Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral) (PVB) as Elucidated by Solid-State NMR

Jing Lv; Xu Chen; Zi-Shuo Wu; Ya-Hui Li; Wei Chen

doi:10.1007/s10118-023-3017-0

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Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral) (PVB) as Elucidated by Solid-State NMR

RESEARCH ARTICLE | Updated：2023-12-26

- Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral) (PVB) as Elucidated by Solid-State NMR
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- Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral) (PVB) as Elucidated by Solid-State NMR
- 高分子科学（英文版） 2024年42卷第1期页码：113-124
- Affiliations：
  
  National Synchrotron Radiation Laboratory, Anhui Provincial Engineering Laboratory of Advanced Functional Polymer Film, CAS Key Laboratory of Soft Matter Chemistry, University of Science and Technology of China, Hefei 230026, China
- Author bio：
  
  wc003@ustc.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. U20A20256).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-3017-0.
- DOI：10.1007/s10118-023-3017-0
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Lv, J.; Chen, X.; Wu, Z. S.; Li, Y. H.; Chen, W. Chain dynamics heterogeneity in plasticized poly(vinyl butyral) (PVB) as elucidated by solid-state NMR. Chinese J. Polym. Sci. 2024, 42, 113–124

Jing Lv, Xu Chen, Zi-Shuo Wu, et al. Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral) (PVB) as Elucidated by Solid-State NMR[J]. Chinese Journal of Polymer Science, 2024,42(1):113-124.
Lv, J.; Chen, X.; Wu, Z. S.; Li, Y. H.; Chen, W. Chain dynamics heterogeneity in plasticized poly(vinyl butyral) (PVB) as elucidated by solid-state NMR. Chinese J. Polym. Sci. 2024, 42, 113–124 DOI： 10.1007/s10118-023-3017-0.

Jing Lv, Xu Chen, Zi-Shuo Wu, et al. Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral) (PVB) as Elucidated by Solid-State NMR[J]. Chinese Journal of Polymer Science, 2024,42(1):113-124. DOI： 10.1007/s10118-023-3017-0.

摘要

The combination of various SSNMR techniques quantified the multiscale dynamics heterogeneity of the plasticized Poly(vinyl butyral) (PVB) system: (1) the mesoscale dynamics heterogeneity where the plasticizer rich and poor domains coexist; (2) the chain dynamics heterogeneity of VB units with different stereogeometries; (3) the local mobility gradient for VB unit.

Abstract

The chain dynamics heterogeneity of the poly(vinyl butyral) (PVB) plasticized by triethylene glycol bis(2-ethylhexanoate) (TEG-EH) was investigated by various solid-state NMR techniques. The plasticized PVB shows two domains in distinct molecular dynamics differences, namely, rigid and soft domains, where the latter is the plasticizer-rich domain. The time domain low field NMR was first used to investigate the dynamics heterogeneity of the plasticized PVB, and the results show the decreasing activated energy of components in the soft domain of plasticized PVB (,E,a,=20.2 kJ/mol) as compared with that of the pristine one (,E,a,=24.3 kJ/mol). Detailed dynamics heterogeneity was obtained by high-field NMR with site-specific features. The quadrupole-echo ,2,H-NMR was adopted to elucidate the dynamics heterogeneity of the vinyl alcohol (VA) units, where only the hydroxyl group of VA is deuterated. The ,1,H-,13,C WISE NMR spectra show that there is not much difference in the mobility of the VB unit in PVB with and without plasticizer, whereas the glass transition temperature differed by approximately 53 °C. This is further supported by Torchia's ,T,1, relaxation measurements. The origin of such an unusual phenomenon is attributed to the critical role of the remaining VA (~22%) in the soft domain, where the VA units locally aggregate through hydrogen bonding. Also, the existence of a mobility gradient in the VB unit has been demonstrated. Moreover, the mobility difference for VB with different stereo-geometry (,meso, or ,racemic, conformation) is observed for the first time. This indicates the importance of modulating the ratio of ,meso, over ,racemic, VB for controlling the macroscopic performance of PVB.

关键词

Keywords

Poly(vinyl butyral)Dynamics heterogeneityPlasticizerSolid state NMR

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