Michel Schappacher, Akira Hirao, Takumi Watanabe, Sangwoo Jin, Koji Ishizu, Kyeong Sik Jin, Moonhor Ree, Stéphane Carlotti, Alain Deffieux, Polymeric and Organic Department, TIT Tokyo, TIT, Pohang University of Science and Technology (POSTECH), Ctr Integrated Mol Syst, Pohang Accelerator Lab, South Korea, Pohang Ctr Integrated Mol Syst, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 1 LCPO : Polymerization Catalyses & Engineering, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)
International audience; A series of the fourth-generation (4G) dendrimer-like star-branched poly(methyl methacrylate)s, (PMMA)s, with high branch densities have been synthesized by the iterative "arm-first" divergent methodology. It involves a two-reaction sequence in each iterative process: (1) a linking reaction of alpha-functionalized living anionic PMMA with either two or four tert-butyldimethylsilyloxymethylphenyl (SMP) groups with benzyl bromide (BnBr)-chain-end-functionalized PMMA and (2) a transformation reaction of the SMP groups into BnBr functions. Accordingly, the branch segments are introduced by the (1) linking reaction based on termination reaction using premade living anionic polymers. The two-reaction sequence has been repeated four times to build up the 4G dendrimer-like star-branched polymers composed of four branch junctures in three generations and two branch junctures in one generation. Likewise, three block copolymers with the same dense 4G branched architectures have been synthesized by the linking reaction of the 3G brominated PMMA with either of living anionic polymers of tert-butyl methacrylate, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate, and 2-vinylpyridine. Unfortunately, however, the synthesis of a highly dense 4G polymer composed of four branch junctures in all generations was not successful possibly due to steric hindrance. The resulting dendrimer-like star-branched (PMMA)s have been analyzed by RALLS, SAXS, and viscosity measurements to obtain their hydrodynamic radii, radii of gyration, intrinsic viscosities, and g' values. The relationship between either of such values and the branched structures, generation, or molecular weight will be discussed. The observation of the largest and most dense 4G polymer by AFM was attempted in order to directly visualize the dendrimer-like star-branched polymer.