molecules

Review
Bio-Based Aromatic Epoxy Monomers for
Thermoset Materials
Feifei Ng, Guillaume Couture, Coralie Philippe, Bernard Boutevin and Sylvain Caillol *
Institut Charles Gerhardt—UMR 5253, CNRS, Université de Montpellier, ENSCM, 8 rue de l’Ecole Normale,
34296 Montpellier, France; feifeing.fr@gmail.com (F.N.); Guillaume.couture@enscm.fr (G.C.);
coralie.philippe@enscm.fr (C.P.); bernard.boutevin@enscm.fr (B.B.)
* Correspondence: sylvain.caillol@enscm.fr; Tel./Fax: +330-467-144-327

Academic Editors: Thomas Farmer and James H. Clark

Received: 24 November 2016; Accepted: 10 January 2017; Published: 18 January 2017

Abstract: The synthesis of polymers from renewable resources is a burning issue that is actively
investigated. Polyepoxide networks constitute a major class of thermosetting polymers and
are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding
mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after
curing, they are used in structural applications as well. Most of these thermosets are industrially
manufactured from bisphenol A (BPA), a substance that was initially synthesized as a chemical
estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost
of fossil resources and the non-recyclability of thermosets implies necessary changes in the field
of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both
from the academic and industrial sides. This review proposes to give an overview of the reported
aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules
that could be obtained from transformed biomass. After a reminder of the main glycidylation
routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review
will provide a brief description of the main natural sources of aromatic molecules. The different
epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic
poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous
aromatic rings and epoxy groups.

Keywords: epoxidation; aromatic; epichlorohydrin; tannin; lignin; cardanol

1. Introduction
Amidst materials widely used in plastic industry nowadays, thermosets (or thermosetting
polymers) represent about 20% of plastic production [1]. They are formed from a liquid or solid
mixture of various ingredients including at least one or more monomers. One of these monomers
at least exhibits a functionality equal or higher than three, thus enabling the creation of a solid
three-dimensional non-fusible network via an external action such as heating or UV irradiation [2].
Thermosets include a wide range of reactive systems such as phenolic and urea formaldehyde
resins, unsaturated polyesters, and polyepoxides, the latter accounting for nearly 70% of the market.
Polyepoxides are one of the most versatile class of compounds with diverse applications, especially
coatings, which dominate the market, but also water containers, automotive primer, printed circuit
boards, semiconductor capsules, adhesives, and aerospace composites. The global production of
epoxy prepolymers is estimated to reach 3 million tons by 2017 for a market of US$ 20 billion in
2015. This success arises from the excellent mechanical strength and toughness, outstanding chemical,
moisture, and corrosion resistance of the epoxy thermosets [3,4]. This list does not include various
interesting process-related characteristics such as: the absence of volatile products emitted during the

Molecules 2017, 22, 149; doi:10.3390/molecules22010149 www.mdpi.com/journal/molecules

Molecules 2017, 22, 149 2 of 48

polymerization reaction, the large choice of monomers available or the high adhesion properties to a
variety of surfaces.
Over 90% of these epoxy materials are based on bis(4-hydroxyphenylene)-2,2-propane, known
as bisphenol A (BPA), a petrol-based molecule first synthesized in the 1890s and used as a synthetic
oestrogen [5]. Aromatic compounds are widely used in organic materials for their stability, their
toughness, and above all their ability to structure the matter by π-stacking, thus allowing BPA to
confer good thermal and mechanical properties to the epoxy thermosets. Commercialized for more
than 50 years, BPA, mainly through its epoxy form DiGlycidylEther of Bisphenol A (DGEBA), is
nowadays spread in many coatings, adhesives, laminates and composites, but also many domestic
or even health related-products such as plastic bags, food containers and metal cans, dental sealants,
soaps and lotions [6,7].
However, epoxy thermosets are sensitive to hydrolysis, which may cause BPA to leach, leading to
widespread human exposure [6–9]. Unfortunately, it has been classified as carcinogen mutagen and
reprotoxic (CMR), and is recognized as an endocrine disruptor [10]. Consequently, many governments
have recently hardened the legislation regarding the production and use of BPA, especially in baby’s
bottles, food containers and medical supplies [11,12]. Moreover, BPA is synthesized from oil-based
phenol and the 3D chemically crosslinked networks of thermosets prevent them from being recycled
by heating. The awareness on BPA toxicity combined with the limited availability and volatile cost
of fossil resources, and the non-recyclability of thermosets implies necessary changes in the field of
epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from
the academic and industrial sides. Over the past decades, many bio-based resources have been tested
as potential candidates for replacing BPA in epoxy resins, but very few of them have reached the
commercialization step. Among these, epoxidized natural oils [13–15] and modified cardanol [16] are
the only two types of epoxy resins based on natural and non-toxic precursors, commercially available
in the market. However, the low reactivity of the epoxy groups along their aliphatic backbone [1]
and the low glass transition temperature caused by the alkyl chain prevent them from competing
with BPA-based materials with their high Tg values and glassy moduli [17]. For this reason, many
researches have been devoted to using glycidylated aromatic bio-based materials as substitutes for
BPA. Very interesting and exhaustive reviews have recently been published on bio-based precursors
for thermosets and their hardeners [1,18–21], but to our knowledge, none of them focuses especially
on aromatic epoxy monomers based on biomass resources. In fact, only aromatic poly-epoxides seem
to be able to compete with DGEBA in terms of thermo-mechanical properties, making them of primary
interest for renewability.
Thus, the present review proposes to give an overview of the reported aromatic multifunctional
epoxide building blocks synthesized from biomass or from molecules that could be obtained from
transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent
knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main
natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from
simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds,
and finally to derivatives possessing numerous aromatic rings and epoxy groups. For each one, the
curing agent used and the thermal properties (especially Tg and thermal degradation) of the crosslinked
material will be given along with their DGEBA-based counterparts if available. The potential toxicity
of the epoxy precursors will also be mentioned. Tables gathering all these results will be given at the
end of each part for comparative purposes.

