Bottlebrush Polymers Based on RAFT and the "C1" Polymerization Method: Controlled Synthesis and Application in...

In this work, we reported a strategy to synthesize well-defined bottlebrush polymers. Diazoacetate macromonomers of polystyrene (1-PS) with controlled molecular weights were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The diazo can tolerate the RAFT polymerization conditions and remained on the chain end of the yielded PS macromonomer. The terminal diazo groups of the macromonomer were polymerized by the allyl PdCl/L catalyst to afford well-defined bottlebrush polymers ((1-PS)s) carrying a side chain on each backbone atom. Meanwhile, an amphiphilic bottlebrush polymer containing brush-shaped PS and polyethylene glycol (PEG) was synthesized by polymerization of the diazoacetate macromonomer of PEG (2-PEG) using Pd(II)-terminated (1-PS) as the macroinitiator. The yielded amphiphilic (1-PS₃₀)₅₀-b-(2-PEG)₁₀₀ could self assemble into a well-defined core-shell micelle in aqueous solutions. The hydrodynamic diameter of the micelle was ca. 146 nm and had good biocompatibility. These results indicate the micelles have great potential in drug delivery.