A new polymerization method, termed as step transfer‐addition and radical‐termination, is developed for the step‐growth radical polymerization of α,ω‐unconjugated dienes under irradiation of visible light at room temperature (25 °C) for the first time. α,ω‐Diiodoperfluoroalkane monomers (signified as A) are added onto α,ω‐unconjugated dienes (signified as B) alternatively and efficiently with the generation of perfluorocarbon‐containing alternating copolymers (AB)n. Based on the combined analyses of polymerization kinetics and NMR spectra (1H and 19F), the mechanism of the novel polymerization method, including the side reaction, is proposed. This novel polymerization method provides a new strategy not only for the step‐growth radical polymerization of α,ω‐unconjugated dienes but also for the construction of high molecular weight perfluorocarbon‐containing alternating copolymers.

A new pulse sequence for obtaining F detected DOSY (diffusion ordered spectroscopy) spectra of fluorinated molecules is presented and used to study fluoropolymers based on vinylidene fluoride and chlorotrifluoroethylene. The performance of F DOSY NMR experiments (and in general any type of NMR experiment) on fluoropolymers creates some unique complications that very often prevent detection of important signals. Factors that create these complications include: (1) the presence of many scalar couplings among H, F and C; (2) the large magnitudes of many F homonuclear couplings (especially J ); (3) the large F chemical shift range; and (4) the low solubility of these materials (which requires that experiments be performed at high temperatures). A systematic study of the various methods for collecting DOSY NMR data, and the adaptation of these methods to obtain F detected DOSY data, has been performed using a mixture of low molecular weight, fluorinated model compounds. The best pulse sequences and optimal experimental conditions have been determined for obtaining F DOSY spectra. The optimum pulse sequences for acquiring F DOSY NMR data have been determined for various circumstances taking into account the spectral dispersion, number and magnitude of couplings present, and experimental temperature. Pulse sequences and experimental parameters for optimizing these experiments for the study of fluoropolymers have been studied. Copyright © 2016 John Wiley & Sons, Ltd.

It is known that poly(3‐alkylthiophene) (P3AT) side‐chain length notably influences the photovoltaic performances of relating devices. However, comprehensively study on its impact on the structures of P3ATs and their blends with [6, 6]‐phenyl‐C61 butyric acid methyl ester (PCBM) is insufficient. By using solid‐state NMR and FTIR techniques, four P3ATs and their PCBM blends are investigated in this work, focusing on the phase structures as modulated by side‐chain length. Recently, we revealed multiple crystalline main‐chain packings of packing a and b together with a mesophase in poly(3‐butylthiophene) (P3BT) films (DOI: 10.1021/acs.macromol.6b01828). Here, the semicrystalline structures are investigated on poly(3‐hexylthiophene) (P3HT), poly(3‐octylthiophene) (P3OT), and poly(3‐dodecylthiophene) (P3DDT) with traditional form I modification, where packing a and the amorphous phase are probed. Furthermore, crystallized side chain within packing a is detected in both P3OT and P3DDT films, which shows a FTIR absorption at 806 cm−1. Structural studies are also conducted on P3AT:PCBM blends. Compared with the pure P3ATs, the polymer crystallinities of the blends show reduction of about 40% for P3OT and P3DDT, whereas only about 10% for P3HT. Moreover, in P3BT:PCBM and P3HT:PCBM, the crystalline polymers and PCBM are phase separated, while in P3OT:PCBM and P3DDT:PCBM, blend components are mostly miscible. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 751–761

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