The past decades have witnessed an increasing interest in developing advanced polymerization techniques subjected to external fields. Various physical modulations, such as temperature, light, electricity, magnetic field, ultrasound, and microwave irradiation, are noninvasive means, having superb but distinct abilities to regulate polymerizations in terms of process intensification and spatial and temporal controls. Gas as an emerging regulator plays a distinctive role in controlling polymerization and resembles a physical regulator in some cases. This review provides a systematic overview of seven types of external-field-regulated polymerizations, ranging from chain-growth to step-growth polymerization. A detailed account of the relevant mechanism and kinetics is provided to better understand the role of each external field in polymerization. In addition, given the crucial role of modeling and simulation in mechanisms and kinetics investigation, an overview of model construction and typical numerical methods used in this field as well as highlights of the interaction between experiment and simulation toward kinetics in the existing systems are given. At the end, limitations and future perspectives for this field are critically discussed. This state-of-the-art research progress not only provides the fundamental principles underlying external-field-regulated polymerizations but also stimulates new development of advanced polymerization methods.

Wastewater contaminated with oil or organic compounds poses threats to the environment and humans. Efficient separation of oil and water are highly desired yet still challenging. This paper reports the fabrication of a smart fiber membrane by depositing pH-responsive copolymer fibers on a stainless steel mesh through electrospinning. The cost-effective precursor material poly(methyl methacrylate)-block-poly(4-vinylpyridine) (PMMA-b-P4VP) was synthesized using copper(0)-mediated reversible-deactivation radical polymerization. The pH-responsive P4VP and the underwater oleophilic/hydrophilic PMMA confer the as-prepared membrane with switchable surface wettability toward water and oil. The three-dimensional network structure of the fibers considerably strengthens the oil/water wetting property of the membrane, which is highly desirable in the separation of oil and water mixtures. The as-prepared fiber membrane accomplishes gravity-driven pH-controllable oil/water separations. Oil selectively passes through the membrane, whereas water remains at the initial state; after the membrane is wetted with acidic water (pH 3), a reverse separation is realized. Both separations are highly efficient, and the membrane also exhibits switchable wettability after numerous cycles of the separation process. This cost-effective and easily mass-produced smart fiber membrane with excellent oil-fouling repellency has significant potential in practical applications, such as water purification and oil recovery.

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Recent studies have demonstrated that gradient copolymers exhibit unique thermal properties. Although these properties can be determined by copolymer composition, other factors such as chain and sequence lengths and their distributions can also influence them. Accordingly, the synthesis of gradient copolymers requires simultaneously tailor-made chain structure and thermal properties. In this work, we carried out a systematic study on the preparation of poly(methyl methacrylate-grad-2-hydroxyethyl methacrylate) [poly(MMA-grad-HEMA)] with synchronously tailor-made chain composition distribution and glass transition temperature (Tg) through semibatch atom transfer radical polymerization. First, a comprehensive model for simultaneously predicting gradient copolymer microstructure and Tg was presented using the concept of pseudo-kinetic rate coefficients and Johnston equation. The model was validated by comparing simulation results with the classical reference data. Furthermore, the model was used to guide the experimental synthesis of the poly(MMA-grad-HEMA) gradient copolymers potentially as excellent damping material. The thermal properties of these gradient copolymer samples were evaluated. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012National Natural Science Foundation of China [20406016, 21076171

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