Polymer Testing: Hafeezullah Memon, Yi Wei, Chengyan Zhu

Polymer Testing 105 (2022) 107420
Contents lists available at ScienceDirect
Polymer Testing
journal homepage: www.elsevier.com/locate/polytest
Recyclable and reformable epoxy resins based on dynamic covalent bonds –

Present, past, and future
Hafeezullah Memon a, Yi Wei b, c, Chengyan Zhu a, *
a
College of Textile Science and Engineering, International Institute of Silk, Zhejiang Sci-Tech University, Hangzhou, 310018, China
b
Center for Civil Aviation Composites, Donghua University, 2999 North Renmin Road, Shanghai, 201620, China
c
Key Laboratory of Textile Science &Technology, Ministry of Education, College of Textiles, Donghua University, 2999 North Renmin Road, Shanghai, 201620, China
A R T I C L E I N F O A B S T R A C T
Keywords: Epoxy resins, as a typical class of thermosetting polymers, have widespread industrial applications such as ad
Epoxy hesives, coatings, electronic encapsulants, and polymer matrices for advanced composites, owing to their
Vitrimers excellent mechanical performance, adhesive capacity, dimensional stability, heat, and chemical resistance.
Dynamic bond
However, conventional epoxy resins cannot be reprocessed, repaired, or recycled due to their permanent
Recycling
crosslinked structures, making it a long-standing challenge to process and recycle the ever-increasing epoxy and
epoxy-based composite similar to thermoplastics. Therefore, both economic and environmental factors are
driving the development of reformable and recyclable epoxy resins. In this paper, various such epoxy vitrimers
containing dynamic covalent bonds are reviewed. Future potentials of these epoxy vitrimers are also discussed.
1. Introduction due to high glass transition temperature (Tg), high modulus, and
chemical resistance [5,6]. However, these resins cannot be recycled,
Epoxy resin is one of the most important thermosetting polymers, reprocessed, or dissolved due to their permanent crosslinking structures
with two or more epoxy groups in the molecule, and it is present in the after cure, making them less environmentally friendly than thermo
liquid, viscous, and solid forms depending on its chemical structure. plastics. Consequently, two choices to get rid of large debris are land
Owing to their superior physical-mechanical performances, versa filling and pyrolysis. However, these are of further environmental
tility, dimensional stability, processability, and resistance to chemicals burden and are improper utilization of resources, urging material sci
as well as heat, epoxy resins are widely used in adhesives, coatings, entists to produce novel epoxy resins capable of retaining their good
construction, electronic packaging materials, and polymer matrices for physical-mechanical properties and, in the meantime, being recyclable
fiber-reinforced composites, as shown in Fig. 1, almost accounting two- and reprocessable [7,8].
third of the total global thermosetting polymer market [1,2]. Making fully recyclable materials are feasible today. Furthermore, it
The demand for epoxy is growing continuously; the estimated epoxy is highly recommended to synthesize them from bio-based resources to
resin market is $12,181.8 Million by 2024, with a compound annual reduce petroleum consumption and corresponding carbon dioxide
growth of 6.46% [3]. The global epoxy demand by different application emissions [6,9–13]. Today’s polymer industry still relies on petroleum
sectors has been reported recently [4], shown in Fig. 2. products and fossil resources, which are pricy, and the scarcity of these
The uncured epoxy resin is an oligomer or monomer with a well- resources is problematic due to the foreseeable consumption and
defined structure that forms a highly crosslinked three-dimensional depletion. Sustainable development strategies are therefore demanded
network through the crosslinking and curing reaction by various to overcome this issue. The use of bio-based resources for the
curing agents (hardeners). Oligomers or monomers must have at least manufacturing of epoxy was once overlooked and stalled.
two epoxy groups per molecule. A great deal of progress has been made Moreover, there are concerns about the toxicity of the existing
towards developing and manufacturing epoxy resin to maximize its commercial epoxies and hardeners. For example, DGEBA has been re
performance. ported as reprotoxic and banned in children’s utensils in some countries
Epoxy resins are the most widely used structural thermoset resins [6,14]. Therefore, developing robust, bio-based, non-toxic, malleable,
* Corresponding author.
E-mail addresses: hm@zstu.edu.cn (H. Memon), weiy@dhu.edu.cn (Y. Wei), cyzhu@zstu.edu.cn (C. Zhu).
https://doi.org/10.1016/j.polymertesting.2021.107420
Received 25 June 2021; Received in revised form 8 October 2021; Accepted 9 November 2021
Available online 10 November 2021
0142-9418/© 2021 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
H. Memon et al. Polymer Testing 105 (2022) 107420
and fully recyclable epoxy resin is necessary.
2. Recyclable epoxy resin based on dynamic covalent bonds
Since the last decade, an interesting approach has been to develop

materials capable of intrinsic darning of internal and external damages.
The keen attention of researchers towards these systems is attributed to
their built-in properties, including but not limited to the prevention of
catastrophic failure, a longer lifetime of materials, reparation of physical
damages, malleability, recyclability, and so on. Meanwhile, the macro
scopic responses of polymers for changes in their environment can be
obtained by introducing reversible or dynamic bonds on a molecular
level [15]. Though covalently adaptable network (CAN) approaches are
beneficial to obtain these macroscopic responses of the polymers by
merely applying heat [16–18], the temperature susceptibility of these
networks does not encourage their use under high-temperature condi
tions [19,20]. Therefore, a higher Tg over 100 ◦ C would be required for
these systems’ hassle-free usage.
Fig. 2. Global epoxy resin demand by sector [4].
Two exchange mechanisms have been observed, as shown in Scheme
1. First, the associative bond exchange mechanism, where the overall
crosslink density remains constant, does not depolymerize upon heating. the following sections. Table 1 summarizes pristine and recycled resin’s
The formation of crosslinks at new places results in the loss of crosslinks mechanical and thermomechanical properties of some common dy
at the previous positions. In other words, crosslinks are merely broken namic covalent bonds used for recyclable and reformable epoxies.
when new ones are created [21]. For the understanding of readers only, Besides epoxy vitrimers, some other epoxies, i.e., cleavable epoxides,
the crosslinking density has been shown as υe. These vitrimers might do not relax the stress, yet they can be recycled or reworked; this class of
undergo an associative bond exchange mechanism or dissociative bond recyclable epoxies is termed cleavable epoxides. vitrimers are thermoset
exchange mechanism depending upon the covalent adaptable network polymers that contain dynamic covalent bonds. The networks or struc
present in the compound [21–24]. To date, various chemical reaction tures of cleavable epoxy resins can be degraded under certain external
mechanisms have been proposed; some of them are discussed in detail in stimuli, such as heat, pH, etc. Some of the vitrimers, i.e., imine or
Fig. 1. Some different applications of epoxy resins. (a) Helicopters; (b) floor finish; (c) electronic industry and applications; (d) wind turbines; (e) aircraft structure;
(f) bicycle parts; (g) automotive structure; (h) ships and marine vehicles; (i) epoxy adhesives; (j) rail and railroad repair; (k) firearm coating; (l) sports i.e., ten
nis racket.
2
Scheme 1. The bond exchange mechanism of covalent adaptable networks.
Table 1
Comparison of tensile strength and glass transition temperature of recyclable and reformable epoxies from common dynamic covalent bonds.
Type of dynamic bond Pristine resins Reprocessed resins Chemically recycled resins Ref.
TSa (MPa) Tg (◦ C) TSa (MPa) Tg (◦ C) TSa (MPa) Tg (◦ C)
Ester 2.8–69.2 30–187 14 2.5 2.8 25–33 [25–27]

