Progress in Polymer Science 38 (2013) 1–29

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Progress in Polymer Science

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The furan/maleimide Diels–Alder reaction: A versatile click–unclick

tool in macromolecular synthesis
Alessandro Gandini ∗
Instituto de Química and Escola de Engenharia de São Carlos, Universidade de São Paulo, 13566-590 São Carlos, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The purpose of this review is to provide a critical survey covering a few decades of growing
Received 10 February 2012 interest in the application to polymer chemistry of the Diels–Alder (DA) reaction between
Received in revised form 20 April 2012 furan and maleimide moieties. The major peculiarity of this specific combination of reagents
Accepted 23 April 2012
is the fact that their click coupling to generate the DA adduct is thermally reversible, through
Available online 28 April 2012
the retro-DA reaction, at about 100 ◦ C, i.e., a viable and non-degradative temperature in
terms of its application to practically all macromolecular structures. The use of furan deriva-
Keywords:
Diels–Alder reaction
tives constitutes an additional positive feature in this context, because of their renewable
Click chemistry character. Attempts were made to insure a comprehensive coverage of the literature, which
Furans deals with vastly different approaches and aims concerning the chemistry, the polymer
Maleimides architectures and the possible application of the ensuing materials. The decision to cite all
Thermoreversible polymerizations publications available on the subject was deliberate in the sense that in doing so, it was
Cyclic crosslinking/decrosslinking possible to examine them critically and highlight excellence and flaws.
© 2012 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Linear polymerizations and thermoreversible or aromatized materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Thermoreversible non-linear polymerizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4. Reactions involving polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5. Stereochemical effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6. Dendrimers and star-like constructs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7. Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
8. Concluding remarks and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

1. Introduction moieties. The choice of these particular systems stems

from the fact that the furan/maleimide DA adduct displays
This review deals specifically with the application of a relatively low temperature of decoupling through its
the Diels–Alder (DA) reaction to the thermoreversible retro-DA reaction, which therefore opens the way to
polymerization or crosslinking of monomers or polymers interesting applications such as recyclable networks, self-
incorporating furan (diene) and maleimide (dienophile) healing materials. The same equilibrium conditions apply
to the furan/maleic anhydride combination, but here its
extension to macromolecular synthesis is obviously pre-
∗ Tel.: +55 16 3373 8679; fax: +55 16 3373 9590. cluded because the unsubstituted maleic anhydride moiety
E-mail address: [email protected] cannot be appended to a polymer or form multifunctional

0079-6700/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.progpolymsci.2012.04.002
2 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 1. The Diels–Alder equilibrium between furan and maleimide end groups in a stepwise macromolecular synthesis.

molecules. An additional reason for emphasizing the above about 110 ◦ C the retro-DA adduct uncoupling
importance of the furan/maleimide couple is the fact that becomes preponderant. It is precisely the experimental
furan derivatives descend from renewable resources and convenience associated with this range of temperatures,
are therefore likely to play a growing role in sustainable together with the fact that side reactions and possi-
approaches to (green) chemistry and materials science. ble thermal degradation mechanisms are negligible, that
The Diels–Alder reaction does not require an extensive the furan/maleimide couple represents a highly suitable
introduction, given its well-established status in different choice for building a large variety of thermoreversible
realms of organic chemistry [1,2]. This [4+2] cycloaddi- macromolecular architectures. An additional interest in
tion between a diene and a dienophile typically bearing an calling upon this combination stems from the possibility of
alkenyl moiety, occurs through a concerted mechanism and exploiting furan reagents, which are derived from renew-
is one of the most attractive members of the click chemistry able resources [13].
family [3], particularly because of its thermal reversibility, An alternative strategy to exploiting the thermal
albeit at different temperature ranges, depending on the reversibility of the furan/maleimide adduct in polymeric
actual diene/dienophile combination [4]. Apart from the materials consists in converting them into counterparts
immense domain of the intervention of the DA reaction that are stable at high temperature, through the chemical
in organic synthesis, more specific issues have been tack- modification of the adduct by aromatization, as shown in
led concerning its features, such as the role of (i) solvents Scheme 2, and as detailed below. Of course in this case only
[5], (ii) Lewis acids or Brønsted acids or bases as cata- the initial DA coupling is relevant to the present review,
lysts [6,7], (iii) water as a medium [7], including aqueous since the adduct is transformed into a thermally stable
emulsions [8], and (iv) mechanical energy instead of ther- moiety.
mal activation to promote the retro-DA reaction of adducts In order to set the stage around this review and under-
incorporated into polymer chains [9]. line its peculiar message, it is important to provide a
The application of the DA reaction to furan derivatives background of recent monographs dealing with cognate
covers a large field of studies, dominated by synthetic topics. Click chemistry has become a standard tool in the
aspects [10], followed in importance by the more recent hands of polymer scientists, as amply described in recent
surge of investigations discussed in this review in which years [14], but the attention placed in those reviews on the
the dienophile counterpart to furans is a maleimide moi- specific issue discussed here was necessarily scant, because
ety. A remarkably thorough study of the DA reaction of their much wider purpose. The same considerations
between furan and maleimide involving kinetic and stere- also apply to essays dealing with healable and mendable
oselectivity aspects [11] sets an exemplary stage for polymers, [15], reversible covalent cross-linking [16], and
the extrapolation to macromolecular syntheses based on recycling [17], which call upon various strategies, includ-
that reaction, in which of course both heterocycles are ing the thermal reversibility of certain DA reactions. Other
now present as substituted furans and maleimides. It is reviews have tackled more specifically the DA reaction
unfortunate however that only a small fraction of the applied to macromolecular synthesis and to the original
investigations discussed here tackle these fundamental properties of the ensuing materials, but again their cover-
kinetic and thermodynamic aspects with sufficient insight, age needs updating [18], or is too broad [19], and hence
as emphasized in each instance. misses some of the relevant features of the present treat-
It follows that the reversible coupling characterizing ment, or falls outside its area of interest [20].
all the systems covered here can be simply pictured as in The specific combination of DA reactants deliberately
Scheme 1 where the endo and exo stereoisomers of the selected for the present contribution provides therefore a
adduct are not differentiated, because their role in the
formation and thermal reversion of this polymer unit rep-
resents a minor issue in most situations. It is important to
emphasize that the presence of specific groups in the vicin-
ity of either heterocycle (i.e., on the polymer chain), such
as carboxylate, amide and hydroxyl functions, can consid-
erably affect the rates of these DA couplings, as pointed out
in the case of reactions involving small molecules [12].
As a rough indication of the role of temperature on
the above equilibrium, up to about 60 ◦ C, the left-to-right
DA condensation to form the adduct dominates, whereas Scheme 2. Aromatization of a furan DA adduct.
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 3

complementary coverage of the field, together with a crit- Two radically different, indeed opposite, approaches are
ical assessment of the relevance of each of the numerous usually associated with the synthesis of linear polyadducts
published studies. by furan/maleimide DA polycondensations, namely (i) with
It is important to emphasize that the term “click” the purpose of exploiting their thermoreversible char-
attributed to reactions involving polymerizations, polymer acter (self-healing, recycling, etc.), or (ii) to transform
couplings and other synthetic macromolecular processes the adducts through an aromatization reaction in order
does not necessarily apply to every situation, as recently to prepare highly thermostable polymers. The seminal
pointed out [3b]. In the specific case of the systems dis- research by Tesoro and Sastri falls within the second strat-
cussed below, some do not comply with the stringent egy: in their first publication [22a], two difuran siloxane
criteria spelled out in that article, despite being defined as monomers, one rather heavily substituted, were made
“click”, and should be viewed instead as modular design to polymerize with three bismaleimides, differing in the
reactions or macromolecular conjugations. nature (stiff to flexible) of the bridging moiety. The ensu-
ing materials were thoroughly characterized in terms of
molecular weight (surprisingly high values in the tens of
2. Linear polymerizations and thermoreversible or thousands), 1 H NMR and IR spectroscopy, TGA and DSC.
aromatized materials Their Tg ranged from 21 to 101 ◦ C, mostly depending on
the bismaleimide used and their decomposition onset tem-
Although the monomers used did not incorporate furan perature was erroneously reported as varying between
or maleimide moieties, it is most appropriate to pay 300 and 415 ◦ C, which in fact reflected the evaporation of
homage here to the pioneering work of Stille and Plum- the monomers regenerated by the retro-DA reaction, since
mer who reported in 1961 the first detailed study of linear the actual polymer “degradation” (depolymerization) obvi-
polymerizations based on the DA reaction to biscyclopen- ously had taken place when the latter reaction became
tadienes and different bisdienophiles [21]. prominent above 100 ◦ C. All the polymers were then sub-
After a quarter of a century without any further printed mitted to an aromatization process of the adducts induced
interest in the general topic of DA polycondensations, by acetic anhydride, following the mechanism shown in
the first investigation on the use of a system involving a Scheme 2. This irreversible chemical modification changed
bisfuran and a bismaleimide monomer combination was drastically the thermal behavior of the materials, which
reported by Tesoro and Sastri [22], who opened the way to became really stable up to 310–470 ◦ C, depending on the
a stream of publications, whose flow, first modest, has been monomer combination adopted for their primary DA syn-
intensifying incessantly, particularly in the last decade. thesis.

