Efficient Synthesis of High Molar Mass, First- to Fourth-Generation Distributed Dendronized Polymers by the Macromonomer Approach
A homologous series of first- to fourth-generation (G1±G4) dendronized macromonomers, 5, 7, 10, and 12, was synthesized, and their poly- merization behavior under radical con- ditions investigated. These conditions were thermally induced radical poly- merization (TRP) and atom-transfer radical poymerization (ATRP). TRP was applied to all monomers and gave polymers PG1±PG4, whose molar masses range from several millions for PG1 to estimated several hundreds of 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 control- led fashion. The hig…
Ion-Induced Stretching of Low Generation Dendronized Polymers with Crown Ether Branching Units
Synthesis of the first (G1) and second generation (G2) dendronized macromonomers MG1 and MG2 with the dibenzo-24-crown-8 moiety as branching unit is reported. The corresponding dendronized polymers, the polymethacrylates PG1 and PG2, were synthesized by free radical polymerization using AIBN as initiator at 60−80 °C. Static and dynamic light scattering revealed a significant chain expansion upon complexation of these polymers’ crown ether side chains with K+ ions. It is concluded that electrostatic repulsion does not significantly contribute to the chain expansion because of excessive counterion binding even well below the Manning limit, as evidenced by 19F NMR and 1H−19F NOE experiments. R…