POLYMER-SUPPORTED RARE EARTH CATALYSTS FOR STYRENE POLYMERIZATION

The neodymium complex supported on styrene-maleic anhydride copolymer (SMA·Nd) has been prepared for the first time and found to be a highly effective catalyst for the polymerization of styrene. The SMA·Nd polymeric complex is characterized by IR and its catalytic activity, and the polymerization features have been investigated in comparison with that of the conventional Ziegler-Natta catalysts. When [Nd]=1×10~(-3) mol/L, [M]=5mol/L, Al/Nd=170(mol ratio) and CCl_4/Nd=50(mol ratio), the polymerization conversion of styrene gets to 51.6% in six hours, and the catalytic activity reaches 1852 gPS/gNd, which is much higher than that of conventional rare earth catalysts. The polymerization reaction has an induction period and shows some characteristics of chain polymerization. The polymerization rate is the first order with respect to the concentration of styrene monomer. Addition of FeCl_3 does not suppress the polymerization.     

EFFECT OF CHEMICAL STRUCTURE OF SULFOXIDE GRAFTED POLY (VINYL ALCOHOL) ON GAS PERMEABILITY

The effects of chemical structure, i. e. side chain structure and their contents, on thepermeability of pure SO_2, N_2 and their mixture gases for the sulfoxide grafted poly (vinylalcohol) (RVSO-PVA) membranes have been investigated:where R=Me, Et, Pr, t-Bu and Ph. It was notable that introduction of sulfoxide group intoPVA side chain greatly enhanced the permselectivity of sulfur dioxide. SO_2 permeability andseparation factor of these polymers increased markedly as the size of side chain increased. Thesulfoxide content of the polymer also played an important role in the pure and mixture gasespermeation. Some explanations have been made to interpret this unique gas separation behaviour.     

三氯化铁掺杂稀土聚乙炔的电性能

自从1981年A.Prón等人用三氯化铁掺杂钛系聚乙炔而得到高电导率掺杂聚乙炔以来,对此掺杂聚乙炔的低温电性能已作了一定的研究。不同作者所报道结果可分为两类:一类报道各种掺杂量聚乙炔的电导率均随温度降低而单调减少;另一类则观察到随温度的降低电导率约在200K时出现最大值(增加5%),接着电导率降低。新近我们报导了三氯化铁掺杂的稀土聚乙炔的基本特性。本文进一步对此掺杂稀土聚乙炔的低温电性能作了研究,观察到与上述两种情况相似但不完全相同的结果。     

乙酰丙酮钇催化环氧氯丙烷的均聚合与共聚合

用过渡金属络合催化剂聚合环氧氯丙烷能获高分子量的聚合物。稀土络合催化剂对环氧乙烷,环氧丙烷及环硫丙烷的开环聚合具有明显效果。本文选用Y(acac)_3-H_2O-Al(i-Bu)_3催化剂,考察环氧氯丙烷的均聚合及其与环氧乙烷,环氧丙烷的共聚合,并用核     

基于二氰根铬的一系列氰根桥联CrⅢ-CuⅡ-CrⅢ三核配合物的合成、结构与磁性

基于一系列二氰根铬与[Cu(cyclam)](ClO₄)₂反应合成了3个氰根桥联Cr^Ⅲ-Cu^Ⅱ-Cr^Ⅲ三核配合物[Cu(cyclam)][Cr(bpmb)(CN)₂]₂·4H₂O(1)(cyclam=1,4,8,11-四氮杂环十四,bpmb^2-=1,2-二(2-吡啶甲酰胺基)-4-甲基苯),[Cu(cyclam)][Cr(bpdmb)(CN)₂]₂(2)(bpdmb^2-=1,2-二(2-吡啶甲酰胺基)-4,5-二甲基苯)和[Cu(cyclam)][Cr(bpClb)(CN)₂]₂·4H₂O(3)(bpClb^2-=1,2-二(2-吡啶甲酰胺基)-4-氯苯)。单晶衍射结果表明:3个化合物是结构类似的中性三核配合物,均含有氰根桥联的Cr(Ⅲ)-CN-Cu(Ⅱ)-NC-Cr(Ⅲ)连接;磁性研究表明:氰根桥在Cr^Ⅲ和Cu^Ⅱ离子间传递弱的铁磁耦合作用,基于自旋哈密顿算符Ĥ=-2J_CrCuŜ_Cu(Ŝ_Cr1+Ŝ_Cr2)拟合得到它们的磁耦合常数分别是J_CrCu=1.53(2) cm^-1(1),0.45(1) cm^-1(2)和0.73(2) cm^-1(3)。     

