Homologous Series of Dendronized Polymethacrylates with a Methyleneoxycarbonyl Spacer between the Backbone and Dendritic Side Chain: Synthesis, Characterization, and Some Bulk Properties

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Abstract
First through fourth generation (G1−G4) dendronized macromonomers, 3, 5, 7, and 9, with a methyleneoxycarbonyl spacer between the polymerizable group and dendritic side chain (dendron) were synthesized, and their polymerization behavior to the corresponding dendronized polymers PG1s, PG2s, PG3s, and PG4s, respectively, was investigated by heating the monomers to 55 °C without intentional addition of initiator. This self-induced polymerization is referred to as thermally induced radical polymerization (TRP). The molar masses of PG1s−PG4s were determined by gel permeation chromatography in DMF calibrated to a recently developed G1 dendronized polymer standard (PG1). A comparison of this homologous series' polymerization results with those of an already existing one, which differed only by the lack of this spacer (referred to as PG1−PG4), was made to contribute to the issue of whether short spacers have an effect on polymerization. Several representatives of both series were also used in the first systematic and generation-dependent investigation of these unusual comb polymers' bulk properties. Both structure and dynamics were investigated by DSC, X-ray diffraction, and dynamic mechanical measurements.

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