In this study, we examined the viscoelastic properties of a series of comb-shaped ring (RC) polystyrene samples with different branch chain lengths, i.e., the molecular weights of the ring backbone Mbb (≃ 4Me where Me is the entanglement molecular weight) and branch chains Mbr (≃ Me, 2Me, and 4Me). Even for the RC sample with the shortest branch chains, a plateau region was observed for the dynamic modulus G*(ω) in the middle angular frequency ω region, suggesting that intermolecular branch chain entanglement occurred. In the ω region between the plateau and terminal regions, G*(ω) was observed with a weaker ω dependence than the terminal relaxation. This behavior was more pronounced for RC samples with shorter branch chains and for the corresponding linear comb (LC) samples than for the RC ones. The molecular weight dependence of the zero-shear viscosity η0 and the steady-state recoverable compliance Jeo of the RC and LC samples was evaluated, and the effects of different backbone molecular structures (i.e., ring or linear) on the terminal relaxation behavior was discussed. Moreover, the G*(ω) data were analyzed with two models: the comb-Rouse model, in which the structures of the RC/LC molecules are taken into account by graph theory, and the Milner-McLeish model for entangled star-shaped polymers. The former model qualitatively described the terminal relaxation behavior of G*(ω) at low ω but failed to reproduce the plateau in the middle ω range. Conversely, the latter model described the entanglement plateau in the middle ω range, but the difference in the terminal relaxation regime for the RC/LC samples seen in the data and the comb-Rouse model disappeared.
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The authors acknowledge Prof. H. Watanabe at Kyoto University for his valuable suggestions, especially for the Rouse analysis. The authors thank Dr. J. Roovers for his kind provision of rheological data for the star polystyrenes. This work was supported by JSPS Research Fellowships for Young Scientists (No. 14J03393 for YD) and Grant-in-Aids for Scientific Research (No. 21K14682 for YD and 24350056 for AT). This work was partly supported by the Collaborative Research Program of the Institute for Chemical Research, Kyoto University (Grant No. 2015-58), and AT is grateful for the support. This work was also supported by the Program for Leading Graduate Schools at Nagoya University entitled “Integrate Graduate Education and Research Program in Green Natural Sciences”.
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Doi, Y., Kitamura, J., Uneyama, T. et al. Viscoelastic properties of comb-shaped ring polystyrenes. Polym J 54, 1267–1277 (2022). https://doi.org/10.1038/s41428-022-00686-0