2. Epoxidation Methods and Processes

Poly-functional epoxy compounds are very reactive building blocks and can lead to materials
by chain-growth polymerization or crosslinking with anhydrides, phenols and amines. They are
generally prepared by direct glycidylation, as showed in Scheme 1 [1,22,23]. It consists in reacting
an alcohol or amine derivative with epichlorohydrin (ECH) in the presence of an alkylammonium
Molecules 2017, 22, 149 3 of 48

halide as a phase transfer catalyst, such as benzyltriethylammonium chloride, tetrabutylammonium

bromide or cetyltrimethyl ammonium chloride. Sometimes, epibromohydrin is used instead of its
chloride analogue
Molecules 2017, 22, 149 [24]. A sodium or potassium hydroxide post-treatment is usually applied in same 3 of 47
pot to increase the number of epoxy rings. In fact, the phenolic oxygen may displace the chlorine
Molecules 2017, 22, 149 3 of 47
atom to product
desired directly viayield
a Sthe
N2 desired product
mechanism, via athe
or open SN 2epoxy
mechanism, or open
ring causing thethe epoxy ring
formation of acausing the
chlorinated
formation of a can
derivative that chlorinated
be closedderivative
by a strongthat
basecan be closed
through a SNiby a strong base
mechanism through
(Scheme a S iSmechanism
2) [25,26]. Ni stands for
desired product via a SN2 mechanism, or open the epoxy ring causing the formation ofN a chlorinated
(Scheme 2) [25,26].
Substitution SN i stands
Nucleophilic for Substitution
internal Nucleophilic
and is a nucleophilic internalmechanism
substitution and is a nucleophilic
that impliessubstitution
a retention
derivative that can be closed by a strong base through a SNi mechanism (Scheme 2) [25,26]. SNi stands for
mechanism that implies a retention of configuration.
of configuration.
Substitution Nucleophilic internal and is a nucleophilic substitution mechanism that implies a retention
of configuration.

Scheme
Scheme1. Synthesis of epoxyofderivatives
1. Synthesis from phenolfrom
epoxy derivatives or aniline by direct
phenol glycidylation
or aniline with epichlorohydrin.
by direct glycidylation
with epichlorohydrin.
Scheme 1. Synthesis of epoxy derivatives from phenol or aniline by direct glycidylation with epichlorohydrin.

Scheme 2. Mechanism of coupling between phenolic compounds and epichlorohydrin (ECH) in the
presence of a phase transfer catalyst (QX) [1,27].
Scheme 2.
Scheme 2. Mechanism
Mechanism of of coupling
coupling between
between phenolic
phenolic compounds
compounds and
and epichlorohydrin
epichlorohydrin (ECH)
(ECH) in
in the
the
presence
presence of a phase transfer
of aglycidylation catalyst
phase transfer ofcatalyst(QX)
(QX)[1,27].
[1,27].
The direct phenol has proven to yield several possible side products [28–32]
including chlorinated and diol derivatives (Figure 1). Furthermore, the higher reactivity of benzoic acid
The direct glycidylation of phenol has proven to yield several possible side products [28–32]
may The
lead direct glycidylation
to an opening of the of phenol
epoxy has proven
via both to yieldleading
carbon atoms, severaltopossible side products
new chlorinated [28–32]
(B2), diol (B3)
including chlorinated and diol derivatives (Figure 1). Furthermore, the higher reactivity of benzoic acid
including
and oxetanechlorinated
ring (B1)and diol derivatives
side-products (Figure
[33–37]. 1). Furthermore,
Another the higher reactivity
important side-product of benzoic
observed during the
may lead to an opening of the epoxy via both carbon atoms, leading to new chlorinated (B2), diol (B3)
acid may leadstep
glycidylation to anwith
opening of the epoxyisvia
epichlorohydrin a both carbon atoms,
benzodioxan leading
derivative to newby
obtained chlorinated (B2), diol
an intra cyclization
and oxetane ring (B1) side-products [33–37]. Another important side-product observed during the
(B3) and oxetane
occurring with tworing (B1) side-products
phenolic [33–37].
groups in ortho Another
position (Schemeimportant
3). side-product observed during the
glycidylation step with epichlorohydrin is a benzodioxan derivative obtained by an intra cyclization
glycidylation step with epichlorohydrin is a benzodioxan derivative obtained by an intra cyclization
occurring with two phenolic groups in ortho position (Scheme 3).
occurring with two phenolic groups in ortho position (Scheme 3).

Figure 1. Common side-products of the direct glycidylation of phenol (A1–A3) and benzoic acid (B1–B3).
 The direct glycidylation of phenol has proven to yield several possible side products [28–32]
including chlorinated and diol derivatives (Figure 1). Furthermore, the higher reactivity of benzoic acid
may lead to an opening of the epoxy via both carbon atoms, leading to new chlorinated (B2), diol (B3)
and oxetane ring (B1) side-products [33–37]. Another important side-product observed during the
glycidylation
Molecules 2017, 22,step
149 with epichlorohydrin is a benzodioxan derivative obtained by an intra cyclization
4 of 48
occurring with two phenolic groups in ortho position (Scheme 3).

Figure 1.
Figure 1. Common
Commonside-products of the
side-products direct
of the glycidylation
direct of phenol
glycidylation (A1–A3)
of phenol and benzoic
(A1–A3) and acid (B1–B3).
benzoic acid
(B1–B3).
Molecules 2017, 22, 149 4 of 47

Scheme
Scheme 3.
3. Products
Productsobtained
obtainedduring
duringthe
theglycidylation
glycidylationofofprotocatechuic
protocatechuicacid
acidwith
withepichlorohydrin
epichlorohydrin[38].
[38].

