Construction of Anisotropic Block Copolymer Particles through Quaternizing Additives-Induced Synergetic Crosslink and Swelling
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We report a facile and robust strategy for fabricating a series of anisotropic block copolymer (BCP) particles by combining the benzyl bromide (BB), 2-(bromomethyl)naphthalene (BN), and 6-(bromohexyl)benzene (BHB) as quaternizing additives showing rather different hydrolyzed properties (e.g. change pH value) in the confined self-assembly of poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) BCP. Additives-induced synergetic quaternization and swelling/deswelling of P2VP chains by surrounding water results in a shape transition of ellipsoidal particles into elongated ellipsoids with swelled layers, conical particles, and capsules. The key driving forces are the quaternization of P2VP and the hydrolysis induced pH change for swelling by BB and BN. The shape transformation of BCP particles by BHB can be mainly ascribed to the improved hydrophilicity by quaternization.