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Interplay of Crosslinking Structures and Segmental Dynamics in Solid-Liquid Elastomers

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Abstract

There have been significant interests in recent years for incorporating dynamic bonds into polymer materials for achieving multiple functionalities, such as self-healing, recycling, stimuli-responsiveness, and so on. Nevertheless, the impact of dynamic bonds on the polymer dynamics is actually less explored. In this study, we investigate a self-healing solid-liquid elastomer (SLE), which is a dual-crosslinked network made by coupling a permanently crosslinked polydimethylsiloxane (PDMS) network with polyborosiloxane (PBS) via abundant dynamic boron/oxygen dative bonds. Proton double-quantum (DQ) NMR reveals that the crosslinking degree is reduced while the structural heterogeneity of network is enhanced with increasing PBS content, i.e., increasing the content of dynamic boron/oxygen dative bonds. Rheological experiments clearly reveal two chain relaxation modes in the SLE samples with a characteristic relaxation time of around 2.1 s and 11.8 s, corresponding to the relaxation of coupled PBS and PDMS chains, respectively. The master curves obtained from variable-temperature frequency-dependent rheological experiments also reveal enhanced heterogeneity of chain relaxation with increasing PBS content. Finally, the impact of boron/oxygen dative bonds on the Rouse dynamics is further revealed by fast-field-cycling (FFC) NMR experiments, where the spin-lattice relaxation rate (R1) of all SLE samples follows the same power law of R1 (ω) ∝ ω−0.33. Nevertheless, the incorporation of PBS did slightly increase the energy barrier of Rouse dynamics. Our study well demonstrates a combined use of rheology and solid-state NMR spectroscopy can provide piercing insights into the interplay of crosslinking structures and dynamics of polymer materials.

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Acknowledgments

RZ acknowledges the financial supports by the R&D program of Guangzhou (No. 202102020941), the National Natural Science Foundation of China (Nos. 21973031 and 22173046), and the Natural Science Foundation of Guangdong Province, China (No. 2019A1515011140).

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Authors and Affiliations

  1. South China Advanced Institute for Soft Matter Science and Technology (AISMST), School of Emergent Soft Matter, South China University of Technology, Guangzhou, 510640, China

    Hao Wang & Rong-Chun Zhang

  2. Key Laboratory of High-Performance Polymer Materials and Technology of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China

    Wan-Su Peng, Yan Zhao & Xiao-Liang Wang

  3. State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu, 610065, China

    Qi Wu & Jin-Rong Wu

  4. Suzhou Niumag Analytical Instrument Corporation, Suzhou, 215151, China

    Shi-Tai Wang & Yi Yang

  5. Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou, 510640, China

    Rong-Chun Zhang

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  1. Hao Wang
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  2. Wan-Su Peng
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  3. Qi Wu
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  4. Yan Zhao
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Correspondence to Jin-Rong Wu, Xiao-Liang Wang or Rong-Chun Zhang.

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Wang, H., Peng, WS., Wu, Q. et al. Interplay of Crosslinking Structures and Segmental Dynamics in Solid-Liquid Elastomers. Chin J Polym Sci 40, 1297–1306 (2022). https://doi.org/10.1007/s10118-022-2742-0

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  • DOI: https://doi.org/10.1007/s10118-022-2742-0

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