To avoid these drawbacks, Meurs et al. [39] developed a process to obtain glycidyl derivatives from
To avoid these drawbacks, Meurs et al. [39] developed a process to obtain glycidyl derivatives
phenol, glycidol and propylene carbonate but it requires the use of high temperatures in autoclave and
from phenol, glycidol and propylene carbonate but it requires the use of high temperatures in autoclave
relatively harsh conditions. A two-step synthesis can also be used to form epoxy compounds: it involves
and relatively harsh conditions. A two-step synthesis can also be used to form epoxy compounds:
the O- or N-allylation of the corresponding alcohol or amine derivatives using an allyl halide, followed
it involves the O- or N-allylation of the corresponding alcohol or amine derivatives using an allyl
by the oxidation of the resulting double bond (Scheme 4). Unfortunately, allyl chloride and allyl bromide
halide, followed by the oxidation of the resulting double bond (Scheme 4). Unfortunately, allyl chloride
are both toxic derivatives. Moreover, hydrogen peroxide exhibitis low reactivity toward allyl ether
and allyl bromide are both toxic derivatives. Moreover, hydrogen peroxide exhibitis low reactivity
oxidation except at high concentrations or in the presence of metal transition catalysts [40]. The use of
toward allyl ether oxidation except at high concentrations or in the presence of metal transition
stronger, more toxic peracids such as m-chloroperbenzoic acid (mCPBA) is sometimes considered, but
catalysts [40]. The use of stronger, more toxic peracids such as m-chloroperbenzoic acid (mCPBA)
Aouf et al. [22] found that an excess of peracid is also required and the m-chlorobenzoic acid formed
is sometimes considered, but Aouf et al. [22] found that an excess of peracid is also required and
during the oxidation of allylated gallic acid is difficult to eliminate. The epoxidation of allyl groups by
the m-chlorobenzoic acid formed during the oxidation of allylated gallic acid is difficult to eliminate.
potassium peroxymonosulfate (also known as Oxone) can be considered a sustainable pathway. It is
The epoxidation of allyl groups by potassium peroxymonosulfate (also known as Oxone) can be
based on the Shi epoxidation, which uses a fructose-derived organocatalyst with Oxone and ketones to
considered a sustainable pathway. It is based on the Shi epoxidation, which uses a fructose-derived
generate in situ dioxiranes [41], which are strong epoxidation agents. However, the epoxidation of
organocatalyst with Oxone and ketones to generate in situ dioxiranes [41], which are strong epoxidation
electron-deficient alkenes such as allyl groups by dioxiranes can be very slow [42–44]. The reaction may
agents. However, the epoxidation of electron-deficient alkenes such as allyl groups by dioxiranes can
require the use of ketones bearing highly electroattractive groups such as 1,1,1-trifluoroacetone to
be very slow [42–44]. The reaction may require the use of ketones bearing highly electroattractive
increase the overall yield [22,45]. Enzymatic catalysts have also been developed as greener alternatives
groups such as 1,1,1-trifluoroacetone to increase the overall yield [22,45]. Enzymatic catalysts have
for the oxidation of carbon-carbon double-bonds. First developed to replace the Prileshajev reaction
also been developed as greener alternatives for the oxidation of carbon-carbon double-bonds. First
applied at an industrial scale to produce epoxy vegetable oils [46], one of these catalyst (immobilized
developed to replace the Prileshajev reaction applied at an industrial scale to produce epoxy vegetable
lipase B from Candida antarctica (Novozym 435)) has also been used by Aouf et al. [40] to obtain epoxy
gallic acid and vanillic acid from their allylated precursors in high yields.
potassium peroxymonosulfate (also known as Oxone) can be considered a sustainable pathway. It is
based on the Shi epoxidation, which uses a fructose-derived organocatalyst with Oxone and ketones to
generate in situ dioxiranes [41], which are strong epoxidation agents. However, the epoxidation of
electron-deficient alkenes such as allyl groups by dioxiranes can be very slow [42–44]. The reaction may
require the use of ketones bearing highly electroattractive groups such as 1,1,1-trifluoroacetone to
Molecules 2017, 22, 149 5 of 48
increase the overall yield [22,45]. Enzymatic catalysts have also been developed as greener alternatives
for the oxidation of carbon-carbon double-bonds. First developed to replace the Prileshajev reaction
applied
oils [46],atone
anofindustrial scale to
these catalyst produce epoxy
(immobilized vegetable
lipase oils [46],antarctica
B from Candida one of these catalyst 435))
(Novozym (immobilized
has also
lipaseused
been B from Candida
by Aouf antarctica
et al. (Novozym
[40] to obtain epoxy435)) has
gallic also
acid been
and usedacid
vanillic by Aouf
from et al. [40]
their to obtain
allylated epoxy
precursors
gallic
in highacid and vanillic acid from their allylated precursors in high yields.
yields.

Scheme 4.
Scheme 4. Synthetic
Syntheticpathway
pathwaytotoobtain
obtainepoxy
epoxyfrom phenol
from oror
phenol aniline using
aniline allyl
using halide
allyl andand
halide oxidation.
oxidation.

Overall, the direct glycidylation remains the main synthetic pathway used for the industrial
Overall, the direct glycidylation remains the main synthetic pathway used for the industrial
synthesis of Diglycidyl Ether of Bisphenol A, as it allows the recovery of both monomers and oligomers
synthesis of Diglycidyl Ether of Bisphenol A, as it allows the recovery of both monomers and oligomers
for tunable properties [23,47]. By reacting bisphenol A with a controlled excess of epichlorohydrin, the
for tunable properties [23,47]. By reacting bisphenol A with a controlled excess of epichlorohydrin, the
“taffy” process yields either monomers or short oligomers of DGEBA (Scheme 5). To increase the chain
“taffy” process
Molecules
yields either monomers or short oligomers of DGEBA (Scheme 5). To increase the5chain
length of2017,
the 22, 149
oligomers, “advancement” (with solvent) or “fusion” (without solvent) processes can of 47
be
length of the oligomers, “advancement” (with solvent) or “fusion” (without solvent) processes can
be chosen.
chosen. They
They both
both consist
consist in in reacting
reacting BPABPA with
with anan excess
excess of of a pre-synthesized
a pre-synthesized DGEBA
DGEBA monomer
monomer to
toextend
extendthethechain.
chain.“Fusion”
“Fusion”process
processisisgenerally
generallypreferred
preferredfor
forthe
the industrial
industrialproduction
productionofof DGEBA
DGEBA
oligomers
oligomersas asthe
thepurification
purification steps are
are easier
easierand
andthe
thechlorine
chlorinecontent
contentofof
thethe final
final product
product is lower
is lower than
than in
inthe
thecase
case of the “taffy” process, which requires an excess of epichlorohydrin.
of the “taffy” process, which requires an excess of epichlorohydrin.