Disulfide 11–88 41–130 9–82 39–135 – – [28–30]
Imine 46–61 71–127 50–80 135–175 41–61 72–124 [31–33]
Siloxane 46.6 83 47.1 83 – – [34]
Boronic ester 6.2–39.5 72–111 5–35 – – – [35]
Hexahydro-s-triazine 65.2–83 117–151 – – – – [36,37]
Silyl Ether 18.1 25–36 24.2 – – – [38]
Spiro diacetal 85–87 157–169 – – – – [39]
Acetal linkages 28.95–67.5 30–110 – – – – [40,41]
Hemiacetal/hemiketal – 75–165 – – – – [42,43]
Carbamate and carbonate groups – 57–176 – – – – [44,45]
Sulfonate ester linkages – 80–117 – – – – [46,47]
Phosphate – 113–191 – – – – [48]
a)
TS = Tensile strength.
disulfide containing epoxy vitrimers, are cleavable epoxides because cyclohexene is formed by an addition reaction of 4 electrons of
they can degrade in amine or thiol solution, respectively; simulta electron-rich diene and 2 electrons of electron-poor dienophile through
neously, they are also vitrimers as they can be reprocessed. However, covalently linked σ-bonds and losing π bonds, thus this reaction is
some of the recyclable epoxies containing acetals, hemiketals, carbon classified as [4 + 2] cyclo-addition reaction, as illustrated in Scheme 2.
ates, etc., are classified as cleavable epoxides since they might be ther As it is an addition reaction, nothing needs to be added, and no
mally reworkable or hydrolyzable but can not be reprocessed. The byproducts are formed during this reaction. Over the years, DA re
classification might be easily understood from the matrix illustrated in action’s “Click” characteristics have made it a common choice for
Fig. 3. designing polymer with a range of functionalities and synthesis under
mild conditions without a catalyst among thermally reversible polymers
[50]. It should also be noted that the DA adduct may break into the
2.1. Diels-Alder’s reaction (mechanism and limitations) primitive Dienophile and Diene group through retro-DA (reverse DA
reaction) at selective temperature.
Otto Paul Hermann Diels and Kurt Alder reported Diels-Alder’s re Among diene-dienophile pairs that have been reported for Diels-Alder
action for the first time in 1928 [49], for which they later received the reaction, i.e., cyclopentadiene pairs forming dicyclopentadienes [51–53],
Nobel Prize in Chemistry in 1950. DA reaction is a reversible reaction maleimide-cyclopentadiene [54], dithiocarbonate-cyclopentadiene
under a specific temperature via appropriate reactants. Since
3
and 4 reacted in ethyl acetate to obtain a pure Exo isomer, i.e., Com
pound 5. Then, two Boc groups on Compound 5 were deprotected by
trifluoroacetic acid, which followed the neutralization of salt by ion
exchange resin in methanol to get diamine DA adduct crosslinker
(Compound 6), as shown in Fig. 4 (a). Finally, the diamine DA adduct
crosslinker was reacted with DGEBA to obtain a thermally reversible
recyclable epoxy polymer (Compound 7). The crushed epoxy resin could
be fully recovered repeatedly on reprocessing it at 120 ◦ C and 140 ◦ C for
the first and second time, respectively, refer to Fig. 4(c–f). Moreover, the
pulverized sample of the first recycled resin could be healed merely at
75 ◦ C within 30 min (see Fig. 4(g–h)).
As selected examples above have illustrated that the potential of DA
polymers is not only limited to long reaction time and creep, but there
are also concerns about the processing of these polymers since the
liquid-like fluidity limits its processing in various applications.
2.2. Transesterification
Fig. 3. Classification matrix of recyclable epoxy.
Transesterification is a reversible exchange reaction that refers to
[55–57], and so on, maleimide-furan possesses better thermo-conversion alcoholysis, acidolysis, and ester interchange, in which one carboxylic
due to lower temperature retro-DA (>100–150 ◦ C) barring substantial acid ester is converted to another carboxylic acid ester of that same
side reactions [58,59]. However, most of the uncatalyzed maleimide-furan carboxylic acid. The reaction can be shifted towards the right by
systems require long reaction times (many hours) for conversion below gel distillation out the volatile byproduct (refer, Scheme 3). In addition, the
point temperature (Tgel) [58]. reaction can be either acid or base-catalyzed; therefore, numerous
To overcome the abovementioned issue of long reaction times, some organic and inorganic catalysts have been proposed for this reaction [67,
other systems, furan-anthracene, hetero-DA, and dithiocarbonate- 68]. It is one of the well-established reactions used in many industries in
cyclopentadiene [60–62], have also been reported to be polymerized several contexts, including the polymer industry. Since mid of the 19th
for shorter reaction times. Since dithioesters-cyclopentadiene can be century, transesterification has been used to produce a lot of acrylic
polymerized in a few minutes due to highly electron-deficient monomers from methyl acrylate [69,70]. The transesterification reac
dithioesters, they are subjected to creep even at room temperature due tion of cyclic monomer and alcohol species assists the ring-opening
to rapid DA and retro-DA reactions. Thus, maleimide-furan networks polymerization of cyclic esters (i.e., lactide or ϵ-caprolactone)
characterize as a promising choice in the field of healable materials [71–73]. Transesterification also produces fatty acid alkyl esters for
using the DA reaction system despite long reaction times. lubricants, additives, and biodiesel fuel from vegetable oil triglycerides
Above Tgel and without substantial side reactions, the crosslinked using alcohol [67].
network of maleimide-furan DA polymer depolymerizes back to primi Pioneering vitrimers, Leibler’s research group incorporated an ester
tive components and behaves like a liquid, and follows the Flory- (from the mixture of carboxylic acids, i.e., triacid: diacids≈7:3) and
Stockmayer equation, where Tgel increases with functionalities, i.e., hydroxyl from the ring-opening of the epoxide of DGEBA through simple
trifunctional furan and difunctional maleimide depolymerizes at ~95 ◦ C transesterification to get a highly crosslinked dynamic epoxy-acid
[58], whereas, tetrafunctional furan and difunctional maleimide can network using zinc acetate catalysts during post-polymerization at
sustain at temperature >150 ◦ C [64,65]. 130–140 ◦ C [23,74]. The uniqueness of this material was its ability to
As discussed in the above cases, the retro-DA reaction requires a relax stress and go through reprocessing at 150–250 ◦ C, which makes
higher temperature in general. Lehn and coworkers [66] developed them a suitable candidate for injection molding and compression
room temperature retro-DA reaction by combining diene and dienophile molding like thermoplastics, along with their behavior as thermosets at
via synthesizing dynamic elastomer of polyethylene glycol, where the a lower temperature. Since the reprocessing was only due to exchange
resulting adduct can self-heal at room temperature. However, such ad reactions, the overall crosslinking density stayed constant, and the
ducts are far from being used as a thermoset for high-tech applications network remained completely insoluble irrespective of temperature (see
due to their lower glass transition temperature. Fig. 5) [23].
Kuang et al. [63] synthesized a diamine DA adduct crosslinker for The topology freezing temperature strictly governs the solid-to-
recyclable epoxy resin. They first reacted N-boc-ethylenediamine liquid transition of this new class of polymer; it is the temperature at
(Compound 1) with maleic anhydride in dichloromethane at room which the viscosity reaches 1012 Pa s; when the temperature goes