Scheme 3. DA polycondensation of a difuran and a bismaleimide followed by the aromatization of the ensuing polyadduct.
4 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 4. Thermoreversible DA linear polymerization of a difuran with BMDP.

The second publication [22b] was similar in purpose, appear to reflect the expected structures and the likely
but both the difuran and bismaleimide monomers were major cause of the flaw was the use of excessively high tem-
changed, as shown in Scheme 3. Curiously, the polymer peratures, which most probably induced the well-known
molecular weights were some fivefold lower than those free radical polymerization of the maleimide functions.
found for the materials prepared in the previous study The approach focusing on the preparation of thermore-
[22a], despite the sterically more accessible furan heterocy- versible linear DA polymers was first discussed and realized
cles. Subsequent studies on other systems involving even by Kuramoto et al. [24] who submitted difurfuryladipate
less substituted furans (see below) strongly suggest that and N,N -bismaleimido-4,4 -diphenylmethane (BMDP) to
the size of the macromolecules reported in the first paper DA polycondensations at temperatures of 30–70 ◦ C, accord-
[22a] was probably overestimated. ing to Scheme 4. A limiting yield of 60% was obtained at
A series of publications by Mikroyannidis and Diak- 70 ◦ C, suggesting that the equilibrium was shifting toward
oumakos [23] tackled a series of linear DA polymerizations the monomers at that temperature (the authors did not
using both furyl-maleimide A–B monomers and combina- give enough time for the equilibrium to be established in
tions of difurans and bismaleimides (A–A + B–B systems) the experiments at lower temperatures, but reported com-
and in all instances the polymer adducts were finally plete conversion at 60 ◦ C). The depolymerization of this
converted into their aromatic counterparts. A number of material through the retro-DA reaction was carried out
problems arise upon reading these papers, namely (i) the at 90 ◦ C and reached 85% of monomer regeneration, indi-
structures of the A–B monomers together with those of cating that higher temperatures are needed to complete
most A–A and B–B counterparts were not unambiguously the process, as discussed above. This study was completed
established; (ii) the same applies to their DA polymers, by a test in which the polymer was submitted to three
which were seldom characterized before their aromati- polymerization/depolymerization cycles and that showed
zation, and which were reported to be insoluble in spite a reproducible pattern.
of the supposedly linear structure; (iii) in most instances This investigation represents the groundbreaking proof
the maleamic acid structures, precursors to the maleimide of the potential associated with preparing DA polyadducts
cycles were treated at temperatures around 200 ◦ C, or which display a clean-cut thermal reversibility.
higher, in order to promote their dehydration and at the The synthesis of the first structurally verified A–B
same time the DA polymerization of the ensuing maleimide monomer, furfurylmaleimide (Fig. 1), was carried out
with the furan counterpart, in stark contrast with the in 1998 [25]. It is indeed the simplest furan/maleimide
fact that in those conditions the retro-DA reaction would molecule, which was prepared in a classical fashion from
predominate, thus barring any chain growth; (iv) the con- furfurylamine and maleic anhydride. Spectroscopic evi-
version of the supposed adduct moieties into aromatic dence suggested that the two heterocycles affect each other
rings was always carried out by heating the DA polymers
at very high temperatures, instead of using the milder O
acetic anhydride process, and hence the fate of the adduct
through the retro-DA reaction was again ignored; (v) the N
aromatized polymers were also reported to be insoluble, O
although their purported linear structure would have pre- O
dicted otherwise. The unfortunate conclusion is that the
materials obtained in these numerous experiments do not Fig. 1. The structure of 2-furfurylmaleimide.
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 5

Scheme 5. DA linear polycondensation involving BMDP and a difuran cyclic diacetal.

electronically in such a way that the two carbonyl groups DPn of only about 10, because of precipitation during the
(and hence the two hydrogen atoms) of the maleimide moi- synthesis.
ety are not equivalent, i.e., their symmetry is perturbed by The other investigation [27] called upon the same
the furan ring. maleimides and two different difuran monomers. The
Contrary to expectations, this compound did not poly- originality of this study stems from the fact that the
merize through a simple DA polycondensation when its DA polymers were synthesized using chirally modified
solutions were heated up to 70 ◦ C, and hexothermic reac- Lewis acids as catalysts and hence the ensuing macro-
tions only occurred at higher temperatures, even for the molecules (with molecular weights between 1000 and
bulk treatment of melted FM. The recovered products were 15,000, depending on the specific system) possessed opti-
mostly insoluble brown solids, although the modest solu- cal activity (Scheme 6).
ble fraction hinted at the presence of the expected adducts. Regrettably, neither of these works looked into the ther-
The reason for this lack of proper DA reactivity remains mal reversibility of the polymers through the retro-DA
obscure, but one plausible explanation could be that the reaction.
special electronic interaction between the two heterocy- Patel and Patel [28] reported a brief study of the linear
cles conjured against their normal DA behavior as diene DA polymerization of an aromatic bismaleimide with difu-
and dienophile, respectively. In other words, the furan and ran monomers incorporating a triazine motif, followed by
maleimide rings were too close for comfort. As discussed the aromatization of the adducts by Ac2 O at 140 ◦ C. Empha-
below, these moieties behave as expected when they lie sis was placed here on the synthesis and characterization
further apart. of the furan monomers, whereas the insoluble polymers
Returning to the A–A + B–B situation, two indepen- received only scant attention.
dent studies were published in 1999 on this linear DA Gaina and Gaina [29a] synthesized a series of stiff
polycondensation. The combination of a difuran monomer bismaleimides with different aromatic–ester bridges and
bearing acetal moieties and an aromatic (BMDP) or an polymerized them with a difuran incorporating a long
aliphatic bismaleimide was the subject of one of them [26]. aliphatic diurethane unit with the aim of synthesizing
Model reactions involving complementary monofunctional linear poly(ester-urethane)s through their DA polycon-
reagents (A + B) and the synthesis of trimers by reacting densation. These materials had DPn lower that 10 and
one of the monomers with the monofunctional model of their structures were not characterized before being sub-
the other (A–A + B and A + B–B) were carefully assessed mitted to the aromatization of their adducts in view of
before proceeding to the actual polymerization sketched preparing the corresponding thermally stable poly(ester-
in Scheme 5. The spectroscopic features of all the models urethane-imide)s. Once more, the thermoreversibility of
served as a useful basis for the interpretation of the struc- the polyadducts was not examined.
ture of the corresponding polymers, which displayed the In another vein, the same authors [29b] prepared two
expected sequence of adducts in their monomer units, but furan/maleimide A–B monomers and submitted them to
6 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 6. Structure of an optically active polymer prepared by the furan/maleimide DA polymerization.

