Polymer-based
catalytic nanoreactors, with the characteristics
of easy preparation, good dispersion, and facile modulation of molecular
structures, have been widely applied for various organic transformations.
Usually, polymeric nanoreactors are fabricated via the self-assembly
of amphiphilic copolymers in water, while the disassembly and instability
of the relevant nanoreactors often compromise their potential applicability.
Molecular brushes (MBs), as a kind of polymer with high-density grafted
side chains on the linear polymer main chain, can be rapidly self-assembled
into highly ordered nanostructures even at low concentrations. This
study reports the fabrication of catalytic nanoreactors from molecular
brushes of polyÂ[norborneneâpolyÂ(bromoethyl methacrylate-co-methyl methacrylate)]-co-polyÂ[norbornene
polyethylene glycol monomethyl ether] (PÂ[NB-(BEMA-co-MMA)]-co-PÂ[NB-PEG]). The amphiphilic molecular
brush was synthesized by combining reversible additionâfragmentation
chain transfer (RAFT) polymerization and ring-opening metathesis polymerization
(ROMP) techniques. Homogeneous catalysts, such as triethylenediamine
and 4-(dimethylamino)Âpyridine analogues, were introduced by nucleophilic
substitution with alkyl bromide on the side chain of molecular brushes.
Furthermore, micellar catalytic nanoreactors were fabricated via self-assembly
in deionized water. The resulted nanoreactors display high catalytic
activities toward the Knoevenagel condensation reaction and acylation
reaction of alcohol in water, respectively. This contribution describes
a general method for constructing highly efficient molecular brush-based
catalytic nanoreactors utilizing postpolymerization modification (PPM)
for aqueous catalysis.