Reverse iodine transfer polymerization of vinyl acetate and vinyl benzoate: synthesis and characterization of homo‐ and copolymers

Homo‐ and copolymers of vinyl esters including vinyl acetate (VAc) and vinyl benzoate (VBz) were synthesized via the reverse iodine transfer radical polymerization technique. Polymerization was carried out in the presence of iodine as the in situ generator of the transfer agent and 2,2′‐azobis(isobutyronitrile) as the initiator at 70 °C. Reverse iodine transfer radical homopolymerization of VAc and VBz led to conversions of 76 and 57%, number‐average molecular weights of 8266 and 9814 g mol^?1 and molecular weight distributions of 1.58 and 1.49, respectively. The microstructure of the synthesized polymers was investigated in detail using gel permeation chromatography, ¹H NMR, ¹³C NMR and distortionless enhancement of polarization transfer (135° decoupler pulse) techniques. Relatively narrow molecular weight distribution and controlled and predictable trend of molecular weight versus conversion were observed for the synthesized polymers, showing that reverse iodine transfer radical homo‐ and copolymerization of VAc and VBz proceeded with controlled characteristics. Results of molecular weight and its distribution along with the ¹H NMR spectra recorded for homo‐ and copolymers indicated that side reactions can occur during the course of polymerization with a significant contribution when VAc, even in a small amount, was present in the reaction mixture. This can result in polymer chains with aldehyde dead end and broadening of the molecular weight distribution. © 2015 Society of Chemical Industry     

One-pot synthesis of soluble wholly aromatic liquid crystalline copoly(ester amide)s with high thermal and dimensional stability

Abstract

Thermotropic liquid crystalline polymers (LCPs) have been of great interest for electronic packaging. Herein, we introduce a series of wholly aromatic, thermotropic LCPs from copoly(ester amide)s of 6-hydroxy-2-naphthalic acid, isophthalic acid, terephthalic acid, and 4-aminophenol, prepared by a convenient one-pot melt polycondensation. Almost synthesized copoly(ester amide)s exhibited good solubility in common organic solvents at room temperature. Furthermore, they possessed high thermal stability with 2% degradation temperatures (T_id) of 359–368?°C and the char yields (at 600?°C) of 50.3–55.6%. The synthesized copoly(ester amide)s had relatively low coefficient of thermal expansion (CTE) values, which were 35.85–41.21?ppm °C^?1 in the temperature range of 50–200?°C. Furthermore, an annealing process could be employed to improve the thermomechanical properties of synthesized polymers. For instance, the CTE of sample LCP3 in range temperature of 275–315?°C was reduced by more than 90% after annealing at 320?°C for 1?h, implying the feasibility for electronic packaging.     

Numerical simulation of gas-assisted polymer-melt electrospinning: Parametric study of a multinozzle system for mass production

In this study, we developed a multiphysics model for simulation of a gas-assisted melt-electrospinning (GAME) process, focusing on jet formation and propagation behavior. By numerically calculating the stresses acting on the jet during a single-nozzle GAME process, the shear viscous stress was identified as the main factor with respect to jet stretch; thus, the relationship between shear viscous stress and jet thickness was investigated. The jet stretch ratio increased sharply when shear viscous stress reached the level at which jet sharpening occurred, leading to stable jet formation. We defined this stress as the critical shear viscous stress to determine stable spinnability. By imposing an electric field distribution calculated for a multi-nozzle array (number of nozzles, tip-to-tip distance, and applied voltage) on the boundary condition of the single-nozzle GAME simulation model, multinozzle GAME was simulated; this enabled proposal of a spinnability diagram for stable spinning.     

Fabrication of multi-filler thermoset-based composite bipolar plates for PEMFCs applications: Molding defects and properties characterizations

The bipolar plate (BP) material should possess contradictory properties. They should also manufacture from low-cost methods and materials. In the current investigation, thermoset-based composite materials reinforced with conductive fillers, and the compression molding process is implemented. In addition to fabricating the bipolar plates (BPs) with and without the flowing channels, alleviating the defects during the molding process is performed. The channels are perfectly formed on the plates with the designed depth of 0.65 mm and 0.5 mm of width. In the meanwhile, we alleviate different molding defects, which spoil the surface appearance and part properties. Regarding the physical properties, the water contact angle is measured to be around 85°. The through-plane electrical conductivity of molded plates showed high values up to 38 S/cm, and the interfacial contact resistance measured to be 18–24 mΩ cm². The mean value of the flexural strength of the produced samples was equal to 47 MPa, which is almost twice the DOE target (>25 MPa).     