a very unusual DA polycondensation in the sense that features quantitatively. This behavior was confirmed by
they applied very high temperatures, both in solution submitting both the model and the polymer to a thermal
(reflux in DMF) and in bulk (180 ◦ C), i.e., conditions that treatment in solution at 160 ◦ C, which fully regenerated the
would not favor the forward (polymerization) DA reac- two monomers, as indicated by 1 H NMR spectroscopy. The
tion. Only IR spectra were provided for these materials, aromatization of its adducts converted the polymer into a
which did not offer sufficient evidence for their detailed polyimide, whose thermal stability improved dramatically
structure. Their subsequent aromatization process also to 400 ◦ C, as expected for a macromolecular structure now
gave poorly characterized products. It is reasonable to devoid of weak moieties.
assume that these unprotected A–B monomers should A similarly clear-cut investigation was reported by Ter-
have polymerized spontaneously via a DA polyconden- amoto et al. [31] who coupled a trehalose-based difuran
sation in solution, even at room temperature, albeit at with an aromatic (BMDP) and an aliphatic bismaleimide
a slow pace, as discussed below in the case of a simi- (Scheme 7) to give DA polycondensates with molecular
lar situation. An inspection of the 1 H NMR spectra of the weights higher than 15,000 in the best synthetic condi-
monomers gives rise to some doubts about their actual tions and the expected structures. Their depolymerization
structure. was studied by DSC (solid samples) and SEC (DMF solu-
Returning to the more conventional A–A + B–B system, tions at 100–140 ◦ C). The broad endotherms between 100
Ahmad et al. [30] carried out a very fine study of the DA and 200 ◦ C suggested the occurrence of the retro-DA reac-
polymerization of equimolar amounts of difurylmethane tion, a fact unambiguously confirmed by the formation of
and BMDP in refluxing methylene chloride. A model trimer the two monomers at the end of the thermal treatment of
was also prepared by the reaction of the bismaleimide with the solutions.
a thirty-fold excess of the difuran. This model was fully Although the purpose of Chou and Liu [32] was to pre-
characterized and submitted to a TGA test, which clearly pare high performance thermosets, the building up to them
revealed the occurrence of the retro-DA reaction thanks consisted in synthesizing a linear DA polycondensate (MW
to the volatility of difurylmethane that produced a weight close to 20,000) based on a difuran monomer bridged
loss between 100 and 200 ◦ C corresponding to the depar- by benzoxazine moieties and BMDP. Its temperature-
ture of the two difuran molecules. The thermogram of modulated DSC tracing clearly exhibited the endotherm
the corresponding DA polymer (DPn ∼ 10) confirmed these associated with the retro-DA at 100–150 ◦ C, followed by

Scheme 7. DA polycondensation involving a saccharidic difuran.

 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 7

Scheme 8. Model DA reaction simulating the linear polymerization shown in Scheme 9.

crosslinking reactions starting at ∼200 ◦ C, associated with complex phenomenology in which aromatization, retro-
oxazine and maleimide branching reactions. DA, and free-radical maleimide crosspropagation reactions
A brief discussion is appropriate at this stage to coexisted, with different relative contributions according
rationalize apparently conflicting results related to the to the actual temperatures and polymer structures, to gen-
various studies reviewed above. The undisputable ther- erate ill-defined network architectures.
mal reversibility of the DA reaction involving furan and Only in later studies, attentive authors pinpointed these
maleimide structures seems to be placed in doubt by some issues and chose systems and/or observation techniques
observations related to the supposedly high “thermal sta- that helped dissipate previous anachronisms and set the
bility” of the DA polymers, which should have displayed the record straight, at least qualitatively. But this little saga
expected features of depolymerization through the retro- took the best part of two decades to sort itself out, despite
DA reaction, already around 100 ◦ C. the fact that in other types of systems, such as some
A close inspection of these situations dispels any doubt, of the non-linear polymerization and reversible polymer
because what took place in those experiments did in fact crosslinking studies discussed below, these notions had
involve the retro-DA reaction, not detected by TGA simply been fully rationalized already in the 1990s.
because the corresponding monomers, and even less their The most recent investigations on linear DA polycon-
oligomers, were not volatile at the corresponding temper- densations have brought the topic to deeper developments,
atures. Furthermore, upon a relatively fast scanning, the in terms of both its quantitative features and its poten-
depolymerization was not necessarily complete. Upon a tial applications. Thus, the conjunct adoption of NMR and
further temperature increase, these fragments crosslinked UV spectroscopy to follow both polycondensation and
progressively through the free radical reactions associated depolymerization has provided much needed information.
with the maleimide unsaturations, while at the same time A study of model monofunction DA reactions (Scheme 8)
undergoing the aromatization of the residual DA adducts. was carried out using those tools in order to obtain kinetic,
The net result was therefore the formation of thermally sta- as well as clear spectroscopic data, before tackling the
ble networks, as indeed shown by the TGA measurements. actual polymerization (Scheme 9) [33,34].
It is important to emphasize here that the simple pos- Fig. 2 shows an example of the evolution of the UV
tulate of aromatization as the key reaction leading to spectrum during the polymerization sketched in Scheme 9,
polymers of high thermal stability is incorrect, particu- carried out at 65 ◦ C in 1,1,2,2-tetrachloroethane. The
larly when, as is often the case, the temperatures used decrease in the intensity of the peak at 300 nm reflects
for the expected aromatization largely exceed their correct the loss of conjugation in the maleimide O C C C C O
values. If this simple picture reflected indeed a chemical chromophore upon formation of the adduct. It is important
reality, all the aromatized polymers would have dis- to note that all the spectra crossover at a single isos-
played the solubility expected for linear macromolecules, bestic point at ∼260 nm, indicating that no side reaction
albeit only in appropriate solvents, whereas, instead, most accompanied this DA polycondensation, as confirmed by
investigations reported the total insolubility of the final the concomitant evolution of the 1 H NMR spectra [33,34].
materials. What happened then reflects a much more This reaction was shown to follow a clean second order

Scheme 9. The DA linear polycondensation described in [33].

8 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

1.0 the non-furan reagent was ␤-alanine, also a renewable

resource.
0.8 The need for protecting one of the DA partners in these
monomers was obviously essential to avoid their prema-
0.6 ture polymerization during isolation, characterization and
Abs

storage. Hence the need of carrying out the deprotection at

0.4 the time of study of their polymerization, which was readily
achieved by heating the solution of the protected molecules
0.2 at 110 ◦ C to remove the furan through the retro-DA reaction
applied to their maleimide-adduct end (Scheme 11). The
0 solutions were then rapidly cooled to 65 ◦ C and the poly-
200 300 400 450 merizations followed by UV and 1 H NMR spectroscopy [35],
250 350
as in the previous investigation discussed above [33,34].
wavelength /nm
These DA polycondensates were fully characterized and
Fig. 2. Progressive decrease in the maleimide peak as the DA polymeriza- then submitted to a study of their retro-DA depolymeriza-
tion (Scheme 9) proceeds [33]. tion, here too followed spectroscopically. Again, a clear-cut
© 2008 by permission from Elsevier Ltd. reversibility was shown to operate.
This investigation represents the first successful study
1.5 of the behavior of a furan/maleimide A–B monomer in
the context of its thermoreversible linear polymerization.
These new polyadducts displayed evidence of the pres-
ence of appreciable proportions of cyclic oligomers [35], in
1.0
contrast to their homologues prepared by the alternative
A–A + B–B route [33,34].
Abs

