Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair

The first enantioselective tungstate‐catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug‐like phenyl and heterocyclic sulfides under mild conditions with H₂O₂, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)‐Lansoprazole, a commercial proton‐pump inhibitor. The active ion‐pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies.     

Synthesis,characterization and energetic properties of novel 1-methyl-1,2,4-triazolium N-aryl/N-pyridinyl ylids

Synthesis, characterization and energetic properties of novel, nitrogen-rich 1-methyl-1,2,4-triazolium N-aryl/N-pyridinyl ylids 3a–m are reported.     

Improving the Flame Retardancy of Polybenzoxazines with a Reactive Phosphorus-Containing Compound

A novel flame retardant resin was prepared by modifying benzoxazines with a reactive phosphorus-containing compound, 2-(6-Oxido-6H-dibenzo[c,e][1,2]oxa-phosphorin-6-yl) 1,4-benzenediol (ODOPB). The curing reactions of the benzoxazines containing ODOPB (ODOPB-BOZ) and a type of bifunctional benzoxazine (B-BOZ) were investigated via differential scanning calorimetry. The ODOPB-BOZ precursors exhibited lower curing temperature in comparison with the B-BOZ. Through dynamic mechanical analysis tests, it was found that the glass transition temperature and storage modulus of the cured ODOPB-BOZ were lower than those of the cured B-BOZ. Moreover, the tensile and flexural properties of the cured ODOPB-BOZ were also lower than those of the cured B-BOZ. The TGA tests proved that, owing to the presence of ODOPB, the char yield of the polybenzoxazines were remarkably raised while the decomposition rates at higher temperature were reduced. It was found that the flame retardancy of cured ODOPB-BOZ attained V-0 grade upon the UL-94 tests while that of cured B-BOZ was V-1 grade. SEM images showed that more compact char layers were formed in the cured ODOPB-BOZ after combustion, resulting in the improvement of flame retardance.     

A finite element model using multi-layered shell element in laser forming

Due to its enormously high flexibility laser forming has been gaining importance in recent years. This rapidness and flexibility demand very precise controlling strategies especially when simulating the process of large plates and challenging the limited computation power of the current workstation. A simple, robust and accurate modeling method of laser forming has been demonstrated to solve this problem. The simplified model is meshed by multi-layered shell element, simulated with a more real scanning method and fewer parameters. The intelligent meshing strategies have reduced the number of elements dramatically. Thus the simulation efficiency has been improved significantly. By comparing the simulation results under the simplified model with the results under the traditional model for laser forming, the applicability of proposed method has been proven. The method of these simplified models is also suitable to simulate complex finite element models, which take much time to simulate. It would throw some light on the thermal mechanically coupled-field simulation of large sheet.     

Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry

Thermomechanical properties of polymers highly depend on their glass transition temperature (T _g). Differential scanning calorimetry (DSC) is commonly used to measure T _g of polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T _g in such type of polymers. The changes in specific heat capacity (Δc _p) at T _g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc _p from flexible polymer (0.28 J g^?1 K^?1 for polystyrene) to rigid CPs (10^?3 J g^?1 K^?1 for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc _p at T _g by a factor of 10, confirming that backbone rigidity reduces the Δc _p. Additionally, an increase in the crystalline fraction of the CPs further reduces Δc _p. We conclude that the difficulties of determining T _g for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1635–1644