Synthesis, Characterization and Properties of 2‐(Perfluorooctyl)ethylacrylate Grafted Segmented Polyurethaneureas

Abstract

AbstractWe report herein that 2‐(perfluorooctyl)ethylacrylate (PFEA) was successfully grafted onto a segmented polyurethaneurea (SPUU). We found that certain PFEA orientated onto the grafted SPUU film surface could significantly improve hemocompatibility. 1,2‐Propanediamine (PD) as a chain extender was used to synthesize the SPUU, which was based on diphenylmethane diisocyanate (MDI), vinyl group‐containing poly(butadiene) diol (PBD), and hydrogenated poly(isoprene) diol (HPIP). PFEA was copolymerized with the SPUU using α,α′‐azobis(isobutyronitrile) (AIBN) as a radical initiator. Various feed ratios of PFEA grafted polymers were synthesized (SPUU‐F‐0.5, SPUU‐F‐0.75, and SPUU‐F‐1.0) while non‐grafted SPUU was abbreviated as NG‐SPUU. The bulk characteristics of the resulting polymers were investigated by infrared spectroscopy (IR) measurement. Mechanical properties of the typical PFEA grafted SPUU were measured by dynamic viscoelasticity and tensile measurements. We found that PFEA orientated on the surface, as revealed by attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), electron spectroscopy for chemical analysis (ESCA), and water contact angle measurements. The hemocompatibility in vitro was evaluated with rabbit platelet‐rich plasma (PRP) contact tests and viewed by electron probe microanalyzer (EPM) using NG‐SPUU as a reference. We found that fewer platelets adhered to the PFEA grafted surfaces. New polymer SPUU‐F‐0.5 showed the best hemocompatibility in the tested samples. Platelet adhesion to PFEA grafted polymers SPUU‐F‐0.5, SPUU‐F‐0.75, and SPUU‐F‐1.0 was inhibited 91%, 58%, and 50% compared with NG‐SPUU. The relative clotting time of the cast films in contact with cow platelet‐poor plasma (PPP) was 3.26, 2.94, 1.95, 2.39 and 1.00 for SPUU‐F‐0.5, SPUU‐F‐0.75, SPUU‐F‐1.0, NG‐SPUU, and glass, respectively. The new polymers also showed the common characters of fluorinated polymers as revealed by water vapor transmission, dielectric constant, and index of refraction measurements.Structure of the synthesized PFEA Grafted SPUU.magnified imageStructure of the synthesized PFEA Grafted SPUU.