Hydrogen‐Bonded Supramolecular Polymer Adhesives: Straightforward Synthesis and Strong Substrate Interaction

Abstract

High‐performance adhesives are of great interest in view of industrial demand. We herein identify a straightforward synthetic strategy towards universal hydrogen‐bonded (H‐bonded) polymeric adhesives, using a side‐chain barbiturate (Ba) and Hamilton wedge (HW) functionalized copolymer. Starting from a rubbery copolymer containing thiolactone derivatives, Ba and HW moieties are tethered as pendant groups via an efficient one‐pot two‐step amine‐thiol‐bromo conjugation. Hetero‐complementary Ba/HW interactions thus yield H‐bonded supramolecular polymeric networks. In addition to an enhanced polymeric network integrity induced by specific Ba/HW association, the presence of individual Ba or HW moieties enables strong binding to a range of substrates, outstanding compared to commercial glues and reported adhesives.

Thiolactone chemistry, a versatile platform for macromolecular engineering

“…: AIBN as initiator, trithiocarbonate chain transfer agents, in dioxane at 65-70 °C): N-isopropylamide (NIPAM), 74,[81][82][83] dimethylacrylamide (DMA), [84][85][86] NIPAM/DMA, 74 N-hydroxyethylacrylamide (HEA) 87 and n-butyl acrylamide. 88 Copolymers with dispersity values between 1.1 and 1.4 and molar masses up to 30 kg mol −1 were obtained. These copolymers typically contained between 5 and 30% of thiolactone units.…”

Bioinspired nucleobase-containing polyelectrolytes as robust and tunable adhesives by balancing the adhesive and cohesive properties

“…Inspired by nature, supramolecular polymeric adhesives have been intensely researched, which possess outstanding merits of both conventional adhesives. 13–17 They can bond to distinct substrates with high adhesion strength and good reversibility by combining multiple supramolecular interactions such as hydrogen bonds, metal-coordination bonds, π–π stacking, and hydrophobic interactions. 18–20…”

“…Inspired by nature, supramolecular polymeric adhesives have been intensely researched, which possess outstanding merits of both conventional adhesives. [13][14][15][16][17] They can bond to distinct substrates with high adhesion strength and good reversibility by combining multiple supramolecular interactions such as hydrogen bonds, metal-coordination bonds, p-p stacking, and hydrophobic interactions. [18][19][20] Actually, catechol-based supramolecular adhesives have been widely developed aer unraveling the molecular structures of adhesive proteins (Mfps-3 and 5) secreted by mussels.…”

High‐Performance Supramolecular Adhesives

“…[ 4–7 ] In general, there are two approaches to fabricating supramolecular adhesives: the self‐assembly of small molecules or oligomers, and the noncovalent cross‐linking of polymers. [ 1,3,8 ] A diversity of noncovalent interactions, including hydrogen bonding, host‐guest interactions, metal‐ligand coordination, electrostatic interactions, and so on, have been exploited to construct supramolecular adhesives. [ 1,3,9–21 ]…”

“…[4][5][6][7] In general, DOI: 10.1002/macp.202200332 there are two approaches to fabricating supramolecular adhesives: the selfassembly of small molecules or oligomers, and the noncovalent cross-linking of polymers. [1,3,8] A diversity of noncovalent interactions, including hydrogen bonding, host-guest interactions, metal-ligand coordination, electrostatic interactions, and so on, have been exploited to construct supramolecular adhesives. [1,3,[9][10][11][12][13][14][15][16][17][18][19][20][21] As early as 1997, Stupp and coworkers reported a supramolecular adhesive material fabricated through 𝜋-𝜋 interactions, which achieved a lap shear strength of 1.2 MPa in bonding glass.…”