temperature for 3 h. The mixture was further reacted under the catalysis beyond it, the vitrimers would behave as a viscoelastic liquid [75]. The
of a dehydrating agent, i.e., acetic anhydride, catalyst, i.e., nickel (II) stress relaxations of these materials, mainly depending upon the choice
acetate, and co-catalyst, i.e., triethylamine in refluxed acetone, to obtain of catalyst [75], are due to the chemical reaction and not due to chain
Compound 2. On the other hand, Furfurylamine (Compound 3) was frictions; therefore, the stress relaxation behavior of this new class of
protected by the Boc group to become Compound 4. Later, Compounds 2 polymer does not obey the classic Williams-Landel-Ferry equation;
Scheme 2. The schematic diagram for the DA Alder reaction.
4
Fig. 4. (a) Synthesis route of diamine DA adduct crosslinker and its curing reaction with DGEBA to obtain epoxy resin; (b) DA and rDA reactions of thermally
reversible transitions in crosslinked epoxy resin; (c) Pristine crosslinked epoxy resin; (d) Crushed pieces of pristine resin; (e) first recycled resin by hot pressing at
120 ◦ C; (f) Second recycled resin by hot compressing at 140 ◦ C; (g) Broken sample of first recycled resin; (h) After healing the 1st recycled resin for 30 min at 75 ◦ C
with its optical microscopic image (The scale bar is 1 cm in all pictures) [63].
Scheme 3. The schematic diagram for transesterification reaction.
instead, it fits Arrhenius equation, mathematically similar to Z-Glass and CNT-vitrimer composite using targeted light exposure. Local stress could
vitreous silica [76]. be relaxed photothermally using a high-intensity IR laser [79]. Since the
Oil-water separation has remained for a particular interest, and above works were scrutinized for the presence of a catalyst, Liu et al.
various techniques have been proposed to achieve this goal. Oil-water [80] have proposed a catalyst-free transesterification reaction; however,
separation has been achieved utilizing the advantages of trans they have not justified the exchange reaction at low temperatures, and
esterification reaction of the bio-based superamphiphilic vitrimer epoxy the final product might be carefully tuned to design the materials with
resin membranes (SAVER) [77], as illustrated in Fig. 6. Robust and specific properties. Furthermore, the catalyst-free transesterification
recyclable SAVER membrane, which can be used in oil-spill remediation, reaction has been investigated widely in the past three years, including
was prepared by direct ball milling sintering process also offered long built-in tertiary amine, intramolecular hydrogen bond, and so on
time filtering. More recently, Altuna et al. [78] have reported the [81–83].
transesterification of epoxy vitrimer using tertiary amine as a catalyst
with a glass transition temperature less than 70 ◦ C. Nevertheless, the
2.3. Disulfide bond
obtained activation energy was comparable with the one obtained by
using the zinc-based catalyst.
The dynamic and labile nature of the disulfide bond has been well-
Since targeted external stimuli can be of particular interest to further
known for vulcanized rubber and proteins for a long time. Disulfide
explore dynamic behavior in the field of vitrimers, Yang et al. studied
bonds can be reversibly broken, formed as well as exchanged under
5
Fig. 5. (a) Schematic diagram of topological rearrangements of a network with exchange reactions retaining the constant number of links and functionality. The
intermediate step signifies exchange without depolymerization; (b) Transesterification reaction of crosslinked networks; (c) Normalized stress relaxation with the
variation of zero-shear viscosity at different temperatures; (d) Shrinkage-free reprocessing of broken samples via injection molding [23].
certain conditions [84–87]; the bond dissociation energies are around bis(4-aminophenyl)disulfide [97]. Later, they also studied the reforming
210–270 kJ/mol [88,89]; therefore, it is reasonable to use this bond ability upon applying heat and pressure to the chemically crosslinked
intentionally to develop recyclable and reformable thermosets while self-healing poly (urea–urethane) elastomers [98].
retaining the original strength [89]. In 1990, the potential of degrada The same research group further extended the potential of aromatic
tion and recyclability of epoxy resins through the disulfide bond was disulfide bonds for advanced applications, i.e., construction, aero
initially presented by Tesoro and coworkers, where they studied resins nautics, automotive, and wind energy sectors. They have studied the
from diepoxide monomers (i.e., Epon 828, Epon 836, and Epon HPT reprocessing, reshaping, and repairing of epoxy resin, as shown in Fig. 7.
1071) and disulfide-containing diamine (i.e., dithiodianiline) [90–92]. Also, they reported the mechanochromism of epoxy vitrimers con
In 2011, Candell et al. [93] proposed an interesting way to bio taining aromatic disulfide, and they maintain it to be helpful for the
mimetic the autonomous healing of damage using disulfide-based damage detection application and the recycling and reforming proper
epoxy. Though the material was elastomer, it opened the door for ties obtained from vitrimers [99]. Interestingly, the mechanochromatic
other researchers to explore this research direction further. In 2014, Lei effect was observed only with 4-aminophenyl disulfide when the side
and coworkers reported an aliphatic disulfide-linked network that could group was at para position, as illustrated in Fig. 8 (a). The p-EPO turned
be fully reprocessed to pristine using a phosphine catalyst, i.e., to green on grinding it into the powder, turning to its original color after
Tri-n-butyl phosphine [94]. They maintained air-insensitive disulfide 24 h at room temperature. Likewise, the green color appears on hitting
metathesis that needs the catalyst to be effective at room temperature spots the GFRC made of p-EPO with the hammer, which disappears after
under alkaline conditions, which is not possible otherwise. The epoxi a similar duration (refer to Fig. 8 (b)).
dized natural rubber having the reprocessing ability at >150 ◦ C due to In the above polymer systems, aromatic disulfides were added as a
disulfide bonds as well as considerable thermal resistance, no change in crosslinking agent; the obtained properties partially rely on epoxy
the properties up to ~100 ◦ C, has also been reported recently [95]. resins. However, Otsuka and coworkers formulated new degradable
In a recent and comprehensive review by Azcune and Odriozola, the epoxy resins, in which two aromatic rings are bridged by disulfide bonds
potential of the aromatic disulfide crosslinks in polymer systems for and cured with different amines [88]. The novel resin possessed com
various applications has been described [96]. The bond exchange parable mechanical properties to conventional epoxy resins without the
mechanism for aromatic disulfide metathesis is illustrated in Scheme 4. disulfide bond, along with the facile degradation of a few tens of a
Odriozola and coworkers designed self-healing poly (urea–urethane) minute. This work was further extended by Zhou and coworkers, who
elastomers at room temperature without any external stimuli or catalyst intentionally increased the disulfide bond content by curing the same
due to aromatic disulfide metathesis by using dynamic crosslinker, i.e., epoxy with 4,4′ -disulfanediyldianiline [30]. As a result, they obtained
6
considerable strength retention over three reprocessing cycles and the

