Prediction of branch on branch and topological characteristics of low‐density polyethylene polymerization by a novel stochastic approach

A novel approach using Monte Carlo method applied to simulation of low‐density polyethylene (LDPE) polymerization in tubular reactor showing topological characteristics, and the comprehensive kinetic mechanism has been taken into consideration. The results show the precise details of the structure of a chain in the three levels of the backbone, the main branches, and branches on branch. The chain types include dead polymer, dead polymer with unsaturated end, and live polymer with primary radical, secondary radical, and tertiary radical. In this work, the branches on branch were identified in terms of number, length, and position of the branch. Sixty percent of branches on branch are 1 to 5 carbons long, and the longest branch on branch is about 50 carbons. Thus, this study provides a tool for more accurately mapping the polymer chains architecture, superior to determine the number, and position of long‐ and short‐chain branches in past researches. Finally, this approach will advance the prediction of microstructure‐related properties of polymer one step further.     

One-pot two step synthesis of unsymmetrically substituted indenes from 3,4-diarylbutadiene sulfones

A new one-pot two step synthesis of unsymmetrically substituted indenes from available 3,4-diarylbutadiene sulfones involves SO₂ thermal extrusion followed by acid- catalyzed cyclization of the diene formed, the cyclization proceeding selectively at the more electron-rich aryl rings. The procedure is efficient for substrates bearing donor, acceptor, as well as bulky substituents.     

Prospects for the combination of mechanochemistry and flow applied to catalytic transformations

The urge of developing modern alternatives regarding industrial production has led to the creation of novel techniques that help overcome critical disadvantages from traditional batch mechanochemistry. One promising strategy includes the merging of flow processes with mechanochemistry. Two technologies are herein highlighted: twin-screw extrusion (TSE) and Impact (induction) in Continuous flow HEated Mechanochemistry (I-CHEM) allowing not only the industrial production of polymers but also active pharmaceutical ingredients, synthesis of (nano)materials, and the obtention of high-added value products from biomass and wastes valorization.     

Automated solvent system screening for the preparative countercurrent chromatography of pharmaceutical discovery compounds

A fully automated countercurrent chromatography system has been constructed to rapidly screen the commonly used heptane/ethyl acetate/methanol/water solvent system series and translate the results to preparative scale separations. The system utilizes “on‐demand” preparation of the heptane/ethyl acetate/methanol/water solvent system upper and lower phases. Elution‐extrusion countercurrent chromatography was combined with non‐dynamic equilibrium injection reducing the screening time for each heptane/ethyl acetate/methanol/water system to 17 min. The result enabled solvent system development to be reduced to under 2 h. The countercurrent chromatography system was interfaced with a mass spectrometer to allow selective detection of target components in crude medicinal chemistry reaction mixtures. Mass‐directed preparative countercurrent chromatography purification was demonstrated for the first time using a synthetic tetrazole epoxide derived from a routine medicinal chemistry support workflow.     

Elution–extrusion counter-current chromatographic separation and theoretical mechanism of antioxidant from Robinia pseudoacacia flower

Robinia pseudoacacia flowers have attracted much attention because of numerous bioactivities. In this study, its extract showed the potential scavenging ability for 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 1,1-diphenyl-2-picrylhydrazyl free radicals. Under the guidance of antioxidant activity, the antioxidant extract was enriched by liquid-liquid extraction. The partition coefficients of the two main components in antioxidant extracts differed greatly, so in this study, elution-extrusion counter-current chromatography with the solvent system of n-hexane-ethyl acetate-methanol-water (2.5:5:2.5:5, v/v) was used to enhance the separation efficiency, and the two main components were successfully obtained. Among them, kaempferol showed strong antioxidant activity, which can be responsible for the activity of the extract. In order to deeply understand the antioxidant mechanism of kaempferol, the thermodynamics, frontier molecular orbital, and kinetics of scavenging free radicals were investigated by density functional theory. The results showed that 4′-OH in kaempferol was the most active group, which can scavenge free radicals by hydrogen atom transfer in non-polar solvents and activate 3-OH to generate double hydrogen atom transfer in the gas phase. But in polar solvents, it was more inclined to clear radicals through single electron transfer and proton transfer. The kinetic result showed that kaempferol needed 9.17 kcal/mol of activation energy to scavenge free radicals.     

