(Super)hydrophobic and Multilayered Amphiphilic Films Prepared by Continuous Assembly of Polymers

Abstract

The continuous assembly of polymers (CAP) is used to fabricate tailored nanocoatings on a wide variety of substrates. Ring‐opening metathesis polymerization (ROMP) is used to mediate the CAP process (CAPROMP) to assemble specifically designed macromolecules into nanoengineered crosslinked films. Different films composed of single or multiple macromolecules are used to tune the surface wetting characteristics on various planar substrates, including porous substrates such as filter paper and cotton, and non‐porous subtrates such as aluminium foil and glass. By judicious selection of the macromolecules, these substrates, which are hydrophilic in nature, can be rendered (super)hydrophobic. The robustness of the ROMP catalysts and the reinitiation ability of the CAPROMP approach allow the production of layered multicomponent amphiphilic films with on‐demand switchable wettability. Such functional nanocoatings can be potentially applied as self‐cleaning surfaces, as waterproof woven fabrics, and for the next generation of microelectronic devices.

Low-Fouling, Biospecific Films Prepared by the Continuous Assembly of Polymers

“…For the CAPROMP process, the surface of the substrate is firstly functionalized with initiators, followed by exposure to a solution of macrocross-linker, which results in one-step assembly of the nanoscale cross-linked films mediated via controlled polymerization across the pendent norbornene groups of the macrocross-linker. 30,33,34 In this study, the substrates were initially functionalized with an allyl-modified poly(ethylene imine), followed by cross-metathesis with the bispyridine modified 2 nd generation Grubbs catalyst C1 (1 mM in dichloromethane) to form towards BSA regardless of the pH conditions. 38,39 The initial zeta-potential measurement of the particles after deposition of the allyl-PEI initiator prelayer was 33 mV, which decreased to -3 mV after the CAPROMP reaction with PAA macrocross-linker P1, before increasing again to +3 mV after subsequent CAP reinitiation and film growth with the PHEA macrocross-linker P2 (Figure 1a).…”

“…[30][31][32] Furthermore, CAP-derived films can be reinitiated for continued film growth using the unreacted polymerizable groups of the macrocross-linkers that are embedded in the film, providing access to multilayered films through so-called reinitiation reactions with the same or different macrocross-linkers. 34 These layer thickness extensions or reinitiation reactions do not depend exclusively on the end-group fidelity of polymer brushes/grafts that are inherent and difficult to preserve in the grafting-from approach. Given that these reactions can occur conveniently via the residual polymerizable moieties of the macrocross-linker in the film, the CAP approach thus overcomes the difficulty of the grafting-from approach to prepare higher order multilayer films.…”

Tailoring Substrate Hydrophilicity Using Grafted Polypeptide Nanocoatings

“…It is well known that an increase in surface roughness causes air pockets to be trapped between the water and substrate surface, leading to significantly lowered solid-liquid adhesion forces, which consequently increases the apparent contact angle. [28,29] As seen in the SEM images (Fig. S3), an increase in surface roughness after 24 h of polymerization was evident when compared with untreated filter paper.…”

Fabrication of Chiral Stationary Phases via Continuous Assembly of Polymers for Resolution of Enantiomers by Liquid Chromatography

“…20%) where distillation‐precipitation polymerization was employed in the fabrication of cross‐linked films . To increase the P1 film thickness on the particles, a process of reinitiation was performed . Firstly, the film made after one CAP step was replenished with initiator C1 through reaction with the terminal alkene, as well as the “left‐over” unreacted norbornene, in the film, followed by exposure to macrocross‐linker P1 under identical conditions to the first CAP reaction (Figure a).…”

“…Herein, the viability of the continuous assembly of polymers (CAP) approach to produce CSPs with engineered features is investigated. The CAP approach utilizes controlled polymerization methodologies to mediate the continuous growth of macrocross‐linkers – (bio)macromolecules functionalized with pendent polymerizable moieties – from initiator‐functionalized surfaces to form surface‐confined, cross‐linked films in a single‐step . As the CAP films are cross‐linked, the resulting CSPs are expected to be robust towards a wide range of HPLC eluents.…”