Abstract
Monodendrons consisting of m-linked phenyleneethynylene repeating unit with trimethylsilyl-, pentamethyldisiloxanyl-, and nonamethyltetrasiloxanyl- peripheral groups were synthesized using the convergent approach. The focal point of monodendrons, terminal acetylene, was polymerized with Rh catalyst to give the corresponding polydendrons with a high molecular weight, e.g., M̅w=2.8×106(D̅P̅=2.8×103). The polydendrons showed good solubility in common organic solvents, and good membrane forming ability. Since we obserbed high ratio of a peak at δ 5.8–6.0, assignable to cis proton of poly(phenylacetylene) main-chain, in 1H NMR of the polydendrons, the polydendrons were found to be cis-rich polymer. The visible absorption maxima (λmax) of the polydendrons significantly increased due to effect of the bulky substituents at m-position in comparison with the corresponding zero generation of poly(phenylacetylene) derivatives having no substituents at m-position. The wide angle X-Ray scattering of the polymers suggested the pseudohexagonal lattice of rod-like molecules. The interplanar d spacing increased with increasing generation or size of the peripheral silyl group.
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Kaneko, T., Asano, M., Yamamoto, K. et al. Polymerization of Phenylacetylene-Based Monodendrons and Structure of the Corresponding Polydendrons. Polym J 33, 879–890 (2001). https://doi.org/10.1295/polymj.33.879
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DOI: https://doi.org/10.1295/polymj.33.879