甲壳质、甲壳胺衍生物保护的贵金属胶体

<正> 高分子保护金属胶体是近年来金属催化剂领域中引人注目的研究课题。它除了具有负载型金属催化剂的优点外,还具备下列新优点:a.胶体分散体系可形成“均相”溶液;b.保护高分子可以屏蔽胶体催化剂,减小毒物或空气的不良影响;c.胶体溶液的透光性能比颗粒要好得多,由此最近高分子保护金属胶体常被用于光化学研究中的催化剂;d.高分子保护金属胶体与普通金属胶体相比较,不仅具有较稳定的特点,而且尺寸小(1—10nm)、分布窄,表现出极高的催化活性和选择性;e.保护高分子对金属的修饰作用,可     

含有不同脂肪环胺侧基的聚丙烯酰胺保护的贵金属胶体制备的研究

<正> 近年来高分子保护金属胶体的研究在金属催化剂领域中受到人们的突出关注。自Hirai等人对聚乙烯吡咯烷酮保护的铂族金属胶体的系统研究工作发表之后,一项重要的研究进展是双金属胶体的制备成功。当前制备窄分布乃至单分散胶体的努力成为众多研究的集中目标,具有重要的理论意义和实际应用价值。Bradley等报道用金属蒸汽冷凝至含有高分子稳定剂的有机溶剂中制备得到2.0—5.0nm直径的金属胶体,Schmid等报道用水溶性三苯膦磺酸钠小分子配位体作为稳定剂制备得到直径为18.6±0.1nm的金胶体。Esumi等用在有机溶剂中热解乙酸钯的方法制备得到不同粒径的均一球形的钯金属胶体。     

胶体滴定法及其应用

胶体滴定法是测定天然和合成聚电解质离子基团的好方法,由日本学者寺山宏首创于1948年。随后经过许多化学家的努力研究和开发,使之成为适应广泛pH值范围的最简单的高分子电解质的定量方法,广泛地用于生物大分子和合成高分子电解质的链化学结构分     

高分子链在球内表面上的吸附/排空转变

应用自洽场理论(SCFT)研究了受限于球内的高分子溶液的结构,重点关注高分子链在受限壁附近的行为.根据自洽场理论数值计算结果,讨论了球半径、高分子与球限制壁的相互作用、高分子平均浓度等因素对球内高分子浓度分布的影响.从高分子浓度分布和吸附/排空层厚度可以发现,在一定的条件下,受限的高分子在受限壁上会发生吸附/排空转变.吸附/排空转变与受限球大小、高分子链长和平均浓度,以及高分子链与受限壁之间相互作用都有关系.理论预测发生吸附/排空转变时的高分子与球限制壁的临界相互作用参数与链长的倒数成线性关系,且斜率与球半径有关.限制球越小,要发生吸附/排空转变,需要高分子与球之间有更大的临界吸引能.     

两性高分子作为保护剂的贵金属胶体的制备及其催化氢化活性

在金属催化领域,近年来人们对于高分子保护金属胶体的研究表现出很大的兴趣。高分散、窄分布金属胶体的制备研究成为众多工作者努力的目标。这在沟通分子催化与凝聚相物质催化间的联系有着重要的理论意义和应用价值。人们作出了种种努力设法获得高分散、窄分布的金属胶体。如:Bradley等报导用金属蒸汽冷凝法,Schmid等用水溶性三苯膦磺酸钠小分子配位体作为稳定剂,Esumi等用在有机溶剂中热解金属化合物的方法,Toshima等利用表面活性剂形成胶束的方法,Nagy的工作也很相似。这些工作在一定程度上取得进展。     

圆柱表面上高分子共混刷微相分离的自洽场理论研究

我们运用高分子自洽场理论方法,结合“masking”技术,研究了高分子共混刷接枝到无限长圆柱表面上的微相分离行为. 理论预言了柱面上高分子共混刷的两种典型相分离形态：平行条纹相和环状相. 我们考察了圆柱半径、接枝密度以及相互作用参数对二者的影响,给出了体系在不同参数下相分离形态的相图,并且从相分离程度的角度对平行条纹相和环状相之间的转变作了解释. 我们还研究了平行条纹相相区数目以及环状相交替周期随圆柱半径的变化. 理论所预言的平行条纹相和环状相的存在以及体系参数对其稳定性的影响将有助于实验上合理设计、制备这类新颖的高分子刷材料.     