A more elaborate approach was then applied to

0.5 furan/maleimide monomers prepared from two renew-
able resources (vegetable oils and furans) using two click
chemistry mechanisms, viz. the thiol–ene and the DA reac-
tions [36], as shown in Scheme 12. The thiol–ene reactions
0 involving 2-furylmethanethiol were found to proceed more
200 300 400 500 slowly than those involving aliphatic thiols, although the
Wavelength /nm cause of this was not associated with steric hindrance,
but rather to an unclear negative effect of the furan
Fig. 3. Progressive regeneration of the maleimide moieties as the retro- heterocycle. Before tackling the polymerization of these
DA operates on the polymer shown in Scheme 9 [33]. macromonomers, the occurrence of the DA reaction with
© 2008 by permission from Elsevier Ltd. furfurylsulfur moieties was first confirmed by UV and 1 H
NMR spectroscopy, using monofunctional model reagents
behavior. Upon heating the polymer solution at 110 ◦ C, and the linear polycondensation of difurfurylsulfide with
both the UV (Fig. 3) and NMR spectra displayed the reverse 1,6-bismaleimidohexane. In the latter case, the expected
trend reflecting the progressive decoupling of the macro- linear polyadduct was also shown to undergo thermal
molecular adducts, until the monomers were regenerated. depolymerization through the retro-DA reaction [36,37].
This was then confirmed by adding an excess of furfuryl Their DA polymerization/depolymerization features
acetate [33] or 2,5-dimethylfuran [34] to the depolymer- were carefully assessed using again 1,6-bismaleimi-
ized systems before cooling them to room temperature, in dohexane as the comonomer for AA and AA (Scheme 13)
order to avoid DA repolymerization. The products isolated and by the preliminary deprotection of the AB monomer
in both instances were respectively the difuran monomer [36,37] and shown to reflect the expected behavior already
and the bisadduct of the maleimide with the added mono- encountered in previous recent studies [33–35]. This is
furan trap, as shown in the example of Fig. 4. the first irruption into the exploitation of two click chem-
This research was pursued by a study on the synthe- istry processes to valorize furans and vegetable oils jointly
sis and DA polymerization of two novel A–B monomers and prepare thermally labile materials from renewable
[35], synthesized according to Scheme 10, where, notably resources.

Fig. 4. The products isolated by cooling the depolymerized system shown in Scheme 9 in the presence of an excess of 2,5-dimethylfuran, a trap that
impeded repolymerization.
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 9

Scheme 10. Synthesis of two DA A–B protected monomers.

Scheme 11. Deprotection and DA polymerization/depolymerization of an A–B monomer.

Scheme 12. Synthesis of two A–A and one A–B monomers from furans and vegetable oil derivatives using the thiol–ene click reaction.
10 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

O
12 O
11 7 5 3 1
13 N
O N 4
14 6 2
10
O n
16 O
S
17
a
O 18
r p n l j g b
S O S 19
n
O s q o m k h f e c 20
O 21
22
65ºC
23
O 110ºC 24
P2
O A
D 25
N 26
n N E C
O
O
O O
28
29
30
S

Scheme 13. Thermally reversible DA polycondensation involving a difuran monomer derived from vegetable oils and an aliphatic bismaleimide.

Patel et al. [38] returned to the topic of preparing DA recombination of the moieties to form novel adducts
heat-resistant materials by carrying out DA polymeriza- across the crack, which thus disappear.
tions involving a difuran monomer incorporating a siloxane This concept has been applied to a whole host of fur-
moiety and a variety of bismaleimides and thereafter con- ther studies, both with combinations of monomers and
verting the macromolecular adducts into aromatic groups, macromonomers and with DA reactions applied to poly-
as already discussed above in several instances. mers (see next section). Liu and Hsieh [41] prepared a
Under the title “re-mendable polyurethanes”, Gaina trismaleimide macromonomer which was reacted with a
et al. [39] reported the A–A + B–B DA synthesis of a series trifuran counterpart to form a dense DA network and the
of polymers bearing urethane functions along their chains. progress of the non-linear polycondensation followed by
The occurrence of the retro-DA depolymerization was FTIR. The self-repairing properties of this material were
hinted at by DSC and mechanical properties measure- thus clearly demonstrated. Plaisted and Nemat-Nasser
ments, although no direct proof was provided, nor a established a quantitative evaluation of fracture, heal-
proper DA/retro-DA cycle conducted under adequate ing and re-healing of networks similar to that shown in
monitoring. Scheme 14 [42] and concluded that full toughness recov-
ery by the statistical restoration of the original crosslinked
3. Thermoreversible non-linear polymerizations macromolecular structure was achieved. This quantitative
assessment clearly carries important implications in terms
Polymer networks prepared from the DA coupling of materials applications. A kinetic and thermodynamic
of multifunctional furan and maleimide monomers or study of the reversible DA polycondensation between a
macromonomers are arguably the first example of ther- trifuran and a bismaleimide [43] provided valuable quan-
mally mendable crosslinked materials, whose interest titative information, thanks to the use of FTIR as a tool to
was heralded in the pioneering work of Wudl et al. a follow both the forward and backward reaction. Together
decade ago [40]. Combinations of tetrafuran and bis- or with remendabilty tests, this investigation emphasized
tris-maleimides were made to polymerize in solution or moreover the possibility of modulating the crosslinking
in bulk (Scheme 14) and the thermal reversibility of the density, while confirming the clean-cut thermal recy-
ensuing networks studied in detail by 13 C NMR and UV clability of the system. In a different vein, crosslinked
spectroscopy, DSC and DMA, whereas their mendability polyurethaners bearing furan/maleimide adducts along
was assessed by fracture toughness tests. The latter prop- their chains were shown to provide phase-change mate-
erty stems from the possibility of repairing a crack, which rials as a function of their monomer compositions and DA
developed in the solid polymer by heating it at 115–150 ◦ C, adduct density [44]. Different combinations of di- and tri-
while pressing the sample in the direction perpendicular functional furan and maleimide monomers were employed
to the crack, to allow the retro-DA reaction to generate to study the progress of non-linear DA polycondensations
furan and maleimide moieties. The subsequent cooling in solution, using relative concentrations, so that the crit-
of the material regenerates the network by statistical ical conversion Pc associated with network formation, as
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 11

foam formulation that included diamine curers and a blow-

ing agent. The aim here was to test the possibility of
removing the foam by using a hot solvent, which was
attained by applying 1-butanol at 90 ◦ C to promote the net-
work breakdown through the retro-DA reaction and the
dissolution of the ensuing macromolecular fragments. A
similar study followed from the same laboratory, this time
applied to epoxy adhesives [47]. The approach has since
inspired other groups with different degrees of novelty.
Chiu et al. reported a very similar system applied to epoxy
resins for electronic applications [48] and Zhang’s group
introduced modest variations on the theme, mostly based
on the use of a tetraepoxy monomer [49]. Kinyanjui and
Hatchett, on the other hand, provided a thorough study
of the changes in the structure and hence in the mechan-
ical properties associated with the thermal treatment of
epoxy foams based on different monomers incorporating
DA adducts [50]. Gaina et al. [51] simply introduced ure-
thane moieties within the bridging structure separating the
epoxide-adduct functions. Recent publications by Peterson
et al. deal with two approaches, viz. either the reversible
DA crosslinking of a furfuryl amine-DGEBA oligomer bear-
ing numerous pendant furan heterocycles with BMDP [52],
or more conventional epoxide compositions incorporating
furan cycles and cured by a diamine, for which healing at
room temperature was insured by pouring a DMBP solu-
tion on the crack, thanks to its incipient DA reaction with
the furan moieties exposed at the fissure site [53]. The lat-
ter investigation also dealt with composites incorporating
glass fibers. In both studies, emphasis was placed on the
mechanical recovery after each type of healing process.
Returning to the classical trifuran/bismaleimide system
using small molecules as monomers, a particularly stim-
ulating investigation [54] showed that films of the DA
crosslinked material could be indented by a hot tip that
produced the local polymer degradation through the retro-
DA reaction. A careful study of the parameters associated
with the process allowed the authors to optimize it and
Scheme 14. Non-linear DA polycondensation between a tetrafuran and a
to show that the network could be successfully applied to
trismaleimide generating a dense network.
maskless lithography with a resolution below 20 nm and
data storage with densities up to 1 Tbin−2 .
predicted by the Flory–Stockmayer equation, was 50, 71
or 100% [34]. Reactions were followed by 1 H NMR and UV 4. Reactions involving polymers
spectroscopy, as well as by the very pronounced increase
in the medium viscosity, which ended in gelling for the first The reaction of a poly(ethylene oxide) (PEO) bearing
two systems. The retro-DA at 110 ◦ C ultimately restored the a methoxy and an OH end group with 3-furanmethanol
original monomer mixture in all instances. This investiga- yielded the corresponding PEO-monofuran derivative,
tion is being pursued using AB2 -type monomers in order which was coupled with mono- and bis-maleimides to
to prepare hyperbranched polymers [45]. generate the corresponding polymers with either a single
Most of the research in this area has however been terminal DA adduct, or an internal counterpart [55]. These
devoted to the study of epoxy networks, because of hydrophilic materials with potential biomedical appli-
the obvious interest in developing thermally removable cations displayed, as expected, the thermal reversibility
adhesives. The first publication dealing with this topic associated with the uncoupling of their adducts via the
concentrated on the synthesis of bismaleimides bearing retro-DA reaction.
flexible bridges and to their reaction with furfuryl glycidyl Yoshie’s group has looked extensively and some-
ether to form DA adduct end groups with pendant epoxy what redundantly into the DA reaction of furyl telechelic
functionalities [46] (Scheme 15). polyesters with di- and tri-functional maleimides [56]
This original study was in fact contemporary to the sem- and the properties of both block and crosslinked mate-
inal work by Wudl et al. [40], but concentrated on a more rials, mostly in terms of recyclability and mendability,
technological aspect, based on the use of the DA-epoxide i.e., the retro-DA features well-established at the time of
bifunctional monomers as components of a commercial these publications, whose only novelty was the fact that
12 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 15. Synthesis of DA epoxy resins.

