Nonfouling biomaterials based on polyethylene oxide-containing amphiphilic triblock copolymers as surface modifying additives: solid state structure of PEO-copolymer/polyurethane blends.

Three novel polyethylene oxide-containing amphiphilic triblock copolymers (PEO-PU-PEO) with PEO MWs 550, 2000, and 5000, were blended with a segmented polyurethane (PU). It was expected that the block copolymers would act as surface modifiers to produce surfaces rich in PEO. The solid state properties of the PEO-copolymer/PU blends were studied by infrared spectroscopy, differential scanning calorimetry, and tensile stress-strain measurements. Infrared analysis showed no significant hydrogen bonding between the PEO blocks of the copolymers and the PU matrix. Differential scanning calorimetry data indicated that for copolymer content up to 5 wt % the microphase structure of the blends was indistinguishable from that of the unmodified PU matrix; for copolymer content of 10% or greater, the blends showed phase separated structures. Similarly the tensile stress-strain properties of the blends were essentially the same as those of the matrix up to 5 wt % copolymer. At higher copolymer content, however, the tensile strength decreased with increasing content of the copolymers; for a given copolymer content the change in tensile properties increased with increasing PEO MW. The structures of the 20% blends were also investigated after extraction with toluene (copolymers soluble, matrix insoluble). Bulk compositional change upon extraction was determined by nuclear magnetic resonance spectroscopy. Surface compositional change was studied by X-ray photoelectron spectroscopy and water contact angles. Surface morphology was observed using scanning electron microscopy and atomic force microscopy. It was shown that the copolymers were removed from the blends by extraction and that the extent of removal increased with decreasing MW of the PEO block. After toluene extraction, the blend surfaces showed advancing water contact angle and surface elemental composition similar to those of the PU matrix. However in contrast to the relatively smooth matrix surface, the extracted blend surfaces were "decorated" with lacunae or pits. Consistent with the weight loss trends, the extent of pitting was greater for the copolymers having shorter PEO blocks, suggesting that surface enrichment of the copolymers increased with decreasing MW of the copolymers.