Scheme 5. Two main industrial processes for the synthesis of monomers and oligomers of diglycidyl
Scheme 5. Two main industrial processes for the synthesis of monomers and oligomers of diglycidyl
ether of vanillyl alcohol (DGEBA): (i) the taffy process with a controlled excess of epichlorohydrin and (ii)
ether of vanillyl alcohol (DGEBA): (i) the taffy process with a controlled excess of epichlorohydrin and
the advancement/fusion process using an excess of a pre-synthesized DGEBA monomer.
(ii) the advancement/fusion process using an excess of a pre-synthesized DGEBA monomer.

In terms of sustainability, both bisphenol A and epichlorohydrin used for the synthesis of DGEBA
In terms of sustainability, both bisphenol A and epichlorohydrin used for the synthesis of DGEBA
are mostly oil-based. BPA is obtained from reaction of acetone and phenol and epichlorohydrin is
are mostly oil-based. BPA is obtained from reaction of acetone and phenol and epichlorohydrin
synthesized in two steps by reacting hypochlorous acid on allyl chloride and then treating the alcohol
ismixture
synthesized in two
obtained with steps by base
a strong reacting hypochlorous
[48]. In acid on allyl
2007, Solvay designed chloride and
the EPICEROL then treating
TM process to produce the
alcohol mixture obtained with a glycerol,
strong base TM
epichlorohydrin from bio-based thus[48]. In 2007,
allowing Solvaythe
to reduce designed thefossil
content of EPICEROL process
resources used for
toDGEBA
produce epichlorohydrin from bio-based glycerol, thus allowing to reduce the
production [49–53]. However, the percentage of carbon atoms in the oligomers coming from content of fossil
resources
ECH is low, used formaking
thus DGEBAtheproduction [49–53].
impact limited. However,whatever
Furthermore, the percentage
syntheticofpathway
carbon atoms in the
or process is
oligomers coming from ECH is low, thus making the impact limited. Furthermore, whatever
chosen, reagents (e.g., epichlorohydrin and allyl halides) are all carcinogen agents (H350). Allyl bromide synthetic
pathway or toxic
is also very process is chosen,
for the reagents
environment. The(e.g., epichlorohydrin
toxicity of these reactionsand
is aallyl
true halides)
issue, andare all carcinogen
alternatives have
agents
to be found over time. Although the production of epoxides is generally well-controlledreactions
(H350). Allyl bromide is also very toxic for the environment. The toxicity of these by the
ismanufacturer
a true issue, and
and alternatives
the resulting have
resinstoand
be found over
materials dotime. Although
not exhibit the production
the toxicity of these of epoxides
reactants, theis
intrinsic toxicity of BPA remains.

3. Toxicity of Bisphenol A and Regulations

Bisphenols (BPs) are part of the common class of endocrine disruptors because of their significant
Molecules 2017, 22, 149 6 of 48

generally well-controlled by the manufacturer and the resulting resins and materials do not exhibit the
toxicity of these reactants, the intrinsic toxicity of BPA remains.

3. Toxicity of Bisphenol A and Regulations

Bisphenols (BPs) are part of the common class of endocrine disruptors because of their significant
hormonal activity, with Bisphenol A being the most famous of them. In fact, BPA exhibits one of
the highest production volume of chemicals worldwide [7], with a manufacture of approximately
3.8 million tons per year in 2006 [54]. About 80% of the global production of BPA is used for the
synthesis of polycarbonate, 18% for epoxy resins and the remainder for other applications, such
as food containers, paper products (e.g., thermal receipts), water pipes, toys, medical equipment,
and electronics [6,7]. As a consequence, human beings and environment are constantly exposed to
BPA: it has been detected in 95% of human urine samples, which indicates that this compound may
leach into food or water [7–9,55]. Furthermore, several studies found that BPA is present in high
prevalence in fetuses and infants [7,8,56] and has undeniably an impact on human health leading
to precocious puberty, cancer, diabetes, obesity, neurological disorders, and so on. Theoretical and
experimental studies can be carried out to forecast the potential toxicity of a compound or to determine
the different types of interactions between this compound and estrogen receptors. For example, the
“read-across” method, based on analogies between substances is currently developing. It first consists
in gathering data on the physical and biological properties of chemicals exhibiting a structure similar
to the target molecule. Then, by taking into account previously observed trends, it is considered
possible to extrapolate on the target molecule’s behavior [57]. QSAR (Quantitative Structure Activity
Relationship) models enable a qualitative and quantitative determination of the endocrine activity
in terms of affinity, and give some information about the underlying mechanism [58]. Recently,
Delfosse et al. [59] described for the first time the mode of action of BPA at the molecular scale and
developed a bio-informatics tool to predict the interactions between bisphenols and the target receptors
(estrogen receptors (ERs) or other members of the nuclear hormone receptor family). Numerous
studies demonstrated that bisphenol A has two major modes of actions: steroid related mode and
epigenetic mode. Concerning the latter, Dolinoy et al. [60] have shown the ability of BPA to alter
DNA methylation. Regarding the steroid related mode, BPA can act as an estrogen agonist when
it binds to nuclear estrogen receptors (ERα and ERβ) [61–64]. More recently, Takayanagi et al. [65]
demonstrated that BPA also binds to the estrogen-related receptor-γ (ERRγ) with high constitutive
activity. Furthermore, BPA also behaves as an androgen receptor antagonist (AR) which affects the
activation and function of the AR [66,67]. According to many lines of evidence, BPA acts as an
endocrine disruptor even at low doses. A review, based on hundreds of studies, concluded that there
is sufficient evidence for low dose effects of BPA. Indeed, for these studies, authors used doses below
those used for traditional toxicological studies, and found nonmonotonic dose-response curves [68].
Bisphenols are composed of two phenols linked by a central carbon atom, which in the case of
BPA bears two additional methyl groups (Figure 2B). These structural features make BPA able to mimic
the natural estrogen 17β-estradiol (Figure 3), in terms of binding ability to estrogen receptors [69,70].
In fact, the main characteristics of the natural ligands required for the steroid activity are the presence
of phenol groups on a hydrophobic backbone [71,72]. A recent paper has demonstrated that all
the structural elements of BPA are prerequisite for binding the estrogen-related receptor-γ (ERRγ),
especially the two phenolic and methyl groups [10]. Firstly, the authors demonstrated that the phenol
structure of BPA is an essential element to bind ERRγ and only one of the two phenolic hydroxy groups
is required for the full binding. Nevertheless, the presence of a second oxygen-based group increases
the steroid activity [73].
al. [65] demonstrated that BPA also binds to the estrogen-related receptor-γ (ERRγ) with high
constitutive activity. Furthermore, BPA also behaves as an androgen receptor antagonist (AR) which
affects the activation and function of the AR [66,67]. According to many lines of evidence, BPA acts as an
endocrine disruptor even at low doses. A review, based on hundreds of studies, concluded that there is
sufficient
Molecules evidence
2017, 22, 149 for low dose effects of BPA. Indeed, for these studies, authors used doses below 7those
of 48
used for traditional toxicological studies, and found nonmonotonic dose-response curves [68].