2004年度我国内地高分子科学基础研究进展概述

对2004年度我国高分子科学领域的某些重要研究成果和动态进行了简要介绍，包括高分子合成、树状高分子及其组装、光电活性聚合物、纳米复合体系、超双疏聚合物表面、聚合物囊泡、酶模拟和胶体晶体图案化组装等。     

Lennard-Jones流体中胶体粒子间耗尽势的密度泛函理论研究

基于Roth, Evans和Dietrich有关耗尽势的密度泛函理论研究了Lennard-Jones (L-J)流体中胶体粒子间的耗尽势. 通过计算胶体稀溶液中两个胶体粒子在不同条件下的耗尽势, 进一步分析了L-J流体的相关因素对耗尽势的影响. 结果表明, L-J流体分子的体积分数、胶体粒子与溶剂分子的尺寸比率、L-J流体分子间的相互作用以及胶体粒子与流体分子之间的弱相互作用等因素均可对胶体粒子间耗尽势产生显著影响. 研究结果可为实验上调控胶体粒子间的相互作用提供可能的线索.     

硬核Yukawa流体中胶体粒子间的耗尽势

基于Roth、Evans和Dietrich有关耗尽势的密度泛函理论研究了硬核Yukawa(HCY)流体中胶体粒子间的耗尽势.在极稀溶液条件下,通过计算两个胶体粒子在不同条件下的耗尽势,分析了HCY流体的相关因素对耗尽势的影响.结果表明,胶体粒子与溶剂分子的尺寸比率、HCY流体分子间的相互作用、HCY流体分子的体相密度以及胶体粒子与流体分子之间的相互作用等因素均可对胶体粒子间耗尽势产生显著影响.研究结果可为实验上调控胶体粒子间的相互作用提供可能的线索.     

胶体粒子间的相互作用

胶体系统的显著特点是具有很高的比表面积,在没有粒子间排斥作用时,分散介质中的胶体粒子倾向于聚集以降低其比表面积。常用的胶体稳定方法包括静电稳定和位阻稳定。简单介绍了胶体粒子间相互作用的性质,并给出了可靠的测定方法,由此对胶体的稳定性进行了简要分析。     

Effects of polymer adsorption on the effective viscosity in microchannel flows: phenomenological slip layer model from molecular simulations

Molecular simulations (Dissipative Particle Dynamics - DPD) were used to quantify the effect of polymer adsorption on the effective shear viscosity of a semi-dilute polymer solution in microchannel Poseuille flow. It is well known that polymer depletion layers develop adjacent to solid walls due to hydrodynamic forces, causing an apparent wall slip and reduced effective viscosity (increased total flow rate). We found that depletion layers also developed in the presence of hydrodynamically rough adsorbed layers on the wall. Polymer-polymer (steric) repulsion between flowing and adsorbed polymer expanded the depletion layer compared to no-adsorption cases, and the effective viscosity was reduced further. Desorption occurred for higher shear rates, reducing the repulsion effect and shrinking the depletion layers. A phenomenological algebraic model for the depletion layer thickness, including a shear modified adsorption isotherm, was developed based on the simulation data. The depletion layer model can be used together with the effective viscosity model we developed earlier.     

Reduction of the effective shear viscosity in polymer solutions due to crossflow migration in microchannels: Effective viscosity models based on DPD simulations

Molecular dynamics simulations (dissipative particle dynamics–DPD) were developed and used to quantify wall-normal migration of polymer chains in microchannel Poseuille flow. Crossflow migration due to viscous interaction with the walls results in lowered polymer concentration near the channel walls. A larger fraction of the total flow volume becomes depleted of polymer when the channel width h decreases into the submicron range, significantly reducing the effective viscosity. The effective viscosity was quantified in terms of channel width and Weissenberg number Wi, for 5% polymer volume fraction in water. Algebraic models for the depletion width δ(Wi, h) and effective viscosity μ_e(δ/h, Wi) were developed, based on the hydrodynamic theory of Ma and Graham and our simulation results. The depletion width model can be applied to longer polymer chains after a retuning of the polymer persistence length and the corresponding potential/thermal energy ratio.     

