Reactive processing of polymers: Structural characterisation of products by 1H and 13C NMR spectroscopy for glycidyl methacrylate grafting onto EPR in the absence and presence of a reactive comonomer

Abstract

Grafted GMA on EPR samples were prepared in a Thermo-Haake internal mixer by free radical melt grafting reactions in the absence (conventional system; EPR–g–GMA CONV) and presence of the reactive comonomer divinyl benzene, DVB (EPR–g–GMA DVB). The GMA-homopolymer (poly-GMA), a major side reaction product in the conventional system, was almost completely absent in the DVB-containing system, the latter also resulted in a much higher level of GMA grafting. A comprehensive microstructure analysis of the formed poly-GMA was performed based on one-dimensional 1H and 13C NMR spectroscopy and the complete spectral assignments were supported by two-dimensional NMR techniques based on long range two and three bond order carbon–proton couplings from HMBC (Heteronuclear Multiple Bond Coherence) and that of one bond carbon–proton couplings from HSQC (Heteronuclear Single Quantum Coherence), as well as the use of Distortionless Enhancement by Polarization Transfer (DEPT) NMR spectroscopy. The unambiguous analysis of the stereochemical configuration of poly-GMA was further used to help understand the microstructures of the GMA-grafts obtained in the two different free radical melt grafting reactions, the conventional and comonomer-containing systems. In the grafted GMA, in the conventional system (EPR–g–GMA CONV), the methylene protons of the GMA were found to be sensitive to tetrad configurational sequences and the results showed that 56% of the GMA sequence in the graft is in atactic configuration and 42% is in syndiotactic configuration whereas the poly-GMA was predominantly syndiotactic. The differences in the microstructures of the graft in the conventional EPR–g–GMA CONV and the DVB-containing (EPR–g–GMA DVB) systems is also reported