Preparation of Styrene–Butadiene Rubber Vitrimers with High Strength and Toughness through Imine and Hydrogen Bonds

Zhu, Liqian; Xu, Li; Jie, Suyun; Li, Bo‐Geng

doi:10.1021/acs.iecr.2c03133

Cited by 16 publications

(8 citation statements)

References 56 publications

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“…Giant crosslinker imine castor oil molecules contain long chain fatty acid that has relatively higher molecular weight than other imine crosslinker which has been already used for making Vitrimers which somehow slow down the dynamic exchange reaction and consequently increases the activation energy of the systems. 8,23 This observation is very different from the literature that discusses epoxy Vitrimers with imine based exchange reactions wherein the topology freezing temperature (T v ) is much lower than what is observed in our case. The giant crosslinker used here besides facilitating in homo-crosslinking offers a transient network in the melt resulting in upcycled ABS.…”

Section: ……contrasting

confidence: 99%

Upcycling acrylonitrile-butadiene-styrene Vitrimer ‘in melt’ using a dynamic crosslinker

Bose

2023

Preprint

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The perception of a sustainable plastic closed-loop circular economy hinges on the transformation of post-consumer recycled (PCR) commodity plastics. Among those, acrylonitrile butadiene styrene (ABS), a widely utilized engineering plastic, can be economically and efficiently upcycled to mark a significant step forward. Very few concrete solutions have been proposed so far for adopting end-of-life ABS into reusable products, mainly due to deterioration in mechanical properties of PCR ABS after subsequent recycling. Our approach introduces a distinctive strategy of creating durable and recyclable dynamic covalent adaptable network (CAN) termed as PCR ABS Vitrimers, all achieved through a melt-based process which holds promise for industrial viability and economic feasibility. In a first of its kind, a designer bio-based crosslinker, imine containing castor oil (iCO) having dynamic imine linkages as CAN was synthesized to form PCR ABS Vitrimers ‘in melt’ resulting in an upcycled ABS with 15% and 19% improvement in ultimate tensile strength and Young’s modulus respectively, in the Vitrimers. Our designer giant crosslinker, besides offering a transient network imparts re-processibility to the formed PCR ABS Vitrimers via melt with better mechanical integrity. This research endeavours to tackle a long-standing obstacle in upcycling PCR ABS in its melt state by producing a more robust, resilient, and solvent-resistant material derived from PCR ABS waste.

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Section: ……contrasting

confidence: 99%

Upcycling acrylonitrile-butadiene-styrene Vitrimer ‘in melt’ using a dynamic crosslinker

Bose

2023

Preprint

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“…7d, PNMET/MWCNT@Fe 3 O 4 composite was dissolved in polar DMF for a period, the composite completely dissolved in the solvent after 12 h, which indicated the valuable llers (MWCNT and nano Fe 3 O 4 ) can be recycled in polar solvent. 4…”

Section: Resultsmentioning

confidence: 99%

Adaptable bio-based dynamically cross-linked networks via disrupting physical cross-linking and chain entanglement for electromagnetic interference shielding materials

Chen

Jia

et al. 2023

Preprint

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Dynamically cross-linked networks combine the uniqueness of thermoplastics and thermosets to allow for reprocessability while being covalently crosslinked, but the lack of functionality seriously limits practical applications. Here, we propose a strategy to develop tung oil based dynamically cross-linked networks (PNMETs) by introducing primary amine to disrupt the physical cross-linking and chain entanglements, and achieved tunable mechanical strength and toughness, chemical stability, self-healing, solid state plasticity, and topological transformation. The constructed PNMETs based on hydrogen bonds and the dynamic imine bond exhibited multiple stimulus responses for light, heat, microwave and infrared radiation, and achieved excellent recycling and self-healing without any catalyst. By doping multiwalled carbon nanotubes (MWCNTs) and nano Fe3O4 in PNMETs, the resulted electromagnetic interference (EMI) shielding materials (PNMETs/MWCNT@Fe3O4) were fabricated and realized dual characteristics of dynamically cross-linked networks and EMI shielding material for the first time. PNMETs/MWCNT@Fe3O4 composite based on the topological rearrangement of PNMETs showed shape memory behavior, reprocessing, recycling and self-healing property under the conditions of infrared radiation and voltage, as well as exhibited EMI shielding effectiveness of 20–23 dB in the X-band with thickness less than 1 mm, meeting the standards for commercial applications. This work provides a simple but highly practical strategy for the fabrication of functional materials that integrated with dynamically cross-linked polymer and EMI shielding performance suitable for harsh environments.

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“…The introduction of dynamic chemical cross-linking is a possible path to solve the above problems without sacrificing the good processability of TPE-Os. The strong yet reversible ester bond, − disulfide bond, , imine bond, − olefin metathesis reaction, and boronic ester bond − have been incorporated into different polyolefins as dynamical chemical cross-links to endow TPE-Os with recycling, self-healing, adhesion, and shape-memory properties. Unlike homogeneous systems, dynamically cross-linked polyolefin can exhibit self-assembly behaviors and hierarchies, including micro- and macro-phase separation.…”

Section: Introductionmentioning

confidence: 99%

High-Performance Olefin Thermoplastic Elastomer Based on Dynamically Cross-Linking Crystalline Macromers and Elastic Backbones

Xiao,

Wang,

et al. 2024

Macromolecules

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Developing novel olefin thermoplastic elastomers (TPE-Os) that outperform those with well-defined block or grafted chain structures is both highly attractive and challenging. Here, we report the preparation of high-performance TPE-Os in a combinatorial way. Semicrystalline ethylene/1-octene/diene copolymers with pendant vinyl groups and crystalline polyethylene macromers with terminal double bonds are synthesized, and they are dynamically linked with a dithiol-based cross-linker containing a boronic ester bond to form a new TPE-O. Due to the synergy between physical crystallization and dynamic cross-linking, it exhibits a significantly increased Young's modulus (E), elongation at break (ε), ultimate strength (σ), and tensile toughness (U T ) of up to 27.2 ± 3.8 MPa, 902 ± 28%, 26.7 ± 1.1 MPa, and 120.1 ± 9.5 MJ•m −3 , respectively, which are among the highest levels of the dynamically cross-linked elastomers and traditional well-defined TPE-Os. It also has good elasticity with a 10-cycle elastic recovery ratio of up to 71.4%; a high melting point of nearly 123.8 °C and the σ can even maintain 0.14−0.42 MPa at 200 °C. The new TPE-O also offers high reprocessing performance with a recovery ratio of 113.2% for E, 98.5% for ε, 95.8% for σ, and 92.5% for U T . We believe that our study will facilitate the development of next-generation TPE-Os with higher performance.

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Preparation of Styrene–Butadiene Rubber Vitrimers with High Strength and Toughness through Imine and Hydrogen Bonds

Cited by 16 publications

References 56 publications

Upcycling acrylonitrile-butadiene-styrene Vitrimer ‘in melt’ using a dynamic crosslinker

Upcycling acrylonitrile-butadiene-styrene Vitrimer ‘in melt’ using a dynamic crosslinker

Adaptable bio-based dynamically cross-linked networks via disrupting physical cross-linking and chain entanglement for electromagnetic interference shielding materials

High-Performance Olefin Thermoplastic Elastomer Based on Dynamically Cross-Linking Crystalline Macromers and Elastic Backbones

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