Abstract

A novel zwitterionic poly[4-vinylbenzoic acid-block-2-N-(morpholino)ethyl methacrylate] (VBA63-b-MEMA123) diblock copolymer was synthesized via atom transfer radical polymerization using protecting group chemistry for the acidic residues. The acidic VBA block has a pKa of 7.1, which is higher than that of the conjugate acid of the MEMA block (pKa = 4.9). This has important consequences for the aqueous solution properties of this zwitterionic diblock copolymer. For example, unlike other zwitterionic diblock copolymers such as poly[methacrylic acid-block-2-(dimethylamino)ethyl methacrylate], precipitation does not occur at the isoelectric point (IEP) of around pH 6.2. This is most likely due to the relatively low degree of charge density on both the VBA and MEMA blocks at this pH. The VBA63−MEMA123 copolymer exhibits interesting “schizophrenic” micellization behavior. Below pH 6, VBA-core micelles are formed, while above pH 6, the diblock copolymer can be dissolved as unimers. In the presence of sufficient ...

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