Spectral analysis and dynamic properties of polyurethanes dyed with rhodamine 6G and rhodamine B as matrices of a solid-state laser element

Abstract

A comparison was carried out of the nature of intermolecular interactions, elastic properties and gas permeability of the crosslinked polyurethanes doped with xanthene dyes and original polyurethane using IR spectroscopy, dynamic mechanical analysis (DMA) and electron paramagnetic resonance (EPR). The introduced dye can be considered as useful microimpurity which, however, can affect the efficiency of the laser. In IR spectra of polyurethanes the complex band of stretching vibrations of C=O groups is sensitive to the nature of intermolecular interaction of urethane groups. From the analysis of that band it is shown that in the presence of dyes, self-association of urethane groups within the hard segment predominates and the interaction of urethane groups with the oligoether component decreases, which can contribute to increasing the mobility of the flexible component. A decrease in the dynamic storage modulus (E’) and a decrease in the glass transition temperature (Tc) of polyurethanes in the presence of dyes is shown by the DMA method. The results of both DMA and IR spectroscopy indicate a greater increase in the mobility of the elastic component with the introduction of the rhodamine B dye, covalently bound to the polyurethane chain. According to nitroxyl paramagnetic probe data the introduction of both rhodamine B and rhodamine 6G dyes into polyurethanes increases their permeability to vapors of low-molecular weight compounds, but rhodamine 6G has a more prominent effect on this characteristic. This is consistent with DMA data indicating a greater increase in the Mc value in the presence of rhodamine 6G in polyurethane. The obtained results make it possible to determine the optimal composition of the active laser medium and are important in assessing the radiation resistance of the polymer matrix. Its increase is facilitated by a decrease in the storage modulus and an increase in the gas permeability of the polymer, leading to a decrease in pressure in the area of local heating.