polyesters were employed as substrates, as in the example the shape recovery cycle was conducted between room
of Scheme 16. temperature and 70 ◦ C, i.e., a temperature range which
In two very similar publications, multi-arm polylac- hardly affects their stability. In a similar vein, a four-arm
tic structures bearing terminal furan moieties were poly(␧-caprolactone) functionalized with terminal furyl
crosslinked by DA coupling with multifunctional heterocycles was crosslinked with a counterpart bearing
maleimides [57] and the thermoreversibility of the four maleimide end groups [58] and the ensuing dense
ensuing networks once again verified. The shape-memory network shown to display thermoreversibility through the
character of these materials was not a consequence retro-DA reaction. In a second study by the same group,
of the presence of DA adducts in their structure, since similar furan-modified semicrystalline polymers based on
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 13

Scheme 16. Monomers and macromonomer used in the DA polycondensations involving an aliphatic polyester.

poly(␧-caprolactone)-urethane chains were mixed with It took another decade before the topic was revived, this
an aromatic bismaleimide to generate thermoreversible time with a different approach, which called upon the reac-
networks [59], with “DA conversions” exceeding 99%. tion of two complementary poly(oxazoline)s, one bearing
This claim, based on FTIR analysis, seems overoptimistic, pendant furan motifs and the other maleimide counter-
since on the one hand IR spectroscopy is not sufficiently parts, with degrees of substitutions (DS) varying from 4
sensitive in this context to allow such conclusion to be to 21% in each case [62]. A series of DA couplings between
validated and, on the other hand, among all the very complementary polymers with similar DS were conducted
numerous preceding studies on this issue, none reported at room temperature in bulk films (Scheme 17), by casting
yields above 80–90% for the furan/maleimide DA reac- the furan and the maleimide polymers onto a glass slide.
tion in a polymerization system of any kind. The two The ensuing gels reached 90–97% network contents after
latter publications dealt also with shape memory effects, one week, provided the DS of both polymers was at least
but again these features were not associated with the 4%. The extent of their water swelling decreased as the DS
presence of DA adducts in the materials macromolecular increased, as expected, by the corresponding increase in
architecture. crosslink density.
The formation of thermoreversible networks by the DA Suspending the gels in a hot medium, chosen so as to
reaction of polymers with pendant furan and/or maleimide dissolve the original linear polymers, produced their total
heterocycles is by far the most widely studied type of solubilization within hours [62] and the 1 H NMR spec-
system within the scope of this review. Indeed, the very trum confirmed that the two polymers had been fully
first investigation involving the DA reaction between that released from one another thanks to the retro-DA reaction
diene/dienophile couple in macromolecular chemistry is (Scheme 18). The authors did not report any re-crosslinking
a report by Stevens and Jenkins about the crosslinking of of the two complementary polymers when their solution
poly(styrene) with maleimide side groups with a difuran was brought back to room temperature, probably because
compound, published in 1979 [60]. The authors however of their low concentration and hence a correspondingly
did not test the thermal reversibility of their gelled mate- slow rate of DA adduct formation, but the isolated polymers
rial. Canary and Stevens [61] completed this work a dozen were shown to react in the same bulk conditions as with
years later by showing that their DA networks were indeed the first network formation, thus confirming the recyclable
thermoreversible. character of the system.

Scheme 17. Network formation by the DA reaction at room temperature of polymer films bearing furan and maleimide pendant units.
14 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 18. Retro-DA reaction at 80 ◦ C, applied to the network shown in Scheme 17.

Ten years later Zewert and Harrington reported essen- in order to avoid the regeneration of the original adducts
tially the same results using the same complementary upon cooling, since in these conditions the freed phenyl-
polymers in the context of a study on materials for isoelec- maleimide reacted, instead, with the added furan trap. The
tric focusing electrophoresis [63], without providing any validity of this stratagem, first reported here, was fully con-
additional information on the system. firmed by the facts that the polymer recovered at room
This pioneering investigation [62] also became unique temperature was identical to that initially used and all the
in its approach, since most of the following studies con- phenylmaleimide introduced in the initial DA modifica-
centrated on systems involving a polymer bearing pendant tion, was now isolated in the form of its DA adduct with
DA motifs, dienes or dienophiles, reacting reversibly with 2-methylfuran. The left-hand side of Scheme 20 illustrates
bisdienophiles or bisdienes, respectively, to give thermally this model part of the study.
reversible networks. This research began with a modest The crosslinking experiments [65] indicated that even
yearly output, but has been gathering momentum in the with as little as 5% of furan-bearing monomer units in the
last several years. styrene copolymer, the addition of stoichiometric amounts
The role of the actual position of the furan hetero- of BMDP insured the quantitative formation of a gelled
cycle incorporated in different modes within a polymer material. The use of the trapping technique, implemented
chain was assessed in terms of its DA reactivity toward a here to the linear copolymers formed by the retro-DA reac-
maleimide partner [64]. Furan polyurethanes bearing the tion applied to the gels heated in suspension at 130 ◦ C,
ring as a pendant group or in 2,5- and 3,4-enchainments confirmed its mechanistic usefulness, since the copolymers
(the former in differently crowded environments, as shown isolated after cooling were identical to those employed at
in Scheme 19), were used to test this effect, together with the start of the experiments and the other product isolated
acrylic copolymers with pendant furan moieties sitting fur- was the bisadduct of BMDP with 2-methylfuran. The right-
ther away from the polymer backbone. As expected on first hand side of Scheme 20 illustrates this reversible network
principles based on steric impediment, the reaction rates formation.
with either N-methylmaleimide or N-phenylmaleimide The present proof of the efficient recyclability of poly-
decreased in the order shown in Scheme 19. These con- mer networks constituted a decisive contribution of the
clusions, although predictable, are important both because DA reaction between furan and maleimide heterocycles to
they indicate that even highly crowded furan rings can the realm of polymer chemistry as a source of functional
undergo the DA reaction, albeit suffering kinetic restric- materials.
tions, and because they provide useful indications about The sequel to this project was a similar investiga-
the choice of furan substitutions and the environment most tion in which the starting copolymers were elastomers
appropriate for efficient adduct formation. simulating conventional rubbers [66]. Two different
The study of the reversible crosslinking of styrene strategies were followed, viz. (i) linear macromolecules
copolymers incorporating variable proportions of pendant bearing pendant furan moieties (low-Tg acrylic copoly-
furan moieties was conducted using BMDP as the DA net- mers), to be crosslinked with an oligoether bismaleimide
work builder [65]. This investigation was preceded by a (Scheme 21), and (ii) linear macromolecules bearing
model system that called upon phenylmaleimide as the pendant maleimide moieties (low-Tg polysiloxane copoly-
DA reagent for the dangling furan heterocycles, so that mers) to be crosslinked with a siloxane difuran reagent
the resulting monoadducts could be clearly identified and (Scheme 22). Both crosslinkers were also characterized by
quantified from a spectroscopic analysis of the modified a high molecular flexibility. All these materials displayed
styrene copolymers. Furthermore, the occurrence of the the expected DA reactions leading to the correspond-
retro-DA reaction, applied to these materials in solution at ing networks, even with low contents of pending furan
130 ◦ C, with the release of phenylmaleimide, was verified or maleimide functions. The ensuing gels were submit-
by adding a large excess of 2-methylfuran to the system ted to thermal decrosslinking via the retro-DA reaction,
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 15

