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261.
de Jong JJ Tiemersma-Wegman TD van Esch JH Feringa BL 《Journal of the American Chemical Society》2005,127(40):13804-13805
The ability to select, amplify, and lock dynamic equilibria is of great interest into understanding and applying chiral systems in Nature. The dynamic equilibrium between P and M helicity of a nonchiral diarylethene switch 3 could selectively be coaggregated in the gel state by complementary chiral switches 1 and 2 (that itself is also subjected to the same equilibrium between P and M helicity). Enantiomeric excess as high as 94% was observed during this dual task for 1 and 2 (arranging itself and 3 in only one conformation during aggregation). Interestingly, opposite chiral induction was observed, although the conformation of both 1 and 2 is R. 相似文献
262.
Jaap Schut Manfred Stamm Michel Dumon Jocelyne Galy Jean-François Gérard 《Macromolecular Symposia》2003,202(1):25-36
Syndiotactic polystyrene (sPS) is a new semi-crystalline thermoplastic which is believed to fill the price-performance gap between engineering and commodity plastics. In order to reduce the high processing temperature of sPS (>290°C), an epoxy-amine model system was used as a reactive solvent. Such a processing aid can be used to achieve a 50 to 500 fold lowering of the melt viscosity. When initially homogeneous solutions of sPS in a stoechiometric epoxy-amine mixture are thermally cured, Reaction Induced Phase Separation (RIPS) takes place, leading to phase separated thermoplastic-thermoset polymer blends. We focus our study on low (wt% sPS < 20%) and high concentration blends (wt% sPS > 60%) prepared by two processing techniques (mechanical stirring in a laboratory reactor or internal mixer/ reactive extrusion respectively). These blends have different potential interests. Low concentration blends (sPS domains in an epoxy-amine matrix) are prepared to create new, tunable blend morphologies by choosing the nature of the phase separation process, i.e. either crystallisation followed by polymerization or polymerization followed crystallisation. High concentration blends (sPS matrix containing dispersed epoxy-amine particles after RIPS) are prepared to facilitate the extrusion of sPS. In this case, the epoxy amine model system served as a reactive solvent. The time to the onset of RIPS is in the order of 7-9 min for low concentration blends, while it increases to 20-45 min for high concentration samples, as the reaction rates are substantially slowed down due to lower epoxy and amine concentrations. During the curing reaction the melting temperature of sPS in the reactive solvent mixture evolves back from a depressed value to the level of pure sPS. This indicates a change in the composition of the sPS phase, caused by (complete) phase separation upon reaction. We conclude that our epoxy amine system is suited for reactive processing of sPS, where final properties depend strongly on composition and processing conditions. 相似文献
263.
Jaap Schut Manfred Stamm Michel Dumon Jean-François Gérard 《Macromolecular Symposia》2003,198(1):355-362
Syndiotactic polystyrene (sPS) has to be processed at high temperatures (i.e. >290°C due to its melting point of 270°C), which approaches its degradation temperature. We aim to facilitate the processing of sPS by lowering its melt temperature and viscosity with a curable epoxy/amine model system as reactive solvent, which will result in a thermoplastic-thermoset polymer blend. As a first step we therefore investigated the melting behaviour of sPS in epoxy monomer, established its phase diagram, and investigated the crystalline form of sPS in these mixtures. DGEBA epoxy monomer is found to be a solvent for syndiotactic polystyrene at temperatures above 220°C. The DGEBA-sPS phase diagram was established by means of DSC, on the basis of crystallization and melting peaks. The form of the curve in the phase diagram indicates that DGEBA is a poor solvent for sPS. In WAXS studies of blends only the β crystalline form was detected, not the δ form, thus no sPS-DGEBA polymer-solvent compounds (clathrates) were detected. However, DGEBA can still serve as a monomer for improved processing as it depresses the crystallization temperature by 20 to 60 K upon addition of 20 to 90 wt% DGEBA respectively, while a 16 to 45 K melting peak depression can be observed by adding 20 to 90 wt% DGEBA. 相似文献
264.
Four series of polymeric model networks were prepared with bimodal chain length distribution between crosslink points and two types of dangling chains as network defects. In the last series the crosslink density was changed without a large change in the chemical composition. The fracture toughness of those networks were compared with that of the defect–free networks. The fracture toughness of the various networks is surprisingly little influenced by the introduction of defects. Neither bimodality, nor dangling chains, nor a high sol fraction alters the toughness of the network. A good correlation between KIc and the weight fraction of polyether is observed. A much smaller dependence of KIc on the strand density can be deduced. The yield stress is high and approximately invariant for all systems studied. It is concluded that the toughness of a polymeric network does not seem to be influenced by its perfection and only to a small extent by its degree of crosslinking. 相似文献