Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by <italic style="font-style: italic">In Situ</italic> Synchrotron SAXS and Time-Domain NMR Experiments

Hong-Ru Wang; Victor Litvinov; Wei Yu; Kar Wee Eddie Peh; Qian-Li Yu; Yong-Feng Men

doi:10.1007/s10118-023-2988-1

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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

RESEARCH ARTICLE | Updated：2023-11-27

- 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
- 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
- 高分子科学（英文版） 2023年41卷第12期页码：1902-1911
- Affiliations：
  
  a.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
  c.BASF Polyurethane Specialties (China) Co. Ltd., Shanghai 200137, China
  d.V. Lit. Consult, Gozewijnstraat 4, 6191 WV Beek, the Netherlands
- Author bio：
  
  v.lit.con@kpnmail.nl (V.L.)
  men@ciac.ac.cn (Y.F.M)
- Funds：
  
  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).
- DOI：10.1007/s10118-023-2988-1
  中图分类号：
- 收稿：2023-03-07，
  
  修回：2023-3-23，
  
  录用：2023-4-12，
  
  网络首发：2023-05-18，
  
  纸质出版：2023-12-01
- Accepted：
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Wang, H. R.; Litvinov, V.; Yu, W.; Peh, K. W. E.; Yu, Q. L.; Men, Y. F. 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. Chinese J. Polym. Sci. 2023, 41, 1902–1911

Hong-Ru Wang, Victor Litvinov, Wei Yu, 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[J]. Chinese Journal of Polymer Science, 2023, 41(12): 1902-1911. DOI: 10.1007/s10118-023-2988-1.
Wang, H. R.; Litvinov, V.; Yu, W.; Peh, K. W. E.; Yu, Q. L.; Men, Y. F. 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. Chinese J. Polym. Sci. 2023, 41, 1902–1911 DOI： 10.1007/s10118-023-2988-1.

Hong-Ru Wang, Victor Litvinov, Wei Yu, 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[J]. Chinese Journal of Polymer Science, 2023, 41(12): 1902-1911. DOI: 10.1007/s10118-023-2988-1. DOI：

摘要

The effect of temperature on the evolution of physical structures and chain dynamics of TPU with low hard segment content is studied using DSC

SAXS and Time-domain NMR. The SSA thermal fractionation analysis shows a wide length distribution of MDI-BD hard blocks. Softening of glassy fraction of hard blocks and melting of nanocrystals take place successively during heating. Hard and soft blocks are mixed on the scale above nanometers in the melt.

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

H-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

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.

关键词

Keywords

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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

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

DOI：10.1007/s10118-023-2988-1

摘要

Abstract

关键词

Keywords

references