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Abstract: This article describes for the first time the development of a new polymerization technique by introducing iniferter-induced ''living'' radical polymerization mechanism into precipitation polymerization and its application in the molecular imprinting field. The resulting iniferter-induced "living" radical precipitation polymerization (ILRPP) has proven to be an effective approach for generating not only narrow disperse poly(ethylene glycol dimethacrylate) microspheres but also molecularly imprinted polymer (MIP) microspheres with obvious molecular imprinting effects towards the template (a herbicide 2,4-dichlorophenoxyacetic acid (2,4-D)), rather fast template rebinding kinetics, and appreciable selectivity over structurally related compounds. The binding association constant Ka and apparent maximum number Nmax for the high-affinity sites of the 2,4-D imprinted polymer were determined by Scatchard analysis and found to be 1.18 × 10^4 M-1 and 4.37 μmol/g, respectively. In addition, the general applicability of ILRPP in molecular imprinting was also confirmed by the successful preparation of MIP microspheres with another template (2-chloromandelic acid). In particular, the living nature of ILRPP makes it highly useful for the facile one-pot synthesis of functional polymer/MIP microspheres with surface-bound iniferter groups, which allows their direct controlled surface modification via surface-initiated iniferter polymerization and is thus of great potential in preparing advanced polymer/MIP materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3217-3228, 2010
Template and target information: 2,4-dichlorophenoxyacetic acid, 2,4-D, 2-chloromandelic acid
Author keywords: iniferter-induced living radical precipitation polymerization, living polymerization, microsphere, modification, molecular imprinting