Ethylene/1‐heptene copolymers as interesting alternatives to 1‐octene‐based LLDPE: Molecular structure and physical properties

Classical linear low density polyethylenes (LLDPEs) are copolymers of ethylene and 1‐octene or 1‐hexene, respectively. In the past, other 1‐olefins have been tested as comonomers but the resulting LLDPEs were never commercialized as large scale products. The present study focuses on the use of 1‐heptene as an interesting comonomer for the synthesis of LLDPE. For a comparison of the molecular structure and the physical properties of 1‐heptene‐ and 1‐octene‐based LLDPEs, five Ziegler–Natta LLDPEs of varying comonomer contents based on 1‐heptene and 1‐octene, respectively, were acquired and analysed using advanced methods. The comonomer contents of the resins were between 0.35 and 6.4 mol %. Crystallization‐based techniques revealed similar bimodal distributions that are due to the formation of copolymer and polyethylene homopolymer fractions. The compositional distribution of the copolymers was studied by high‐temperature (HT) HPLC and HT‐2D‐LC. The analytical results indicate similar chemical heterogeneities and molar mass distributions of the two sets of LLDPE up to a comonomer content of 3 mol %. Similar to the molecular structure, the physical properties of the materials are quite similar. At comonomer contents of ≥3 mol % differences between the two sets of samples are seen that are attributed to differences in the abilities of 1‐heptene and 1‐octene in disrupting the crystal arrangements of the polymer chains in solid state. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 962–975     

Two crystal populations with different melting/reorganization kinetics of isothermally crystallized polyamide 6

Differential scanning calorimetry and fast scanning chip calorimetry heating experiments were carried out in a wide range of rates of temperature change from 0.2 to 60,000 K s^?1 for isothermally crystallized polyamide 6. Multiple melting peaks were observed. With increasing heating rate, the highest‐temperature endotherm shifts toward lower temperatures and finally disappears due to suppression of the reorganization. The critical heating rate to suppress reorganization was 15–50 times higher than the critical cooling rate to cause complete vitrification. On heating at rates higher than the critical heating rate to suppress reorganization, there were observed two melting processes of different kinetics. Four possible assignments were considered regarding the two crystal populations. These are (i) crystals grown during primary and secondary crystallization, (ii) crystals grown in the bulk and nucleated at the surface/substrate, (iii) crystals, which are subjected to different local stress originating from heterogeneities in interlamellar regions, and (iv) the crystal/mesophase polymorphism. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2126–2138     

Exothermic nonreversing process in the phase transition of poly(N‐isopropylacrylamide) studied with stochastic temperature‐modulated DSC

Exothermic nonreversing process is predicted to present in the phase transition of poly(N‐isopropylacrylamide) (PNIPAM). By employing TOPEM‐DSC, exothermic nonreversing heat flow peak is observed for the first time, and it usually appears under nonquasi‐static conditions. The exothermic nonreversing heat flow is proved to be from the formation of hydrogen bonds by the comparative studies on the phase transition of poly(N,N‐diethylacrylamide) (PDEAM) and cyclic heating and cooling of PDEAM and PNIPAM. Further TOPEM‐DSC studies on the phase transition of poly(NIPAM‐co‐DEAM) and poly(NIPAM‐co‐AAm) prove that hydrophobic force rather than hydrogen bonding is the main driving force for the phase transition, and hydrophobic force is also the driving force for the formation of inter‐ and intrachain hydrogen bonding. However, the phase transition driven by only hydrophobic force is a slow process. The combined action of hydrogen bonding and hydrophobic force makes the phase transition occur much faster. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1869–1877     

压力对Zr46.75Ti8.25Cu7.5Ni10Be27.5大块非晶合金玻璃转变和晶化动力学的影响

利用X射线衍射和差示扫描量热分析研究了高温高压下Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5大块非晶合金的玻璃转变和晶化行为，结果发现压力降低了该大块非晶合金中的自由体积、热焓和晶化激活能. 关键词： 大块非晶合金 高压 差示扫描量热分析 玻璃转变     

