PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation alpha ', slower than the bulky segmental alpha and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

Automated summary

By incorporating a star polymer with a POSS core and PEG groups into polyurethane during the polymerization process, various aspects of the resulting blends, including morphology, molecular dynamics, and charge mobility, were studied. The presence of POSS was found to reduce the crystallinity of the hard segments and affect the glass transition temperature of the soft phase. Different responses of slow and fast modes in the system were hypothesized to explain the observed discrepancies in the dynamic glass transition. Additionally, the introduction of POSS altered the conductivity mechanism in polyurethane, highlighting the impact of different architectural incorporations of POSS on the physical properties of the material.