POLYURETHANE-BASED POLYMER SURFACE MODIFIERS WITH ALKYL AMMONIUM CO-POLYOXETANE SOFT BLOCKS: REACTION ENGINEERING, SURFACE MORPHOLOGY AND ANTIMICROBIAL BEHAVIOR

摘要

Concentrating quaternary (positive) charge at polymer surfaces is important for applications including layer-by-layer polyelectrolyte deposition and antimicrobial coatings. Prior techniques to introduce quaternary charge to the surface involve grafting of quaternary ammonium moieties to a substrate or using polyurethanes with modified hard segments however there are impracticalities involved with these techniques. In the case of the materials discussed, the quaternary charge is introduced via polyurethane based polymer surface modifiers (PSMs) with quaternized soft segments. The particular advantage to this method is that it utilizes the intrinsic phase separation between the hard and soft segments of polyurethanes. This phase separation results in the surface concentration of the soft segments. Another advantage is that unlike grafting, where modification has to take place after device fabrication, these PSMs can be incorporated with the matrix material during device fabrication. The soft segments of these quaternized polyurethanes are produced via ring opening copolymerization of oxetane monomers which possess either a trifluoroethoxy (3FOx) side chains or a quaternary ammonium side chain (C12). These soft segments are subsequently reacted with 4,4’-(methylene bis (p-cyclohexyl isocyanate)), HMDI and butanediol (BD) to form the PSM. It was initially intended to increase the concentration of quaternary ammonium charge by increasing PSM soft segment molecular weight. Unexpectedly, produced blends with surface microscale phase separation. This observation prompted further investigation of the effect of PSM soft segment molecular weight on phase separation in PSM-base polyurethane blends and the subsequent effects of this phase separation on the biocidal activity. Analysis of the surface morphology via tapping mode atomic force microscopy (TMAFM) and scanning electron microscopy (SEM) revealed varying complexities in surface morphology as a function of the PSM soft segment molecular weight and initial annealing temperature. Many of these features include what are described as nanodots (100-300 nm), micropits (0.5-2 um) and micropeaks (1-10 um). It was also observed that surface morphology continued to coarsen with time and that the larger features were typically observed in blends containing PSMs with low molecular weight soft segments. This appearance of surface morphological feature correlates with decreased biocidal activity of the PSM blends, that is, the PSM blends exhibit little to no activity upon development of phase separated features. A model has been developed for phase separation and concomitant reduction of surface quaternary charge. This model points the way to future work that will stabilize surface charge and provide durability of surface modification.