full recovery of the conductive fillers.
Kessler and coworkers integrated different functional building
blocks, such as photo-responsive azobenzene molecules, thermally
responsive liquid crystals, and dynamic disulfide bonds, to obtain shape
memory and photomechanical behaviors under different external stim
uli (light or heat) [100]. In the epoxy network, dynamic disulfide bonds
facilitated the repairing under UV light and recycling using 2-mercap
toethanol by taking advantage of the thiol-disulfide interchange and
disulfide exchange reaction, refer to Fig. 9(b–c). The attention was paid
to demonstrating different functionalities into one liquid crystalline
epoxy network rather than achieving higher performance.
The epoxy vitrimers can be activated without the aid of the catalyst
via dynamic disulfide bonds present either in the epoxy backbone or
curative; however, obtained resins often have lower mechanical prop
erties and inferior chemical resistance than conventional counterparts.
The research, as mentioned above, emphasis only the recycling and
reprocessing of the polymers obtained from petroleum-based sources.
Recently, Ma and coworkers synthesized bio-based epoxy vitrimers; they
epoxidized isosorbide to form IS-EPO, which was later cured with 4,4′ -
methylenedianiline (MDA) and 4,4′ -disulfanediyldianiline (MDS) to
form MDA-EPO and MDS-EPO, respectively, as illustrated in Fig. 10 (a),
with MDS-EPO as bio-based recyclable epoxy vitrimers based on disul
fide exchange reaction [29]. The MDS-EPO was reformable in the hot
press at 100 ◦ C within 1 h and degradable on immersing it in 5 wt %
NaOH aqueous solution for 3 h, while MDA-EPO was neither reformable
Fig. 6. Schematic illustration of the target closed-loop cycle of bio-based nor degradable, refer to Fig. 10 (c). However, they could not get high Tg
superamphiphilic vitrimer epoxy resin (SAVER) membrane [77]. for MDS-EPO, even using rather complicated chemistry.
It is unusual for vitrimers containing disulfide bonds in the polymer
Scheme 4. The schematic diagram for aromatic disulfide metathesis.
Fig. 7. (a) Comparison of the reprocessing experiments of reference and aromatic disulfide-containing epoxy under similar conditions of the hot press; (b) Healing of
the scratched dynamic epoxy with a household iron to get a healed sample; (c) Reprocessing of dynamic epoxy film to get dumbbell-shaped samples wrecked and
crushed into powders [28].
7
Fig. 8. (a) Synthesis of epoxy vitrimers with and without mechanochromism; (b) color changing phenomenon of p-EPO resin [99]. (For interpretation of the ref
erences to color in this figure legend, the reader is referred to the Web version of this article.)
backbone to possess higher tensile strengths and chemical resistance. In epichlorohydrin to get glycidyl ether of imine-embedded bisphenol
addition, much research has been done focusing on disulfide-based (GE-VAN-AP). Finally, they cured this epoxy with Jeffamine to obtain
curative rather than incorporating disulfide bonds into the epoxy aromatic imine-containing resin, as shown in Fig. 11 (a). The resin was
structure. Compared to other vitrimer systems, the potential of recy degradable in the solution of DMF and HCl and can be fully recycled
clable resins based on the disulfide bonds has been inadequately studied, upon the evaporation of the solvent. A polymer gel of partially cross
particularly for the resins obtained from bio-resources. linked epoxy network was obtained by distilling off the DMF and HCl
solution, as illustrated in Fig. 11 (b), and malleable (refer, Fig. 11 (c)).
2.4. Imine chemistry The resin was solvent resistant in different solvents for two days at 65 ◦ C
and weldable (refer, Fig. 11 (d-e)).
The dynamic covalent imine bond, also known as the Schiff Base, was Two broken dog-bone-shaped samples were welded at 120 ◦ C for 4 h
first elaborated in 1997 by Huc and Lehn, where the existence of a by overlapping them in the middle, and the broken pieces of the welded
molecular trap (carbonic anhydrase) influenced the composition of a sample showed tensile failure, not a cohesive failure. Also, the resin
virtual combinatorial library of imines [101]. Currently, work is focused showed water-driven malleability. In this demonstration, 0.4 mm thick
on chemistries containing the formation and contravention of covalent film was stretched after being softened by immersing in the water at
imine bonds beneath thermodynamic control. room temperature for 4 h on a round glass mold followed by drying
Rowan et al. [102] reviewed several dynamic covalent chemical under reduced pressure in a desiccator. The dried sample retained its
reactions maintained upon reduction of the imines; the carbon-nitrogen new shape even under 240 g load (see Fig. 11 (f)). Although they have
double bond corresponds to the carbon-nitrogen single bond, in addition claimed this resin to be fully recyclable, the reported resin has relatively
to both carbon and nitrogen correspond to hydrogen. This bond can be inferior mechanical and thermomechanical properties. In addition, the
used to develop dynamic epoxy using its well-known three dynamic processing of this epoxy is very complicated; it can only be either pro
reactions, i.e., imine metathesis, imine exchange, and imine con cessed by using very high temperature, i.e., melt polymerization, or
densation/hydrolysis, as illustrated in Scheme 5 [103,104]. In these using high boiling point solvents, which limits its handling [32]. Ma and
three dynamic reactions, there is no need to use any catalysts. Other coworkers synthesized high-performance and recyclable imine-based
dynamic covalent chemistry of imines was reviewed by Stoddart [105]. epoxy resin; however, to guarantee bubble-free samples, the epoxy
A large variety of commercially available amines and aldehydes effec must be molded using heat and pressure since water is generated during
tively facilitates the design of various imine-containing vitrimers. its curing.
An extensive literature review reveals that there has always been a Mai et al. [106] synthesized a recyclable and malleable epoxy resin
compromise between the high-performance and full recyclability of by reacting DGEBA with Schiff base of vanillin and hexane-1,6-diamine,
imine-containing vitrimers [31,32]. Recently, Zhao and Abu Omar which had malleability due to imine metathesis and recyclability due to
synthesized a novel recyclable aromatic imine-containing epoxy [32]. imine hydrolysis, as shown in Fig. 12. Though the curing agent can be
They first reacted vanillin (VAN) and aminophenol (AP) to obtain easily synthesized and processed, the resin yielded very low Tg due to a
imine-embedded bisphenol (VAN-AP), which was later reacted with long hexane chain in its structure.
8
Fig. 9. (a) Repairing under UV light for different duration of times; (b) Recycling at room temperature for 16 h; (c) Recycling at 160 ◦ C for 1 h under reflux using 2-
mercaptoethanol [100].
2.5. Polysiloxane chemistry 2.7. Hexahydro-s-triazine
In 1954, Osthoff et al. [107] reported the stress relaxation behavior Another dynamic bond brought under the consideration of epoxy
of polydimethylsiloxane. Recently, Zheng and McCarthy synthesized vitrimer is hexahydro-s-triazine; recently, You et al. [36] have devel
self-healing crosslinked polydimethylsiloxane (Silicon rubber) by oped a high-performance (i.e., Tg = 151 ◦ C, and modulus 2 GPa) epoxy
anionic ring-opening polymerization of cyclotetrasiloxanes used as an vtrimer which can be degraded and triggered via acid. This
anionic initiator [108]. The anionic initiator initiates nucleophilic ex hexahydro-s-triazine bond in epoxy vitrimer has also been explored by
changes of Si–O bonds among siloxane moieties carried silanolate end Ma et al. [37], they incorporated hexahydro-s-triazine bond in hyper
groups leading to self-healing at 90 ◦ C for 24 h. Using similar dynamic branched epoxy vitrimer and found it promising for composite
chemistry, Schmolke et al. [109] tuned the self-healing and stress applications.
relaxation behavior of crosslinked polydimethylsiloxane networks at
25 ◦ C by changing the concentration of the anionic groups. Nishimura 2.8. Silyl ether bonds
et al. [110] reported strong, thermally stable, and robust silicone
rubber-based siloxanes and silyl ether linkages and tuned its dynamic Liu et al. [38] synthesized a series of reformable epoxy resins con
properties to Si–O exchange by neighboring amino groups. Using the taining dynamic silyl ether bonds in which the exchange reaction be
same dynamic siloxane chemistry, Wu et al. [34] have recently syn tween two silicon-oxygen occurs via nucleophilic attack. They