Figure 2. Chemical structures of bisphenol analogues (A); bisphenol A (B); bisphenol F (C) and bisphenol S (D).

Bisphenols are composed of two phenols linked by a central carbon atom, which in the case of BPA
bears two additional methyl groups (Figure 2B). These structural features make BPA able to mimic the
natural estrogen 17β-estradiol (Figure 3), in terms of binding ability to estrogen receptors [69,70]. In fact,
the main characteristics of the natural ligands required for the steroid activity are the presence of phenol
groups on a hydrophobic backbone [71,72]. A recent paper has demonstrated that all the structural
elements of BPA are prerequisite for binding the estrogen-related receptor-γ (ERRγ), especially the two
phenolic and methyl groups [10]. Firstly, the authors demonstrated that the phenol structure of BPA is
an essential element to bind ERRγ and only one of the two phenolic hydroxy groups is required for the
fullFigure 2. Chemical
Figure
binding. structures
Chemical of bisphenol
structures
2.Nevertheless, the analogues
of bisphenol
presence (A);oxygen-based
bisphenol
analogues
of a second A (B);group
bisphenol
(A); bisphenol (B);Fbisphenol
(C) and
A increases thebisphenol Sactivity
F (C) and
steroid (D).
[73]. bisphenol S (D).
Bisphenols are composed of two phenols linked by a central carbon atom, which in the case of BPA
bears two additional methyl groups (Figure 2B). These structural features make BPA able to mimic the
natural estrogen 17β-estradiol (Figure 3), in terms of binding ability to estrogen receptors [69,70]. In fact,
the main characteristics of the natural ligands required for the steroid activity are the presence of phenol
groups on a hydrophobic backbone [71,72]. A recent paper has demonstrated that all the structural
elements of BPA are prerequisite for binding the estrogen-related receptor-γ (ERRγ), especially the two
phenolic and methyl groups [10]. Firstly, the authors demonstrated that the phenol structure of BPA is
an essential element to bind ERRγ and only one of the two phenolic hydroxy groups is required for the
full binding. Nevertheless, the presence of a second oxygen-based group increases the steroid activity
[73].

Figure3.3.Structure
Figure Structure of
of 17β-estradiol.
17β-estradiol.

By analogy with 17β-estradiol, these two hydroxyl groups are essential to establish interactions
By analogy with 17β-estradiol, these two hydroxyl groups are essential to establish interactions
with the hydrophobic pocket created by the receptor [74,75]. This pocket consists of several combining
with the hydrophobic pocket created by the receptor [74,75]. This pocket consists of several combining
sites where estrogen or other ligands can bind. The size of the pocket is 440 Å [74–76], which is bigger
sites where estrogen or other ligands can bind. The size of the pocket is 440 Å [74–76], which is bigger
than the natural estrogen molecule size (245 Å) allowing hydrogen binding interactions (Figure 4). Liu et
than the natural estrogen molecule size (245 Å) allowing hydrogen binding interactions (Figure 4).
Liu et al. [77] also showed that the substitution of one of the two aromatic rings by a methyl or ethyl
group led to a decrease of the interaction with the hydrophobic part of the receptor, whereas the
presence of chlorine substituents on the 3–5 positions of the first aromatic ring strengthens affinity
with the receptor. Figure 3. Structure of 17β-estradiol.
The presence and the distance between the two hydroxyl groups are not the only critical factors.
Okada Byetanalogy
al. [10] with 17β-estradiol,
clearly demonstrated these
thattwo
the hydroxyl groups
alkyl groups arecentral
on the essential to establish
carbon atom ofinteractions
bisphenol
with the hydrophobic pocket created by the receptor [74,75]. This pocket consists of several
play a key role in selection of the human estrogen receptors: ERRγ or ERα. ERα prefers the bulkier combining
sitesmore
and whereelectrophilic
estrogen or alkyl
other groups,
ligands whereas
can bind.ERRγ
The size of the
prefers thepocket is 440and
less bulky Å [74–76], which is bigger
less electrophilic alkyl
than the A
groups. natural
bulkyestrogen
group onmolecule size carbon
the central (245 Å)atom
allowing hydrogendisadvantageous
is obviously binding interactions (Figure
in terms of 4). Liu et
binding
BPA to ERRγ’s binding pocket and reduces its activity. Furthermore, it was shown that one of the
two methyl groups on the central carbon atom of BPA is involved in the hydrophobic intermolecular
interaction with the receptor residue, such as CH3 -alkyl and CH/π interactions.
The increasing concerns about the detrimental effects of BPA has led governments to enforce
regulations mostly in the European Union and North America in order to limit the exposition of their
citizens to this substance. For example, in 2014, in line with the opinion adopted by the RAC (Risk
Assessment Committee), Bisphenol A has been classified in the hazard class reproductive toxicity
category 1B “may damage fertility”. In the frame of the REACH regulation, the French proposition of
the restriction of BPA in thermal papers was approved on the 6 July 2016 by the REACH Committee.
The BPA European legislation involves different elements such as the restriction of the contact of
infants and young people with this substance, through toys, feeding bottles, etc. [11,78–80]. BPA is
authorized as additive or monomer in the manufacture of plastic materials and articles in contact with
Molecules 2017, 22, 149 8 of 48

