Controlled Preparation of Well-Defined Mesoporous Carbon/Polymer Hybrids via Surface-Initiated ICAR ATRP with a High Dilution Strategy Assisted by Facile Polydopamine Chemistry

Well-defined mesoporous carbon/poly(glycidyl methacrylate) (PGMA) hybrids were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) from mesoporous carbons with different steric configurations and structural properties. In the initial step, a robust polydopamine (PDA) layer was deposited on the surface of the mesoporous carbons by exploiting the strong pi-pi interaction between the PDA aggregates and the carbonaceous surface, which facilitated the immobilization of initiator molecules. PGMA brushes were then grown by using the initiators for continuous activator regeneration (ICAR) ATRP method. Almost identical PGMA grafting fraction was found for CTNC due to the spatial confinement of the cubic bicontinuous structure, regardless of molecular weight of the free polymer. The utilization of a high dilution strategy led to a better control of the PGMA growth within the mesoporous carbon framework and could obtain polymer chains with better preserved chain end functionality (CEF). This work paved a new way for the preparation of well-defined mesoporous carbon/polymer hybrids capable of further modification.