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Zheng, Ying; Kafle, Navin; Schwarz, Derek; Eagan, James M.; Hayano, Shigetaka; Nakama, Yuki; Pan, Pengju; Miyoshi, Toshikazu (, ACS Macro Letters)
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Kafle, Navin; Makita, Yuta; Zheng, Ying; Schwarz, Derek; Kurosu, Hiromichi; Pan, Pengju; Eagan, James M.; Nakama, Yuki; Hayano, Shigetaka; Miyoshi, Toshikazu (, Macromolecules)null (Ed.)Stereoregularity significantly influences the crystallization, mechanical, and thermal properties of polymers. In this work, we investigate crystallization behaviors and molecular dynamics of atactic (a)-, isotactic (i)-, and syndiotactic (s)-hydrogenated poly(norbornene) (hPNB)s by using small-angle X-ray scattering and solid-state (ss) NMR. a-hPNB exhibits a much higher crystallinity (Φc) (82%) and long period (L) (80 nm) than i- and s-hPNB (50–55% and 17–21 nm). Moreover, in the s-hPNB crystalline region, chain dynamics is not thermally activated up to the melting temperature (Tm), while in the crystalline regions of i- and a-hPNB, small amplitude motions occur in a slow dynamic regime of 10–2–102 s. The molecular dynamics follows Arrhenius behavior in a-hPNB up to the crystal–crystal transition temperature (Tcc), while these dynamics are surprisingly saturated in i-hPNB under these conditions. Temperature dependence of the molecular dynamics leads to different crystal–crystal transitions between i- and a-hPNBs: i-hPNB changes the trans conformation to the gauche one due to the localized bond rotations where chain dynamics is restricted, whereas a-hPNB keeps a nearly trans conformation and conducts fast chain dynamics due to the amplified C–C bond rotations in the high-temperature phase. Such fast chain dynamics leads to unique crystallization behaviors of hPNB, specifically in the atactic configuration due to configurational disorder coupled with conformational flexibility.more » « less
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Xie, Qing; Chang, Xiaohua; Qian, Qian; Pan, Pengju; Li, Christopher Y. (, ACS Macro Letters)