Solid state NMR study of segmented polymer networks: fine-tuning of phase morphology via their molecular design

Segmented polymer networks (SPNs) based on thermo-sensitive poly(N-isopropyl acryl amide) (PNIPAA) and poly(tetrahydrofuran) (PTHF) have been synthesized by free radical copolymerization of PTHF bis-macromonomers with N-isopropyl acrylamide. The nature of the polymerizable end group on the bis-macromonomer has been varied, respectively from acrylate to acrylamide end groups. The multiphase behaviour of the corresponding SPNs has been examined as a function of the nature of the end group by making use of solid-state ¹³C CP/MAS NMR relaxometry, ¹H wideline NMR relaxometry and dynamic mechanical analysis (DMA). When PTHF with acrylate end groups was used during the SPN formation, analysis of proton spin-lattice relaxation times (T_1H) and proton spin-lattice relaxation times in the rotating frame (T_1ρH) revealed phase separation with domain sizes larger than 5 nm when the PTHF fraction exceeds 10 wt%. Only for lower PTHF-amounts, the SPNs were homogeneous on the nanometer scale. On the other hand, when PTHF with acrylamide end groups was used as macromolecular cross-linker, the NMR results showed the absence of any domain formation for SPNs with PTHF fractions up to 50 wt%. The major impact of the molecular design on the ultimate phase morphology of bicomponent polymer networks has been confirmed in all cases by DMA-analysis.