Molecular Insight into the Effect of Polymer Topology on Wettability of Block Copolymers: The Case of Amphiphilic Polyurethanes.

The microstructure design of multiblock copolymers is essential for achieving desired interfacial properties in submerged applications. Two major design factors are the chemical composition and polymer topology. Despite a clear relationship between chemical composition and wetting, the effect of polymer topology (i.e., linear vs cross-linked polymers) is not very clear. Thus, in this study, we shed light on the molecular origins of polymer topology on the wetting behavior. To this end, we synthesized linear and three-dimensional (3D) cross-linked network topologies of poly(ethylene glycol) (PEG)-modified polycarbonate polyurethanes with the same amount of hydrophilic PEG groups on the surface (confirmed by X-ray photoelectron spectroscopy (XPS)) and studied the wetting mechanisms through water contact angle (WCA), atomic force microscopy (AFM), and molecular dynamics (MD) simulations. The linear topology exhibited superhydrophilic behavior, while the WCA of the cross-linked polymer was around 50°. AFM analysis (performed on dry and wet samples) suggests that PEG migration toward the interface is the dominant factor. MD simulations confirm the AFM results and unravel the mechanisms: the higher flexibility of PEG in linear topology results in a greater PEG migration to the interface and formation of a thicker interfacial layer (i.e., twice as thick as the cross-linked polymers). Accordingly, water diffusion into the interfacial layer was greater in the case of the linear polymer, leading to better screening of the underneath hydrophobic (polycarbonate) segments.

Microphase Arrangement of Smart Superhydrophilic Segmented Polyurethanes at Their Interface with Water.

Smart coatings have aroused a growing interest because of the performance of predefined surface functions upon reacting to external stimuli. Among them, responsive polymer coatings to water, which often benefit from the presence of a mobile hydrophilic material, are of great interest. Polyurethanes (PUs) are versatile materials with respect to the structure-property relationship. Therefore, the incorporation of hydrophilic segments in PUs is a rational way to produce water-sensitive smart coatings; however, having a considerable amount of hydrophilic material deteriorates the physical properties because of a large amount of water uptake. In this study, we have analyzed previously synthesized smart PUs, based on hydrophobic polycarbonate (PC) and hydrophilic polyethylene glycol (PEG) soft segments, in which only a limited amount of PEG is used. These coatings maintain, more or less, zero water contact angle, whereas the water uptake remains below 15 wt %. The combination of experimental analysis and coarse-grained molecular dynamics (CG MD) simulations reveals that PEG segments migrate to the coating/water interface and partially cover the surface, whereas the hydrophobic nature of the PC keeps the bulk of the coating intact when the coating is covered with water. Moreover, our CG MD simulations and experimental analysis suggest a reversible phase arrangement under wet/dry cycles on molecular and macroscopic scales.