Materials modelling: A bridge from atoms to bulk properties

The use of molecular-level materials modelling techniques in the development of advanced performance polymers is discussed, with particular emphasis upon bridging the large difference in the scales of dimensions between atomic structure and fabricated parts. The advantages and disadvantages of bulk quantitative structure-property relations and atomistic modelling are assessed, and the method of group interaction modelling is suggested as a means of bridging the dimensional scales.After a brief introduction to the concept of group interaction modelling, examples of modelling the engineering properties of polymers are presented which are difficult to model quantitatively by any other means. The important phase transitions from the crystal and glassy states of matter to those of rubber- and liquidlike states are shown quantitatively to be due to the same isoenergetic condition. The viscoelastic properties of a polymer are critical for many applications and expressions are derived for the loss and storage components of the complex modulus, with reference to failure initiation conditions. The effect of crosslinking in thermosets upon the glass transition temperature and viscoelastic properties is outlined. Finally, the scaling of time from atomic vibrations to the years involved in creep and ageing effects are discussed.     

分子印迹技术及其应用

分子印迹技术是将高分子科学、材料科学、生物学、化学工程等有机集成。基于分子印迹技术所制备的分子印迹聚合物具有选择性高、稳定性好、应用范围广等特点 ,近年来得到了日益广泛和深入的研究。介绍了分子印迹技术的原理、分子印迹聚合物的制备方法、分子印迹技术的应用场合和实例 ,并简要预测了分子印迹技术领域未来的发展趋势。     

Quantum chemical studies of Li cation binding to polyalkyloxides

A quantum chemical study of the binding of Li⁺ cation to polyalkyloxides has been carried out. The lithium cation interaction with three polyalkyloxides (polyethylene oxide (PEO), polytrimethylene oxide (PTMO), and polypropylene oxide (PPO)) has been investigated using ab initio molecular orbital theory at the HF/6-31G^* level with molecular models for the polymers. Coordination by one to six oxygens was considered. In addition, higher level calculations were carried out using G3(MP2) theory for coordination of Li⁺ by one oxygen. For coordination of lithium by one oxygen, the binding energy ordering is PTMO>PPO>PEO, with PTMO having the largest lithium cation affinity. The same ordering is found for larger coordination numbers with the exception of coordination by six oxygens, where the ordering changes due to the steric interactions.     

Molecular correlations in sheared thermotropic copolyesters showing banded textures

Banded textures produced in a thermotropic liquid crystal polymer by shearing between glass slides are examined by using both transmission electron and polarized light microscopy. The periodic variation in director orientation about the shear axis, as measured by light microscopy, is shown to be distinctly different from that indicated by electron diffraction. Measurements of birefringence and observation of Zernicke phase contrast indicate periodic variations in optical properties of the polymer, in step with the bands. Such effects are accounted for in terms of a synchronous rotation of the planar aromatic groups about the molecular chain axes. Evidence for an out-of-plane component of molecular orientation is also presented.     

改进尿素包装工艺 不断提高产品质量

通过对尿素包装工艺的不断改进，提高了尿素粒度、减少粉尘含量，效果明显。     

Intramolecular crosslinking of poly(vinyl alcohol)

Poly(vinyl alcohol) is crosslinked in dilute solution (c=0.1 wt%) with glutaraldehyde. The reaction product is characterized by viscometry and gel permeation chromatography (g.p.c.). The intrinsic viscosity decreases with increasing degree of crosslinking and does not depend on temperature. G.p.c. reveals that the reaction product is not homogeneous, but consists of a mixture of particles with different sizes, possibly both intra- and intermolecularly crosslinked molecules. The intramolecularly crosslinked molecules are smaller in size than the initial polymer molecules and their size depends on the degree of crosslinking. They possess a narrow particle size distribution even if the initial polymer sample had a broad molecular weight distribution.     

合成直链烷基苯的锆磷铝固体酸催化剂 I.催化剂合成及其影响因素

合成了一系列用于苯与直链烯烃烷基化反应的含有杂原子的磷铝分子筛固体酸催化剂 (MeZrAPO 5 ) ,同晶取代磷铝分子筛骨架中磷和铝的杂原子包括锆和至少一种选自硅、硼、镓、锗、铁、镁、锡等的元素。考察了晶化温度、晶化时间、杂原子种类、铝源等因素对催化剂合成的影响 ,探索了合成样品中模板剂脱除的最佳条件。结果表明 ,晶化温度高于 15 0℃、n(TEA) /n(Al2 O3 )≥ 1 5以及加入Zr原子都有利于直接生成MeZrAPO 5晶相 ;用小晶粒和高结晶度的铝源合成时 ,分子筛的结晶度高。     

奎宁印迹聚合物的吸附与识别特性的研究

以奎宁为模板分子 ,利用分子印迹技术合成了一种新型的类似于人工受体的印迹聚合物 ,研究了它对奎宁和其它底物的吸附特性和选择性识别能力 ,并对其固相萃取性能做了初步的研究。     

Cholesterol‐imprinted polymer receptor prepared by a hybrid imprinting method

A novel cholesterol‐imprinted polymer (CMIP‐H) was prepared by a hybrid method of covalent imprinting and non‐covalent imprinting. This approach involves the copolymerization of a template‐containing monomer, cholesteryl 2‐hydroxyethyl methacrylate carbonate, and a cross‐linker, followed by hydrolysis to afford a flexible guest‐binding site accompanied with the easy and efficient removal of a ‘sacrificial spacer’. The effect of solvent on the binding capacity of CMIP‐H towards cholesterol was studied, indicating that a good binding capacity towards cholesterol could be achieved in a less‐polar solvent. The binding experiments of CMIP‐H towards a series of structural analogues of cholesterol, including cholesterol acetate, progesterone and stigmasterol, were carried out in hexane. The results showed that CMIP‐H almost did not bind cholesterol acetate at all because the hydrogen‐bonding site is blocked. It exhibited a similar binding towards both cholesterol and stigmasterol, but much higher binding towards progesterone. Copyright © 2005 Society of Chemical Industry     

Retaining maximum antioxidative potency of wheat germ oil refined by molecular distillation

A process of physical refining wheat germ oil using the technique of molecular distillation (MD) is presented in this work. Wheat germ oil was obtained from the germ by solvent extraction using hexane and also by cold pressing. The oil extracted with hexane was degummed and bleached before deacidification in order to modify the parameters of phosphorus and color. The goal in carrying out the stage of physical refining by MD was to preserve the maximum amount of original antioxidative potential obtained from extraction of the crude oil. The effect of evaporation temperature of one‐stage MD on the efficiency of free fatty acid elimination was studied. The antioxidant portion was followed by means of analytic determination of tocopherols by high‐performance liquid chromatography. Tocopherol retention up to 98% was achieved in the oil extracted by pressing, and yields of up to 96% were achieved in the oil extracted with hexane. Copyright © 2007 Society of Chemical Industry