thesized siloxane epoxy vitrimers by curing diglycidyl ether of ethoxy fine-tuned a series of resins’ mechanical and dynamic properties by
lated bisphenol A (DGEBAEO) with bis(potassium) changing the ratio of DGEBA and polypropylene glycol diglycidyl ether.
oligoaminopropylmethylsiloxanediolate (K-PAMS). The synthesis and Dynamic silyl ether bonds were formed by adding potassium hydroxide
dynamic siloxane equilibration are demonstrated in Fig. 13 (a); the resin into the resin of epoxy blends and a silane coupling agent, i.e., 3-amino
had considerable mechanical and thermomechanical properties (i.e., Tg propyl triethoxysilane.
≈ 83 ◦ C and tensile strength ≈ 46.6 MPa). Also, the resin had excellent
strength retention efficiency after several mechanical reforming cycles 2.9. Boronic ester
(i.e., 10 MPa, 130 ◦ C for 40 min) as demonstrated in Fig. 13 (c).
Moreover, the resin was able to heal its cracks at 110 ◦ C doe 24 h. Zeng et al. [35] have studied dynamic reversible covalent boronic
ester bonds in epoxy vitrimer recently. The systematic study analyzed
the effect of increasing boronic ester bonds on the mechanical, thermal,
2.6. Boroxine bonds
and thermomechanical properties and the reprocessing and chemical
degradability of these vitrimers. They studied the self-healing shape
Dynamic boroxine bonds have been incorporated into thermosets by
memory performance of this epoxy vitrimer, as illustrated in Fig. 14.
Odgen and Guan recently [111]. Moreover, Yuan et al. [112] prepared
an interesting epoxy vitrimer based on the dynamic boroxine bonds;
their bioinspired self-healing polymer was water-responsive as well.
9
Fig. 10. (a) Synthetic route of isosorbide-derived epoxy (IS-EPO) and its curing with 4,4′ -Methylenedianiline (MDA) and 4,4′ -disulfanediyldianiline (MDS). Com
parison of (b) reformability and (c) degradability of MDA-EPO and MDS-EPO under similar conditions [29].
Scheme 5. The schematic diagram for the reversible reactions related to imine chemistry (a) imine formation; (b) transamination between amines and imines (c)
imine metathesis reaction.
10
Fig. 11. (a) Synthetic of resin; (b) Recycling steps of the crosslinked epoxy network: (a) Crosslinked epoxy network dissolved in DMF and HCl solution (b) Partially
polymerized gel (c) Viscous gel restored crosslinked epoxy network; (c) Malleability; (d) Solvent resistance; (e) Weldability of the crosslinked epoxy network: front
view and side view of the welded (a) and (b) and broken (c) and (d) samples; (f) Water-driven malleability: (a) 0.4 mm thick thermoset film (b) the soft film stretched
on a round glass mold (c) dried sample (d) under 240 g load, and its (e) enlarged photograph [32].
2.10. Some other recyclable epoxides (VBGE) and cyclohexane dimethanol vinyl glycidyl ether (CHDMVG), as
presented in Scheme 6. Ma et al. further explored the potential of epoxy
The cleavable epoxides contain acetals, hemiketals, carbonates, etc. vitrimers based on the acetal linkages, i.e., [–O–CH(CH3)–O–], recently
These materials can be considered thermally reworkable or hydrolyz [39]. They investigated spiro diacetal epoxy resin and found it degrad
able, and these structures do not relax stress; they will not have topology able in acidic conditions, though this new epoxy showed comparable
freezing transition temperature. Their behavior and performance are properties with DGEBA.
different from that of vitrimers since they also can be recycled; thus, they González et al. [42,43] have synthesized a series of dynamically
have been reported here. reworkable epoxy resins through cationic copolymerization of DGEBA
In 1996, Buchwalter and Kosbar reported a series of cleavable with 6,6-dimethyl (4,8-dioxaspiro [2.5]octane-5,7-dione) (MCP), 7,
cycloaliphatic epoxies with acetal linkage, which can be readily dis 7-dimethyl-6,8-dioxaspiro [3.5] nonane-5,9-dione (MCB) and 2,2,5,
solved into acid-containing solutions [41]. The study was further 5-tetramethyl-4,6-dioxo-1,3-dioxane (MDM). The dynamic bonds be
extended by Hashimoto et al. [40], who synthesized four novel epoxies tween these resins were hemiacetal/hemiketal ester linkage. Wang et al.
from two phenols, i.e., bisphenol A (BA) or cresol novolak (CN) and [44,45] reported a series of thermally reworkable epoxies based on
vinyl ethers containing a glycidyl group 4-vinlyoxy butyl glycidyl ether carbamate and carbonate groups, as shown in Scheme 7. Lee and
11
Fig. 12. Synthesis and performance of malleable and recyclable epoxy vitrimers from vanillin-based imine hardener and DGEBA [106].
Fig. 13. (a) Synthesis and dynamic siloxane equilibration of epoxy vitrimers; (b) Mechanical reprocessing; (c) Stress-strain curves of pristine and reprocessed
samples; (d) Surface morphology of the cracks before after the healing; (d) Stress-strain curves of pristine and healed samples [34].
12
Fig. 14. Performance and mechanism of boronic ester-based epoxy vitrimer (a) Self-healing performance of boronic ester-based epoxy vitrimer (b) welding through
heating for boronic ester-based epoxy vitrimer (c) transesterification reaction mechanism of boronic ester linkages (d) shape memory performance of boronic ester-
based epoxy vitrimer.
Scheme 6. The synthesis scheme of epoxy vitrimer containing acetal linkages [40].
13
coworkers have further explored these carbonate linkages in epoxy to Later they synthesized a sulfite-containing cycloaliphatic diepoxide by
synthesize a photo-patternable epoxy network [113]. In which they replacing O–– P with O–
– S, hoping to reduce the decomposing temper
reacted oxirane groups in bis(2-(oxiran-2-ylmethyl)-1,3-dioxoisoindo ature of the networks further [115]. Also, they tuned the thermal
lin-5-yl) carbonate with the carboxylic acid groups in a polymer con degradation temperature and studied the thermal degradation mecha
taining 9-anthracenyl-methylmethacrylate (AMMA), p-tert-butoxy nism of the reworkable epoxy. The structure is shown in Scheme 8 (c).
styrene (PTBS), and methacrylic acid (MAA) monomeric units.
Shirai and coworkers synthesized a series of photo crosslinkable 3. Possible future research subjects
epoxy resins having sulfonate ester groups [46,47]. The cured resin was
dissolved into water or organic solvents upon heating up to 200 ◦ C. The Vitrimers are a relatively new class of polymer; although a significant
same research group later synthesized three epoxy resins (see Scheme 8 improvement over the last decade was made, several fundamental
(a)), which were able to crosslink and de-crosslink thermally [114]. This questions will need to be answered. Herein we have proposed some
thermal crosslinking and de-crosslinking character are due to two research directions to be explored in Fig. 15.
thermally degradable sulfonate ester linkages in the structure of these
resins. Interestingly, the thermal click chemistry was active at temper 3.1. Fundamental research on epoxy vitrimers
atures much lower than the degradation temperature. However, it
should be noted that these materials are considered thermally rework There is a need to understand bond exchange properties with iden
able or hydrolyzable, which are very different from those with dynamic tical crosslink density or concentrations of dynamic bonds. The
behavior as vitrimers or dynamers. reformability and recyclability of vitrimers at a given crosslink density
Wang’s research group synthesized reworkable flame retardant may also be studied as a function of changes in the numbers of dynamic
cycloaliphatic epoxies based on phosphate bonds (see Scheme 8 (b) bonds [116]. Similarly, the constant number of dynamic bonds may be
[48]). The reworkable test exhibited that after heat-treatment at 260 ◦ C studied at varying crosslink densities by adding epoxy monomers, such
for 4 min only, the residue of cured trifunctional epoxide on a glass slide as monoepoxide, as a capping agent. This approach could help under
could be easily cleaned off utilizing acetone to get a very clean substrate stand the correct self-healing behavior of vitrimers, regardless of the
so that supplementary grinding and polishing methods are not required. change in properties related to numbers of dynamic bonds and crosslink
Scheme 7. Thermally reworkable epoxies based on carbamate (a) and carbonate (b) group [44,45].
14
vitrimers reported have high enough Tg, their robustness can be further
improved. These vitrimers are often very brittle, which hinders their use
in various applications. Thus, we need to develop high-performance yet
not very brittle epoxy vitrimers.
3.4. Biodegradable epoxy vitrimers
The research of vitrimers is advancing at a high pace, and one area of

