Micromorphology and phase behavior of cationic polyurethane segmented copolymer modified with hydroxysilane

A series of cationic waterborne polyurethane dispersions (SiPU) modified with hydroxysilane (HPMS) were successfully synthesized based on poly(oxytetramethylene) glycols (PTMG) and isophorone isocyanate (IPDI), and the films were obtained by casting the dispersions on tetrafluoroethylene (TFE) plates. Effects of HPMS content on micromorphology, particle size of the dispersions were studied, as well as thermal properties, phase behavior and surface structure of the films. The particles had the morphology of a solid sphere, with particle size varying from 17.1 nm to 114.4 nm corresponding to the increase of HPMS concentration, which can be attributed to the increase of interfacial tension. XPS spectra indicated the surface migration of Si element in the process of film forming, and the SiPU surface was mainly composed of soft segments. DSC analysis, together with TG-DTG-DTA results demonstrated the HPMS soft segment merged with the transition region of PU matrix, forming part of polyurethane backbone, but an improved microphase separation was observed when HPMS concentration greater than 15%. It was also found that incorporation of flexible HPMS prevented the degradation of polyurethane backbone, resulting in the increase of thermal stability in ultimate copolymer.