Sustainable developments in polyolefin chemistry: Progress, challenges, and outlook

Progress in Polymer Science, Journal Year: 2023, Volume and Issue: 143, P. 101713 - 101713

Published: June 25, 2023

Language: Английский

---

Polyolefins Vitrimers: Design Principles and Applications

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(23), P. 10249 - 10271

Published: Nov. 21, 2022

Less than 10% of plastics are recycled worldwide, among which polyolefins, form two-thirds all produced polymers, the most discarded ones. This stems from nonpolar nature limits their degradation and recycling. As such, any approach that may promote recycling polyolefins can significantly shift statistics polymer toward a more sustainable future. To account for that, vitrimer concept proposes unique solution not only increases polarity as such promotes degradation, but also expands utility polyolefin elastomers compensates significant loss mechanical properties upon sequential in thermoplastic polyolefins. Vitrimers networks formed by reversible covalent cross-links undergo percolation-conserving exchange reactions at high temperatures. Therefore, while they solid network service conditions, be reprocessed above temperature threshold. Thanks to this, have applications interface thermoplastics thermosets ranging recyclable, self-healing, adhesive materials creep-resistant shape-memory networks. Review aims classify cross-linking chemistries employed production polyolefin-derived vitrimers highlight subsequent changes material further development novel vitrimers.

Language: Английский

---

Ultrastable, Superrobust, and Recyclable Supramolecular Polymer Networks

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 18, 2024

Abstract Supramolecular polymer networks (SPNs), crosslinked by noncovalent bonds, have emerged as reorganizable and recyclable polymeric materials with unique functionality. However, poor stability is an imperative challenge faced SPNs, because SPNs are susceptible to heat, water, and/or solvents due the dynamic reversible nature of bonds. Herein, design a cooperative network (NCoN) simultaneously stabilize reinforce reported, resulting in ultrastable, superrobust, SPN. The NCoN constructed multiplying H‐bonding sites tuning conformation/geometry segment optimize multivalence cooperativity H‐bonds. rationally designed high conformational compliance favors formation tightly packed H‐bond arrays comprising higher‐density stronger Consequently, H‐bonded crosslinks display covalent crosslinking effect but retain on‐demand dynamics reversibility. resultant ultrastable SPN not only displays remarkable resistance heat up 120 °C, water soaking, broad spectrum solvents, also possesses superhigh true stress at break (1.1 GPa) ultrahigh toughness (406 MJ m −3 ). Despite covalent‐network‐like stability, through activating its reversibility high‐polarity solvent heated threshold temperature.

Language: Английский

---

Ultra‐Strong and Tough Bio‐Based Polyester Elastomer with Excellent Photothermal Shape Memory Effect and Degradation Performance

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: April 8, 2024

Abstract The exploitation of bio‐based materials derived from renewable resources represents a pivotal strategic approach in addressing environmental pollution and alleviating the scarcity fossil resources. 2,5‐Furandicarboxylic acid (FDCA) is most potential substitute for terephthalic acid. Lignin abundant aromatic biomass resource. However, preparation high‐performance lignin/FDCA‐based bio‐polyesters remains formidable challenge. Herein, multifunctional lignin‐modified polyester elastomer (LFPEe) designed using FDCA‐based oligomer (PPeF) lignin (AOH) as building blocks. LFPEe exhibits superior mechanical properties with optimum tensile strength, fracture strain, elastic recovery ratio up to 58.9 MPa, 610% 88.9%, respectively, attributing formation dual cross‐linking network nanophase separation structure. Furthermore, leveraging inherent characteristics lignin, demonstrates excellent light‐controlled shape memory UV shielding performance. This innovative work not only breaks performance dependence on high molecular weight but also highlights novel paradigm value‐added utilization sustainable bio‐polyesters.

Language: Английский

---

Synthesis and characterization of polyolefin thermoplastic elastomers: A review

The Canadian Journal of Chemical Engineering, Journal Year: 2023, Volume and Issue: 101(9), P. 4886 - 4906

Published: Jan. 4, 2023

Abstract Polyolefin thermoplastic elastomers (TPE‐Os) are high‐performance polyolefins consisting of both plastic and rubber phases. Compared with other elastomers, the TPE‐Os possess better chemical stability, transparency, re‐processability, electrical insulation, which renders their broad applications possible. By manipulating chain structures topologies TPE‐Os, differently structured improved thermal mechanical properties have been developed, including ethylene α‐olefin random copolymers (POEs), olefin block (OBCs), comb‐shaped polyolefin (CPOEs), dynamically cross‐linked elastomers. Herein, we review synthesis POE, OBC, CPOE, dynamical elastomer, catalyst systems, polymerization techniques, processes, kinetic modelling. The characterization relationships between TPE‐O structure, aggregated state, product performance discussed. future development higher‐performance is envisaged.

