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  • Title: Model fluorous polyurethane surface modifiers having co-polyoxetane soft blocks with trifluoroethoxymethyl and bromomethyl side chains.
    Author: Wynne KJ, Makal U, Kurt P, Gamble L.
    Journal: Langmuir; 2007 Oct 09; 23(21):10573-80. PubMed ID: 17824629.
    Abstract:
    Polyurethanes containing poly(2-trifluoroethoxymethyl-2-methyl)-co-(2-bromomethyl-2-methyl)-1,3-propylene oxide (co-polyoxetane) soft blocks, P[3FOx:BrOx-m:n], were prepared and used (0.5-2 wt %) to modify the surface properties of a conventional polyurethane. The substrate polyurethane was composed of an isophorone diisocyanate/butanediol hard block and a polytetramethylene oxide soft block [IPDI/BD(50%)-PTMO(2000)]. A combination of tapping mode atomic force microscopy (TM-AFM), X-ray photoelectron spectroscopy (XPS), and dynamic contact angle (DCA) studies showed that the fluorous polyurethane surface modifiers confer surface properties similar to those of the parent at 0.5-1.0 wt %. The retention of initial wetting behavior in water was enhanced with higher ratios of 3FOx:BrOx that corresponds to increasing fluorous character. A semifluorinated chaperone is necessary to surface concentrate -CH2Br groups. Negligible Br was detected by XPS when the P[BrOx]-soft block polyurethane was used as a surface modifier (0.5%) and the wetting behavior was similar to that of the bulk polyurethane. Despite being hydrophobic (theta adv = 102 degrees) the P[BrOx]-soft block polyurethane is not a polymer surface modifier under the conditions described herein. The calculated solubility parameters for PTMO and P[BrOx], which are similar, support the notion of BrOx miscibility with the base polyurethane. The combination of miscibility of BrOx repeat units and lack of an end-group-like architecture minimizes BrOx surface concentration in the chosen bulk polyurethane.
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