ,剪切应力有 70 0Pa     

Effects of mesoscopic poly(3,4-ethylenedioxythiophene) films as counter electrodes for dye-sensitized solar cells

Counter electrode coated with chemically polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) in a dye-sensitized solar cell (DSSC) was studied. The surface morphology and the nature of I⁻/I₃⁻ redox reaction based on PEDOT film were investigated using Atomic Force Microscopy and Cyclic Voltammetry, respectively. The performance of the DSSCs containing the PEDOT coated electrode was compared with sputtered-Pt electrode. We found that the root mean square roughness decreases and conductivity increases as the molar ratio of imidazole (Im)/EDOT in the PEDOT film increases. The DSSC containing the PEDOT coated on fluorine doped tin oxide glass with Im/EDOT molar ratio of 2.0, showed a conversion efficiency of 7.44% compared to that with sputtered-Pt electrode (7.77%). The high photocurrents were attributed to the large effective surface area of the electrode material resulting in good catalytic properties for I₃⁻ reduction. Therefore, the incorporation of a multi-walled carbon nanotube (MWCNT) in the PEDOT film, coated on various substrates was also investigated. The DSSC containing the PEDOT films with 0.6 wt.% of MWCNT on stainless steel as counter electrode had the best cell performance of 8.08% with short-circuit current density, open-circuit voltage and fill factor of 17.00 mA cm⁻², 720 mV and 0.66, respectively.     

Film formation properties of inkjet printed poly(phenylene-ethynylene)-poly(phenylene-vinylene)s

Inkjet printing was used here as a precise and fast dispensing technique to prepare thin-film libraries of a poly-(phenylene-ethynylene)-poly(phenylene-vinylene)s copolymer. The films were prepared with a systematic variation of the ink composition, the dot spacing and the substrate temperature. Homogeneous films with a thickness of 100 nm were obtained when printed at room temperature and from a solvent mixture of toluene and ortho-dichlorobenzene in a volume ratio of 90/10. This approach can be used for optoelectronic applications, where the layer homogeneity is extremely important but where the ink compositions may vary per device, as well as the exact layer thickness. Our approach can be applied for the preparation of films by inkjet printing for any other (polymer) ink solution and represents a fast and efficient screening of the parameters to obtain homogeneous films with a precise thickness.     

iCVD growth of poly(N-vinylimidazole) and poly(N-vinylimidazole-co-N-vinylpyrrolidone)

The imidazole group plays an important role in α-chymotrypsin catalysis, metal-ion complexation, counterion or dye binding. Poly(N-vinylimidazole), PVI, is also a good model polymer interacting with neutral salts. The poly(N-vinylimidazole-co-N-vinylpyrrolidone) copolymer P(VI-co-VP), can be used to produce highly functionalized polymers.PVI and P(VI-co-VP) thins films were achieved via initiated chemical vapor deposition (iCVD), a solvent-free process to form films under mild conditions. The polymerization was initiated by hot wire heated tert-butyl peroxide (TBPO). The chemical structure and compositions of the polymers were analyzed using FTIR and XPS. The growth rate of PVI as a function of the pressure inside the iCVD reactor was measured to be 1 nm/h mTorr. The XPS results show that the functional groups were retained in the polymer deposited. For the P(VI-co-VP) deposition, there are more VI groups found in the co-polymer chain even when the reacting monomers were fed in the same ratio.     

Synthesis and characterization of a novel multiblock copolyester containing poly(ethylene succinate) and poly(butylene succinate)

Multiblock copolyester (PBS-b-PES) containing poly(butylene succinate) (PBS) and poly(ethylene succinate) (PES) was successfully synthesized by chain-extension of dihydroxyl terminated PBS (HO-PBS-OH) and PES (HO-PES-OH) using 1,6-hexmethylene diisocyanate (HDI) as a chain extender. The chemical structures, molecular weights, crystallization behaviors, thermal and mechanical properties of the copolyesters were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), wide-angle X-ray diffraction (WAXD), tensile testing and hydrolytic degradation. High-molecular-weight copolyesters with M_w more than 2.0 × 10⁵ g mol⁻¹ were easily obtained through chain-extension. The copolyesters showed a single glass transition temperature (T_g) which increased with PES content. The melting point temperature (T_m) and relative degree of crystallinity (X_c) of the copolyesters decreased first and then increased with PES content. The copolyesters manifested excellent mechanical properties, for example, PBS₅-b-PES₅ had fracture stress of 61.8 MPa and fracture strain of 1173%. The chain-extension reaction provided a very effective way to produce high molecular weight multiblock copolyesters.     

Electrochemical characteristics of coated steel with poly(N-methyl pyrrole) synthesized in presence of ZnO nanoparticles

Poly(N-methyl pyrrole) (PMPy) coating was electrodeposited on steel substrates in mixed electrolytes of dodecyl benzene sulphonic acid with oxalic acid in the absence and the presence of ZnO nanoparticles (NPs). The morphology and compositions were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform Infrared Spectroscopy and Energy-dispersive X-ray spectroscopy. Electrode/coating/electrolyte system was studied by Electrochemical Impedance Spectroscopy. The comparison between the pore resistance (R_po) of synthesized PMPy in the absence and presence of ZnO NPs indicated that the existence of ZnO increased the R_po of the coating. The FESEM micrographs indicated that the size of micro-spherical grains in the morphology of PMPy is significantly reduced and the surface area of PMPy is increased with the presence of ZnO NPs. The increase of the ability to interact with the ions liberated during the corrosion reaction of steel and the increase of the rate probability for the occurrence of cathodic reduction of oxygen on the PMPy with the increase of the surface area can be considered as reasons for improvement of protective properties of synthesized PMPy in the presence of ZnO NPs.     

Electrochemical surface plasmon excitation and emission light properties in poly(3-hexylthiophene) thin films

The attenuated total reflection (ATR) and emission light properties utilizing surface plasmon (SP) excitations were measured for the electrochemical change of poly(3-hexylthiophene-2,5diyl) (P3HT) thin films in-situ. The SP emission light could detect the SP excited by molecular luminescence of P3HT. The ATR and SP emission light properties were observed for the doped–dedoped states of P3HT thin film. The ATR and SP emission light properties were remarkably changed with the electrochemical doping and dedoping. The SP emission light also decreased by decrease of the molecular luminescence of P3HT by doping. For the dedoped-state P3HT thin film, SP emission light also increased by increase of the molecular luminescence. The SP emission light excited by molecular luminescence can be controlled by the control of doping–dedoping state.     

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.