particular interest is functional vitrimers. The functionalities might be
achieved by manipulating the chemical structure; a functional radical
might be introduced during the synthesis of the vitrimers, making it
useful for a particular application. Likewise, biodegradable vitrimers
might be developed just by adding a group or segment that bacteria can
break. To the best of our knowledge, no research has been reported for
biodegradable vitrimers yet. However, biodegradable and bio-based
conventional epoxy has already been published recently [122].
3.5. Catalyst-free epoxy vitrimers
Most of the reported epoxy vitrimers use metallic catalysts, which

increases the cost and complicates the process. This toxic metallic
catalyst might not be environmentally friendly, which might be prob
lematic for using epoxy vitrimers in biomedical and childcare applica
tions. We have reported high-performance imine-based epoxy vitrimer
that can be fully recycled, reprocessed, welded for repeated times
without the need for catalysts [11]. Moreover, we also have reported
weldable disulfide-based epoxy resin, which does not need any catalysts
for the bond exchange reactions [123].
The possibility of catalyst-free vitrimers is not limited to certain
dynamic bonds, i.e., disulfide, imine, etc., only. Wang et al. [81,83] have
proposed UV-curable mechanically robust catalyst-free trans
esterification based epoxy vitrimer, in which the vitrimer properties can
be tuned by incorporating appropriate intramolecular H-bonds only.
There are also some valuable strategies reported recently as other
catalyst-free epoxy vitrimer systems, including but not limited to the
incorporation of glycerol [124], hydroxyl-rich epoxy prepolymer, and
Scheme 8. Thermally degradable reworkable epoxies based on (a) Sulfonate
tertiary amine [125].
ester groups; (b) Phosphate bond; (c) Sulfite linkage.
3.6. 100% bio-based epoxy vitrimers

