Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
Macromol Rapid Commun. 2022 May;43(10):e2200091. doi: 10.1002/marc.202200091. Epub 2022 Apr 7.
An air-tolerant reversible complexation mediated polymerization (RCMP) technique, which can be carried out without prior deoxygenation, is developed. The system contains a monomer, an alkyl iodide initiating dormant species, air (oxygen), an aldehyde, N-hydroxyphthalimide (NHPI), and a base. Oxygen is consumed via the NHPI-catalyzed conversion of the aldehyde (RCHO) to a carboxylic acid (RCOOH). The generated RCOOH is further converted to a carboxylate anion (RCOO ) by the base. The RCOO generated in situ works as an RCMP catalyst; the polymerization proceeds with the monomer, alkyl iodide dormant species, and RCOO catalyst. Thus, the system is not only air-tolerant but also does not require additional RCMP catalysts, which is a notable feature of this system. (NHPI is used as an oxidation catalyst for converting RCHO to RCOOH.) This technique is amenable to methyl methacrylate, butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, and styrene, yielding polymers with relatively low-dispersity (M /M = 1.20-1.49), where M and M are the weight- and number-average molecular weights, respectively.
开发了一种无需预先脱氧即可进行的耐氧可逆配位聚合（RCMP）技术。该体系包含单体、烷基碘引发休眠物种、空气（氧气）、醛、N-羟基邻苯二甲酰亚胺（NHPI）和碱。通过 NHPI 催化醛（RCHO）转化为羧酸（RCOOH）来消耗氧气。生成的 RCOOH 被碱进一步转化为羧酸盐阴离子（RCOO ）。原位生成的 RCOO 用作 RCMP 催化剂；聚合在单体、烷基碘休眠物种和 RCOO 催化剂的作用下进行。因此，该体系不仅具有耐氧性，而且不需要额外的 RCMP 催化剂，这是该体系的一个显著特点。（NHPI 用作将 RCHO 转化为 RCOOH 的氧化催化剂。）该技术适用于甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸苄酯、2-羟乙基甲基丙烯酸酯和苯乙烯，得到相对低分散度的聚合物（M / M = 1.20-1.49），其中 M 和 M 分别为重均分子量和数均分子量。