food and water but a specific migration limit value of 0.6 mg/kg of food has been set [12]. Regarding
cosmetic products,
Molecules 2017, 22, 149 Bisphenol A is recorded in the list of the prohibited substances [81]. All the products 7 of 47
made of BPA can’t be eligible for a positive Eco-Label [82] and the indicative limit of occupational
al. [77] also[83]
exposure showed
to BPA that the substitution
particles is 10 mg/m 3 . Some
of one of the countries
two aromatic
suchrings by a methyl
as France have or ethyl group
established led
even
to a decrease
more of the interaction
strict legislations towards with
BPA the
[84],hydrophobic part of
and this country the receptor,
proposed BPA aswhereas
a REACH the Regulation
presence of
chlorine substituents
candidate substance of onvery
the 3–5 positions
high concernof(SVHC)
the first[85]
aromatic ring strengthens
and confirmed affinity
its advert on thewith the receptor.
30 August 2016.

Figure 4.
Figure 4. X-ray
X-ray structure
structure ofof the
the hydrophobic
hydrophobic pocket
pocket of of estrogen
estrogen receptor
receptor (ER)α
(ER)α [76],
[76], according
according to
to the
the
works of Brzozowski et al. [74] and Tanenbaum et al. [75].
works of Brzozowski et al. [74] and Tanenbaum et al. [75].

The presence and the distance between the two hydroxyl groups are not the only critical factors.
Following the public concern and the stringent regulations on the production and use of BPA,
Okada et al. [10] clearly demonstrated that the alkyl groups on the central carbon atom of bisphenol play
several bisphenol analogues have been produced as alternative substances. These following analogues,
a key role in selection of the human estrogen receptors: ERRγ or ERα. ERα prefers the bulkier and more
BPF (4,40 -methylenediphenol) and BPS (4-hydroxyphenyl sulfone) (Figure 2C,D), are frequently
electrophilic alkyl groups, whereas ERRγ prefers the less bulky and less electrophilic alkyl groups. A
found in most scientific and environmental studies because they are among the main substitutes
bulky group on the central carbon atom is obviously disadvantageous in terms of binding BPA to
of BPA in polycarbonate-based plastics and epoxy resins. Available studies have reported a variety of
ERRγ’s binding pocket and reduces its activity. Furthermore, it was shown that one of the two methyl
detrimental effects of these bisphenol analogues [86] and showed that the toxicity of these analogs
groups on the central carbon atom of BPA is involved in the hydrophobic intermolecular interaction
is similar to or even greater than that of BPA [87,88]. The toxic effects include endocrine disruption,
with the receptor residue, such as CH3-alkyl and CH/π interactions.
cytotoxicity, genotoxicity, reproductive toxicity, neurotoxicity, etc. A recent article by Rochester
The increasing concerns about the detrimental effects of BPA has led governments to enforce
and Bolden [89], focusing on the hormonal activities of BPF and BPS demonstrated that these two
regulations mostly in the European Union and North America in order to limit the exposition of their
analogues have a hormonal action similar to BPA in vitro and in vivo. Hexafluorobisphenol A (BPAF)
citizens to this substance. For example, in 2014, in line with the opinion adopted by the RAC (Risk
and 4,40 -(1-methylpropylidene) bisphenol (BPB), two others substituents of BPA, have also shown
Assessment Committee), Bisphenol A has been classified in the hazard class reproductive toxicity
estrogenic and anti-androgenic activities [88]. Therefore, a harmless let alone renewable epoxy building
category 1B “may damage fertility”. In the frame of the REACH regulation, the French proposition of the
block is still required [90]. For this reason, bio-mass has been considered a cheap source of potentially
restriction of BPA in thermal papers was approved on the 6 July 2016 by the REACH Committee. The
functionalizable monomers or oligomers. As previously stated, the already commercialized bio-based
BPA European legislation involves different elements such as the restriction of the contact of infants and
epoxy monomers cannot compete with DGEBA-based materials in terms of thermo-mechanical
young people with this substance, through toys, feeding bottles, etc. [11,78–80]. BPA is authorized as
properties, because of their characteristic structure and low aromatic content. Thus, the next part will
additive or monomer in the manufacture of plastic materials and articles in contact with food and water
briefly present the natural sources of renewable aromatic compounds potentially capable of standing
but a specific migration limit value of 0.6 mg/kg of food has been set [12]. Regarding cosmetic products,
up for BPA replacement.
Bisphenol A is recorded in the list of the prohibited substances [81]. All the products made of BPA can’t
beMain
4. eligible for a positive
Natural SourcesEco-Label [82]Moieties
of Aromatic and the indicative limit of occupational exposure [83] to BPA
particles is 10 mg/m3. Some countries such as France have established even more strict legislations
The BPA
towards present
[84],part
andwill
this briefly
countrysummarize the main
proposed BPA sourcesRegulation
as a REACH of aromaticcandidate
moietiessubstance
bearing reactive
of very
groups suitable for the introduction of epoxy moieties. This
high concern (SVHC) [85] and confirmed its advert on the 30 August 2016. summary will include resources
Following the public concern and the stringent regulations on the production and use of BPA,
several bisphenol analogues have been produced as alternative substances. These following analogues,
BPF (4,4′-methylenediphenol) and BPS (4-hydroxyphenyl sulfone) (Figure 2C,D), are frequently found in
most scientific and environmental studies because they are among the main substitutes of BPA in
briefly present the natural sources of renewable aromatic compounds potentially capable of standing up
for BPA replacement.