density.
Biomass is inexpensive, abundant, and, more importantly, renew
3.2. Epoxy vitrimers containing different types of dynamic bonds able. Though several research papers have either proposed a bio-based
curing agent or bio-based epoxy, the other components are often
A number of choices exist today for dynamic covalent bonds. Since petroleum-based [11]. Therefore, it is worth making 100% bio-based
the nature of the dynamic bonds plays a vital role in the overall dynamic vitrimers [126]. For example, the nucleophilic attack of 10-undecenoic
properties of vitrimers, introducing a combination of dynamic bonds acid and limonene oxide derived from castor oil and citrus oil, respec
into the crosslinking structures, such as dynamic imine and disulfide tively, followed by epoxidation, yielded 100% bio-based vitrimers
[117], as well as dynamic imines and boronic esters [118], and studying [127]. However, the reported vitrimers from the derived epoxy possess
the properties of final vitrimers have already been explored. Accord relatively low Tg, thermal resistance, and mechanical strengths
ingly, the disulfide epoxy synthesized may be reacted with the imine compared to conventional thermosets. Bio-based dynamic epoxies can
hardeners to prepare a resin with dynamic imine and disulfide bonds, be reacted with bio-based hardeners to obtain 100% bio-based vitrimers.
and the combined chemistries of synergistic dynamic bonds in epoxy
vitrimers can be explored in the future. Moreover, recently the dynamic 3.7. Natural fiber-reinforced epoxy vitrimers
urea bond based on primary amine has been proposed for self-healing
materials [119–121], which might be combined with existing Besides, natural fiber-reinforced composites are gaining much
well-established epoxy vitrimers. It is easy to prepare a primary attention due to sustainable development. The use of solvents and high
amine-terminated dynamic urea compound, efficiently developing temperatures to achieve the chemical recyclability of the resin inhibits
recyclable and reformable epoxy resins. their potential application to the natural fiber-reinforced vitrimers.
Recently, we have reported that the resin matrix in carbon fiber-
3.3. High-performance epoxy vitrimers reinforced epoxy composite (CFRC) could be degraded entirely by
heating at 100 ◦ C for 2 h [8]. A similar mild chemical recycling might be
Most of the recently reported vitrimers are of low performance or used for natural fibers. Also, more sustainable solutions are worth
vitrimers with low Tg. There is a solid reason for developing damage exploring to overcome these limitations, such as a cleavable polyamine
tolerant and long service time vitrimers for high-performance applica Recyclamine® 301 patented by Connora Technology, which offers full
tions. The high-performance vitrimers would make their use possible in recycling of resin and fibers in mild aqueous solutions 80 to 120 ◦ C [128,
the field of aerospace, windmills, and automobiles. Although some 129]. Moreover, the application of biodegradable bio-based epoxy
15
Fig. 15. Some possible future research subjects in the field of recyclable epoxy.
vitrimers, as proposed in section 3.10, for natural fiber-reinforced 4. Future potential applications
composites would also be one of the exciting research approaches to
design reprocessable green composites. In this section, we have presented some potential applications of
Fig. 16. Some potential application of recyclable epoxies.
16
epoxy vitrimers. These are some potentially promising applications for which might be reacted or incorporated with the recyclable hardeners
recyclable epoxies illustrated in Fig. 16. reported above to synthesize novel flame retardant vitrimers. Recently
reported reprocessable and degradable phosphate-based epoxy covalent
4.1. Epoxy vitrimers as adhesives and coatings adaptable networks exhibited excellent flame retardancy [139].
Study is needed on adhesive bond strengths using various substrates 4.5. Shape memory epoxy vitrimers
and comparing epoxy vitrimers to conventional adhesives and thermo
plastics. Moreover, since the disulfide exchange may be induced by UV Similar to conventional shape memory polymers, shape memory
light [130], the study on welding can be done in the presence of UV light vitrimers are also worth studying; since one of our resins [108] can be
by photoadhesion [131] rather than merely by heat. Since we know that reshaped upon heat and external force application, more research is
epoxy vitrimers are well suited for self-healing materials thus, needed to allow these resins to reshape without external force. If a
self-healing coatings are of particular interest using epoxy vitrimers. A self-healable epoxy also possesses a reversible shape memory effect,
novel epoxy vitrimer coating was prepared by curing hyperbranched large cracks in the composite can be autonomously closed and healed
epoxy prepolymers with succinic anhydride, which offered excellent whenever it appears. The concept of this idea, autonomous intrinsic
protection from electrolyte erosion and adhesion properties for joining self-healing of more extensive cracks in polymers, has been proven
two metallic plates [132]. Interestingly this coating can also be recently [140]. Recently, shape memory epoxy vitrimer has been
self-healed at 150 ◦ C within 1 h. developed from waste frying sunflower oil [141], which might be a good
research direction to utilize organic waste to produce valuable, sus
4.2. Epoxy vitrimers for advanced composites tainable products.
To follow the burgeoning trend in the design of CFRCs, that adven 4.6. Conductive epoxy vitrimers
tures the dynamic covalent bond to access structurally dynamic cross
links that demonstrate macroscopic responses (i.e., welding, healing, The global electronic waste is 20–50 million tons/year [142], which
and reprocessing) and full recyclability (chemically as well as mechan is expected to grow further due to the fast upgrading of electronic
