Quantifying the cooperative evolution of microphase segregation and nanostructural order in annealed polyurethanes of MDI-BDO-PTHF

Here, we quantify the relationship between microphase segregation and local structure development in thermoplastic polyurethanes. Samples were prepared with varying ratios of 4,4 '-methylene diphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) to polytetrahydrofuran (PTHF) and annealed at temperatures T-a between RT-140 degree celsius for 20 h each. Distinct populations of smaller and larger ordered domains are distinguished by pair distribution function analysis. The intermediate-range order of nanoscale hard domains in the paracrystalline state (form I) is directly extracted and characterized. The results suggest that form I of the MDI-BDO:PTHF system presents a conformational and packing order similar to the form III structure, typically obtained from stretching/annealing, but with limited spatial coherence of 3-7 nm. Heating above T-g of the hard segments is necessary to achieve a substantial structural response from the annealing treatment. Increasing T-a promotes purification of the soft phase via microphase segregation, coalescence of the hard blocks, and growth of paracrystalline phase, while a minority fraction of longer-range ordered domains left over from production remains relatively constant. We observe a composition-dependent decrease in the average nearest-neighbor distance that can be correlated with the greater number of C=C, C=N, and C=O bonds with increased hard segment content. A non-linear deviation in the trend is observed to correlate with sample densification. The mechanical and thermal behavior of the samples is intimately tied to the segregation state.