Scheme 19. Relative reactivity of furan heterocycle in their DA coupling with maleimides, as a function of their mode of enchainment in a macromolecular
structure.

in the presence of a trap, following the principle elabo- the polymer combination already described [62], was
rated previously [65], namely 2-methylfuran for (i) and used in conjunction with tetramethoxysilane to generate
ethylmaleimide for (ii). Both types of combinations were the hybrid IPN, whereas in the second [70], the authors
optimized to give excellent reversibility without detectable called upon the styrene copolymers reported by others
side reactions. [65], but crosslinked them with a mixed reagent bearing
Two important pieces of evidence were gathered in this one maleimide and three ethoxy groups attached to a
work. The first had to do with the fact that the TGA tracings silicon atom. This system operated therefore through both
of systems (ii) displayed a weight loss around 150 ◦ C (i.e.,
after the occurrence of the retroDA reaction) equivalent to
the stoichiometric amount of difuran compound used for
preparing the corresponding network, indicating its com-
plete retroDA release and subsequent evaporation [18a,67].
The second feature was related to the dynamic-mechanical
properties of the networks obtained from systems (i),
which exhibited the typical fall in the elastic modulus asso-
ciated with the glass transition and the subsequent rubbery
plateau, but with the major difference that at about 100 ◦ C
the modulus started to decrease drastically and the record-
ing stopped when the polymer turned into a viscous liquid,
as shown in Fig. 5, because of the retro-DA reaction [68].
Two publications from Chujo’s laboratory dealt with
the synthesis of interpenetrating organic–inorganic hybrid
Fig. 5. Variation of the elastic modulus (Pa) as a function of temperature
networks based on previously studied furan–maleimide for a DA network based on a low-Tg furan acrylic copolymer crosslinked
systems in conjunction with a silica network generated with an oligoether bismaleimide, as in Scheme 21 [68].
in situ by the sol–gel process. In the first study [69], © 2002 by permission from author.
16 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 20. Reversible DA reactions applied to pendant furan rings, using mono- and di-functional maleimides and the application of a trap to preserve
the products of the retro-DA reaction.

furan/maleimide DS and sol–gel reactions to generate copolymerization and on the atmospheric stability of the
transparent hybrid IPN materials. materials, which decreased with increasing contents of the
Huglin’s group devoted considerable attention to the furan comonomer. The authors however also carried out
DA reversible crosslinking of styrene–furfuryl methacry- some preliminary experiments related to the formation
late copolymers in the presence of BMDP [71]. The first of a network and to its thermal reversion. The second
part of this investigation [71a] concentrated on the actual contribution [71b] dealt with an ingenious approach
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 17

Scheme 21. Reversible crosslinking of low-Tg copolymers bearing pendant furan rings (n  m) with a low-Tg oligomeric bismaleimide, using a trap to
preserve the products of the retro-DA reaction.

to the kinetics of the retro-DA thermal breakdown of crosslinking by monitoring the progressive disappearance
the network inside the thimble of a Soxhlet extractor, of the maleimide moiety by UV and NMR spectroscopy,
using UV spectroscopy to monitor the reappearance of and provided an approximate value for the second-order
maleimide moieties with time at different temperatures rate constant at 25 ◦ C of (1–4) × 10−5 dm3 mol−1 s−1 . On the
(solvents with different boiling points). A clean-cut first whole, this contribution represents undoubtedly the most
order behavior gave an activation energy for the retro-DA comprehensive exploration of a single DA polymeriza-
reaction of 21 kJ mol−1 . Interestingly, no breakdown was tion system, which makes many previous and subsequent
detected at 64 ◦ C, the lowest temperature used, which reports look rather pale.
corroborates the practice of using 65 ◦ C as the highest Liu’s group examined the kinetics of the DA crosslink-
reasonable temperature for conducting the forward DA ing reaction between poly(amide)s bearing pendant
reaction between furan and maleimide functions. maleimide functions and a trifuran derivative in the tem-
The third aspect studied [71c] was the characteriza- perature range of 20–60 ◦ C, using FTIR spectroscopy [72].
tion of the networks in terms of mechanical, swelling and Second-order rate constants of 1–5 × 10−5 dm3 mol−1 s−1
thermal properties, which provided information about the were reported, with an activation energy of 32 kJ mol−1 ,
crosslink density, Young’s modulus and the occurrence of but regrettably no quantitative evidence was provided
the endothermic retro-DA reaction. The final part of this about these measurements. The properties of the ensu-
extensive approach [71d] looked into the kinetics of the DA ing gels were also assessed, including of course their
18 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 22. Reversible crosslinking of low-Tg copolymers bearing pendant maleimide rings (n  m) with a low-Tg difuran compound, using a trap to
preserve the products of the retro-DA reaction.

thermoreversible character. In a subsequent study, Liu furan rings and BMDP as crosslinking agent [74]. The only
and Chen [73] modified some of their maleimide-bearing qualitative feature distinguishing these studies from pre-
polyamides in order to append furan functions on them. vious counterparts was the fact that the copolymers were
The original polymer was then made to react with the synthesized by an ATRP process. The rest of the inves-
latter in order to induce the formation of the corresponding tigation was devoted to assessing various aspects, such
DA network. as the kinetics of the retro-DA reaction, the properties of
The crosslinked polyamides were characterized in the gels and their remendable character, without any sub-
terms of thermal and mechanical properties and, again, stantial conceptual novelty. The same can be said of two
the retro-DA reaction was exploited to show thermal contributions by Broekhuis’s group, who appended furan
reversibility and mendability, i.e., confirming features heterocycles to linear polyketones and crosslinked them
which had already been well established at the time of this with BMDP [75]. The title of the first study [75a] carried the
publications [72,73]. question “the next step to recycling thermoset polymers?”,
Kavitha and Singha published four papers between a surprising interrogation, considering that before 2009
2007 and 2010 dealing with reversible DA network forma- numerous laboratories had already provided a clear-cut
tion from linear acrylic copolymers incorporating pendant positive answer to this issue. In the conclusions of the
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 19

Scheme 23. Reversible DA formation of a hydrogel formed by the reaction of a furan copolymer with an oligomeric bismaleimide.

