水溶性疏水缔合聚合物在高岭土/水界面的吸附

表面活性剂;水溶性疏水缔合聚合物在高岭土/水界面的吸附     

超声化学法制备高岭土/二甲亚砜插层复合物的研究

采用与传统方法不同的超声化学法,用二甲亚砜(DMSO)对高岭土进行插层,大大缩短了处理时间,而且达到了较理想的插层效果。采用X -衍射研究插层间距,发现硅酸盐片层间距从0.714 nm增加至1.123 nm左右,插层率为90.9%,并对不同超声条件对插层率的影响进行了探讨。同时用FT-IR和TG/DTA等方法对插层机理进行了分析和研究。     

机械力诱导聚合反应的研究进展

机械化学作为一种温和、绿色的化学反应方法,近年来受到越来越多的关注.使用研磨、超声等形式的机械力调控聚合反应是一种重要的高分子合成方法,在聚合过程调控和刺激响应性材料的制备方面已经显示出独特的优势.本文总结了由超声、球磨等形式的机械力诱导的聚合反应,包括自由基聚合、氧化聚合、开环易位聚合,以及缩合聚合和点击聚合等.同时,探讨了机械应力作用、超声空化作用以及压电效应对聚合过程的影响.最后对机械力诱导聚合反应的研究进行了总结,对领域存在的问题和挑战进行了展望.     

机械力响应高分子体系的原理、构建与应用

具有刺激响应特性的高分子材料是目前高分子研究中的重要领域。机械力作为一种新型的刺激源,具有与传统光、热等刺激源不同的特点。机械应力刺激可以从来源上分为宏观机械力与微观机械力,宏观机械力早在人类发展初期已被广泛用于高分子材料的处理。而微观机械力对高分子作用的原理和应用近年来才逐渐成为研究重点。本文从高分子机械力响应的原理出发,分类阐述了各种机械力响应系统。其中,按照断裂的化学键将其分为共价键体系和非共价键体系。而共价键体系可以进一步按照环状结构与线型结构分为两大类。此外,本文还总结了已有应用,包括用于应力拆分外消旋体、应力活化催化剂及应力用于研究反应机理等。     

机械力诱导发光高分子材料

发展具有机械力诱导发光性质的高分子是目前高分子力化学领域的一个新兴前沿课题.这类响应性高分子材料由于能够将机械能转换成灵敏的光信号,是连接微观分子水平研究与宏观材料性能表征的桥梁,因而有望作为高灵敏(在空间和时间2个维度上)应力探针在高分子材料损伤探测与失效机理研究方面发挥重要作用.本文详细介绍了机械力诱导发光高分子的设计与合成策略,以及研究者对发光机理的探索、发光效率的优化、发光过程的应用,揭示这类高分子的发光特点及其作为应力探针的优势,归纳总结已取得的初步进展,并对这类新型响应性高分子材料的发展进行简单的评述和展望.     

高岭土原位无溶剂法合成小粒径ZSM-5分子筛

结合原位水热法和无溶剂法的优点,在不添加有机模板剂和溶剂的基础上,以高岭土为原料通过晶种诱导绿色高效地合成出ZSM-5分子筛。运用X射线衍射、N2吸附-脱附、扫描电镜、透射电镜和NH3程序升温脱附(TPD-NH3)等技术对ZSM-5分子筛进行表征。表征结果与原位水热法合成的ZSM-5分子筛相比,原位无溶剂法合成ZSM-5分子筛的结晶度较高、晶体粒径较小、酸强度略高、孔结构相似。     

荧光探针法研究疏水改性聚丙烯酰胺溶液的疏水缔合行为

采用胶束共聚 共水解方法合成疏水改性水溶性聚合物聚(丙烯酰胺/丙烯酸钠/N 辛基丙烯酰胺)[P(AM/NaAA/C8AM)],并以芘为荧光探针,应用稳态荧光光谱法研究了它的疏水缔合行为。结果表明,随聚合物浓度、疏水单体摩尔分数、疏水侧链长和温度的增加,疏水缔合作用增强;不同疏水单体含量的P(AM/NaAA/C8AM)的临界缔合浓度为1.5~3.0 g/L;表面活性剂十二烷基硫酸钠(SDS)与P(AM/NaAA/C8AM)发生了强烈的疏水相互作用,形成混合胶束,得到SDS的临界胶束浓度(CMC)为8×10-3 mol/L;由于聚合物链上羧基的存在,使其具有良好的 pH敏感性,随 pH值的增大,P(AM/NaAA/C8AM)的疏水缔合作用呈现先减弱后恒定再增强的变化。     

