Synthesis and structural peculiarities of 1,1‐dimethylhydrazine‐based polyurethanes

Novel polyurethanes (PUs) based on poly(oxytetramethylene glycol), 4,4′-methylenediphenyl diisocyanate, and 1,1-dimethylhydrazine (DMH) were prepared. Stoichiometric (1 : 1) and nonstoichiometric (2 : 1 to 20 : 1) prepolymer/DMH ratios were studied. The number-average molecular masses and possible structures of the obtained polymers were evaluated by potentiometric nonaqueous titration analysis of terminal groups, the Kieldal method (the evaluation of the nitrogen atom content), the aminolysis method, viscosimetry, IR spectroscopy, rheology, and small-angle X-ray scattering. Only in the case of the stoichiometric (1 : 1) ratio was a low-molecular-mass PU with a linear structure formed, whereas for all studied nonstoichiometric ratios, PUs with branched structures were formed. The level of hard and flexible block segregation increased with the increase in the prepolymer/DMH ratio. Dielectric results for the dynamic glass transition and water sorption measurements provided additional support to the structural studies. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009