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Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by In Situ Synchrotron SAXS and Time-Domain NMR Experiments

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Abstract

The microstructural evolution of a thermoplastic polyurethane (TPU) with low hard segment content has been monitored utilizing in situ real-time synchrotron small angle X-ray scattering (SAXS) and time-domain nuclear magnetic resonance (NMR) measurements. The TPU is composed of 23 wt% of [4,4-methylenediphenyl diisocyanate (MDI)]-[1,4-butanediol (BD)] chain segments, which form hard domains, as [polytetrahydrofuran (PTHF)] forming soft domains. The number and distribution of monomer units in hard blocks is determined by the successive self-nucleation and annealing thermal fractionation technique. In situ SAXS method reveals heating-induced increase in the spacing of hard and soft domains, while time-domain 1H-NMR characterizes the changes in the phase composition and chain dynamics in these domains. A glassy fraction of short MDI-BD chain segments in hard domains passes through Tg above ambient temperature. At higher temperatures, MDI-BD nanocrystals start to melt. Sequence length distribution of MDI-BD chain segments causes a distribution in crystal sizes and wide melting temperature range. The melting is accompanied by the mixing of MDI-BD with PTHF segments in soft domains, and by increase in segmental mobility in these domains. Above 180 °C, the TPU melt is homogeneous on the scale above nanometers according to SAXS data.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 22161132007) and BASF within the framework of NAO (Network for Advanced Materials Open Research).

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Authors and Affiliations

  1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Hong-Ru Wang, Victor Litvinov & Yong-Feng Men

  2. School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Hong-Ru Wang & Yong-Feng Men

  3. BASF Polyurethane Specialties (China) Co. Ltd., Shanghai, 200137, China

    Wei Yu, Kar Wee Eddie Peh & Qian-Li Yu

  4. V. Lit. Consult, Gozewijnstraat 4, 6191, WV Beek, The Netherlands

    Victor Litvinov

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  1. Hong-Ru Wang
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Correspondence to Victor Litvinov or Yong-Feng Men.

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Wang, HR., Litvinov, V., Yu, W. et al. Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by In Situ Synchrotron SAXS and Time-Domain NMR Experiments. Chin J Polym Sci 41, 1902–1911 (2023). https://doi.org/10.1007/s10118-023-2988-1

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