Flow‐induced structure formation is investigated with in situ wide‐angle X‐ray diffraction with high acquisition rate (30 Hz) using isotactic polypropylene in a piston‐driven slit flow with high wall shear rates (up to ≈900 s−1). We focus on crystallization within the shear layers that form in the high shear rate regions near the walls. Remarkably, the kinetics of the crystallization process show no dependence on either flow rate or flow time; the crystallization progresses identically regardless. Stronger or longer flows only increase the thickness of the layers. A conceptual model is proposed to explain the phenomenon. Above a certain threshold, the number of shish‐kebabs formed affects the rheology such that further structure formation is halted. The critical amount is reached already within 0.1 s under the current flow conditions. The change in rheology is hypothesized to be a consequence of the “hairy” nature of shish. Our results have large implications for process modelling, since they suggest that for injection molding type flows, crystallization kinetics can be considered independent of deformation history.
Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH2CHPh][OTf] (Mes*=2,4,6-(t-Bu)3C6H2) occurred under mild conditions at 60 °C in CD2Cl2, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu4][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C6Cl4O2)3) followed by chromatography on silica removed [NBu4][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH2CHPh][Δ-TRISPHAT]?x[NBu4][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P. 相似文献
Convenience food products tend to alter their quality and texture while stored. Texture-giving food components are often starch-rich ingredients, such as pasta or rice. Starch transforms depending on time, temperature and water content, which alters the properties of products. Monitoring these transformations, which are associated with a change in mobility of the starch chain segments, could optimize the quality of food products containing multiple ingredients. In order to do so, we applied a simple and efficient in situ 13C solid-state magic angle spinning (MAS) NMR approach, based on two different polarization transfer schemes, cross polarization (CP) and insensitive nuclei enhanced by polarization transfer (INEPT). The efficiency of the CP and INEPT transfer depends strongly on the mobility of chain segments—the time scale of reorientation of the CH-bond and the order parameter. Rigid crystalline or amorphous starch chains give rise to CP peaks, whereas mobile gelatinized starch chains appear as INEPT peaks. Comparing 13C solid-state MAS NMR experiments based on CP and INEPT allows insight into the progress of gelatinization, and other starch transformations, by reporting on both rigid and mobile starch chains simultaneously with atomic resolution by the 13C chemical shift. In conjunction with 1H solid-state MAS NMR, complementary information about other food components present at low concentration, such as lipids and protein, can be obtained. We demonstrate our approach on starch-based products and commercial pasta as a function of temperature and storage. 相似文献
Trihalide salts were found to efficiently promote photochemical dediazotizing halogenations of diazonium salts. In contrast to classical Sandmeyer reactions, no metal catalysts are required to achieve high yields and outstanding selectivities for halogenation over competing hydridodediazotization. Convenient protocols are disclosed for synthetically meaningful brominations, iodinations, and chlorinations of diversely functionalized derivatives. 相似文献
An increasing number of organic light-emitting diodes (OLEDs) is nowadays based on the use of polymers as the emissive material. For this material class in particular, solution-processing of the OLEDs has gained traction in both research and industry. However, in order to access multilayer material systems, orthogonal solvents must be used to prevent dissolution of previously prepared layers. The use of crosslinkers can facilitate this production method by reducing the number of orthogonal solvents needed since insoluble networks are generated. In this work, a novel bisazide crosslinker is employed to insolubilize Super Yellow, a polyphenylene-vinylene emitter. This allows the use of an additional poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine electron blocking layer (EBL) from the same solvent. Devices including the blocking layer show improved efficacies compared to reference devices without the additional EBL, while also maintaining the emission spectrum. Using the upscalable technique of doctor blading, OLEDs were fabricated which showed a particularly noticeable effect of the blocking layer with a nearly twofold increase in luminance and a 56% increase in current efficacy. 相似文献