Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
Hiroshima R&D Center, Mitsubishi Chemical Corporation, 20-1 Miyuki-cho, Otake, Hiroshima, 739-0693, Japan.
Macromol Rapid Commun. 2022 Nov;43(21):e2200468. doi: 10.1002/marc.202200468. Epub 2022 Jul 20.
This work reports the first use of organic chloride salts as catalysts for reversible complexation mediated living radical polymerization. Owing to the strong halogen-bond forming ability of Cl , the studied four tetraalkylammonium chloride catalysts (R N Cl ) successfully control the polymerizations of methyl methacrylate, yielding polymers with low dispersities up to high monomer conversion (>90%). Benzyldodecyldimethylammonium chloride is further exploited to other methacrylates and yields low-dispersity block copolymers. The advantages of the chloride salt catalysts are wide monomer scope, good livingness, accessibility to block copolymers, and good solubility in organic media. Because of the good solubility, the use of the chloride salt catalysts can prevent agglomeration of catalysts on reactor walls in organic media, which is an industrially attractive feature. Among halide anions, chloride anion is the most abundant and least expensive halide anion, and therefore, the use of the chloride salt catalysts may lower the cost of the polymerization.
这项工作报道了首次将有机氯化物盐用作催化剂，用于可逆配位介导的活性自由基聚合。由于 Cl 的强卤素键形成能力，所研究的四种四烷基氯化铵催化剂（R₃NCl）成功地控制了甲基丙烯酸甲酯的聚合，得到了低分散度直至高单体转化率（>90%）的聚合物。苄基十二烷基二甲基氯化铵进一步用于其他甲基丙烯酸酯，并得到低分散度嵌段共聚物。氯化物盐催化剂的优点是单体范围广、良好的活性、可制备嵌段共聚物以及在有机溶剂中具有良好的溶解性。由于良好的溶解性，氯化物盐催化剂的使用可以防止催化剂在有机介质中的反应器壁上聚集，这是一个在工业上有吸引力的特点。在卤化物阴离子中，氯离子是最丰富和最便宜的卤化物阴离子，因此，氯化物盐催化剂的使用可能会降低聚合成本。