To pursue FexCoy-PANI/CNT catalysts for oxygen reduction reaction in acid medium with controlled molecular self-assembly method

The mainstream of pyrolyzed transitional metal-nitrogen-carbon (M-N-C) catalysts for ORR still confront difficulty in PEMFC application. To pursue M-N-C structure from wet chemistry at ambient temperature, this paper prepares Fe_xCo_y-PANI/CNT porous structures composed of amorphous Fe and Co NPs into PANI layer on CNT surface, supported by the controlled molecular self-assembly mechanism (MS). For their ORR behaviors in acid medium, all Fe_xCo_y-PANI/CNT catalysts demonstrate similar features as Pt-based catalyst in low current density region, and 4e pathway and active sites in pore utilization in high current density region. Specifically, we disclosed nitrogen in PANI matrix dominates specific activity for ORR, and a little transitional metal attain mass activity at maximum. The active sites mounted into PANI matrix and 4e pathway help catalysts to achieve high durability. Thus, we extend a new type of platinum-free catalyst and develop a bottom-up approach for preparation-structure-activity, expecting to drive PEMFC remarkably.     

On‐surface polymerization – a versatile synthetic route to two‐dimensional polymers

Two‐dimensional (2D) polymers are novel covalent sheet materials with promising properties, but also great synthetic challenges. The inadequacy of traditional wet chemical synthesis calls for new synthetic paradigms. In this respect, employing surfaces as inherently 2D reaction venues appears an adequate choice and has recently already yielded encouraging results. Polymerization at air ? liquid and liquid ? liquid interfaces has been reported from time to time over the last decades, whereas recent efforts on solid surfaces are less traditional. In either case, both movement and coupling of monomers are already confined in two dimensions at interfaces or on surfaces. Accordingly, this approach naturally affords low‐dimensional reaction products. To achieve 2D reticulation, monomers are functionalized with multiple reactive groups of the same or a different kind, whereby their number and stereochemical arrangement predefines the ideal structure of the resulting 2D polymer. This perspective article exemplifies different approaches, i.e. types of surfaces, coupling chemistry and activation schemes, to employ surfaces for novel synthetic routes for the bottom‐up synthesis of 2D polymers. © 2015 Society of Chemical Industry     

Experimental study on the propagation characteristics of hydrogen/methane/air premixed flames in a narrow channel

This work is focused on the explosion characteristics of premixed gas containing different volume fractions of hydrogen in a narrow channel (1000 mm × 50 mm × 10 mm) under the circumstance of stoichiometric ratio. The ignition positions were set in the closed end and the middle of the pipeline respectively. The results showed that when the gas was ignited at the pipeline closed end, the propagating flame was tulip structure for different premixed gas. When the hydrogen volume fraction was less than 40%, the flame propagation speed increased significantly with the rise of hydrogen volume fraction, and the overpressure peak also appeared obviously in advance. However, when the volume fraction of hydrogen was more than 40%, the increase of flame propagation speed and the overpressure peak occurrence time varied slightly. Furthermore, when the ignition position was placed in the middle of the pipeline, the flame propagation speed propagating to the opening end was much faster than that propagating to the closing end, and there was no tulip shape when the flame propagates to the opening end. The flame propagating to the closed end appeared tulip shape under the influence of airflow, and high-frequency flame oscillation occurred during the propagation. This work shows that the hydrogen volume fraction and ignition position significantly affected the flame structure, flame front speed, and explosion overpressure.     

Predetermination of potential plastic hinges on reinforced concrete frames using GFRP reinforcement

In the past, glass fiber-reinforced polymer (GFRP)-reinforcement has been successfully applied in reinforced concrete (RC) structures where corrosion resistance, electromagnetic neutrality, or cuttability were required. Previous investigations suggest that the application of GFRP in RC structures could be advantageous in areas with seismic activity due to their high deformability and strength. However, especially the low modulus of elasticity of GFRP limited its wide application as GFRP-reinforced members usually exhibit considerably larger deformations under service loads than comparable steel-reinforced elements. To overcome the aforementioned issues, the combination of steel and GFRP reinforcement in hybrid RC sections has been investigated in the past. Based on this idea, this paper presents a novel concept for the predetermination of potential plastic hinges in RC frames using GFRP reinforcement. To analyze the efficiency of the concept, nonlinear finite element simulations were performed. The results underscore the high efficiency of hybrid steel-GFRP RC sections for predetermining potential plastic hinges on RC frames. The results also indicate that the overall seismic behavior of RC structures could be improved by means of GFRP as both the column base shear force during the seismic activity as well as the plastic deformations after the earthquake were considerably less pronounced than in the steel-reinforced reference structure.     

纺粘非织造聚合物拉伸模型初探

为探究纺粘非织造工艺中工艺参数对纤维最终直径的影响,文章基于纺粘非织造聚合物拉伸过程,构建了纺粘非织造聚合物拉伸理论模型,并应用MATLAB对模型进行数值计算。同时,选取纺粘工艺参数中的气流初始速度、聚合物初始温度、聚合物质量流量3个因素,通过控制变量法比较观察不同方案下经过数值求解后得到的纤维直径,得出3个因素分别对纤维最终直径的影响。结果表明,气流初始速度越大,聚合物初始温度越高,聚合物质量流量越小,最终形成的纤维直径越细。