“Click Chemistry” in Tailor-Made Polymethacrylates Bearing Reactive Furfuryl Functionality: A New Class of Self-Healing Polymeric Material

Abstract

This investigation reports the effective use of the Diels-Alder (DA) reaction, a "click reaction" in the preparation of thermally amendable and self-healing polymeric materials having reactive furfuryl functionality. In this case, the DA and retro-DA (rDA) reactions were carried out between the tailor-made homo- and copolymer of furfuryl methacrylate prepared by atom-transfer radical polymerization and a bismaleimide (BM). The kinetic studies of DA and rDA reactions were carried out using Fourier transform infrared spectroscopy. The DA polymers were insoluble in toluene at room temperature. When the DA polymers were heated at 100 degrees C in toluene, it was soluble. This is because of the cleavage between furfuryl functionality and BM. The chemical cross-link density was determined by the Flory-Rehner equation. The cross-linked polymer showed much greater adhesive strength at room temperature, but the adhesive strength was quite low at higher temperature. The self-healing capability was studied by using scanning electron microscopy analysis. The thermal and dynamic mechanical properties of the thermally amendable cross-linked materials were investigated by thermogravimetric analysis and dynamic mechanical analysis.

Diels–Alder Cycloaddition‐Cycloreversion: A Powerful Combo in Materials Design

“…[5][6][7][8] polymeric materials that have excellent mechanical properties and are thermally remendable. [9] Interestingly, there are only a few examples in the literature that involve polymers appended with maleimides towards fabrication of thermoreversible materials.…”

Thermally reversible cross-linked poly(ether-urethane)s

“…The DA cycloaddition of furan and maleimide can be accomplished at or slightly above room temperature, while the rDA reaction is performed at elevated temperatures. Thermally rDA reactions have been used in numerous studies including polymer synthesis [10][11][12][13][14][15][16][17], dendrimers [18][19][20][21], epoxy resins [22][23][24][25], crosslinked polymer networks [26][27][28][29][30], organic-inorganic polymer hybrids [31][32][33], surfactants [34], surface modification [35,36] and remendable selfhealing polymers [37]. Due to the fact that these reactions can proceed under mild conditions without a catalyst, they are attractive for designing covalently reversible bonds with furan and maleimide functional groups which are responsible for association and disassociation [35,37,38].…”

Hydrogel synthesis by aqueous Diels‐Alder reaction between furan modified methacrylate and polyetheramine‐based bismaleimides

“…15,16 One of the strategies for the design of cross-linked hydrogels through the DA reaction is the use of a bismaleimide as cross-linking agent. 5 In the present work, bismaleimides were employed for the cross-linking of the furan modified poly(2-aminoethyl methacrylate hydrochloride).…”