Unravelling Main- and Side-Chain Motions in Polymers with NMR Spectroscopy and Relaxometry: The Case of Polyvinyl Butyral

Polymers (Basel). 2021 Aug 11;13(16):2686. doi: 10.3390/polym13162686.

Abstract

Polyvinyl butyral (PVB) is an amorphous polymer employed in many technological applications. In order to highlight the relationships between macroscopic properties and dynamics at a microscopic level, motions of the main-chain and of the propyl side-chains were investigated between Tg - 288 °C and Tg + 55 °C, with Tg indicating the glass transition temperature. To this aim, a combination of solid state Nuclear Magnetic Resonance (NMR) methods was applied to two purposely synthesized PVB isotopomers: one fully protonated and the other perdeuterated on the side-chains. 1H time domain NMR and 1H field cycling NMR relaxometry experiments, performed across and above Tg, revealed that the dynamics of the main-chain corresponds to the α-relaxation associated to the glass transition, which was previously characterized by dielectric spectroscopy. A faster secondary relaxation was observed for the first time and ascribed to side-chains. The geometry and rate of motions of the different groups in the side-chains were characterized below Tg by 2H NMR spectroscopy.

Keywords: 2H NMR; FID analysis; field cycling NMR relaxometry; glass transition; secondary relaxation; α-relaxation.