4. Main Natural Sources of Aromatic Moieties

Molecules 2017, 22, 149 9 of 48
The present part will briefly summarize the main sources of aromatic moieties bearing reactive
groups suitable for the introduction of epoxy moieties. This summary will include resources naturally
containingcontaining
naturally small, phenolic compound
small, phenolic such assuch
compound eugenol extractible
as eugenol from from
extractible plantplant
natural oils,oils,
natural or
polyphenolic
or polyphenoliccrosslinked polymers
crosslinked polymerssuch as tannins
such andand
as tannins lignin that
lignin thatcancanbebe
directly functionalized
directly functionalized or
depolymerized
or depolymerized into into
smaller molecules
smaller prior to
molecules epoxidation
prior steps. Some
to epoxidation steps.information on their availability
Some information on their
or worldwide
availability or production
worldwidewill be givenwill
production as well as theasmain
be given wellknown characteristics
as the main of their structure.
known characteristics The
of their
reader mayThe
structure. refer to themay
reader vastly documented
refer review
to the vastly from Lochab
documented et al. from
review [91] and booketfrom
Lochab Belgacem
al. [91] and
and book
Gandini
from [92] onand
Belgacem renewable resources
Gandini [92] and naturally
on renewable occurring
resources phenolic
and naturally derivatives
occurring to obtain
phenolic more
derivatives
detailed
to obtaindata.
more detailed data.

4.1. Lignin
Lignin
Lignin is the
the widest
widest distributed
distributed aromatic
aromatic biopolymer
biopolymer and the the second
second most
most abundant
abundant naturally
naturally
occurring
occurring macromolecule after cellulose, constituting from 1% to 43% by weight of the dry
macromolecule after cellulose, constituting from 1% to 43% by weight of dry
lignocellulosic biomass,with
lignocellulosic biomass, with a potential
a potential availability
availability exceeding
exceeding 300 billion
300 billion tons [17,93–95].
tons [17,93–95]. It is a
It is a cell-wall
cell-wall
component component
bonding bonding cells together
cells together in thestems,
in the woody woodyproviding
stems, providing
them withthem with
their their well-known
well-known rigidity
rigidity and impact resistance. Although its absolute structure remains unknown and
and impact resistance. Although its absolute structure remains unknown and varies according to the varies according
to the plant
plant it originates
it originates fromfrom
and and
its its environment,
environment, lignin
lignin is isananamorphous
amorphous three-dimensional
three-dimensional polymer
network of three
three main
main methoxylated
methoxylated phenyl
phenyl propane
propane units
units (Figure
(Figure 5)
5) with
withseven
sevenmajor
majorlinkages:
linkages: β-O-4
β-O-4
(aryl ether),
ether), α-O-4, β-β (pinoresinol),
α-O-4, β-β β-5 (phenylcoumaran),
(pinoresinol), β-5 (phenylcoumaran), β-1 β-1 (diphenylmethane),
(diphenylmethane), 5,5 5,5 and 4-O-5
4-O-5
(diphenyl ether) linkages. It exhibits various functional
functional groups such as aliphatic and phenolic hydroxyl,
carboxylic, carbonyland
carboxylic, carbonyl andmethoxy
methoxymoieties.
moieties.

Figure5.5.Main
Figure Mainaromatic
aromatic subunits
subunits found
foundin
inlignin.
lignin.

Usually, lignin is viewed as a waste material derived from the wood pulp in the paper industry
and available in large quantity (50–70 million of tons estimated) [96]. Unfortunately, only 1% to 2% of
overall lignin is used for more specific applications, the remaining primarily serving as a (bio)fuel for
the cellulose extraction [97]. Lignin is extracted from lignocellulosic biomass by two main categories
of processes: (i) sulfur processes yielding lignosulfate and Kraft lignin and (ii) sulfur-free processes
yielding organosolv and soda lignin. These extraction methods greatly influence the already complex
structure of the polymer, sometimes making it difficult to directly use it as a chemical precursor.
For this reason, works have been carried out to depolymerize lignin into smaller, simpler aromatic
molecules suitable for chemical modification and/or polymerization. For example, when lignin is
depolymerized, compounds such as vanillin, phenols derivatives, cresols, ferulic and coumaric acids
are released (Figure 6). All these molecules are already oil-based but this pathway offers an interesting
solution for their renewability, thus increasing thermosets renewability.
the polymer, sometimes making it difficult to directly use it as a chemical precursor. For this reason,
works have been carried out to depolymerize lignin into smaller, simpler aromatic molecules suitable for
chemical modification and/or polymerization. For example, when lignin is depolymerized, compounds
such as vanillin, phenols derivatives, cresols, ferulic and coumaric acids are released (Figure 6). All these
molecules
Molecules are
2017, 22,already
149 oil-based but this pathway offers an interesting solution for their renewability,
10 of 48
thus increasing thermosets renewability.

Figure 6. Various aromatic moieties obtained from lignin depolymerization [93,94].

Figure 6. Various aromatic moieties obtained from lignin depolymerization [93,94].

