Yuto Eguchi, Sadahito Aoshima and Arihiro Kanazawa*,
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Sequence-Controlled Cationic Terpolymerization of Styrene Derivatives, Oxiranes, and Aromatic Aldehydes: Synthesis of Acidically or Oxidatively Degradable Terpolymers
In this study, we investigated the cationic terpolymerization of styrene derivatives, oxiranes, and aromatic aldehydes to achieve precise sequence control. Cationic terpolymerization of p-methoxystyrene (pMOS), 1,2-epoxy-4-vinylcyclohexane (VCHO), and benzaldehyde (BzA) proceeded via crossover reactions, yielding terpolymers with high molecular weights (MWs). In addition, selective crossover reactions consisting of pMOS → VCHO, VCHO → BzA, and BzA → pMOS proceeded, resulting in terpolymers with controlled [(pMOS)x–(VCHO)y–BzA]n sequences. The BzA-derived propagating end, which has a structure similar to that of the styrene-derived propagating end, was important for effective terpolymerization as judged by inefficient crossover reactions using methyl ethyl ketone instead of benzaldehyde. By optimizing polymerization conditions, homopropagation reactions of styrene derivatives and oxiranes were almost suppressed in the terpolymerization of 4-tert-butoxystyrene, VCHO, and 2,4-dimethoxybenzaldehyde, resulting in terpolymers with ABC-type periodic sequences. The terpolymers were degraded into low-MW products by acid or oxidant via the cleavage of the crossover reaction-derived, secondary benzylic ether moieties in the main chain.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.