Molecular weight dependence of zero-shear viscosity in atactic polypropylene bottlebrush polymers

Samuel J. Dalsin, Marc A. Hillmyer, Frank S. Bates

Research output: Contribution to journalArticlepeer-review

106 Scopus citations


A series of bottlebrush polymers with atactic polypropylene side chains were synthesized via ring-opening metathesis polymerization using Grubbs' third-generation catalyst (H2IMes)(3-BrPy)2(Cl) 2Ru=CHPh. Polymers were prepared with fixed side chain length and variable backbone degree of polymerization (DP) ranging from 11 to 732 (M w = 22-1500 kg/mol) and include the largest reported polyolefin-based bottlebrush polymers. The zero-shear viscosity of each polymer sample was measured using small-amplitude oscillatory shear measurements. Power law fits of zero-shear viscosity (η0) versus weight-average molar mass (η0 ∼ Mwα) revealed distinct regimes with differing molecular weight dependences. A weak dependence (α < 0.5) was observed at low molecular weight due to the increasingly compact nature of short bottlebrush polymers with the continued addition of side chains. The scaling transitioned to Rouse-like dynamics (α = 1.2) at high molecular weight as a consequence of a sphere-to-cylinder conformational change with increasing DP of the bottlebrush backbone.

Original languageEnglish (US)
Pages (from-to)423-427
Number of pages5
JournalACS Macro Letters
Issue number5
StatePublished - May 20 2014


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