Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Continuous Flow Fabrication of Block Copolymer–Grafted Silica Micro‐Particles in Environmentally Friendly Water/Ethanol Media

Polymer‐grafted inorganic particles (PGIPs) are attractive building blocks for numerous chemical and material applications. Surface‐initiated controlled radical polymerization (SI‐CRP) is the most feasible method to fabricate PGIPs. However, a conventional in‐batch reaction still suffers from several disadvantages, including time‐consuming purification processes, low grafting efficiency, and possible gelation problems. Herein, a facile method is demonstrated to synthesize block copolymer–grafted inorganic particles, that is, poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMEMA)‐b‐poly(N‐isopropylacrylamide) (PNIPAM)–grafted silica micro‐particles using continuous flow chemistry in an environmentally friendly aqueous media. Immobilizing the chain transfer agent and subsequent SI‐CRP can be accomplished sequentially in a continuous flow system, avoiding multi‐step purification processes in between. The chain length (MW) of the grafted polymers is tunable by adjusting the flow time or monomer concentration, and the narrower molar mass dispersity (Р< 1.4) of the grafted polymers reveals the uniform polymer chains on the particles. Moreover, compared with the in‐batch reaction at the same condition, the continuous system also suppresses possible gelation problems.     

Improvement of polyamide/thermoplastic polyurethane blends with polyamide 6-polyurethane copolymer prepared via suspension polymerization as compatibilizer

The polyamide 6-polyurethane copolymer (PA6-b-PU-b-PA6) was synthesized through anionic suspension polymerization and then mixed with polyamide 6/thermoplastic polyurethane (PA6/TPU) and polyamide 6, 6/thermoplastic polyurethane (PA66/TPU) blends using as the compatibilizer. The results show that the PA6-b-PU-b-PA6 copolymers powders several can be obtained through suspension polymerization using dimethicone as disperse medium. The average diameter of PA6-b-PU-b-PA6 copolymer powders decreased with the increasing of PU content. With the addition of PA6-b-PU-b-PA6, the TPU phase dispersed more uniformly in PA6 or PA66 matrix, and the size of TPU dispersed phase decreased obviously. The PA6-b-PU-b-PA6 copolymer with higher PU content shows better compatibilizing effect. Addition of PA6-b-PU-b-PA6 can improve both strength and toughness of the PA/TPU blends. When the amount of PA6-PU25% copolymer was 5 phr, the tensile strength and notched impact strength of PA6/TPU/PA6-PU25% blends increased 29 and 159.4%, respectively, compared to the PA6/TPU blend without compatibilizer.     

Decorating surface charge of graphite nanoplate using an electrostatic coupling agent for 3-dimensional polymer nanocomposite

Here, we report a facile approach to electrostatically couple the surface charges of graphite nanoplate (GNP) fillers and poly(methyl methacrylate) (PMMA) polymer particles using ethylene maleic anhydride (EMA) copolymer as an electrostatic coupling agent. Our strategy involved switching the intrinsic repulsive electrostatic interactions between the directly exfoliated GNPs fillers and the PMMA particles to attractive electrostatic surface interactions for preparing core(PMMA)-shell (GNP) precursor in order to optimizing 3-dimensionally dispersed polymer nanocomposite. As a result, the electrical conductivity of the composites dramatically increased by a factor of 16.7 in the EMA-coupled GNP/PMMA composites compared with that of the EMA-free GNP/PMMA composites. In addition, the percolation threshold was also notably reduced from 0.32 to 0.159 vol% after electrostatic coupling of the GNPs fillers and PMMA particles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48390.     

Study of Compatibilized Liquid Crystalline Polymer/Cyclic Olefin Copolymer Blends

The technology to produce compatibilized blends of liquid crystalline polymer and highly amorphous cyclic olefin copolymers through two novel approaches were studied. The first approach was to use silane-functionalized halloysite nanotube as nonspecific compatibilizer and the second method was reactive compatibilization. The study of blends and their resulting microstructure; their thermal, mechanical, and viscoelastic properties were investigated. The kinetic study of blends compatibilized through both routes was performed.     

驱油用抗盐聚合物KYPAM的应用性能

新研制并已投入工业生产的驱油用抗盐聚合物KYPAM，为具有梳形分子结构的超高分子量的AM／AHPE共聚物（共聚单体AHPE结构未知）。按大庆企业标准《驱油用聚丙烯酰胺》的规定测定6项质量指标，KYPAM均优于大庆2B838和日本三菱MO－4000；在矿化度为1000－19334mg/L的大庆（45℃），胜利（70℃，80℃）5种清水，污水中，1000mg/L的KYPAM溶液的粘度较对比超高分子量HPAM高30％－40％；在不脱氧180小时溶液老化测试中，KYPAM粘度保持率最高，KYPAM溶液45℃剪切稳定性略高于2B838和MO－4000溶液；KYPAM在3种水中的增粘性能（粘浓曲线，45℃和70℃）均远好于2B838和MO－4000。在70℃岩心驱油实验中，KYPAM污水溶液提高水驱后采收的幅度，阻力系数和残余阻力系数均高于英国胶体公司的HPAM1285清水溶液。     

Role of chain symmetry and hydrogen bonding in segmented copolymers with monodisperse hard segments

Thermoplastic segmented polyurethane and polyurea copolymers whose monodisperse hard segments are based on only a single diisocyanate molecule are discussed. The solid-state structure-property behavior of these materials demonstrates that a proper selection of the level of symmetry and/or cohesiveness of the hard microdomains may allow elimination of the traditional requirement of chain extension to obtain melt processable segmented urethanes, and more specifically, urea copolymers with useful structural properties.     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Synthesis,characterization and properties of functionalized styrene–maleimide copolymers

New functionalized styrene–maleimide copolymers were prepared by free radical copolymerization of styrene (St) and N‐4‐carboxybutylmaleimide (NBMI) in chloroform, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator. Monomer and copolymer characterization was carried out by ¹H‐ and ¹³C‐NMR. Copolymer composition was determined by elemental analysis and Fourier‐transform infrared (FTIR) spectroscopy. The glass transition temperature (from DSC) and the thermogravimetric analysis (TGA) of the copolymers were consistent with the thermal behavior and stability observed for alternating St–maleimide copolymers. St–NBMI copolymers crosslinked with divinylbenzene (DVB) were also synthesized and their cation exchange properties evaluated in order to assess the capacity of the new copolymers to bind metallic ions. Copyright © 2005 Society of Chemical Industry