Post-polymerization Modification of Surface-Bound Polymers

Abstract

Surfaces that have been intricately functionalized with reactive polymers have attracted scientific attention recently because of their potential use in a broad range of applications. Polymers containing chemically reactive functional groups can be utilized for subsequent modification of various surfaces. Reactive polymeric surfaces can be produced by surface-initiated polymerization, such as atom transfer radical polymerization, nitroxide-mediated polymerization, and ring-opening metathesis polymerization. Such surfaces can subsequently undergo postpolymerization modification to alter their physicochemical properties. Postpolymerization modification has a number of advantages, including the fact that diverse polymer structures are rapidly accessible without individual synthesis; polymerization of new functional monomers can produce a variety of surfaces and interfaces; and other materials can be easily modified, which would be difficult using conventional direct polymerization. In addition, the libraries of chemical reactions and materials that can be used in post-polymerization modifications are abundant. Therefore, post-polymerization modification opens up new platforms for the facile and versatile modification of various surfaces. This chapter focuses on a discussion of post-polymerization modification of various surface-bound polymers, from planar surfaces to three-dimensional objects, and on the extended applications of the reactive surfaces.

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

“…While the concept is as old and extensive as polymer science itself, 1 much recent work is based on vinyl systems and the architectural control offered by the suite of reversible deactivation radical polymerization (RDRP) methods. [2][3][4][5] For a reactive group to be suited for postpolymerization modification, it must (i) be compatible with polymerization conditions (or come with an easily removable protecting group) and (ii) allow for selective and efficient chemical modification, ideally under mild conditions. Commonly used chemical groups include the nucleophile-reactive epoxide, 6,7 azlactone, [8][9][10][11] and activated esters 12 as well as unsaturated groups such as dienes and alkynes which can undergo cycloadditions and reactions with thiols.…”

Production of New Functionalized Polymer Nanoparticles and Use for Manufacture of Novel Nanobiocatalysts

“…Particularly, many studies have been attempting to develop new functionalization techniques, to allow the production of functionalized polymer materials that may interact more efficiently with specific enzymes. [ 5–15 ]…”

“…Thus, distinct polymer structures can be synthesized, new surfaces and interfaces can be produced and new materials with distinct properties can be obtained through functionalization reactions. [ 6–17 ]…”

“…Click chemistry concept was first described by Kolb et al, [ 18 ] who defined that click chemistry reactions must necessarily involve simple and fast reactions that occur under mild conditions, including thiol‐ene addition, epoxide ring opening, Michael addition, Cu‐catalyzed alkyno‐azide addition, and fluorine reactions. [ 7,12,14–16,18,19 ]…”

“…Particularly, many studies have been attempting to develop new functionalization techniques, to allow the production of functionalized polymer materials that may interact more efficiently with specific enzymes. [5][6][7][8][9][10][11][12][13][14][15] Functionalization of polymer supports frequently involves the addition of specific chemical groups onto the surfaces of polymer particles, leading to more versatile materials that cannot be produced through classical polymerization processes. [6,7,12,14,15] It is important to highlight that the functionalization process can occur through different routes.…”