Mochizuki Shuto, Ogiwara Naoki, Takayanagi Masayoshi, Nagaoka Masataka, Kitagawa Susumu, Uemura Takashi
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.
Department of Complex Systems Science, Graduate School of Informatics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan.
Nat Commun. 2018 Jan 23;9(1):329. doi: 10.1038/s41467-017-02736-1.
The design of monomer sequences in polymers has been a challenging research subject, especially in making vinyl copolymers by free-radical polymerization. Here, we report a strategy to obtain sequence-regulated vinyl copolymers, utilizing the periodic structure of a porous coordination polymer (PCP) as a template. Mixing of Cu ion and styrene-3,5-dicarboxylic acid (S) produces a PCP, [Cu(styrene-3,5-dicarboxylate)] , with the styryl groups periodically immobilized along the one-dimensional channels. After the introduction of acrylonitrile (A) into the host PCP, radical copolymerization between A and the immobilized S is performed inside the channel, followed by decomposing the PCP to isolate the resulting copolymer. The predominant repetitive SAAA sequence in the copolymer is confirmed by monomer composition, NMR spectroscopy and theoretical calculations. Copolymerization using methyl vinyl ketone also provides the same type of sequence-regulated copolymer, showing that this methodology has a versatility to control the copolymer sequence via transcription of PCP periodicity at the molecular level.
聚合物中单体序列的设计一直是一个具有挑战性的研究课题，尤其是在通过自由基聚合制备乙烯基共聚物方面。在此，我们报告一种策略，利用多孔配位聚合物（PCP）的周期性结构作为模板来获得序列规整的乙烯基共聚物。铜离子与3,5-苯二甲酸（S）混合生成一种PCP，即[Cu(3,5-苯二甲酸酯)]，其中苯乙烯基沿一维通道周期性固定。在将丙烯腈（A）引入主体PCP后，A与固定的S在通道内进行自由基共聚，随后分解PCP以分离得到的共聚物。通过单体组成、核磁共振光谱和理论计算证实了共聚物中主要的重复SAAA序列。使用甲基乙烯基酮进行共聚也能得到相同类型的序列规整共聚物，表明该方法具有在分子水平上通过转录PCP周期性来控制共聚物序列的通用性。
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