Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter Street, Columbia, South Carolina, 29208, USA.
Macromol Rapid Commun. 2014 Jan;35(2):254-259. doi: 10.1002/marc.201300558. Epub 2013 Sep 11.
A facile method to prepare cationic cobaltocenium-containing polyelectrolyte is reported. Cobaltocenium monomer with methacrylate is synthesized by copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction between 2-azidoethyl methacrylate and ethynylcobaltocenium hexafluorophosphate. Further controlled polymerization is achieved by reversible addition-fragmentation chain transfer polymerization (RAFT) by using cumyl dithiobenzoate (CDB) as a chain transfer agent. Kinetic study demonstrates the controlled/living process of polymerization. The obtained side-chain cobaltocenium-containing polymer is a metal-containing polyelectrolyte that shows characteristic redox behavior of cobaltocenium.
本文报道了一种简便的方法来制备阳离子型钴卟啉聚合物。通过铜催化的叠氮-炔基环加成(CuAAC)反应,将 2-叠氮乙基甲基丙烯酸酯和乙炔基钴卟啉六氟磷酸盐反应合成了含甲基丙烯酸酯的钴卟啉单体。然后通过可逆加成-断裂链转移聚合(RAFT),以芴基二硫代苯甲酸酯(CDB)为链转移剂,进一步实现了可控聚合。动力学研究表明聚合过程具有可控/活性。所得的侧链含钴卟啉聚合物是一种含有金属的聚电解质,表现出钴卟啉的特征氧化还原行为。