Ultra-strong long-chain polyamide elastomers with programmable supramolecular interactions and oriented crystalline microstructures

Abstract

Polyamides are one of the most important polymers. Long-chain aliphatic polyamides could bridge the gap between traditional polyamides and polyethylenes. Here we report an approach to preparing sustainable ultra-strong elastomers from biomass-derived long-chain polyamides by thiol-ene addition copolymerization with diamide diene monomers. The pendant polar hydroxyl and non-polar butyrate groups between amides allow controlled programming of supramolecular hydrogen bonding and facile tuning of crystallization of polymer chains. The presence of thioether groups on the main chain can further induce metal–ligand coordination (cuprous-thioether). Unidirectional step-cycle tensile deformation has been applied to these polyamides and significantly enhances tensile strength to over 210 MPa while maintaining elasticity. Uniaxial deformation leads to a rearrangement and alignment of crystalline microstructures, which is responsible for the mechanical enhancement. These chromophore-free polyamides are observed with strong luminescence ascribed to the effect of aggregation-induced emission (AIE), originating from the formation of amide clusters with restricted molecular motions.

An Ultrastrong and Highly Stretchable Polyurethane Elastomer Enabled by a Zipper‐Like Ring‐Sliding Effect

“…The latter two features indicated the formation of hydrogen bonds between polymer chains. [ 57 ] The peaks at 1685 cm −1 of PPS1 and PPS2 increased in intensity compared with those of PU , and the peak intensities at 1715 and 1660 cm −1 decreased. These changes indicated that the large PS groups disrupted the PU chain regularity and weakened the hydrogen bonds.…”

Polymeric Complex Nanoparticles Enable the Fabrication of Mechanically Superstrong and Recyclable Poly(aryl ether sulfone)-based Polymer Composites

“…Thermoplastic polymers exhibiting a combination of high mechanical strength, good recyclability, processability, and thermal/mechanical durability have received much attention in scientific research and industrial applications. [1][2][3][4][5][6][7][8][9][10] Although strategies such as alignment of polymer chains, crystallization, controlled phase separation, interpenetrating, and dual polymer networks could significantly enhance the mechanical strength of thermoplastic polymers, 4,7,[11][12][13] it is hard for their tensile strength to reach or exceed one hundred megapascals (MPa). 4,7,10,[11][12][13] Meanwhile, superstrong thermoplastic polymers are usually difficult to dissolve in proper solvents and to process.…”

“…[1][2][3][4][5][6][7][8][9][10] Although strategies such as alignment of polymer chains, crystallization, controlled phase separation, interpenetrating, and dual polymer networks could significantly enhance the mechanical strength of thermoplastic polymers, 4,7,[11][12][13] it is hard for their tensile strength to reach or exceed one hundred megapascals (MPa). 4,7,10,[11][12][13] Meanwhile, superstrong thermoplastic polymers are usually difficult to dissolve in proper solvents and to process. 3,5,14,15 A conventional and widely employed strategy for reinforcement of thermoplastic polymers is homogeneously dispersing stiff nanofillers, such as silica, 9,16 clays, 10,17,18 carbon nanotubes, [19][20][21] graphene oxides, 20,[22][23][24] cellulose nanocrystals, 25,26 metal nanoparticles, 27,28 and other nanofillers 3,[29][30][31] within them.…”

Synthesis of New Siloxane‐Containing Polyamide Based on Limonene and Comparison of Their Properties with Non‐Siloxane Analog

“…[17] Preparation of sustainable ultra-strong elastomers from biomass-derived long-chain polyamides by thiolene addition copolymerization with diamide diene monomers was recently discussed as well. [18] More recently, poly(amide thioether)s with crystallinity more than 95 % were prepared by addition of ethanedithiol to diallylamides. [19] These approaches became possible due to available monomeric base from natural products.…”

“…Degradable polymers were synthesized with thiol‐(meth)acrylate or acrylamide by one‐pot polyaddition and based on cysteamine with 10‐undecenoate, methyl oleate . Preparation of sustainable ultra‐strong elastomers from biomass‐derived long‐chain polyamides by thiol‐ene addition copolymerization with diamide diene monomers was recently discussed as well . More recently, poly(amide thioether)s with crystallinity more than 95 % were prepared by addition of ethanedithiol to diallylamides .…”