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.     

Material encapsulation in poly(methyl methacrylate) shell: A review

Material encapsulation is a relatively new technique for coating a micro/nanosize particle or droplet with polymeric or inorganic shell. Encapsulation technology has many applications in various fields including drug delivery, cosmetic, agriculture, thermal energy storage, textile, and self-healing polymers. Poly(methyl methacrylate) (PMMA) is widely used as shell material in encapsulation due to its high chemical stability, biocompatibility, nontoxicity, and good mechanical properties. The main approach for micro/nanoencapsulation of materials using PMMA as shell comprises emulsion-based techniques such as emulsion polymerization and solvent evaporation from oil-in-water emulsion. In the present review, we first focus on the encapsulation techniques of liquid materials with PMMA shell by analyzing the effective processing parameters influencing the preparation of PMMA micro/nanocapsules. We then describe the morphology of PMMA capsules in emulsion systems according to thermodynamic relations. The techniques to investigation of mechanical properties of capsule shell and the release mechanisms of core material from PMMA capsules were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48039.     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

A highly transparent and thermally stable copolymer of 1‐adamantyl methacrylate and styrene

Thermal and optical properties of copolymers of 1‐adamantyl methacrylate (AdMA) and styrene (St) prepared by free radical polymerization in the bulk are investigated. The copolymer forms an azeotrope when the composition is AdMA/St = 55/45 mol%. The glass transition temperature and decomposition temperature of the azeotropic copolymer are 170 and ca 340 °C, respectively. The refractive index increases nonlinearly with St content from 1.522 to 1.591. The light scattering loss at 633 nm is 28.1 dB km^?1, which is less than half of that of polystyrene. The total optical loss including molecular vibrational absorption, which is evaluated using a copolymer‐based optical fiber, is 292–645 dB km^?1 at 500–700 nm. These values correspond to transmittances of 86–93% for a 1 m optical path length. © 2014 Society of Chemical Industry     

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.     

Physico-chemical characterization of hybrid polymers obtained by 2-hydroxyethyl(methacrylate) and alkoxides of zirconium

Hybrid monolithic materials were prepared through polymerisation of 2-hydroxyethyl methacrylate (HEMA) mixed with zirconium alkoxides (Zr(OBuⁿ)₄, Zr(OPrⁿ)₄ and Zr(OEt)₄), modified by acetylacetonate groups. The molar ratio HEMA/Zr varied between 1 and 4. Thermo-Gravimetry coupled with Mass Spectroscopy (TG-MS) analyses, ¹³C MAS NMR and Dynamical Mechanical Thermal Analysys (DMTA) indicated the polymeric chains were interconnected by the inorganic component.The presence of zirconium alkoxides modified substantially the poly-HEMA properties. Glass transition temperature of hybrid materials derived from butoxy and propoxy was found in the range 50-80 °C, depending on the composition. The typical swelling of p-HEMA in the water, was suppressed by the presence of zirconium compounds. After immersion in distilled water, hybrid polymers showed an initial slight weight increase, followed by a small mass loss, which increases proportionally to the length of alkoxyl group (ethoxide(propoxide(butoxide) and reaches a constant value after about 40 days. The hybrids remained always rigid and transparent. Flexural modulus and strength of about 400-900 and 4-8 MPa were measured.     

甲基丙烯酸乙酯合成工艺研究

以大孔强酸性离子交换树脂为催化剂,甲基丙烯酸(MAA)与乙醇直接酯化合成甲基丙烯酸乙酯(EMA)。在MAA与乙醇摩尔比为1:3、反应温度89～93℃、空速0.3h~(-1)的条件下,MAA转化率不低于98％,EMA的选择性不低于99％。     

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.