Organic and Macromolecular Chemistry
Freie Universität Berlin Fachbereich Biology, Chemie, Pharmazie Institut für Chemie
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Zhang, A.; Zhang, B, Wächtersbach, E.; Schmidt, M.; Schlüter, A.D.
"Efficient Synthesis of High Molar Mass, First- to Fourth-Generation Distributed Dendronized Polymers by the Macromonomer Approach,"
DOI: 10.1002/chem.200305142, Chem. Eur. J. 2003, 9, 6083-6092.

Keywords Dendrimers, dendronized polymers, macromonomers, polymerization, radical polymerization  
   
Abstract A homologous series of the first to fourth (G1-G4) generation dendronized macromonomers, 5, 7, 10, and 12, was synthesized and their polymerization behavior under radical conditions investigated. These conditions are thermally induced radical polymerization (TRP) and atom transfer radical poymerization (ATRP). TRP was applied to all monomers and gave polymers PG1-PG4, whose molar masses decrease from several millions for PG1 to estimated several hundred thousands for PG2 and PG3 and to the oligomeric regime for PG4. ATRP was applied only to the G1 and G2 monomers 5 and 7. Kinetic studies on monomer 5 provide evidence that its polymerization proceeds in a controlled fashion. The highest monomer to initiator ratio which still gave monomodal molar mass distributions is 300 : 1 (for 5) and 100 : 1 (for 7) which corresponds to achievable molar mass regime for PG1 and PG2 of approximately Mn = 100,000 [DPcalc (PG1) = 200; DPcalc (PG2) = 90]. The polydispersities lie in the usual range (PDIs 1.1-1.2). The molar masses were determined by GPC in DMF calibrated by absolute molar masses of A homologous series of the first to fourth (G1-G4) generation dendronized macromonomers, 5, 7, 10, and 12, was synthesized and their polymerization behavior under radical conditions investigated. These conditions are thermally induced radical polymerization (TRP) and atom transfer radical poymerization (ATRP). TRP was applied to all monomers and gave polymers PG1-PG4, whose molar masses decrease from several millions for PG1 to estimated several hundred thousands for PG2 and PG3 and to the oligomeric regime for PG4. ATRP was applied only to the G1 and G2 monomers 5 and 7. Kinetic studies on monomer 5 provide evidence that its polymerization proceeds in a controlled fashion. The highest monomer to initiator ratio which still gave monomodal molar mass distributions is 300 : 1 (for 5) and 100 : 1 (for 7) which corresponds to achievable molar mass regime for PG1 and PG2 of approximately Mn = 100,000 [DPcalc (PG1) = 200; DPcalc (PG2) = 90]. The polydispersities lie in the usual range (PDIs 1.1-1.2). The molar masses were determined by GPC in DMF calibrated by absolute molar masses of PG1 determined by light scattering. determined by light scattering.