Fabrication of Surface Polymer Brushes Via Thin Film Crystallization and Solvent Annealing.

Abstract

Polymer single crystals have been used as templates to synthesize polymer brushes, known as the "polymer-single-crystal-assisted-grafting-to" (PSCAGT) approach. Polymer brushes with controlled grafting densities and spatial tethering locations have been demonstrated. Previous works focused on solution crystallization, which involves large amounts of organic solvent, and the grafting density can only be tuned by varying crystallization temperatures. In this work, thin film crystallization was utilized to fabricate two-dimensional (2D) polymer crystals on flat surfaces. Subsequent chemical tethering led to polymer brushes that retained the original morphology of the crystals with high fidelity. Furthermore, we show that the grafting density of the polymer brushes fabricated using this method depends on the chain end distribution on the top/bottom surfaces of the crystal, which can be facilely controlled by annealing the crystals at various nonsolvent media. Our work broadens the scope of the PSCAGT method and provides a new route to achieve polymer brushes with controlled structures. This article is protected by copyright. All rights reserved.