title: Model fluorous polyurethane surface modifiers having co-polyoxetane soft blocks with trifluoroethoxymethyl and bromomethyl side chains.
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.
authors.affiliation: Department of Chemical and Life Science Engineering, Virginia Commonwealth University, Richmond, Virginia 23284, USA. kjwynee@vcu.edu
authors.forename: Kenneth J
authors.initials: KJ
authors.lastname: Wynne
authors.forename: Umit
authors.initials: U
authors.lastname: Makal
authors.forename: Pinar
authors.initials: P
authors.lastname: Kurt
authors.forename: Lara
authors.initials: L
authors.lastname: Gamble
mesh_terms: D004988:Ethers, Cyclic / Q000737:chemistry*; D018625:Microscopy, Atomic Force; D011140:Polyurethanes / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods; D014965:X-Rays