可溶性聚苯胺的合成及研究

本文报道了可溶性聚苯胺(PAn)的合成方法。通过对比可溶和不可溶PAn的导电性、电化学行为及IR光谱,说明它们的分子链基本结构相同。并测得了PAn在DMF-d_7中的~13C-NMR 谱。     

溴化锌-季(鎓)三溴盐催化二氧化碳和环氧化合物偶联反应

研究了溴化锌-季鎓三溴盐催化二氧化碳和环氧化合物偶联反应,考察了反应温度、压力和不同金属盐对反应的影响以及催化剂的循环使用性能.结果表明,在413 K和1.0 MPa条件下,以溴化锌为催化剂,苯基三甲基三溴化铵为共催化剂,无需加入任何溶剂就可以使二氧化碳和环氧化合物发生偶联反应,并以很高的收率得到环碳酸酯.     

Cu2(μ-dppb)2(μ-Cl)2的合成、晶体结构及非线性光学性质

The complex Cu₂(μ-dppb)₂(μ-Cl)₂ has been synthesized from the reaction of CuCl， dppb and (n-Bu)₄NCl. The crystal belongs to the triclinic with space group P1. The unit cell parameters are: a=9.939(4)?， b=10.083(6)?， c=14.104(5)?， α=76.46(3)°， β=71.02(2)°， γ=70.87(5)°. The single crystal X-ray diffraction analysis reveals that it has a bi-ring structure with a symmetry center at the middle of two Copper atoms. The outer ring is a 14-membered ring of Cu-dppb-Cu-dppb， and the inner ring is a 4-membered ring composed of two Cl^- and two Cu(Ⅰ). Investigation of third-order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self-defocusing effect with α₂=1.75×10^-13m·W^-1 and n₂=3.19×10^-18m²·W^-1. CCDC: 193113.     

PROPERTIES OF TEMPERATURE DEPENDENCE OF THRESHOLD IN PURE AND IMPUHITY-DOPED BLUE BRONZES

Temperature dependence of the threshold of pure and impurity-doped blue bronzes has been studied. It is found that for pare blue bronzes the threshold field near 100K has an anomalous peak, but for impurity-doped samples no anomaly is observed in the range of liquid nitrogen temperature, and the value of the threshold field gradu-ally increases with the decrease of temperature. The results show that in the high-quality pure blue bronzes, there may exist an incommensurate to quasi-commensurate transition near 100K. But for the impurity-doped or "dirty" pure samples, such an incommensurate to quasi-commensurate transition near 100K can be extensively re-strained by impurities or defects, which leads to a pure incommensurate CDW in a wide temperature range.     

用高分辨质谱研究二茂铁类化合物

研究了八种N－二茂铁甲基苯胺衍生物的电子电离质谱（EI－MS），并与快原子轰击质谱（FAB－MS）作了比较，讨论了这些化合物的质谱特征。通过精确质量测量，确认了M^ -2 OH离子，并采用碰撞诱导裂解（CID）探讨了化合物质谱中主要离子间的关系。     

掺杂态聚苯胺的共振拉曼光谱研究

观测了聚苯胺(PAn)在不同状态(掺杂、反掺杂、碱式、氧化、还原)下的拉曼光谱.根据其光谱特性,结合其它实验结果,提出了掺杂态PAn分子链包含电荷分布不等的三种苦环和二种氮原子的四单元苯醌变体模型,指出质子酸掺杂系分子内氧化还原反应,讨论了PAn氧化程度对掺杂效率的影响.     

非晶高聚物对聚(ε-己内酯)在其与苯乙烯-丙烯腈共聚物相容共混物中球晶生长速率的影响

本文研究了聚(ε-己内酯)(PCL)在其与苯乙烯-丙烯腈共聚物(SAN)的相容共混物中球晶生长速率与共混组成和结晶温度的关系.发现聚己内酯的球晶生长速率随着SAN的含量增加而下降.由于PCL与SAN是相容共混物,因此在用二次成核动力学方程描述PCL球晶生长速率时,我们引进了相互作用参数X.结果由共混体系的结晶动力学方程计算到的X值与由平衡熔点下降方法计算到的X_(23)值是相同的;而PCL晶体的折叠表面自由能则随着SAN含量的增加而下降.这些结果说明非晶高聚物SAN有碍于PCL球晶的生长.     

Synthesis and Characterization of Poly-Ortho-Methylaniline With Different Degrees of Oxidation

Poly-ortho-methylanilines (POT) in three states fully oxidized, fully reduced and oxidized in varying degrees were synthesized by the reaction of common POT (C-POT) having nearly equal amounts of benzenediamine and quinonediimine units with iodine or phenylhydrazine, and the resulting polymers were characterized by IR,~(13)C-NMR, SEM and elemental analysis. The results showed that the quinonediimine unit in C-POT could be reduced by phenylhydrazine to the benzenediamine unit,forming the polymer with low OD (oxidation degree) or in a fully reduced state and that iodine-oxidation resulted in the increase of quinonediimine unit and decrease of benzenediamine unit. The solubility and flexibility of the formed polymers depend strongly on the amount of quinonediimine unit in it. It is necessary to reduce the content of quinonediimine structure unit in order to improve the solubility of aniline-class polymers.     

聚乙烯醇硫酸钾水凝胶电机械化学行为研究

通过将交联聚乙烯醇硫酸酯化的方法制备了一种新型电刺激响应性聚乙烯醇硫酸钾(PVSK)智能水凝胶,并探讨了溶液离子强度和pH对PVSK水凝胶的溶胀吸水率、机械性能以及电机械化学行为的影响.结果表明,制备的PVSK水凝胶的平衡溶胀比随NaCl溶液离子强度的增大而减小,在pH2.39～10.83范围内基本不受溶液pH的影响;经不同离子强度和pH的NaCl溶液充分溶胀的PVSK水凝胶具有良好的机械性能,在非接触的直流电场作用下,该水凝胶向电场负极弯曲,凝胶的弯曲速度和弯曲偏转量随外加电场强度的增加而增大,随NaCl溶液离子强度的增大出现临界最大值,但不随溶液pH(2.08～10.53)的改变而改变;在循环电场作用下,PVSK水凝胶的电机械化学行为具有良好的可逆性.     

Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts

We herein report on solution structural studies of Ru^Ⅱ catalysts （3a, 9） composed of achiral bisphosphine ligands （4, 8） and the enantiopure 1,2-diphenylethylenediamine （DPEN）. Complete chiral induction from enantiopure （R,R）-DPEN to achiral bisphosphine ligand 3a was observed in solution, with the complex adopting a single, stable and non-fluxional （even at 70 ℃） configuration. The coordination of the C=O moiety in 4 to the cationic Run center is considered to be of key importance in providing the higher thermodynamic and kinetic rotation barrier for the flexible bisphosphine ligand in the complex. The obtained enantioselectivity （91% enantiomeric excess） and sense of chiral induction in the hydrogenation of acetophenone were found to be solely dependent on the chirality of the 1,2-diamine. Consistent with the hydrogenation product, the （R,R）-DPEN induces a M-conformation （fight-handed） chirality for flexible phosphine ligand 4 in the complex, resulting in a 2,2-configuration about the Ru^Ⅱ center.