Diels-Alder-based thermo-reversibly crosslinked polymers: Interplay of crosslinking density, network mobility, kinetics and stereoisomerism

Orozco, Felipe; Li, Jing; Ezekiel, Unwana; Niyazov, Zafarjon; Floyd, Lauren; Lima, G. M. R.; Winkelman, Jozef G. M.; Moreno‐Villoslada, Ignacio; Picchioni, Francesco; Bose, Ranjita K.

doi:10.1016/j.eurpolymj.2020.109882

Cited by 43 publications

(48 citation statements)

References 38 publications

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“…[11][12][13] Through the electron cloud density regulation of disulfide bonds and addition of catalysts, disulfide bonds can be weakened, which is further beneficial for the reversibility of disulfide bond crosslinks. [14][15][16][17][18][19] Besides disulfide bonds, the Diels-Alder reactions, [20][21][22] coordination bonds, [23][24][25] ionic bonds, 26,27 transesterification, [28][29][30][31] and imine bonds 32,33 can be used as dynamic bond network in the elastomers. The characteristic of previous investigations mainly focuses on replacing the conventional sulfur network with a novel reversible crosslinking network.…”

Section: Introductionmentioning

confidence: 99%

Based on transalkylation reaction the rearrangeable conventional sulfur network facile design for vulcanized diolefin elastomers

et al. 2021

J of Applied Polymer Sci

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Achieving the reversibility of conventional sulfur crosslinking network is beneficial for the sustainability of rubber products. However, sulfur crosslinking network has been considered as an irreversible network. Here, natural rubber (NR) is chosen as an example and trimethylsulfonium iodide (TMSI) can enable the transalkylation reaction between aliphatic sulfonium salts and the alkyl chains of vulcanized NR, which further realizes the rearrangements of sulfur crosslinking network in the elastomers. Such rearrangement reaction enhances the interfacial adhesion and fuse the fractured surface of vulcanized NR. Moreover, the rearrangements of sulfur crosslinking network induced by TMSI conforms to the characteristics of vitrimer network. This work solves the rearrangement problem of conventional sulfur crosslinking network, which is beneficial for the sustainability of rubber products.

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Section: Introductionmentioning

confidence: 99%

Based on transalkylation reaction the rearrangeable conventional sulfur network facile design for vulcanized diolefin elastomers

et al. 2021

J of Applied Polymer Sci

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“…FTIR spectra of the studied FM-TRCP were taken at isothermal conditions over three hours ( Figure 3 a). The spectra taken at the beginning of the measurements display the thermo-reversible equilibrium already displaced towards the reactants (free furan and maleimide groups), since the retro-DA kinetics are quite fast [ 8 , 14 ]. Figure 3 a shows the peaks at 1180 and 1146 cm −1 corresponding to the CNC bending mode of the succinimide and maleimide rings, respectively [ 3 , 18 , 19 , 20 ].…”

Section: Resultsmentioning

confidence: 99%

“…Nowadays, in the polymer field, MDP-BMI receives much more attention as a Diels-Alder (DA) dienophile, with furan as its diene counterpart ( Figure 1 c) [ 4 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ]. This DA pair reacts thermo-reversibly, which allows for preparation of polymer networks with crosslinking points that cleave and form thermodynamically.…”

Section: Introductionmentioning

confidence: 99%

“…This DA pair reacts thermo-reversibly, which allows for preparation of polymer networks with crosslinking points that cleave and form thermodynamically. The DA pair also presents fast kinetics and forms and cleaves at practical temperatures, at approximately 60 and 110 °C, respectively [ 8 , 14 ]. Over the last two decades, many furan/maleimide-based thermo-reversibly crosslinked polymers (FM-TRCP) have been explored as reprocessable thermosets and elastomers, and self-healing materials [ 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

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Maleimide Self-Reaction in Furan/Maleimide-Based Reversibly Crosslinked Polyketones: Processing Limitation or Potential Advantage?

et al. 2021

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Polymers crosslinked via furan/maleimide thermo-reversible chemistry have been extensively explored as reprocessable and self-healing thermosets and elastomers. For such applications, it is important that the thermo-reversible features are reproducible after many reprocessing and healing cycles. Therefore, side reactions are undesirable. However, we have noticed irreversible changes in the mechanical properties of such materials when exposing them to temperatures around 150 °C. In this work, we study whether these changes are due to the self-reaction of maleimide moieties that may take place at this rather low temperature. In order to do so, we prepared a furan-grafted polyketone crosslinked with the commonly used aromatic bismaleimide (1,1′-(methylenedi-4,1-phenylene)bismaleimide), and exposed it to isothermal treatments at 150 °C. The changes in the chemistry and thermo-mechanical properties were mainly studied by infrared spectroscopy, 1H-NMR, and rheology. Our results indicate that maleimide self-reaction does take place in the studied polymer system. This finding comes along with limitations over the reprocessing and self-healing procedures for furan/maleimide-based reversibly crosslinked polymers that present their softening (decrosslinking) point at relatively high temperatures. On the other hand, the side reaction can also be used to tune the properties of such polymer products via in situ thermal treatments.

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“…Self-healing thermosets have been efficiently prepared by modifying polyketone with furan groups which can undergo thermally reversible Diels-Alder reactions with maleimides compounds [ 16 , 17 , 23 , 24 ]. Diels-Alder adducts can be easily formed at 50 °C and broken via retro Diels-Alder reaction at around 120 °C, thus appearing very useful to repair surface scratches or bulk cracks of polymeric materials [ 16 , 17 , 25 ]. The mechanical properties of these materials can also be tuned by adding fillers within the matrix as demonstrated in earlier works [ 13 , 15 ].…”

Section: Introductionmentioning

confidence: 99%

Thermally Switchable Electrically Conductive Thermoset rGO/PK Self-Healing Composites

et al. 2021

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Among smart materials, self-healing is one of the most studied properties. A self-healing polymer can repair the cracks that occurred in the structure of the material. Polyketones, which are high-performance thermoplastic polymers, are a suitable material for a self-healing mechanism: a furanic pendant moiety can be introduced into the backbone and used as a diene for a temperature reversible Diels-Alder reaction with bismaleimide. The Diels-Alder adduct is formed at around 50 °C and broken at about 120 °C, giving an intrinsic, stimuli-responsive self-healing material triggered by temperature variations. Also, reduced graphene oxide (rGO) is added to the polymer matrix (1.6–7 wt%), giving a reversible OFF-ON electrically conductive polymer network. Remarkably, the electrical conductivity is activated when reaching temperatures higher than 100 °C, thus suggesting applications as electronic switches based on self-healing soft devices.

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Diels-Alder-based thermo-reversibly crosslinked polymers: Interplay of crosslinking density, network mobility, kinetics and stereoisomerism

Cited by 43 publications

References 38 publications

Based on transalkylation reaction the rearrangeable conventional sulfur network facile design for vulcanized diolefin elastomers

Based on transalkylation reaction the rearrangeable conventional sulfur network facile design for vulcanized diolefin elastomers

Maleimide Self-Reaction in Furan/Maleimide-Based Reversibly Crosslinked Polyketones: Processing Limitation or Potential Advantage?

Thermally Switchable Electrically Conductive Thermoset rGO/PK Self-Healing Composites

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