Study of hydrogen bonds in polyester-polyurethanes by solution n.m.r.

Abstract

High resolution 1H n.m.r. spectra are used to investigate the hydrogen bonds in polyester-polyurethanes based on 4,4′-diphenylmethane diisocyanate, N-methyldiethanolamine and poly(ethylene-propylene) adipate and their zwitterionomers. There are several NH peaks in the 1H n.m.r. spectra resulting from different kinds of hydrogen bonds. In concentrated dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) solutions, there are few hydrogen bonds between the polyurethanes and the solvent or water. The solvent effect can be ignored for hydrogen bonds. The relative amounts and the half-widths of each NH peak remain the same in the temperature range 23–82°C. The chemical shifts of the NH peaks move to lower frequency at higher temperature. The strong hydrogen bonds between groups of the hard segments make the hard segments align in a very orderly fashion. The percentage of NH groups forming hydrogen bonds with CO groups of the hard segment is large (> 45%). Neither the solvent nor H 2O can destroy the strong hydrogen bonds of the hard segment groups in concentrated solution. We deduce the conformation of the hard segments from two-dimensional nuclear Overhauser effect spectroscopy. There is no exchange between NH groups. The conformation of the polyester-polyurethanes in concentrated solution is similar to that in the solid state. Thus we can study the hydrogen-bonding interactions in concentrated solution and deduce those interactions in the solid state.