Dual-Dynamic Chemistries-Based Fast-Reprocessing and High-Performance Covalent Adaptable Networks.

Covalent adaptable networks (CANs) possess multiple functions including reprocessing (or recyclability), self-healing, welding, shape shifting, 3D printing, etc., due to the network rearrangement from dynamic bonds, and favorable performance from their cross-linked feature, and they are supposed to be as sustainable alternatives to thermosets. However, the thermal and mechanical properties, and stability of CANs are often sacrificed for rapid network rearrangement. In this paper, fast-reprocessing CANs with high performance are facilely constructed by in situ polymerization and dynamic cross-linking of styrene (St), maleic anhydride (MA), and acetal diol (BHAD). The rigid and hydrophobic polymer backbone endow the materials with high glass transition temperatures, mechanical performance, and water resistance. Besides, carboxylic group-catalyzed dual dynamic ester and acetal-based networks exhibit faster stress relaxation and realize extrusion reprocessing. This work provides an ingenious and simple strategy of construction of CANs combining rapid network rearrangement and excellent comprehensive performance, which is beneficial for the application of CANs.

Upcycling of thermosetting polymers into high-value materials.

Thermosetting polymers, a large class of polymers featuring excellent properties, have been widely used and play an irreplaceable role in our life. Nevertheless, they are arduous to be recycled or reused on account of their permanently cross-linked networks, and the main recycling approaches used currently include energy recovery through incineration, utilization as fillers after mechanical grinding, and pyrolysis, which only reclaim a small fraction or partial value of thermosetting polymers and their downstream materials. In this minireview, we provide an overview of the efforts undertaken towards upcycling thermosetting polymers in recent years. The research progress on physical upcycling, carbonization, solvolysis and vitrimerization of thermoset waste to high-value materials, including oil-water separation materials, 3D printable materials, functional carbon materials (supercapacitors, photothermal conversion materials, and catalytic materials), additives, emulsifiers, biolubricants, and vitrimers, are summarized and discussed. Perspectives on the future development of the art of upcycling thermosets are also provided.

Crystallizable Aliphatic Chains Enhanced Covalent Adaptable Networks: Fast Reprocessing and Improved Performance.

Covalent adaptable networks (CANs) exhibit recyclability such as reprocessing, but it's a challenge to address the contradiction between reprocessing rate and performance. Here, pendent aliphatic chain anhydride monoesters are innovatively introduced into epoxy CANs based on transesterification, which efficiently accelerates the reprocessing without sacrificing thermal and mechanical properties. The transesterification rate is raised on account of the flexible aliphatic chain-promoted segment movement and dynamic transfer auto-catalysis. When the carbon number reflecting the length of the pendent chain is 12, the epoxy CAN exhibits the fastest stress relaxation or reprocessing. Computation via molecular dynamics simulation demonstrates that the increased segmental mobility from the pendent aliphatic chains contributes to enhanced reprocessability. Interestingly, the crystallization of the pendent aliphatic chains maintains or even improves the thermal and mechanical properties. Thus, introducing a flexible and crystallizable aliphatic side chain is an innovative and efficient approach to accelerate dynamic reactions and network arrangement while improving performance.

Fast-Reprocessing, Postadjustable, Self-Healing Covalent Adaptable Networks with Schiff Base and Diels-Alder Adduct.

Covalent adaptable networks (CANs) are a new type of polymers, which possess excellent performance of thermosets and reprocessability of thermoplastics. Nevertheless, it is still a challenge to realize rapid reprocessing and postadjusting (adjust properties after preparation). Herein, for the first time, a method of combining Schiff base and Diels-Alder adduct in one network is developed to achieve rapid reprocessing and postadjusting. Through the dissociation of the Diels-Alder adduct at high temperatures, the cross-link densities of the networks are reduced, thereby accelerating the rearrangement of the networks and realizing the rapid reprocessing and self-healing. Moreover, the reconnecting degree of network after dissociation of Diels-Alder adduct can be easily controlled by annealing; as a result, the properties of the obtained CANs are postadjustable. This work provides a simple and promising approach of achieving excellent reprocessing and postadjusting for CANs via the synergism of an associative dynamic chemistry with a dissociative dynamic chemistry.

Synthesis and properties of a bio-based epoxy resin with high epoxy value and low viscosity.

A bio-based epoxy resin (denoted TEIA) with high epoxy value (1.16) and low viscosity (0.92 Pa s, 258C) was synthesized from itaconic acid and its chemical structure was confirmed by 1H NMR and 13C NMR spectroscopy. Its curing reaction with poly(propylene glycol) bis(2-aminopropyl ether) (D230) and methyl hexahydrophthalic anhydride (MHHPA) was investigated. For comparison, the commonly used diglycidyl ether of bisphenol A (DGEBA) was also cured with the same curing agents. The results demonstrated that TEIA showed higher curing reactivity towards D230/MHHPA and lower viscosity compared with DGEBA, resulting in the better processability. Owing to its high epoxy value and unique structure, comparable or better glass transition temperature as well as mechanical properties could be obtained for the TEIA-based network relative to the DGEBA-based network. The results indicated that itaconic acid is a promising renewable feedstock for the synthesis of bio-based epoxy resin with high performance.

The properties of poly(lactic acid)/starch blends with a functionalized plant oil: tung oil anhydride.

Bio-sourced polymers, polylactide (PLA) and starch, have been melt-blended by lab-scale co-extruder with tung oil anhydride (TOA) as the plasticizer. The ready reaction between the maleic anhydride on TOA and the hydroxyl on starch led TOA molecules to accumulate on starch and increased the compatibility of PLA/starch blends, which was confirmed by FT-IR analyses and SEM. The TOA could change the mechanical properties and physical behaviors of PLA/starch blends. DSC and DMA analysis show that the TOA layer on starch has an effect on the thermal behavior of PLA in the ternary blend. The enrichment of TOA on starch improves the toughness and impact strength of the PLA/starch blends. The adding amount of TOA in PLA/starch blends primarily determined the compatibility and mechanical properties of the resulted ternary blends. The tensile and impact fracture modes of the PLA/starch blend with or without TOA has also been investigated by SEM analysis.

Effect of castor oil enrichment layer produced by reaction on the properties of PLA/HDI-g-starch blends.

Blends of entirely bio-sourced polymers, namely polylactide (PLA) and starch, have been melt-compounded by lab-scale co-extruder with castor oil (CO) as a plasticizer. The enrichment of castor oil on starch had great effect on the properties of the blends. If the castor oil was mainly dispersed in PLA matrix, the properties of the blends were poor, but when the hexamethylenediisocyanate (HDI) was grafted on starch granules the ready reactions between the hydroxyl on CO and the isocyante on the HDI-grafted starch (HGSTs) brought CO molecules enriched on starch particles. DSC analysis shows that the CO layer on starch has a positive effect on the crystallization of PLA in the ternary blend. The accumulation of CO on starch greatly improves the toughness and impact strength of PLA/starch blends. The grafting content of HDI on the starch granules primarily determined the compatibility and properties of the resulted blends.