Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by In Situ Synchrotron SAXS and Time-Domain NMR Experiments

The microstructural evolution of a thermoplastic polyurethane(TPU)with low hard segment content has been monitored utilizing in situ real-time synchrotron small angle X-ray scattering(SAXS)and time-domain nuclear magnetic resonance(NMR)measurements.The TPU is composed of 23 wt% of[4,4-methylenediphenyl diisocyanate(MDI)]-[1,4-butanediol(BD)]chain segments,which form hard domains,as[polytetrahydrofuran(PTHF)]forming soft domains.The number and distribution of monomer units in hard blocks is determined by the successive self-nucleation and annealing thermal fractionation technique.In situ SAXS method reveals heating-induced increase in the spacing of hard and soft domains,while time-domain ^(1)H-NMR characterizes the changes in the phase composition and chain dynamics in these domains.A glassy fraction of short MDI-BD chain segments in hard domains passes through T_(g) above ambient temperature.At higher temperatures,MDI-BD nanocrystals start to melt.Sequence length distribution of MDI-BD chain segments causes a distribution in crystal sizes and wide melting temperature range.The melting is accompanied by the mixing of MDI-BD with PTHF segments in soft domains,and by increase in segmental mobility in these domains.Above 180℃,the TPU melt is homogeneous on the scale above nanometers according to SAXS data.