Hierarchical fractal‐structured allophanate‐derived network formation in bulk polyurethane synthesis

Abstract

Polyurethanes are among the most applied and researched polymers worldwide. Nevertheless, polyurethane synthesis is accompanied by a side‐reaction occurring between isocyanate groups and the secondary nitrogen of already formed urethane groups, leading to the formation of crosslinking allophanates. This inevitably requires the development of highly diagnostic direct analytical methods that can be performed in the solid state of the polymer. The present research focused on the direct investigation and diagnostic determination of the chemical structure formation in bulk polyurethane synthesis, using a combination of Fourier transform infrared and solid‐state 13C nuclear magnetic resonance analysis. Polyurethane syntheses were performed in bulk and designed as to obtain significantly strong diagnostic analytical measurements signals for the accurate identification of each of the investigated chemical structures. The present research results led to the conclusive analytical identification of allophanate formation during polyurethane synthesis. In addition, the occurrence of a new reaction mechanism was discovered in the present research. It was demonstrated in the present research that this newly described reaction occurs via the further reaction of the allophanate secondary nitrogen with an isocyanate group, the reaction creating a tertiary nitrogen and an additional reactive secondary nitrogen, and so on, in a consecutive step progression, leading to the formation of a 3‐dimensional hierarchical fractal‐like crosslinked polymeric structure. Solid‐state 13C nuclear magnetic resonance analysis results were highly consistent with the Fourier transform infrared results. The discovery of this newly described reaction can facilitate the optimization of industrial processes and potentially opens a new door to the development of a vast variety of biomedical and nanotechnology applications.