Abstract
The branched polymers containing different amounts of the highly branched fraction are synthesized by the radical copolymerization of styrene and divinylbenzene under conditions of the reversible inhibition by 2,2,6,6-tetramethylpiperidine-1-oxyl. The branched polystyrenes are studied by size-exclusion chromatography combined with static light scattering, viscometry, and pulsed-field gradient nuclear magnetic resonance. The branched polymers prepared by living radical polymerization (in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl) feature reduced intrinsic viscosities and increased self-diffusion coefficients compared with their linear analogs. As the content of the highly branched fraction in the synthesized polymers grows, the Zimm contraction factor in toluene solution decreases to g′ = 0.13. The Kuhn-Mark-Houwink parameters for these polymers in toluene solution (a = 0.43) confirm the nonlinear architecture of macromolecules.
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