Solid-state NMR study of spin dynamics and local disorder in smart polymers: PDMAEMA

Abstract

The solid-state 1H and 13C NMR spectra as well as the 1H–13C cross-polarization upon magic angle spinning (CP MAS) kinetics were studied for poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA), i.e. a smart pH- and thermo-responsive polymer. The stereochemical content of PDMAEMA was determined from the complex shaped 13C MAS signal of CH3 group. The kinetic data were processed using the Hirschinger and Raya spin dynamics model that includes the complete scheme of rotating frame spin-lattice relaxation pathways. The general solution was adapted for the spin cluster treatment. The earlier studied experimental CP MAS kinetics data of poly [2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC), i.e. one of its quaternized form, were revisited and newly processed applying this model. The spin-lattice relaxation of protons in the rotating frame in PDMAEMA and PMETAC occurs in the same scale from one to tens of milliseconds. Very high anisotropy of spin-diffusion was found for both polymers. However, the local disorder of various spin sites in PDMAEMA is significantly higher than in PMETAC. It is characterized by the order parameters 0.71–0.77 and 0.87–0.91, respectively. The main chain in PDMAEMA is also more disordered and more flexible than in PMETAC.