Adding Value in Production of Multifunctional Polylactide (PLA)–ZnO Nanocomposite Films through Alternative Manufacturing Methods

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)–ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA–ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1–3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA–ZnO nanocomposites.     

How to Obtain the Maximum Properties Flexibility of 3D Printed Ketoprofen Tablets Using Only One Drug-Loaded Filament?

The flexibility of dose and dosage forms makes 3D printing a very interesting tool for personalized medicine, with fused deposition modeling being the most promising and intensively developed method. In our research, we analyzed how various types of disintegrants and drug loading in poly(vinyl alcohol)-based filaments affect their mechanical properties and printability. We also assessed the effect of drug dosage and tablet spatial structure on the dissolution profiles. Given that the development of a method that allows the production of dosage forms with different properties from a single drug-loaded filament is desirable, we developed a method of printing ketoprofen tablets with different dose and dissolution profiles from a single feedstock filament. We optimized the filament preparation by hot-melt extrusion and characterized them. Then, we printed single, bi-, and tri-layer tablets varying with dose, infill density, internal structure, and composition. We analyzed the reproducibility of a spatial structure, phase, and degree of molecular order of ketoprofen in the tablets, and the dissolution profiles. We have printed tablets with immediate- and sustained-release characteristics using one drug-loaded filament, which demonstrates that a single filament can serve as a versatile source for the manufacturing of tablets exhibiting various release characteristics.     

不同管径聚乙烯管的旋转挤出

通过口模旋转挤出制备3种管径聚乙烯(PE)管,系统研究其结构与性能。结果表明,相较于传统挤出PE管内串晶平行与轴向,旋转挤出过程中聚合物熔体的流动是轴向牵引流动和环向拖曳流动的叠加,其方向偏离轴向,可诱导串晶偏离轴向排列,从而提高PE管的环向取向度,实现PE管的环向增强,抑制裂纹在PE管内沿轴向扩展。随PE管管径的增加,在相同旋转角速度下环向流动线速度增大,串晶偏离轴向的夹角增加,环向取向度更高,因而旋转挤出制备的大口径PE管具有更优的性能。     

Influence of M w of LDPE and vinyl acetate content of EVA on the rheology of polymer modified asphalt

Asphalt binder was modified by low-density polyethylene (LDPE) and ethyl vinyl acetate (EVA) polymers to investigate the structure–property relationships of polymer-modified asphalt (PMA). The PMA was prepared in a high-shear blender at 160 °C. The optimum blending time (OBT) for each polymer was determined following a separate investigation. OBT was influenced by M_w, MWD, and polymer structure. The influence of M_w of LDPE and vinyl acetate (VA) content of EVA on PMAs was studied by rheological tools. Polymer modification improved the rheological properties of base asphalt. EVA–PMAs were found to be less temperature sensitive than LDPE-modified asphalts. LDPE modification increased flow activation energy (E_a) but EVA modification decreased E_a. Both VA content and M_w of LDPE have influenced the storage stability of PMAs. The low-temperature properties of PMAs and short ageing tests were not influenced by polymer type. On the other hand, the high-temperature properties of PMAs were strongly influenced by M_w of LDPE and VA content of EVA. Overall, EVA with low VA content showed the best temperature resistance to high- temperature deformations, the highest upper service temperature as well as the best storage stability.     

Thermal Behavior of Polypropylene-g-glycidyl Methacrylate Prepared by Melt Grafting

The thermal behaviors of glycidyl methacrylate (GMA)-grafted polypropylene (PP) (PP-g-GMA) with two different grafting degrees, namely, GPP1 and GPP2, were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), and thermogravimetrical analysis (TGA). DSC results suggested that the GMA grafted PP exhibited higher crystallization temperature T_c, higher melting temperature T_m, and higher crystallinity compared with the neat PP. The isothermal crystallization kinetics was analyzed with the Avrami equation and the total crystallization activation energy was calculated. It was concluded that the crystallization processes of PP and the grafted PP were controlled by nucleation and the values of the crystallization activation energy of PP and the grafted PP were almost identical. POM results suggested that the GMA grafted PP exhibited smaller spherulites size compared with the neat PP. WAXD patterns indicated that the neat PP encouraged the formation of γ phase, compared with the grafted PP, during the crystallization process. DMA results showed that melt grafting did not induce a clear effect on the γ-transition and β-transition of the amorphous phase but resulted in a decrease in mobility of the PP chains in the crystals. TGA curves suggested that the melt grafting slightly improved the thermal stability of PP.