Synthesis of surface-modifying macromolecules for use in segmented polyurethanes

Polyurethanes are one of the most important classes of thermoplastic elastomers and have been widely used in medical-device manufacturing as well as in other applications. However, their function can be limited, particularly under environmental conditions that render them susceptible to hydrolysis. Using polymeric additives that are hydrolytically stable may be one approach to modifying the surface of polyurethanes for the purpose of improving their hydrolytic resistance without compromising their structural features. In this paper, the development of a series of novel fluorine-containing polyurethane surface modifying macromolecules (SMMs) is described and their synthesis conditions are investigated. The material structure and mixing properties of the synthesized SMMs with base polyurethanes was dependent on the reactant stoichiometry and concentration for the SMM components, as well as the reaction temperature and the amount of catalyst used in the SMM synthesis. This study describes the use of low surface energy components (fluorinated tails) which showed selective migration towards the surface when added to a polyester-urea-urethane. These novel macromolecules generated a nonwettable surface while not significantly altering the apparent bulk structure of the base polymer. The advancing and receding contact angle results indicated that the surface of these modified polyurethanes showed wettability characteristics similar to that of Teflon.(TM) The differential scanning calorimetry thermograms for the mixtures of the SMM with the polyurethane showed that, at 5% w/w SMM in the base polyurethane, the thermal transitions were similar to that of the native base polyurethane, indicating that the additives had no detectable effect on the polyurethane structure. (C) 1996 John Wiley & Sons, Inc.