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Preparation and characterization of optically active polymers containing pendent and terminal chiral units via atom transfer radical polymerization
Authors:Wenjian Xu  Xiulin Zhu  Jian Zhu  Zhenping Cheng
Abstract:Optically active homopolymers and copolymers, bearing chiral units at the side chain and end chain, were prepared via atom transfer radical polymerization (ATRP) techniques. The well‐defined optically active polymers were obtained via the ATRP of pregnenolone methacrylate (PR‐MA), β‐cholestanol acrylate (CH‐A), and 20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one acrylate (HPD‐A) with ethyl 2‐bromopropionate as the initiator and CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalytic system. The experimental results showed that the polymerizations of PR‐MA, CH‐A, and HPD‐A proceeded in a living fashion, providing pendent chiral group polymers with low molecular weight distributions and predetermined molecular weights that increased linearly with the monomer conversion. Furthermore, the copolymers poly(pregnenolone methacrylate)‐b‐poly(dimethylamino)ethyl methacrylate] and poly(pregnenolone methacrylate‐co‐methyl methacrylate) were synthesized and characterized with 1H NMR, transmission electron microscopy, and polarimetric analysis. In addition, when optically active initiators estrone 2‐bromopropionate and 20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one 2‐bromopropionate were used for ATRPs of methyl methacrylate and styrene, terminal optically active poly(methyl methacrylate) and polystyrene were obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1502–1513, 2006
Keywords:atom transfer radical polymerization (ATRP)  β  ‐cholestanol  estrone  20‐(hydroxymethyl)‐pregna‐1  4‐dien‐3‐one  kinetic (polym  )  optically active  pregnenolone  radical polymerization  specific rotation
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