疏水改性聚电解质的荧光探针光谱

流水改性聚电解质或聚皂（PolysoaP）是在亲水性聚电解质的侧链或主链上键合少量的强流水性基团的聚合物l'，'］流水基团一般采用长链烷基（通常碳原子数大于刚＊一、也有用硅氧烷、氟碳化合物进行疏水改性问由干这种聚合物分子链上带有两性亲媒基团，因此，又被称为高分子表面     

大豆蛋白动态超高压微射流均质中机械力化学效应

以大豆蛋白为对象, 研究大豆蛋白在动态超高压均质过程中存在的机械力化学效应, 同时探究机械力化学效应对大豆蛋白热稳定性的影响. 结果表明, 在动态超高压微射流均质的机械力作用下, 蛋白颗粒粒度变小, 粒度分布范围变窄, 蛋白内部的二硫键和疏水基团被破坏, 致使巯基和疏水基团暴露, 并随着工作压力的增大破坏作用力增强. 同时经过机械力化学效应改性的大豆蛋白热稳定性增强, 并随着工作压力的增加改善效果增强.     

改性聚丙烯酰胺水溶液的疏水缔合性质

合成了一种疏水缔合水溶性聚丙烯酰胺共聚物,使用荧光光谱法并结合紫外及流变性实验,对制备的疏水缔合水溶性聚丙烯酰胺共聚物在水溶液中形成疏水微区、超分子聚集体及空间网络结构进行了研究,并用扫描电子显微镜证实了溶液中网络结构的存在.     

The mechanochemical reduction of AgCl with metals

Faraday induced the mechanochemical reduction of AgCl with Zn, Sn, Fe and Cu in 1820, using trituration in a mortar. This experiment is revisited, employing a mortar-and-pestle and a ball mill as mechanochemical reactors. The reaction kinetics depends both on the thermochemical properties and the hardness of the reactants. When using Zn as the reducing agent, Faraday likely observed a mechanically induced self-sustaining process (MSR), or at least he came very close to doing so.     

Solid-phase mechanochemical incorporation of a spin label into cellulose

Samples of cellulose labeled with stable nitroxyl radicals were prepared by mechanochemical synthesis. The samples were studied by IR and EPR spectroscopies, X-ray phase analysis, and electron microscopy. The EPR spectral patterns indicate a uniform distribution of “grafted” paramagnetic centers over the cellulose macromolecular chains. X-Ray diffraction patterns obtained and the results of crystallinity index calculations for the samples showed that strong bonding of spin labels causes changes in the cellulose structure up to nearly complete amorphization of the material. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1127–1130, May, 2005.     

Impact factors and thermodynamic characteristics of aquatic humic acid loaded onto kaolin

The adsorption of humic acid (HA) on kaolin particles was studied at various conditions of initial solution pH, ionic strength and solid-to-liquid ratio. The resulting affinity of interactions between humic acid and kaolin was attributed to the surface coordination of HA in ambient suspensions of mineral particles and the strong electrostatic force at low pH. Addition of inorganic salt can also influence the adsorption behavior by affecting the HA molecular structure, the clay particle zeta potential and so on. Equilibrium data were well fitted by the Freundlich model and implied the occurrence of multilayer adsorption in the process. In addition, the enthalpy dependent of system temperature was 79.17 kJ/mol, which proved that the mechanism of HA adsorption onto kaolin was comprehensive, including electrostatic attraction, ligand complexation and hydrogen bonding.     

