Amphiphilic pentablock copolymers and their blends with PDMS for antibiofouling coatings

Abstract

Well-defined amphiphilic pentablock copolymers Siy-(EGx-FAz) 2 composed of polysiloxane (Si), polyethylene glycol (EG), and perfluorohexylethyl polyacrylate (FA) blocks are synthesized by ATRP of FA monomer starting from a difunctional bromo-terminated macroinitiator. Diblock copolymers EGx-FAz are also synthesized as model systems. The block copolymers are used, either alone or blended with a PDMS matrix in varied loadings, to prepare antibiofouling coatings. Angle-resolved XPS and contact angle measurements show that the coating surface is highly enriched in fluorine content but undergoes reconstruction after contact with water.Protein adsorption experiments with human serum albumin and calf serum highlight that diblock copolymers resist protein adhesion better than do pentablock copolymers. Blending of the pentablock copolymer with PDMS results in increased protein adsorption. By contrast, the PDMS-matrix coatings show high removal percentages of sporelings of the green fouling alga Ulva linza. V C 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 000: 000-000, 2015

Amphiphilic Polymer Platforms: Surface Engineering of Films for Marine Antibiofouling

“…Amphiphilic copolymers have been used to prepare AF/FR films as either individual systems [77−81] or dispersed within an elastomeric, supporting matrix . The amphiphilic surface‐active copolymer and the elastomeric matrix are generally combined together according to one‐ and two‐layer geometries.…”

Prolate and Temperature‐Responsive Self‐Assemblies of Amphiphilic Random Copolymers with Perfluoroalkyl and Polyoxyethylene Side Chains in Solution

“…Random copolymers based on the latter type of monomers have the advantage to be soluble in both water and organic solvents and to be thermally responsive in water solution, due to the occurrence of a lower critical solution temperature‐type (LCST) transition . The introduction of fluorinated comonomer units is known to drastically affect both bulk and surface properties of a copolymer, enhancing for example its ability to spontaneously organize at low energy surfaces and interfaces, both phenomena being driven by the lowest surface energy perfluorinated moieties . Amphiphilic random copolymers of PEGMA with fluoroalkyl methacrylates (FMA) were recently synthesized by ruthenium‐catalyzed living radical polymerization and shown to give rise to single‐chain self‐assemblies, referred to as unimer micelles, in water and 2 H ,3 H ‐perfluoropentane solutions …”

Model Amphiphilic Block Copolymers with Tailored Molecular Weight and Composition in PDMS-Based Films to Limit Soft Biofouling

“…[25][26][27][28] Several strategies have been employed to improve the properties of PDMS coatings, including the addition of oils, 29 nanofillers, 30 antimicrobials, 31 amphiphilic oligopeptides 32 and surface-active polymers. [33][34][35][36] However, commercial coatings that employ some of these strategies accumulate microfouling 37,38 and may require grooming for optimum performance. 39 Amphiphilic copolymers containing both polar and non-polar components 40 have been shown to act as AF materials.…”