Language: Английский

---

Functional and Environmental Friendly Polyimine Elastomer Based on the Dynamic Covalent Network for a Flexible Strain Sensor

Macromolecules, Journal Year: 2023, Volume and Issue: 56(23), P. 9766 - 9777

Published: Nov. 29, 2023

With environmental concerns increasing, the development of durable, degradable, and reprocessable elastomers is crucial for advancement environmentally friendly wearable electronics. Herein, self-healing, polyimine with a cross-linked network constructed by dynamic imine bonds were synthesized under room temperature flexible strain sensor. Owing to formation microphase separation structure polyetheramine as soft segments adipic acid dihydrazide hard segments, obtained elastomer exhibited superior mechanical properties elongation at break 1158% tensile strength 2.51 MPa. Moreover, endowed outstanding self-healing capability reprocessability. The healing efficiency reached 96.0% after 24 h, reprocessed maintained 80.6% original three reprocessing cycles. In addition, was able completely degrade into monomers acidic condition within 180 min. elastomer-based sensor liquid metal conductive material processed excellent recovery ability sensing performance even being cut two halves. findings in this work conceivably stand out new methodology preparation functional

Language: Английский

---

Covalent Adaptable Networks Made by Reactive Processing of Highly Entangled Polymer: Synthesis-Structure-Thermomechanical Property-Reprocessing Relationship in Covalent Adaptable Networks

Macromolecules, Journal Year: 2024, Volume and Issue: 57(6), P. 2756 - 2772

Published: March 6, 2024

Reactive processing provides a simple approach for grafting dynamic covalent cross-linkers onto linear or branched polymers, resulting in adaptable networks (CANs). We synthesized poly(n-hexyl methacrylate) (PHMA) CANs from neat, entangled PHMA using radical-based reactive to graft the cross-linker called BiTEMPS methacrylate (BTMA) between side chains. By tuning BTMA loading, we achieved range of cross-link densities and characterized how stress relaxation, elevated-temperature creep, reprocessability are affected by density. The cross-links chains allowed novel comparison our reversible, polymers described sticky reptation theory, which long-time relaxation occurs unraveling backbone entanglements, process enabled dissociation subsequent exchange side-chain "stickers." observed two regimes that required their fitting combination stretched exponential decay functions extract pertinent parameters. apparent activation energies creep viscosity same within experimental uncertainty these CANs, verifying shared mechanisms governing temperature dependence viscoelastic responses, independent CAN Notably, made linking ∼50–60% those reported previously with chain backbones. These outcomes demonstrate importance synthesis-structure-property-reprocessing relationships may be various methods varying position incorporation structure.

Language: Английский

---

Ultrastable, Superrobust, and Recyclable Supramolecular Polymer Networks

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(10)

Published: Jan. 18, 2024

Abstract Supramolecular polymer networks (SPNs), crosslinked by noncovalent bonds, have emerged as reorganizable and recyclable polymeric materials with unique functionality. However, poor stability is an imperative challenge faced SPNs, because SPNs are susceptible to heat, water, and/or solvents due the dynamic reversible nature of bonds. Herein, design a cooperative network (NCoN) simultaneously stabilize reinforce reported, resulting in ultrastable, superrobust, SPN. The NCoN constructed multiplying H‐bonding sites tuning conformation/geometry segment optimize multivalence cooperativity H‐bonds. rationally designed high conformational compliance favors formation tightly packed H‐bond arrays comprising higher‐density stronger Consequently, H‐bonded crosslinks display covalent crosslinking effect but retain on‐demand dynamics reversibility. resultant ultrastable SPN not only displays remarkable resistance heat up 120 °C, water soaking, broad spectrum solvents, also possesses superhigh true stress at break (1.1 GPa) ultrahigh toughness (406 MJ m −3 ). Despite covalent‐network‐like stability, through activating its reversibility high‐polarity solvent heated threshold temperature.

Language: Английский

---

Synthesis of Cross-Linked Polyolefin Elastomers with High Performance Yet Good Reprocessability

Industrial & Engineering Chemistry Research, Journal Year: 2025, Volume and Issue: 64(9), P. 5080 - 5086

Published: Feb. 24, 2025

The development of polymer materials with high performance and good reusability is critical to sustainability the industry. However, balance these two aspects in elastomers rubbers highly challenging. Here, we report synthesis a novel polyolefin elastomer (POE) dynamically cross-linked by an imine-linked boronic ester. It improves tensile strength at break (σ) POE 148.2%, Young's modulus (E) 92.6%, toughness (UT) 49.4%, slightly decreased elongation break. also has higher thermal resistance than pristine one presents steady storage plateau 2.8 MPa above 150 °C. Moreover, it can be reprocessed impressive recovery ratio UT 89.7% because dynamic exchanges ester imine. Dynamic mechanical analysis shows that cross-linking short characteristic relaxation time 9.6 min low apparent activation energy 65.1 kJ·mol–1. Our study on POEs provides new way for sustainable elastomers.

Language: Английский

---

Vitrimeric Polylactide by Two-step Alcoholysis and Transesterification during Reactive Processing for Enhanced Melt Strength

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(40), P. 45966 - 45977

Published: Sept. 27, 2022

Because of its rather low melt strength, polylactide (PLA) has yet to fulfill promise as advanced biobased and biodegradable foams replace fossil-based polymer foams. In this work, PLA vitrimers were prepared by two-step reactive processing from commercial thermoplastics, glycerol, diphenylmethane diisocyanate (MDI) using Zn(II)-catalyzed addition transesterification chemistry. The reaction glycerol occurs with zinc acetate the catalyst, chain scission will take place due alcoholysis chains free hydroxyl groups glycerol. Long-chain can be obtained then cross-linked MDI. Rheological analysis shows that formed network significantly improve strength promote strain hardening under extensional flow. still maintain ability thermoplastic via extrusion compression. enhanced rearrangement topology facilitate foaming processing. An expansion ratio large 49.2-fold microcellular foam a uniform cell morphology for gel fraction 51.8% through supercritical carbon dioxide technique. This work provides new way scale-up possibility enhance PLA, broadened range applicability brought is truly valuable in terms realization sustainable society.

Language: Английский

---