基底界面效应对聚苯乙烯薄膜分子运动行为的影响

本文研究了Si／Si02、Si／Si—H基底与聚苯乙烯（Ps）之间的界面相互作用对Ps薄膜的玻璃化转变及相关力学性能的影响．结果显示,无论何种基底,Ps薄膜的玻璃化转变温度（L）都随其厚度降低而降低．但相同厚度（〈110nm）下,以Si／Si-H为基底时Ps薄膜的瓦比以Si／Si02为基底的PS薄膜高．Si／Si02表面Ps薄膜疋开始下降的临界厚度为110nm,远高于以Si／Si—H为基底时的40nm．对Ps薄膜的膨胀系数和弹性模量进行研究,也得到相似的临界厚度．另外,与Si／Si02基底相比,在Si／Si-H上的Ps薄膜具有更低的膨胀系数以及较高弹性模量．可能原因是Si／Si-H与Ps具有较强的相互作用,限制了该界面分子的运动能力,导致基底／PS界面效应对薄膜分子运动的影响力增强,造成该薄膜瓦的厚度依赖性下降,并呈现出相对较硬的力学特征．     

聚丙烯酸双(乙氧羰基)甲酯及其螯合物的合成和磁性能的检测

以溴代丙二酸二乙酯、丙烯酸钠为原料合成了聚丙烯酸双(乙氧羰基)甲酯(PEOCMA),并制备了其相应的与稀土金属Gd3+、Nd3+以及过渡金属Ni2+的高分子螯合物.利用FTIR、1H-NMR、GPC对聚合物和高分子螯合物的结构进行了表征,通过电感耦合等离子质谱仪(ICP)测得了高分子螯合物中的金属含量,借助多功能材料物理特性测试系统(PPMS,physical property measurement system)测定螯合物的磁性能.结果表明这些高分子螯合物具有较高的磁饱和强度,在低温下呈现出一定的铁磁相互作用,且为软磁性材料.     

Kinetic model of gas phase polymerization of 1,3-butadiene catalyzed by supported rare earth coordination system

Gas phase polymerization of 1,3-butadiene (Bd) catalyzed by supported rare earth coordination system is studied and a new kinetic model is proposed. Four elementary reactions or processes: the process of exposure and activation of potential active catalytic center, propagation, deactivation and chain transfer reaction to alkyl aluminum, are considered in this model. Some important parameters, such as monomer-consuming rate, are well expressed as the functions of macroscopic polymerization conditions such as pressure, temperature, and duration. The model can simulate the whole polymerization procedure satisfactorily.     

聚γ-(2-脲基噻唑)丙基甲基硅氧烷金属配合物的制备及磁学性能研究

合成了一种新的γ-(2-脲基噻唑)丙基甲基二乙氧基硅烷单体及聚硅氧烷聚合物,采用溶胶-凝胶法制备了聚硅氧烷的铜、镍金属离子的配合物,利用红外光谱、核磁共振氢谱及质谱等手段表证了其结构.并分析和讨论了它们的磁学性能.此类金属配合物在低温区,磁化率倒数与温度的关系不服从居里-外斯定律,存在着铁磁耦合,是一类有机铁磁体.另外,发现在含噻唑基团的硅氧烷链中引入5倍当量的二甲基硅氧烷链节,其居里-外斯温度增大了近2倍.     

稀土席夫碱配合物催化己内酯可控开环聚合

 通过稀土氯化物与席夫碱钠盐的交换反应制备了一系列以 3,5-二叔丁基水杨醛缩苯胺为配体的稀土席夫碱配合物. 对其中的钕席夫碱配合物进行了 X射线单晶衍射分析, 发现其单晶结构为五角双锥构型, 所得席夫碱稀土配合物可以单组分催化 ?-己内酯开环聚合. 深入研究了钕席夫碱配合物催化己内酯的开环聚合机理, 考察了不同聚合条件对单体转化率、产物分子量及分子量分布的影响. 结果表明, 该聚合反应速率为一级, 聚合反应具有较好的可控性. 聚合物端基分析表明, 聚合反应以配位-插入机理进行.