same publication [75a], the authors state “To the best of furan polymers with polymers bearing the O C C C C O
our knowledge, this system introduces a new and practi- dienophile [77], which was however not tested for ther-
cally applicable concept to recycle thermosetting polymers mal reversibility. The latest contribution by Wei’s group
through a Diels–Alder and Retro-Diels–Alder reaction to the topic of DA hydrogel deals with the other well-
sequence”, which is in stark contrast to ten years of accu- documented furan-polymer + maleimide polymer system
mulated evidence to that effect, most of it actually quoted in [78] and concentrates on the reversible swelling behavior
the references to their paper! The interest of these two con- of the networks as a function of temperature.
tributions lies in the thorough examination of the thermal An original addition to the realm of the DA reversible
(DSC) and static as well as dynamic mechanical properties crosslinking comes from a recent study of the introduc-
of the networks as a function of their crosslink density. tion of both furan and maleimide pendant groups onto an
Hydrogels generated by the DA reaction of various ethylene copolymer incorporating oxirane moieties [79],
water-soluble copolymers with pendant furan moieties are as shown in Scheme 24. The novelty here stems from the
the subject of a series of publications by Wei’s group [76]. fact that all operations, i.e., DA network formation and
The network formation was insured by a bismaleimide retro-DA decrosslinking were performed in the bulk poly-
bridged by an ethylene oxide oligomer and their retro- mers using conventional extrusion technologies and the
DA decoupling occurred at a growing rate as expected, corresponding chemical changes assessed in situ by torque
between 80 and 100 ◦ C in solvents such as DMF and DMSO, measurements and on thin films by FTIR spectroscopy. The
with no apparent return at 60 and 70 ◦ C, again as expected. reversibility of the reaction, verified over several temper-
Scheme 23 illustrates one such system. ature cycles, represents an important step forward in the
An interesting and surprising feature of all these sys- extension of this feasibility to the real world of polymer
tems is their resistance to disassembling in hot water [76]. processing.
The authors interpreted this behavior on the basis of a Wouters et al. looked at the application of DA reversible
higher rate of the forward DA reaction in water, but no crosslinking to coatings [80] and binders [81] using the by-
proof was provided for this postulate. The real question in then conventional systems based on acrylic copolymers
fact is not related to the kinetics of the adduct formation, with pendant furan motifs and DBMP. Self-healing pow-
but instead to the position of the DA equilibrium, which der coatings were developed and shown to give technically
a priori should not be so highly sensitive to the reaction viable results with excellent reproducibility throughout
medium. The DA hydrogel prepared a decade earlier in several cycles [80]. Similarly, transparent adhesives pre-
the seminal study discussed above [62] had been found to pared from various compositions displayed interesting
decrosslink within a few hours in a water/methanol mix- potential applications with reversible tenacity as a function
ture at 80 ◦ C, a fact not retained by the present authors. of temperature, thanks to the occurrence of the retro-DA
The issue remains therefore open to further investigation. reaction that ultimately allows delamination to take place
Another important point, ignored here, is the fact that smoothly [81].
the DA reaction had already been exploited in the late Shoichet et al. recently developed an original hydro-
1990s to prepare hydrogels, albeit through the reaction of gel by appending furan heterocycles onto hyaluronic
20 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 24. Reversible DA crosslinking within a polymer melt.

acid and thereafter crosslinking it by the DA reaction Partially acetalized poly(vinylalcohol) (PVA) bearing
with an oligoethylene oxide bismaleimide, as shown in pendant furan rings [83] was crosslinked with various bis-
Scheme 25 [82]. The characterization of the ensuing gel maleimides [84] and the ensuing networks were shown to
included swelling, biodegradation and cytocompatibility, display the expected thermal reversibility by the retro-DA
with results that suggested a high suitability for tissue engi- reaction, as monitored by DSC and FTIR spectroscopy. The
neering and regenerative medicine. The authors did not relevant contribution of this study is not related to the con-
look into the thermal reversibility of the hydrogel. firmation of the DA/retroDA cycle applied to a polyadduct

Scheme 25. Hydrogel synthesis through the DA reaction of furan-modified hyaluronic acid with a water-soluble oligomeric bismaleimide.
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 21

based on the furan/maleimide coupling, since in 2012 this thermodynamically driven endo–exo isomerization was
had become common knowledge in the field, but to the also closely inspected. This groundbreaking study empha-
use of a readily accessible furan copolymer, easily pre- sized that when planning to investigate a novel system, it
pared from furfural and PVA [83]. The authors measured is important to consider how it would fit within the trends
the water absorption of the networks, but did not consider associated with the different situations examined in this
the possibility of hydrolysis of the acetal groups borne by paper [86]. What remains to be seen is the role, if any, of
the modified PVA chains. the relative proportion of the two adduct stereoisomers in
a DA macromolecule on its properties.
5. Stereochemical effects
6. Dendrimers and star-like constructs
This important facet of the furan/maleimide DA reaction
has received much attention including the seminal work McElhanon’s group initiated the study of furan/
by Rulišek et al., evoked in the introduction, dealing with maleimide DA dendrimers and has pursued it in the last
the actual unsubstituted reagents [11]. Jegat and Mignard decade. In the original contribution [87], a central aro-
[85] studied the retro-DA reaction of the adducts of fur- matic core diverged through three DA adducts bearing two
furyl alcohol with N-phenylmaleimide, using the pure exo hydroxyl functions, which were etherified with different
stereoisomer or a 71/29 endo/exo mixture. When heated in aromatic branching moieties. Fig. 6 depicts the structure of
bulk, the onset of the thermal decoupling was some 25 ◦ C the third generation dendrimer. All structures were shown
higher for the exo isomer, with endo–exo isomerization to revert to the starting maleimide and furan dendrons
taking place around 115 ◦ C. When the adducts were incor- upon heating them in solution at 110 ◦ C, thanks to the retro-
porated into different polymer matrices, no changes were DA reaction. Reassembly took place at 65 ◦ C, albeit at a slow
observed in the absence of miscibility, whereas homoge- pace.
neous systems favored a decrease in the retro-DA reaction In a subsequent publication [88], a similar approach was
temperature. adopted, but using BMDP as a double dienophile, which
A thorough investigation was recently published on the was coupled with the same furan dendrons, which gave
role of stereoisomerism on the retro-DA reaction applied rise to first-to-fourth generation DA dendrimers possessing
to furan/maleimide adducts [86]. The authors first syn- thermal reversibility.
thesized a series of model adducts varying in the type of The latest addition to this small saga [89] introduces the
substituents appended on either heterocycle, and looked use of two click-chemistry mechanisms to build an origi-
into the role of these structural differences on the endo/exo nal macromolecular assembly made up of a central linear
thermal behavior during their retro-DA reaction, moni- DA polymer (prepared by standard A–A + B–B [89a], or fol-
tored by DSC and 1 H NMR spectroscopy. The endo adduct lowing the A–B principle discussed above [89b]), which
was found to decouple at temperatures which were always showed the expected thermal reversibility, from whose
30–50 ◦ C lower than those associated with the reversion of monomer units stem two dendritic structures assembled
the exo isomer (typically 90–100 and 120–140 ◦ C, respec- by the alkyne-azide Huisgen click reaction. Scheme 26
tively), but with little influence by the specific structure. sketches the strategy followed to build and depolymerize
An acrylic copolymer bearing pendant furan rings was one of these dendronized architectures made up of a cylin-
then used as a macroreagent for the DA reaction with der (linear DA polymer) on which regularly spaced conical
the monofunctional maleimides and the retro-DA reac- macromolecules are appended.
tion again followed with the ensuing polyadducts. The Glassy networks incorporating electro-optic chro-
results indicated that with aliphatic maleimides, the tem- mophores were prepared using different combinations
peratures associated with the retro-DA reaction of the based on three dendritic macromonomers with comple-
isomers were similar to those measured for the model com- mentary DA termini, i.e., either furan heterocycles, or
pounds, whereas with N-phenylmaleimide, the endo and maleimide dienophiles [90]. A high electro-optic activity
exo stereoisomers underwent the retro-DA reaction at tem- of 150 pm V−1 was attained by optimizing the monomer
peratures too close to be distinguished, viz. around 120 ◦ C. composition and was preserved up to 130 ◦ C. The authors
The reaction of the same copolymers with bis- did not comment about the reasons for the dramatic failure
maleimides yielded the expected DA networks, whose of the materials between 130 and 150 ◦ C and seemed to be
retro-DA behavior showed a general increase in the onset unaware of the occurrence of the retro-DA reaction at these
temperatures, particularly with the aromatic crosslinker, temperatures, which was the obvious culprit, responsible
which again gave a single transition for both isomers [86]. for disassembling the network and regenerating the three
These results indicated that the reduced chain mobility dendritic monomers.
associated with the network structure tended to retard Two dendrimers bearing different structures and incor-
the occurrence of the adduct decoupling. The next step porating respectively a furan and a maleimide tail were
consisted in preparing linear DA polymers based on the joined by the DA reaction to give an unsymmetrical dou-
A–A + B–B approach using a single difuran and three bis- ble dendrimer [91], whose sides were held together by
maleimides. Their depolymerization behavior simulated the ensuing adduct and whose original elements could be
that of the model compounds in the three instances sug- recovered through its retro-DA reaction.
gesting that viscosity did not play a significant role on The combined use of alternating alkyne-azide and DA
the onset of the retro-DA reaction. In all the specific DA click chemistry was applied to the divergent construc-
combinations examined here, the important aspect of the tion of an original dendrimer [92]. The starting reagents
22 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Fig. 6. The first dendrimer based on furan/maleimide reversible DA coupling.