Density functional theory of polymer-polymer phase separation behavior

Polyatomic density functional theory is applied to a binary polymer blend. The polymer reference interaction site model (PRISM) liquid state theory provides the homogeneous state correlation functions necessary for the application of density functional theory. An effective chi parameter can be recognized from the density functional expression; however, the phase separation criteria does not depend solely upon the chi parameter, rather it depends upon various combinations of the species-dependent direct correlation functions of the blend. The Flory-Huggins chi parameter along with the associated phase diagram is obtained when the monomer volumes of the blend species are equal and for a range of monomer-monomer attractive interactions. Calculations are performed both with and without the assumption of incompressibility. The density functional theory along with the PRISM determined “input” predict that an isotopic polymer blend shows an upper critical solution temperature (UCST) phenomena. © 1995 John Wiley & Sons, Inc.     

毛细管内高分子溶液的浓度分布

采用连续自洽场理论分析了毛细管中发生凝胶化之前的聚合物溶液浓度分布的影响因素及其规律. 结果表明, 体系尺寸有限时, 改变聚合物链段、溶剂与壁面的相互作用参数之差, 聚合物溶液浓度分布会发生贫化/吸附转变; 临界作用参数与聚合物链长的倒数呈线性关系, 且拟合常数与体系尺寸、聚合物溶液平均体积分数有关; 聚合物分子量分布为多分散时, 分子量较低的组分更容易接近容器壁面, 分子量较大的组分则相反. 总之, 增加聚合物溶液浓度、链长, 选择优良溶剂, 减小体系尺寸等都会使浓度分布更加均匀.     

MOLECULAR FIELD THEORY FOR NEMATIC LIQUID CRYSTAL POLYMER COMPRISING FLEXIBLE SPACER

Basea on the new model and concept of mtramolecular orientational order parameter, a molecular field theory was built up for main chain liquid crystalline polymer (MC-LCPs) with flexible spacers. The theory takes account of orientational correlation among all mesogens in a polymer chain and the relationship between the intramolecular orientation and spatial orientation of the mesogens. The free energy, temperature and entropy of the nematic-isotropic transition were determined with the theory and compared with experiments in current work. It was found that many unique transition properties of the MC-LCPs comprising flexible spacer are correctly predicted by the theory and the agreement of the theory with the experiments is impressive.     

Polymer Polydispersity Effect on Depletion Interaction between Colloidal Particles

The effect of polymer polydispersity on the polymer‐induced interaction between colloidal particles due to non‐adsorbing ideal chains is investigated. An analytical theory is developed for the polymer‐segment density between two plates and in the space surrounding two spheres by extending a recently proposed superposition approximation to include polymer polydispersity. Monte Carlo computer simulations were made to test the validity of the analytical theory. The polymer densities predicted by the superposition approximation are in reasonable agreement with simulation results for the polydisperse case. The simulations show that depletion leads to a size fractionation of the polymers. It is shown that size polydispersity has a small effect on the interaction between two parallel plates but a more significant effect on the interaction between two spheres. The range of the potential increases and the contact potential drops with increasing polydispersity.

Polymer‐segment density as a function of y for three values of x, as indicated, in the space surrounding two colloidal spheres with radius R = R_g0 and h = 0.48R_g0. Symbols are the MC results: polydisperse polymer (○; z = 1) and monodisperse polymer (•) samples. Curves are the predictions of the product‐function approximation for monodisperse polymer (solid lines) and polydisperse polymer (z = 1, dashed lines).     

Thermodynamical study on pressure-induced compatibility in UCST polymer-containing mixtures

The pressure effect on polymer-containing systems has been intensely studied in the past decades, and there has been increased interest in the effects of pressure on the miscibility of polymers[1—6]. One reason is the realization that such pressure effects could be important in many situations where such blends are used, e.g. when mixing a blend in an extruder or in forming arti-cles from a blend by injection molding. Another is the thermodynamics of typical polymer blends that are understood…     

Distribution of chain ends at the surface of a polymer melt: Compensation effects and surface tension

We consider the surface of a nearly incompressible polymer melt, extending the usual ground-state analysis of self-consistent field theory to describe finite length polymers in the ground-state potential. To maintain self-consistency, further corrections to the potential are calculated within linear response theory. From this, we find an excess of ends near the surface, followed by a compensating depletion on the R_g length scale, which relies crucially on the finite compressibility of the melt. The attraction of ends to the surface can be described as resulting from a surface potential for ends with a strength on the order of k_BT. Our results address the long-standing controversies of the distribution of chain ends, the chain-length dependence of the surface tension, and the interaction between objects immersed in a melt. © 1995 John Wiley & Sons, Inc.