Supramolecular thermoplastic elastomers via self‐complementary quadruple hydrogen bonding between polybutadiene‐based triblock copolymers

Abstract

Two series of triblock copolymers, polycaprolactone‐b‐polybutadiene‐b‐polycaprolactone (PCL‐b‐PB‐b‐PCL, CBC) and polylactide‐b‐polybutadiene‐b‐polylactide (PLA‐b‐PB‐b‐PLA, LBL), have been synthesized through the ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL)/D,L‐lactide (D,L‐LA) catalyzed by Sn(Oct)2 with hydroxyl‐terminated polybutadiene (HTPB) as a macroinitiator. Then, these triblock copolymers are end‐functionalized with 2‐ureido‐4[1H]‐pyrimidinone (UPy) groups to obtain the supramolecular multiblock copolymers UCBC and ULBL as supramolecular thermoplastic elastomers (TPEs). The thermal properties of UCBC and ULBL samples are measured by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The tensile tests of all the samples prepared are carried out to investigate the influence of the content of hard segments and the microstructure of PB soft segments on the mechanical properties of supramolecular TPEs.

Self-Strengthening, Self-Welding, Shape Memory, and Recyclable Polybutadiene-Based Material Driven by Dual-Dynamic Units

“…Most importantly, Figure b shows that upon adjusting the cross-link intensity, the tensile strength of PB-SSCN-12% jumps to 19.27 MPa from the original 13.53 MPa after heating, even exceeding the strength index (17 MPa) of traditional vulcanized high-vinyl polybutadiene rubber (HVPB). To the best of our knowledge, the material we fabricated has the highest tensile strength among nonvulcanized PB-based polymer materials (prepared without adding fillers or any other additives); the comparative information is displayed in Figure a. ,,,− The exact values and the corresponding references are listed in Table S2.…”

Renewable Vanillin-Based Thermoplastic Polybutadiene Rubber: High Strength, Recyclability, Self-Welding, Shape Memory, and Antibacterial Properties

“…As shown in Figure a and Table , the tensile strength of PB-PV- x % increases with increasing PV content, while the elongation at break is reversed, which can be attributed to the gradual deepening of chain entanglement. Notably, the comparison in Figure b shows that PB-PV-11% achieves a very high tensile strength (16.24 MPa), ranking among the best in the field of recyclable and/or self-healing polybutadiene-based materials. ,− Specific data for the comparative materials are listed in Table S2. It is easy to find that the tensile strength of PB-PV-11% is one of the best among the comparative materials but with a relative low elongation at break.…”

“…(a) Stress–strain curves of PB-PV- x %. (b) Comparison of tensile strength (the highest value in each literature) in polybutadiene-based materials with recyclability and/or self-healing. ,− (c) Arrhenius analysis of the characteristic relaxation time τ versus 1000/T for PB-PV- x %. (d) TGA curves of PB-PV- x % (note: x = 8, 9, 10, 11).…”