STUDY ON THE MECHANISM OF 1-OCTENE ZIEGLER-NATTA POLYMERIZATION BASED ON THE NUMBER OF ACTIVE CENTERS

The number of active centers (C_p)-t and k_p-t profiles of Solvay type TiCl_3 - AlR_3 (R=C_2H_5, i-C_4H_9) or Stauffer AA TiCl_3-Al (C_2H_5)_3 catalyzed 1-octene polymerization were determined by using an acetyl chloride quenching method as well as kinetic data. The results show that in the studied systems k_p decreases when C_p increases, indicating the presence of two or more types of different active centers. The C_(p~(-t)) plots of the Solvay TiCl_3-AlR_3 systems show the presence of both stable active centers and unstable centers which decay in the polymerization process. The phenomena are explained based on a model of active center plurality. The increases of C_p in the induction periods are also discussed.     

丙烷直接氨氧化制丙烯腈催化剂的研究进展

丙烷直接氨氧化制丙烯腈是一条潜在的具有巨大经济效益的丙烯腈生产路线。本文概述了丙烷直接氨氧化制丙烯腈的催化反应机理，对丙烷直接氨氧化制丙烯腈的催化反应路径进行了归纳，同时对丙烷直接氨氧化制丙烯腈催化剂设计的思想以及日前所开发的几类丙烷直接氨氧化制丙烯腈催化剂体系加以了总结，重点介绍了锑酸盐和钼酸盐催化剂，对锑酸盐和钼酸盐催化剂活性相的结构、影响活性相形成的因素以及催化剂的结构与催化反应性能的关系等问题作了阐述。     

密闭系统中微波辅助萃取机制探讨

通过与普通加热萃取虎杖中白藜芦醇的产率进行对比 ,对密闭系统中微波辅助萃取的机理进行了探讨。结果表明 ,微波辅助萃取与普通加热萃取二者的活化能相差不大 ,分别为30.06和30.32kJ·mol-1。但微波辅助萃取的表观速率常数约是普通加热萃取的20倍。并且还利用电子扫描显微镜对样品微结构进行了观察 ,研究表明 ,细胞内极性成分如水吸收了微波能后压力迅速增加导致细胞结构的破坏是MAE快速高效的关键 ,由于细胞的破坏 ,萃取剂和萃取目标化合物更容易通过细胞壁 ,加速了扩散速度 ,进而加速了萃取速度。     

Oxidative transformation of azides to aryl nitriles using DIB/TBHP: scope and mechanistic insights

Bis(tert-butylperoxy)iodobenzene, generated in situ by the reaction between diacetoxyl iodobenzene (DIB) and tert-butyl hydroperoxide (TBHP), was used in the oxidative transformation of primary azides to nitriles, and secondary azides to ketones.     

甲磺酸帕珠沙星的热分解机理及动力学

采用热重(TG)和差示扫描量热(DSC)法测定了甲磺酸帕珠沙星(PZFX)在氮气氛和空气氛中的热分解过程,测定了PZFX及其在热分解过程中不同阶段残余物的红外光谱,运用量子化学GAMESS软件计算了PZFX分子的键级,推断了PZFX的热分解机理.结果表明PZFX的热分解过程的起始步骤是甲磺酸的分解.采用Ozawa方法计...     

溶剂诱导聚合物结晶的研究进展

溶剂诱导结晶(SINC)又称为液体诱导结晶,它是结晶性高聚物在溶剂(或包括其蒸汽)作用下,在低于通常Tg下诱导结晶,而在高于通常Tg时能加速结晶的现象。本文主要对溶剂诱导结晶的机理、动力学和形态学进行了讨论。     

试论应璩《百一诗》和阮籍《咏怀》八十二首

应璩《百一诗》和阮籍《咏怀》八十二首都以大型五言组诗的形式出现，创作动机也基本上都是为了劝谏讽喻。这现象并不是偶然的，而是与当时的浮华倾交风气的社会以及以子书为务的批评传统密切相关。     

Investigations providing a plausible mechanism in the hexamethyldisilazane-catalyzed trimerization of alkyl isocyanates

Using HMDS as catalyst for the trimerization of isocyanates presents many advantages as the expected isocyanurate is not contaminated by the catalyst or other side-products resulting from its degradation. In addition, HMDS presents a low toxicity, and is compatible with industrial applications. This article describes the hexamethyldisilazane (HMDS)-catalyzed trimerization of octylisocyanate. Experimental investigations and mechanistic considerations indicate that the true catalyst of the trimerization is trimethylsilyloctylamine, which results from the preliminary condensation of HMDS with octylisocyanate.     

试论嵩山地区亮甲山组白云岩和燧石的成因

本文应用野外和室内相结合的研究方法,对篙山地区亮甲山组白云岩和燧石的成因进行了探索。白云岩中燧石的产状有纹层状、树丛状、斑状、结核状及团块状等。室内岩石薄片、扫描电子显微镜及阴极发光显微镜等研究表明,该组原始沉积的CaCO_3沉积物及早期形成的石灰岩曾先后遭受了初次云化、初次硅化、二次云化及二次硅化作用的改造才形成了目前的含有燧石的白云岩。本文提出了白云岩及其燧石成因的解释机理。