A copper‐based reverse atom‐transfer radical polymerization process for the living radical polymerization of polyacrylonitrile

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexasubstituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was firstly used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 57.4 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 226–231, 2006     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid

FeCl₃ coordinated by isophthalic acid was first used as a catalyst in the azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile. N,N‐Dimethylformamide was used as a solvent to improve the solubility of the ligand. An FeCl₃‐to‐isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided rather a rapid reaction rate. The effects of different solvents on the polymerization of acrylonitrile were also investigated. The rate of the polymerization in N,N‐dimethylformamide was faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. The rate of polymerization increased with increasing polymerization temperature, and the apparent activation energy was calculated to be 59.9 kJ mol^?1. Reverse atom transfer radical polymerization was first used to successfully synthesize acrylonitrile polymers with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 219–225, 2006     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

Novel photoswitching dithienylethenes with ferrocene units

Two novel dithienylethenes with ferrocene units were synthesized by Wittig reaction. The structure of 2a has been established by X‐ray diffraction studies. They could reversibly interconvert between two thermally stable forms, an open and a closed one, using light of different wavelengths as triggers. Copyright © 2006 John Wiley & Sons, Ltd.     

纳米晶Y_2SiO_5∶Eu的浓度猝灭研究

报道了分别用溶胶－凝胶法合成的Ｙ２ＳｉＯ５∶Ｅｕ纳米晶和用高温固相法合成常规尺度的Ｙ２ＳｉＯ５∶Ｅｕ材料的光致发光光谱和猝灭浓度的实验研究．结果表明：纳米Ｙ２－ｘＥｕｘＳｉＯ５比常规尺度的Ｙ２－ｘＥｕｘＳｉＯ５有更高的猝灭浓度和更高的发光亮度．理论分析认为这是由于在纳米材料中能量共振传递被阻断和猝灭中心在各个纳米晶内分布的涨落造成的．这个结果为高亮度的Ｙ２ＳｉＯ５∶Ｅｕ纳米材料的实际开发应用展示了广阔前景．     

聚合物电致发光材料研究进展

本文较详细地综述了聚合物电致发光材料的研究进展，重点介绍了聚对苯撑乙烯（ＰＰＶ），并提出了有关聚合物电致发光材料及器件构造研究的一些观点。     

大孔膦酸树脂吸附镧的研究

本文测定了大孔膦酸树脂对La3 的吸附容量，介质pH、温度、吸附时间等因素对吸附的影响。测得吸附速率常数K298＝7．64×10－5S－1，树脂功能基与La3 的络合比为3：1，用化学及红外光谱等方法，得到大孔磷酸树脂吸附La3 的基本参数及其机理。     

X荧光滤纸片薄样法测定铅锌矿选矿流程样中Pb,Zn,Cu,Fe

本法将Ｘ荧光滤纸片薄样法用于具有复杂组分的铅锌矿选矿样品中Ｐｂ，Ｚｎ，Ｃｕ，Ｆｅ的分析，样品经化学溶样后滴于定量滤纸片上，标准样品可直接用纯试剂人工配制，用同样制成滤纸片薄样标准系列，因薄样测定可不作基体效应校正，标样使用数量少，又无需化学法标定。故方法实验周期短，样品测定手续简便快速，元素分析含量适应范围宽，可适用于组分复杂，元素含量变化范围大的试样分析，样品分析结果与化学法相符，方法准确度与精