Interfacial Thermoreversible Chemistry on Functional Coatings: A Focus on the Diels–Alder Reaction

Abstract

Stimuli‐responsive materials have properties that depend on the environment in which they are used. In most cases, the material itself is formulated to react to the corresponding stimulus. However, many phenomena occur at the surface of the material. In this context, the design and the investigation of the reactivity of stimuli‐responsive surfaces are particularly interesting. More precisely, this review focuses on functional coatings that react via Diels–Alder (DA) chemistry, a thermoreversible reaction between a diene and a dienophile. According to the nature of the substrate, these coatings are mainly based on self‐assembled monolayers or silane assemblies, on polydopamine derivatives, or on polymer thin films deposited by vapor‐phase processes including plasma polymerization. The different works discussed here show that interfacial thermoreversible reactions occur between a DA‐functionalized surface and a DA reactant in solution but also between two solid substrates are possible. The direct cycloaddition is always described in the cited papers but the reversibility of the reaction is less discussed. The latter however remains very challenging for smart applications in material science.

Furoic acid and derivatives as atypical dienes in Diels–Alder reactions

“…Since its discovery in 1929, [1] the furan Diels-Alder (DA) reaction has been extensively applied in organic chemistry, with the resulting 7-oxabicyclo[2.2.1]heptanes being exploited in natural product synthesis, drug discovery, bioconjugation, as well as in polymer and material science applications. [2][3][4][5][6][7] Indeed, furan DA reactions allow versatile synthons of considerable molecular complexity to be generated in an atom-economical fashion, making it a highly attractive strategy for green chemical synthesis of cyclic compounds. [8] The reactivity of furan derivatives as dienes has been the subject of numerous theoretical and experimental studies.…”

Diels-Alder-Chitosan based dissociative covalent adaptable networks

“…Going further, retro Diels-Alder has never been revealed for chitosan-based compounds even if its use has been recognized for many applications such as self-healing of various polymers (Gandini et al, 2018) (Vauthier et al, 2019) (Yang et al, 2020).…”

A Universal Coating Strategy for Controllable Functionalized Polymer Surfaces

“…There are two types of surface functionalization strategies, i.e., chemical anchoring and physically attachment, to coat stimuli‐responsive polymers and retain their stimuli‐responsive properties on the surfaces in a controllable way, including surface‐initiated atom transfer radical polymerization, [ 9 ] catechol derivatives codeposition, [ 10 ] thiol‐ene click‐chemistry, [ 11 ] and diels‐alder reaction. [ 12 ] Chemical anchoring strategies require the premodification of a surface with initiators for polymerization, but it is easier to achieve a higher grafting density and a stronger surface adhesion. [ 13 ]…”