水中α,β-不饱和酮与3-甲基-1-苯基-2-吡唑啉-5-酮的加成反应

在水溶剂中有三乙基苄基氯化铵（TEBA）存在下，α,β-不饱和酮与3-甲基- 1-苯基-2-吡唑啉-5-酮发生迈克尔加成反应，以良好的产率生成相应的1,3-二芳基 -3-（3'-甲基-1'-苯基-5'-羟基-2'-吡唑啉-4'-基）-1-丙酮。     

三元体系Ln(ClO4)3-4-ClCH2COAp-H2O(30℃)的相平衡研究(Ln=La,Sm,Er)

我们测定了三元体系Ln(ClO4)3-4-ClCh2COAp-H2O(Ln=La,Er)在30℃时的溶度及饱和溶液的折光指数,绘制相应的溶度图和饱和溶液的折光指数曲线图。体系的溶度曲线和折光指数曲线均由四支组成,分别与4-ClCh2COAp、Ln(4-ClCh2COAp)3·nH2O(Ln=La,n=7;Sm,8;Er,4)、Ln(4-ClCH2COAp)2(ClO4)3·nH2O(Ln-La,n=7;Sr,6;Er,4)和Ln(ClO4)3·nH2O(Ln=La,n=8;Sm,9;Er,6)相对应,两类配合物均为固液异组成化合物。     

离子选择性PVC膜电极中溶剂化作用的研究 I: 碱金属离子由水相到TBP溶剂相的标准迁移自由能

电位法测量了碱金属离子由水相到TBP(磷酸三丁酯)-CH~3OH混合溶剂相的标准迁移自由能△G^0~t。研究了溶剂化作用同PVC膜对金属离子选择性的关系。碱金属离子的△G^0~t随着TBP在混合溶剂中含量的增加而增大。△G^0~t还随着离子半径的增大而增大, 这同TBP-PVC膜对碱金属离子的选择性次序相一致; 而与四苯硼酸盐-TBP-PVC膜对碱金属离子的选择性次序不完全相同。说明了TBP为溶剂的四苯硼酸盐膜对金属离子的选择性除了同溶剂化作用有关外, 还同膜相和水相中离子的交换反应常数等因素相关。     

STUDIES ON STRUCTURE AND PHASE BEHAVIOR OF MULTICOMPONENT POLYMERS THROUGH RHEOLOGICAL TESTS

Rheological measurement has been a preferred approach to the characterization of the structure and phase behaviors for multi-component/multi-phase polymer systems, due to its sensitive response to the changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on rheology for heterogeneous polymer systems including phase-separated polymeric blends and block copolymers are reviewed, mainly depending on the results by the authors＇ research group. By means of rheological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, also the corresponding results are significant for design and preparation of novel polymeric structural materials and functional materials.     

ADSORPTION OF CHLOROFORM AND TRICHLOROETHYLENE IN WATER WITH A NEW KIND OF HYPERCROSSLINKED RESINS

In this paper two newly developed hypercrosslinked resins were used to treat micropolluted drinking water and their static and kinetic adsorption were investigated at 293 K. The results show that these two adsorbents are superior to Amberlite XAD-4 for removing chloroform and trichloroethylene in aqueous solutions. The breakthrough capacity and the total capacities from mini-column adsorption studies for chloroform and trichloroethylene on XAD-4, ZH-01 and ZH-00 are calculated respectively under experimental conditions     

反相离子对色谱中离子对试剂浓度对保留值的影响

本文采用热力学与Gouy-chapmann理论相结合的方法, 考察了离子对试剂浓度对反相离子对色谱保留值的影响, 获得了反相离子对色谱ink'与离子对试剂浓度间的近似线性关系。同时考察了溶质疏水性和熔质电荷数对线性关系式中斜率和截距的影响。     

Structure Development and Interfacial Interactions in Flexible Polyurethane Foam-Layered Silicate Nanocomposites

Unmodified Na-montmorillonite (MMT) was swollen in a polyol/water mixture using an ultrasound technique. Polyurethane (PU) foam nanocomposites were formed via reaction of these polyol/water/Na-MMT mixtures with toluene diisocyanate (TDI). Forced-adiabatic attenuated total reflectance FTIR spectroscopy was used to determine the kinetics of both the PU copolymerisation and of the microphase separation between poly(ether-urethane) soft segments and polyurea hard segments. Consumption of TDI during the initial stages of the copolymerisation was accelerated significantly by the addition of ≤10 wt% Na-MMT. The initial rate of formation of urea groups also increased significantly upon addition of Na-MMT, but at reaction times >100 s a significant retardation occurred in the development of hydrogen bonding within the urea groups of the hard-segment phase that was recovered only after 1000 s. The reasons for this extensive disruption in structure development were investigated using flow microcalorimetry (FMC), diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS), and wide angle X-ray scattering (WAXS) to monitor the adsorption process and any chemical reaction between hydrated Na-MMT and a model monoisocyanate; 4-ethylphenyl isocyanate (4-EPI). DRIFTS spectra of 4-EPI adsorbed on Na-MMT revealed urea groups, indicating formation of N,N′-bis(4-ethylphenyl) urea. FMC indicated that a significant quantity of this urea formed at the surface and then desorbed. In addition, DRIFTS spectra indicated that the 4-EPI reacted with hydroxyl groups present at the edges of the silicate platelets to form urethane linkages. Thus, in a PU-foam reaction mixture, the water will tend to associate with the Na-MMT, either within the galleries or on the surfaces of silicate lamellae. Upon reaction with isocyanate, the presence of the Na-MMT both promotes the formation of urea and generates urethane linkages between silicate lamellae and the polyurethane.     

YbCl3·3H2O-18-C-6-CH3COCH3体系(25℃)的相化学研究与 固态配合物的合成与 性质

采用半微量相平衡方法研究了YbCl3·3H2O-18-C-6-CH3COCH3三元体系(25℃)的溶度,测定了各饱和溶液的折光率,绘制了体系的溶度图与饱和溶液折光率曲线,考察了相平衡过程中水的行为。体系中形成两种化学计量的新配合物：2YbCl3·18-C-6·6H2O·CH3COCH3(1)与YbCl3·18-C-6·3H2O·0.5CH3COCH3(2),两者均为固液异成分溶解的配合物。比较讨论了盐的阴离子与溶剂对形成配合物的影响。在相平衡结果指导下,制备了固态配合物,用化学分析、元素分析、IR,DTG,TG与DSC研究了固态配合物的组成与性质,预示了固态配合物YbCl3·18-C-6·3H2O与YbCl3·18-C-6的配位结构。     

CTAB反相微乳液中水辛烷分子的自扩散研究

利用电导测量确定了CTAB/正丁醇/正辛烷/水四组分体系的相态,在反相微乳液区有明显的渗滤现象,通过脉冲梯度场核磁共振方法研究了反相微乳液中水和辛烷分子的自扩散行为,采用双指数拟合得出辛烷的自扩散系数。对于体系中出现的渗滤现象以及水和辛烷分子自扩散系数反常的原因,从分子水平上进行了解释。水和自扩散系数(2～7×10^-10m·s^-1)比一般文献值高,其原因：一是水在油相中有较大的溶解度;二是渗滤现象的存在,由于液滴间相互作用的增强和：粘性“碰撞而导致液滴的融合,以及由此而形成的瞬时水相连续通道,使水的自扩散系数增大。而辛烷自扩散系数比一般文献值小,则是由于在微乳液液滴的栅栏中表面活性剂分子烃链与辛烷分子间范德华引力所造成。