included a difuran molecule bearing an azide group, which hydrophobic particles to migrate to the surface of the film
was coupled with an aromatic trialkyne to prepare a (Scheme 28), which enabled the dispersion/migration of
first-generation dendrimer with six furan end groups particulate additives to be controlled. In a second investi-
(Scheme 27). This was then converted into a DA dendrimer gation [94], silica nanoparticles were grafted with a short
by its reaction with a meleimide incorporating two alkyne moiety bearing a maleimide end group, which was then
functions, which was finally coupled with the difuran azide DA coupled with a furan-terminated PEO. The introduction
to produce the third generation structure possessing 24 of these modified nanoparticles into a PMMA matrix pro-
furan termini. The DA adducts were disassembled by heat- duced homogeneously dispersed transparent films, which
ing the dendrimers in DMSO at 105 ◦ C. The application of turned opaque upon heating because the retro-DA reac-
this strategy to the preparation of thermoresponsive nano- tion released the PEO chains and allowed the particles to
materials seems quite promising. aggregate.
Beyer’s group exploited the reversible furan/maleimide A model DA system was successfully tested to show the
DA reaction in two interesting applications in which feasibility of the reversible release of arms from a star-
star-decorated nanoparticles were submitted to radical shaped polymer [95]. A trifuran urea was coupled with
modifications associated with the retro-DA reaction. In N-butylmaleimide via the DA reaction and the ensuing star
the first study [93], gold nanoparticles were grafted molecule was liberated of its maleimide arms by heating it
with a styrene–PEO block copolymer in which the two at 90 ◦ C. The cycle was repeated several times to assess the
blocks were joined through a furan/maleimide adduct reproducibility of the operation. Regrettably, the authors
(Scheme 28) and dispersed in a polar PEO film. Upon heat- did not extend this predictable behavior to polymeric arms,
ing, the PEO blocks were released, inducing the resulting i.e., maleimide-terminated macromolecules.
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 23

Scheme 26. Building a “perpendicular” macromolecular architecture based on two click chemistries and exploiting the thermally reversible character of
the DA reaction. G-n represents different generations of dendronized structures normal to the linear DA polymer.

Shoichet’s group [96] showed how to generate immune- to be quite effective in capturing and thermally releasing
polymeric nanoparticles by preparing macromolecular maleimide compounds under conditions compatible with
micelles surface-decorated with furan moieties, which intermediate synthetic steps. Examples of such processes
were then coupled with maleimide-modified antibodies included peptide coupling techniques and the synthesis of
through the DA reaction. This fine biochemical application a variety of complex alcohols by epoxide ring opening.
obviously does not call for the exploitation of the corre- McElhanon et al. [98] proposed a clever trick aimed at
sponding retro-DA reaction. removing simply and efficiently the roles played by a sur-
factant in an aqueous medium, when these roles are no
7. Miscellaneous more required. They synthesized anionic surfactant struc-
tures in which the polar and non-polar moieties were
This section discusses a number of applications of the joined by a furan/maleimide DA adduct. Their classical
thermoreversible furan/maleimide DA reaction, some of features of reducing the surface tension and generating
which fall outside its strict utilization in macromolecular micelles were thoroughly assessed and then the corre-
synthesis, but that are relevant to the topic, particularly sponding aqueous systems heated at 95 ◦ C to initiate the
because they illustrate the breadth of its scope in terms of retro-DA reaction of the linker. Within roughly 1 h, the sur-
the development of novel functional materials and nano- face tension grew from about 55 mN m−1 to the water value
technology. of 72 mN m−1 and, in the case of media containing micelles,
A study describing the use of this reaction for solid- loss of these aggregate structures within 2 h was detected
phase synthesis [97], called upon the preparation of a by SANS measurements. The splitting of the two compo-
furfuryl-substituted poly(styrene) resin, which was shown nents of the surfactants by the total decoupling of the DA
24 A. Gandini / Progress in Polymer Science 38 (2013) 1–29

Scheme 27. Synthesis of the first generation dendrimers with external furan decoration.

adduct, thus destroying their function, was clearly proven the maleimide copolymers were not contaminated by the
by these results. Recombination of the fragments by the DA interference of side reactions involving free radicals and
reaction was made extremely unlikely because of the very the heterocycle.
low concentrations involved and because the furan-bearing Gold nanoparticles are at the forefront of the nanopan-
C12 hydrophobic fragment was insoluble in water. demic and the DA reaction has found its way in this context.
Dispinar et al. [99] made use of the adduct to protect the Conjugated polymers bearing pendant furan rings were DA
maleimide functions during the synthesis and copolymer- coupled with gold nanospheres decorated with maleimide
ization of an acrylic monomer bearing that dienophile. The moieties to generate organic-inorganic nanohybrids [100],
retro-DA full release of the furan molecule was achieved in which the electronic interactions between the gold par-
by heating the materials at 125 ◦ C after their isolation, as ticles and the conjugated macromolecules were highly
shown by the TGA weight loss. This stratagem insured that enhanced. In a very similar vein, the same group reported

Scheme 28. Gold nanoparticles decorated with thermally labile PEO branches and their migration after the retro-DA reaction, which made them hydropho-
bic.
 A. Gandini / Progress in Polymer Science 38 (2013) 1–29 25

the linking through the DA reaction of gold nanoparticles The claimed DA crosslinking of cellulose furoate with
decorated with furan moieties with p-phenylenevinylene 1,6-bis-(N-maleimido)hexane [107] was not supported by
oligomers bearing terminal maleimide functions [101]. convincing spectroscopic evidence. Furthermore, a model
Yamashita et al. [102] studied the release of PEO reaction of the bismaleimide with methyl-2-furoate was
chains from gold nanorods on which they had anchored reported to give 20% yield after 4 days at 70 ◦ C and there-
them via a DA adduct. They synthesized a PEO with a after slow down even further, leaving doubts about the
maleimide end group and coupled two of these macro- actual nature of that reaction, whose features did not
molecules by the DA reaction with furfuryl disulfide. resemble those of a typical DA behavior. Furan–carbonyl
The ensuing diblock macromolecules were split by tris(2- moieties are known for their lack of reactivity as dienes in
caboxyethyl)phosphine hydrochloride to give PEO chains the DA coupling and this probably explains the anomalous
with a terminal DA adduct bearing an SH group, which was results found in this study.
used to attach them to the gold surface. Near IR light was The recent publication of an undergraduate laboratory
then shined on the nanorods to heat them and thus induce experiment based on the thermally reversible DA reaction
the retro-DA reaction that released the PEO-maleimide of BMDP with a tetrafuran compound [108] was conceived
chains. The aim of this study focused on medical applica- to illustrate the self-healing properties of the ensuing net-
tions such as the controlled release of drugs. work. In other words, the topic of this review has reached
The control of surface energy constitutes another the status of a concept recognized as representative of
promising application of the thermally reversible issues on the borderline between organic chemistry and
furan/maleimide DA reaction. Dirlam et al. [103] attached materials science and technology.
polar grafts terminated by furan moieties to the surface
of a glass slide using siloxane chemistry and then coupled
8. Concluding remarks and perspectives
them with perfluorinated compounds bearing maleimide
functions through the DA reaction. As a result, the ensuing
The topic of this survey is in full bloom in both funda-
modified surface displayed a strong hydrophobic character
mental and technological areas and is branching toward a
with water contact angles close to 100◦ , but the subse-
growing number of different domains and applications. As
quent application of the retro-DA reaction by refluxing
with most novel and promising research fields, redundan-
toluene removed the fluorinated maleimide molecules
cies and “rediscoveries” accompany original contributions,
and regenerated a hydrophilic surface.
hence the sometime critical tone of the review.
The enhancement of interfacial adhesion between
matrix and fibers in macromolecular composites is an
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