ically) on exposure to temperature and pressure; the epoxy vitrimers products worldwide. It is worth exploring the potential of vitrimers for
might be beneficial. Mechanical properties are critical for launch vehi the electronic industry. Conductive vitrimers would also be an area of
cles and space applications [133,134]. The formulation and optimiza interest. Some research groups have managed to get electrical conduc
tion of epoxy vitrimers used at low and subzero temperatures are needed tivity by adding conductive nanomaterials, i.e., carbon nanotubes, into
to develop lunar and planetary missions materials. To our best knowl vitrimers [143]. Nevertheless, the intrinsically conductive vitrimers are
edge, no such study for launch vehicles and space applications has been yet to be developed to perform similarly to those conductive polymers,
conducted yet. such as polyacetylene, polypyrrole, and polyaniline. Recently,
polypyrrole-based electromagnetic shielding vitrimers have been re
4.3. Epoxy vitrimer as a sustainable material for recycling ported [144]; again, they achieved this by adding nanoscale
MWNT/Fe3O4 into polypyrrole vitrimers. Similarly, other nanofillers
Nevertheless, reclaiming carbon fiber from a three-dimensional can be added to the epoxy vitrimers to produce low electrical resistance
permanent crosslinked network structure with good mechanical, ther composites or electromagnetic shielding materials [145]. Recently, an
mal and chemical properties without affecting the properties of carbon epoxy resin-based polysulfide elastomer on embedding silver nanowires
fiber in a practical nondestructive manner seems a prospective research has been proposed to be used in wearable electronics [125].
goal [135,136]. The CFRC has been studied by Everitt et al. for the
infusion of damage by the vascular network [137], although they can 4.7. Epoxy vitrimers as soft actuators
only be used a limited number of times.
Yu et al. [26] have proposed near 100% recycling of CFRCs using Liquid crystalline epoxy vitrimers have been studied widely, and
transesterification reaction; they also proposed repairing the surface of they can be utilized to develop soft actuators. Recently, Chen et al.
CFRCs. In addition, Ma et al. [138] have also proposed the closed-loop combined two layers of two different epoxy vitrimers by hor pressing.
recycling of resin and carbon fiber from CFRC. Ruiz de Luzuriaga Layer-A was a rigid and humidity-inert, i.e., smaller shrinkage ratio
et al. [28] have studied the reprocessing, reshaping, and repairing of upon dehydration, whereas Layer-B was soft, sunlight-responsive, and
epoxy resin, long-lasting glass fiber prepregs, and repairing and me humidity-sensitive, i.e., larger shrinkage ratio upon dehydration.
chanical recycling of its glass fiber-reinforced composites (GFRCs) Therefore, if this bilayer was placed in high humidity and/or no light
thermoformation of cured CFRCs and carbon fiber reclamation from it. intensity environment, it could bend and recover its flat shape when
They also reclaimed carbon fibers from the aromatic placed in low humidity and/or high light intensity. Since each has
disulfide-containing resin using a thiol-based solvent at room tempera different physical and chemical properties, i.e., thus they could serve as
ture [28]. soft actuators. Recyclable epoxy vitrimer based thermocouples might
Hashimoto et al. [40] prepared CFRCs with and bisphenol A - also be designed in the future using a similar approach.
cyclohexane dimethanol vinyl glycidyl ether (BA-CHDMVG) or cresol
novolak - cyclohexane dimethanol vinyl glycidyl ether (CN-CHDMVG) 4.8. Epoxy vitrimers as biolubricants
and found them to be to degradable in 0.1 mol/L HCL in THF/H2O (9/1
v/v) at room temperature for 24 h, and recycled carbon fibers were Qi et al. [146] have proposed a new method to generate high-value
reclaimed. Wang et al. have reclaimed carbon fibers from Schiff-based dicarboxylic acid esters by depolymerizing epoxy vitrimer wastes
epoxy under mildly acidic conditions recently [31]; however, it through transesterification reaction into Zn(Ac)2/2-ethyl-hexanol solu
cannot be claimed as fully recyclable due to acidic conditions used. tion for 6 h at 170 ◦ C. Later on; they reclaimed this catalyst, i.e., Zn(Ac)2
to be used again. This strategy is beneficial for getting rid of a high
4.4. Flame retardant epoxy vitrimers amount of epoxy thermosets and converting the epoxy waste into a
useful product, i.e., biolubricants. Moreover, it would also lessen the
Similarly, the functional groups known for flame retardant might be burden of using lubricants from scarce fossil resources. This strategy
introduced into the structure to get flame retardant vitrimers. Various might be further expanded to develop or produce other valuable prod
nonrecyclable flame retardant epoxies have already been synthesized, ucts from epoxy wastes as well.
17
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Contents lists available at ScienceDirect

Recyclable and reformable epoxy resins based on dynamic covalent bonds –

and fully recyclable epoxy resin is necessary.

2. Recyclable epoxy resin based on dynamic covalent bonds

Since the last decade, an interesting approach has been to develop

Scheme 1. The bond exchange mechanism of covalent adaptable networks.

TSa (MPa) Tg (◦ C) TSa (MPa) Tg (◦ C) TSa (MPa) Tg (◦ C)

Ester 2.8–69.2 30–187 14 2.5 2.8 25–33 [25–27]

Scheme 2. The schematic diagram for the DA Alder reaction.

Scheme 3. The schematic diagram for transesterification reaction.

considerable strength retention over three reprocessing cycles and the

Scheme 4. The schematic diagram for aromatic disulfide metathesis.

2.5. Polysiloxane chemistry 2.7. Hexahydro-s-triazine

3.4. Biodegradable epoxy vitrimers

The research of vitrimers is advancing at a high pace, and one area of

3.5. Catalyst-free epoxy vitrimers

Most of the reported epoxy vitrimers use metallic catalysts, which

3.6. 100% bio-based epoxy vitrimers

Fig. 16. Some potential application of recyclable epoxies.

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