The random copolymer of chloroprene and acrylonitrile is a newly developed rubber whose features and value propositions are not scientifically explored yet. This article focuses on the basic characterizations and properties of acrylonitrile-chloroprene rubber. Qualitative analyses through infrared (FTIR) and nuclear magnetic resonance (1H-NMR) spectra confirm the presence of both the -Cl and -CN groups in the new rubber. As evidenced through differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA), the single glass transition temperature of acrylonitrile-chloroprene rubber reflects its monophasic random microstructure. While compared against commercial grades of chloroprene rubber (CR) and nitrile rubber (NBR), the new rubber provides a distinctive combination of properties that are not available with either of the elastomer alone. Acrylonitrile-chloroprene rubber demonstrates slightly lower specific gravity, an improved low-temperature compression set, higher flex-fatigue resistance, and lower volume swelling in IRM 903 and Fuel C to chloroprene rubber. As compared to nitrile rubber, the new copolymer shows appreciably better heat aging and ozone resistance. Good abrasion resistance, low heat buildup, and remarkably high flex-fatigue resistance indicate excellent durability of the acrylonitrile-chloroprene rubber under dynamic loading. Based on the preliminary results, it is apparent that the new copolymer can be a candidate elastomer for various industrial applications which demand good fluid resistance, high heat and low-temperature tolerances, good weatherability, and durability under static and dynamic conditions.

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The reversible addition-fragmentation chain transfer (RAFT) polymerization of chloroprene (CP) in an emulsion system using a dithiocarbamate-type RAFT agent was studied. The controlled RAFT-mediated emulsion polymerization was achieved by the appropriate combination of a RAFT agent and nonionic surfactant (polyoxyethylene phenyl ether) using a water-soluble initiator (VA-044) at 35 8C. An almost linear first-order kinetic plot was observed until relatively high conversion (>80%) with molecular weights between 22,300 and 33,100 and relatively narrow molecular weight distributions (M w /M n Ϲ 1.5) were achieved. The amount of the emulsifier used and the pH of the system were found to affect the controlled character, polymerization rate, and induction period, which are related to the size of the emulsion particles. Large-scale RAFT-mediated emulsion polymerization was also employed to afford industrially applicable poly(CP) (M w > 25 3 10 4 , resulting product > 2300 g). The vulcanized CP rubber obtained from the RAFT-synthesized poly(CP) exhibited better physical properties, particularly tensile modulus and compression set, which may be due to the presence of the reactive end groups and the absence of low-molecular-weight products. We also evaluated the impact of the chain-end structure on the mechanical and physical properties of these industrially important CP rubbers with carbon black.

Introduction Because of the ubiquitous availability of sodium resources and its relatively low electrode potential, rechargeable sodium batteries have been extensively studied for energy storage applications. However, a major obstacle to realize sodium batteries is the absence of suitable negative electrode materials. Titanium-based layered materials, e.g., P3-type Na0.58Cr0.58Ti0.42O2,1 are proposed as potential candidates for this purpose. Nevertheless, when poly(vinylidene fluoride), PVdF, is used as a binder, large irreversible capacities for initial cycle are observed, which hinders its use for practical applications. In this study, instead of PVdF, acrylonitrile-grafted poly(vinyl alcohol) copolymer, PVA-g-PAN,2 is used as the binder for P3-type Na0.58Cr0.58Ti0.42O2. PVA-g-PAN is a non-fluorine polymer with a branched structure prepared by graft polymerization, and the branched structure associated with PAN side chains is beneficial for better dispersion of nanosize carbon and higher coatability to active materials.2 For comparison, acrylonitrile and ether-based monomers grafted PVA, PVA-g-P(AN-co-E), is also prepared and is used as the binder. This polymer has better interaction with electrolyte associated with the presence of negatively charged oxygen species. By using these three different polymer binders, factors affecting electrode performance of Ti-based composite electrode are discussed in detail. Experimental Ti-based layered oxides were used as negative electrode materials, and the samples were prepared by conventional calcination method. Composite electrodes with carbon and binder were prepared with AB (HS-100, Denka) as the conductive agent and PVdF (#1100, Kureha), PVA-g-PAN, and PVA-g-P(AN-co-E) as the binders. Electrochemical properties of these composite electrodes were evaluated in two-electrode cells (Type TJ-AC, Tomcell, Japan). Results and discussion Electrochemical properties of the P3-type Na0.58Cr0.58Ti0.42O2 composite electrodes with three different binders in Na cells are compared in Fig. 1. PVA-g-PAN and PVA-g-P(AN-co-E) are effective binders, and small irreversible capacities on initial charge is observed when compared with the electrode with PVdF. Our study on polymer binders reveals that the large initial irreversible capacity with PVdF originates from defluorination of PVdF on electrochemical reduction which is the unique chemistry in Na cells, and is not observed for Li cells. Because electrode resistance with PVA-g-PAN is much lower than that with PVdF, a rapid charge test was conducted. The composite electrode with PVA-g-PAN delivers a discharge capacity of >70 mA h g-1 even by constant voltage charge only for 1 min as shown in Fig. 2. Furthermore, >90% of discharge capacity is obtained by constant voltage charge for 3 min. Excellent rapid charge performance originates from that conductive carbon is more uniformly dispersed for PVA-g-PAN associated with the branched structure of polymer and better interaction with carbon. Together with the results of PVA-g-P(AN-co-E), we further discuss factors affecting the electrochemical properties of Ti-based negative electrode materials with different functional binders in detail. References 1) Y. Tsuchiya et al. and N. Yabuuchi, Chemistry of Materials, 28, 7066 (2016). 2) S. Tanaka et al. and N. Yabuuchi, Journal of Power Sources, 358, 121 (2017). Figure 1