Overcoming Kinetic Trapping for Morphology Evolution during Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly (PISA) is a powerful technique to synthesize assemblies with various morphologies. However, PISA mediated by long, stabilizing chains usually produces kinetically trapped spheres; thus, the morphology evolution remains a challenge. Here, a convenient and general strategy for facilitating the morphological evolution by the copolymerization of solvophilic monomers is reported. With the incorporation of only 7% (molar ratio) solvophilic 3-(triethoxysilyl)propyl methacrylate (TESPMA) into poly(N,N-dimethylaminoethyl methacrylate)-b-poly(benzyl methacrylate) (PDMA-b-PBzMA) spheres, PDMA-b-P(BzMA-co-TESPMA) assemblies evolve from spheres to worms, octopi-like and jellyfish-like structures, vesicles, and large compound vesicles. This non-specific effect is further confirmed by the copolymerization of BzMA with other solvophilic monomers, including N,N-dimethylaminoethyl methacrylate (DMA), N,N-diethylaminoethyl methacrylate (DEA), and 2-hydroxypropyl methacrylate (HPMA). This work provides a convenient approach to promote morphology evolution and develops the formulations design of PISA.