Thiol‐functionalized 1,3‐benzoxazine: Preparation and its use as a precursor for highly polymerizable benzoxazine monomers bearing sulfide moiety

We describe a new strategy for preparation of benzoxazine monomers based on in situ preparation of a thiol‐functionalized benzoxazine and successive chemical modification of the thiol moiety. The thiol‐functionalized benzoxazine can be prepared from its precursor bearing two benzoxazine moieties linked by disulfide bond. Reductive cleavage of the disulfide bond of the precursor with using triphenylphosphine as a reducing agent allows successful preparation of the thiol‐functionalized benzoxazine. By performing this reduction process in the presence of epoxides and acrylates, the formation of the thiol moiety and its successive reaction with those electrophiles proceed efficiently to give the corresponding benzoxazines with sulfide moieties. The benzoxazine monomers thus prepared exhibit much higher polymerization ability than those without sulfide moiety. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1448–1457     

Quiescent crystallization of polypropylene: Experiments and modeling

The quiescent crystallization of several polypropylenes (PPs) was examined using Differential Scanning Calorimetry (DSC) and Polarized Optical Microscopy (POM). The half‐times of crystallization were obtained from the DSC thermographs employing the Avrami/Nakamura equation to fit and predict crystallization kinetics under isothermal and nonisothermal conditions. The induction times under nonisothermal conditions were estimated from isothermal crystallization data and used in conjunction with the Nakamura model in order to capture the crystallization behavior of the studied PPs. The Avrami/Nakamura model is found to fit and predict the nonisothermal crystallization data of the various PPs well over a range of cooling rates supporting its use in the simulation of polymer processes of industrial relevance. POM was used in line with parallel plate rheometry (Anton Paar, MCR 502) under no flow conditions to study the shape and growth rate of crystals of various PP resins at different temperatures or cooling rates. The growth rate of crystals is impeded exponentially with increase of temperature. The various PP resins of different molecular architecture have shown different nucleation and growth rate characteristics behavior under similar processing conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1259–1275     

Enhanced electrochemical properties of a novel polyvinyl formal membrane supporting gel polymer electrolyte by Al2O3 modification

Polyvinyl formal (PVFM)‐based dense polymer membranes with nano‐Al₂O₃ doping are prepared via phase inversion method. The membranes and also their performances as gel polymer electrolytes (GPEs) for lithium ion battery are studied by field emission scanning electron microscope, X‐ray diffraction, differential scanning calorimetry, mechanical strength test, electrolyte uptake test, electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge test. The polymer membrane with 3 wt % nano‐Al₂O₃ doping shows the improved mechanical strength of 12.16 MPa and electrolyte uptake of 431.25% compared with 10.47 MPa and 310.59% of the undoped sample, respectively. The membrane absorbs and swells liquid electrolyte to form stable GPE with ionic conductivity of 4.92 × 10^?4 S cm^?1 at room temperature, which is higher than 1.77 × 10^?4 S cm^?1 of GPE from the undoped membrane. Moreover, the Al₂O₃‐modified membrane supporting GPE exhibits wide electrochemical stability window of 1.2–4.8 V (vs. Li/Li⁺) and good compatibility with LiFePO₄ electrode, which implies Al₂O₃‐modified PVFM‐based GPE to be a promising candidate for lithium ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 572–577     

Rigid chain ribbon‐like metallopolymers

A set of new copolymers is here reported in which the repeating units are connected each other through Cu(II) metal centers. The coordination link is based on the bis‐chelating properties of salicylaldiminate groups of two different monomers. Due to their chemical structure, the two monomers afford, respectively, flexible and rigid repeating units in the metallocopolymers constitution upon coordination to copper centers. All the copolymers were soluble and easily processable. As shown by XRD analysis, rigid units' rich copolymers adopt a ribbon‐like structure in solid state in which highly planar strands of polymer stack thanks to π?π interactions, similarly to the polymer composed exclusively by rigid units. This behavior can be justified assuming the existence of a partial block character in copolymer constitution where long sequences of rigid units are alternated to sequences of flexible units. This assumption is supported also by DSC and UV–Vis analysis. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2412–2421