Study of phase separation in polyurethane using paramagnetic labels. Effect of soft segment molecular weight, structure, and thermal history

The morphology of segmented polyurethane (PU) elastomers was studied by means of ESR at various temperatures ranging from 100K‐450K. The PU's were based on 4,4'‐diphenylmethane diisocyanate (MDI), poly (oxytetramethylene) glycols (PTMO) and hydroxyl‐terminated random compolymers of tetrahydrofuran and 3‐methyl‐tetrahydrofuran (THF/Me‐THF). Purified 1,4‐butanediol (BD) was used as a chain extender. The nitroxide probe, 4‐hydroxy‐2‐2',6‐6'‐tetramethylpiperidine‐1‐oxyl (TEMPOL), was used to label the polyurethanes by reaction with an NCO group of MDI. Analysis of the electron spin resonance (ESR) spectra suggested that the label situates at heterogeneous sites, which means that a two‐phase domain is present. The morphologies at 300K and 400K were compared. It was found from ESR spectra that polyurethanes made from soft segments having higher MW exhibited greater phase separation at 300K than their corresponding elastomers made from lower MW soft segments. However, at 400K the more isotropic ESR spectra for the PUs containing higher MW soft segments suggested that the PUs were more mobile than their analogs having lower MW soft segments. The introduction of 3‐methyl side groups decreased the phase mixing at 400K due to steric hindrance.