RHEOLOGICAL CHARACTERIZATION OF PROCESSABILITY OF UNVULCANIZED POLYBUTADIENE

Rheological investigation on a series ot unvulcamzed polybutadiene elastomers of different processability has been carried out by means of a capillary extrusion rheometer. It is found that the processability of unvulcanized polybutadiene can be correlated with the occurrence of unsteady flow and the wall stress, dependence of the dimensionless number e characterizing the entrance elongational elasticity which has been found to be sensitive to the branching structure and the molecular weight distribution of the samples. Interpretations based on the structural data of unvulcanized polybutadiene were discussed.     

STUDIES ON THE EXCIMER FLUORESCENCE AND THE STERIC TACTICITY OF POLYPHENYLSILSESQUIOXANES

The steric tacticity of polyphenylsilsesquioxanes (PPS) was studied by exeimer fluorescence spectroscopy. It was found that the fluorescence of PPS come mainly from its intramolecular excimers, The experimental results indicated that the steric-structure of PPS is most probably cisisotactic rather than the cis-syndiotactic as suggested in the literature. With the increase in defect content monomer fluorescence intensity increases because of the enhanced mobility of phenyl groups. Molecular weights and molecular weight distributions do not affect the fluorescence spectra of PPS.     

邻硝基乙酰苯胺衍生物的XPS振起伴峰及其价带谱的研究

研究了一组邻硝基乙酰苯胺衍生物的X射线光电子能谱(XPS).观察到硝基的N1s光电子谱有明显分裂,可认为是N1s振起伴峰的反映,而且苯环上的取代基对该振起伴峰强度有影响,按照Pignataro等关于振起伴峰与主峰的能量分离以及分子内电荷转移有关的观点,计算了振起伴峰与主峰的面积比.结果表明,峰间距与面积比的趋势一致.因此二者都可作为分子内电荷转移的粗略估计.     

N-二异丙基磷酰基氨基酸的电子电离和快原子轰击质谱的比较

N-二异丙基磷酰基(DIPP)氨基酸的快原子轰击(FAB)和电子电离(EI)质谱都有相似的丢失两分子丙烯和一分子甲酸的碎裂过程.在FAB中,连续失掉两个丙烯,然后脱去甲酸的过程较为有利;在EI中则主要为先脱去甲酸,随后失去丙烯,本文对DIPP-氨基酸的FAB和EI质谱碎裂历程进行了比较,对分子离子峰的形式与碎裂方式的关系进行了讨论.     

1,1-二甲基-2-(9-菲基)-环丙烷的直接同面1,3氢迁移

二甲基被氘代的标题环丙烷光解生成2-甲基d3-4-(9-菲基)-1-丁烯-d3,它的结构系根据光谱和化学降解推断.基于分子轨道跟踪法和激发分子基础轨道对间的键序变化讨论.标题化合物最合理的开环模式是同面的1,3氢迁移.     

二烷氧基膦酰乙酸酯的电子轰击正离子和化学电离负离子质谱研究

本文报道一系列二烷氧基膦酰乙酸酯的电子轰击(EI)正离子和甲烷化学电离负离子(NCI)质谱.在EI谱上出现特征的[M+H]^+离子,进一步发生氢重排,然后失去烯烃,再失水和脱CH2CO.而在NCI谱中则生成[M-H]^-离子(基峰),易失去烷基,再失烷氧基和CH2CO,或氢重排后脱烯烃.正、负离子的断裂机理不同,但数据可以互相补充,以利于类似未知物的结构分析.     

Study on the Cracking Mechanism of 1,1,2-Trichloro-1,2,2-trimethyldisilane Catalyzed by Aluminum Chloride

The cracking mechanism of 1,1,2-trichloro-l,2,2-trimethyldisilane catalyzed by aluminum chloride is investigated by DFT and MP2 methods. The reactants decompose in two ways, which are competing response. The reaction pathways are both by three steps. And the two reaction channels were both exothermic reaction. The heat of the overall reaction was –293.372 kJ·mol-1. The rate determining steps are the third and first steps, respectively. The Standard Gibbs Free Energy Change is the same, –297.55 kJ·mol-1. The Standard Equilibrium Constant is 1.354 × 1052. The theoretical productivity is high under normal temperature and pressure. The theoretical results agreed well with the experimental data.     

链式钴微米六方片的溶剂热合成及磁性

以十二硫醇和聚乙烯吡咯烷酮（PVP）为结构导向剂、乙二醇和乙二胺为混合溶剂,利用溶剂热技术成功地制备了Co粒子,并用XRD、SEM、TEM、HRTEM及SQUID对材料的晶体结构、形貌及磁性进行研究. 结果表明：Co粒子属hcp相,呈六方片状,直径约为2 μm,厚度约为80 nm,大量的六方片相互交叉连接成链式结构,并且六方薄片由更为细小的丝带状的纳米片（厚度约为10 nm）构成;室温下样品表现出良好的铁磁性特征,其饱和磁化强度Ms、剩余磁化强度Mr及矫顽力分别为126.6 emu/g、13.7 emu/g和163.4 Oe.     

疏水/亲水大孔聚二乙烯基苯/聚(N-2-氨基乙基丙烯酰胺)IPN树脂的合成及对水杨酸吸附性能研究

采用分步悬浮聚合法制备了聚二乙烯基苯/聚丙烯酸甲酯(PDVB/PMA)大孔互穿聚合物网络,将其中的聚丙烯酸甲酯用乙二胺氨解,合成了具有疏水/亲水性能的聚二乙烯基苯/聚(N-2-氨基乙基丙烯酰胺)(PDVB/PNAEAM)大孔互穿聚合物网络(IPN);测定了该树脂的孔结构、含水量、弱碱交换量和溶胀性能;测定了该树脂对水杨酸在不同温度下的吸附等温线,利用热力学函数关系计算出了吸附焓、自由能和熵.推测PDVB/PNAEAM IPN树脂中疏水性的PDVB一网具有疏水作用吸附能力、亲水性的PNAEAM一网具有氢键作用吸附能力.动态吸附及脱附实验表明湿态PDVB/PNAEAM IPN树脂对水溶液中水杨酸的饱和吸附量达到46.1mg/mL.树脂可以通过4%NaOH溶液再生.PDVB/PNAEAM IPN树脂在分离工业废水中水杨酸等芳香有机酸有良好的应用前景.     

胺甲基化聚丙烯酰胺阳离子交换剂的合成与表征

采用反相悬浮聚合法合成20%交联度的聚丙烯酰膀(Polyacrylamide,PAM)树脂,经过Mannich反应修饰(nacrylamide:nformaldehyde:ndimethylamine=1:1:1.2)得到高亲水性弱碱性阴离子交换剂氨甲基化聚丙烯酰胺(Aminomcthylated Polyacrylamide,APAM).随着修饰反应时间的增加,得到的APAM的弱碱交换量与蛋白质吸附量增加,在选定的实验条件下,确定Mannich反应时间以1h为宜,所得树脂对牛血清白蛋白吸附量达到433mg/g,过长的反应时间导致树脂结构有一定程度的破坏.树脂对蛋白质的吸附等温线符合Langmuir方程,实际分离牛血清白蛋白和血红蛋白效果较好,柱体积不随洗脱液中盐浓度的增加而变化.