Comparison of surface properties between kaolin and metakaolin in concentrated lime solutions

The surface adsorption of calcium hydroxide onto kaolin and metakaolin was investigated by monitoring with atomic emission spectroscopy and pH measurements the amounts of ions left in solution after exposing clays to calcium hydroxide solutions of various concentrations. Both clays adsorb calcium and hydroxyl ions but differently. Kaolin adsorbs calcium hydroxide not only at the edges of the clay particles but also onto the basal faces. The adsorbed hydrated calcium ions form a layer on the clay particle surfaces, preventing further dissolution of the clay mineral platelet. Metakaolin shows high pozzolanic activity, which provides the quick formation of hydrated phases at the interfaces between metakaolin and lime solutions. The nature of the hydration products has been investigated using X-ray diffraction (XRD) and differential thermal analysis (DTA). The most important hydrated phases like CSH (hydrated calcium silicate) and C₂ASH₈ (gehlenite) have been identified.     

A novel catalyst-free mechanochemical protocol for the synthesis of 2,3-dihydro-1H-perimidines

A rapid, efficient, and green grinding assisted method for the synthesis of 2,3-dihydro-1H-perimidines has been developed. 1,8-Diaminonaphthalene and aldehydes were ground using mortar and pestle for 5 minutes affording the product in moderate to excellent yields. The methodology minimises the use of conventional workup and column chromatographic techniques.     

The kinetics of Al-Si spinel phase crystallization from calcined kaolin

The crystallization of Al-Si spinel from medium ordered kaolin with high content of kaolinite was investigated using the differential thermal analysis (DTA). The apparent activation energy of the process was evaluated from the dependence of exothermic peak of crystallization on heating rate. Within the applied interval of heating rate (1-40 K min⁻¹) the temperature of peak maximum increases from initial value of 1220.5 K in about 54.2 K. The apparent activation energy of the process 856±2 kJ mol⁻¹was calculated using the Kissinger equation. The growth morphology of Al-Si spinel crystal was evaluated from the Avrami parameter. The average value of morphology parameter determined within the observed interval of heating rate is 3.08±0.03. This value indicates that crystallization mechanism of Al-Si spinel phase proceeds by bulk nucleation of the new phase with constant number of nuclei and that the three-dimensional growth of crystals is controlled by the reaction rate on the phases interface.     

Rational mechanochemical processes with less intensive stressing for their affordable application

An overview is given on the application of mechanical activation to various fields of solid state processes. Opposite to the historical development, emphasis is laid to give mechanical energy as sparingly as possible to the point where mechanical stressing is indispensable. Case studies were demonstrated in three different genres, i.e., organic synthesis, electroceramics and utilization of mineral resources.     

Effect of intramolecular crosslinker properties on the mechanochemical fragmentation of covalently folded polymers

The mechanochemical stability of polymers in solution is enhanced if the chains are covalently folded. Under shear forces, the additional bonds absorb mechanical energy and inhibit unfolding, and as a result, slow down fragmentation. However, not all crosslinkers are equal in terms of their properties (length, strength, etc.). In order to understand the role of these added bonds in the polymers' stability under mechanical stress, a thorough study compares the rate of mechanochemistry on single-chain polymer nanoparticles which have been folded with crosslinkers with different lengths, strengths, positioning, and valencies. The usage of bonds with different mechanical strengths in the crosslinkers was found to be the most powerful way to change the mechanochemical fragmentation rate. In addition, positioning and valency also play significant role in the mechanical stabilization mechanism. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 , 58, 692–703     

Reaction rates in a theory of mechanochemical pathways

If one applies mechanical stress to a molecule in a defined direction then one generates a new, effective potential energy surface (PES). Changes for minima and saddle points (SP) by the stress are described by Newton trajectories on the original PES (Quapp and Bofill, Theor. Chem. Acc. 2016, 135, 113). The barrier of a reaction fully breaks down for the maximal value of the norm of the gradient of the PES along a pulling Newton trajectory. This point is named barrier breakdown point (BBP). Depending on the pulling direction, different reaction pathways can be enforced. If the exit SP of the chosen pulling direction is not the lowest SP of the reactant valley, on the original PES, then the SPs must change their role anywhere: in this case the curve of the log(rate) over the pulling force of a forward reaction can show a deviation from the normal concave curvature. We discuss simple, two‐dimensional examples for this model to understand more deeply the mechanochemistry of molecular systems under a mechanical stress. © 2016 Wiley Periodicals, Inc.