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Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-(N,N- dimethylamino)ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA), were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-olefin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K+). PIB-O-K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography (GPC). These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.
Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly [2- (N, N- dimethylamino) ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly ) were synthesized via oxyanion-initiating polymerization, and their multiple self-assembly behaviors have been studied. An exo-olefin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl- terminated PIB (PIB-OH) via hydroboration- oxidation of C = C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K +). PIB-O-K + was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) ester groups in PtBMA block. The functional PIB and bl ock copolymers have been characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography (GPC). These samples allowed us to systematically investigate the effects of block compositions on the pH responsivity and various self-assembled morphologies of the copolymers in THF / water mixed solvent. Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.