4.2. Tannins
4.2. Tannins
Tannins are the second bio-based source of natural phenolic moieties and the third most abundant
Tannins are the second bio-based source of natural phenolic moieties and the third most abundant
compounds extracted from wood biomass, with 160,000 tons bio-synthesized each year [98,99]. They can
compounds extracted from wood biomass, with 160,000 tons bio-synthesized each year [98,99]. They
be found mainly in the soft tissues such as wood, bark, leaves or needles of all vascular and some
can be found mainly in the soft tissues such as wood, bark, leaves or needles of all vascular and some
non-vascular plants, in which they play a protective role against outside aggressions and in plant growth
non-vascular plants, in which they play a protective role against outside aggressions and in plant
regulation [100]. Tannins are polyphenol derivatives with low molecular weights and can be divided
growth regulation [100]. Tannins are polyphenol derivatives with low molecular weights and can be
into three main categories: hydrolysable tannins, condensed tannins and complex tannins, the latter
divided into three main categories: hydrolysable tannins, condensed tannins and complex tannins, the
being a combination of the first two.
latter being a combination of the first two.
Hydrolysable tannins are a mixture of phenolic esters of sugars (Figure 7A) readily hydrolyzed by
Hydrolysable tannins are a mixture of phenolic esters of sugars (Figure 7A) readily hydrolyzed
acids, alkalis or enzymes, and present a low availability (less than 10% of the world’s commercial
by acids, alkalis or enzymes, and present a low availability (less than 10% of the world’s commercial
production) [101]. They are mainly used in the tanning industry. The condensed tannins may represent
production) [101]. They are mainly used in the tanning industry. The condensed tannins may represent
the most interesting derivatives with 90% of global production. They are based on four types of
the most interesting derivatives with 90% of global production. They are based on four types of
repeating flavonoid units: profisetinidin, procyanidin, prorobinetidin, and prodelphinidin linked by C4–
repeating flavonoid units: profisetinidin, procyanidin, prorobinetidin, and prodelphinidin linked
C6 or C4–C8 bonds (Figure 7B). Thanks to their availability, aromatic moieties and rigid structure, their
by C4–C6 or C4–C8 bonds (Figure 7B). Thanks to their availability, aromatic moieties and rigid
numerous functionalizable hydroxyl functions and nucleophilic sites, condensed tannins may represent
structure, their numerous functionalizable hydroxyl functions and nucleophilic sites, condensed
an interesting candidate for BPA substitution. Similarly to lignin, some studies are conducted on the
tannins may represent an interesting candidate for BPA substitution. Similarly to lignin, some studies
depolymerization of tannins to obtain phenolic monomers as building units for thermosets [98,102,103].
are conducted on the depolymerization of tannins to obtain phenolic monomers as building units
For example, Roumeas et al. [102] successively used thiol and furan derivatives as nucleophiles for the
for thermosets [98,102,103]. For example, Roumeas et al. [102] successively used thiol and furan
derivatives as nucleophiles for the acid-assisted depolymerization of condensed tannins into catechin
and thioether or furan derivatives of catechin.
Finally, a last class of tannins, phlorotannins, can be found in non-vascular plants such as algae and
are based on polymerized phloroglucinol (1,3,5-trihydroxybenzene) with a large range of molecular
weights [98]. They play a role similar to condensed tannins in vascular plant and can as well be
divided into categories according to the link between phloroglucinol units e.g., ether, phenyl bonds,
a combination of both, or a dibenzo-p-dioxin bond (Figure 8).
 acid-assisted depolymerization of condensed tannins into catechin and thioether or furan derivatives of
catechin.
Molecules 2017, 22, 149 10 of 47

acid-assisted
Molecules depolymerization
2017, 22, 149 of condensed tannins into catechin and thioether or furan derivatives of
11 of 48
catechin.

Figure 7. Main structures of tannins from vascular plants: hydrolysable tannins (A) and condensed
tannins (B).

Finally, a last class of tannins, phlorotannins, can be found in non-vascular plants such as algae and
are based on polymerized phloroglucinol (1,3,5-trihydroxybenzene) with a large range of molecular
weights [98]. They play a role similar to condensed tannins in vascular plant and can as well be divided
Figure 7.
7. Main
Main structures
structures of
of tannins
tannins fromvascular
vascular plants:
plants: hydrolysable
hydrolysable tannins
tannins (A)
(A) and
and condensed
condensed
Figure
into categories according to the linkfrom
between phloroglucinol units e.g., ether, phenyl bonds, a
tannins (B).
tannins (B).of both, or a dibenzo-p-dioxin bond (Figure 8).
combination
Finally, a last class of tannins, phlorotannins, can be found in non-vascular plants such as algae and
are based on polymerized phloroglucinol (1,3,5-trihydroxybenzene) with a large range of molecular
weights [98]. They play a role similar to condensed tannins in vascular plant and can as well be divided
into categories according to the link between phloroglucinol units e.g., ether, phenyl bonds, a
combination of both, or a dibenzo-p-dioxin bond (Figure 8).

Figure
Figure 8. Exampleofofphlorotannins
8. Example phlorotannins linkages
linkages with
with phenyl
phenyl bonds
bonds(in
(inred),
red),ether
etherbonds
bonds(in(ingreen) and
green) and
dibenzo-p-dioxin bond (in blue).
dibenzo-p-dioxin bond (in blue).

4.3. Cardanol
4.3. Cardanol
Cashew nut shell liquid (CNSL) is a reddish-brown liquid that can be extracted from the soft
Cashew nut
honeycomb shell liquid
structure located(CNSL)
inside theis acashew
reddish-brown liquid
nut shell and that can from
constitutes be extracted
30 to 35 from
wt %theof soft
it
honeycomb structure
Figure 8. With
[16,91,104]. Example located inside
of phlorotannins
approximately the cashew
linkagesofwith
2.1 millions nut
tonsphenylshell and
bonds
of cashew constitutes
(inproduced
nuts from
red), etherevery 30
bondsyear, to 35
(in green) wt
mainlyand % of
from
it [16,91,104].in With
Asia approximately
dibenzo-p-dioxin
countries blue). 2.1
bond (inVietnam)
(India, andmillions of tons of
Africa (Nigeria, cashew
Ivory nuts
Coast), produced
CNSL every
represents anyear, mainly
abundant
from countries
non-edible in Asia (India,
by-product that hasVietnam)
alreadyand Africa
found (Nigeria,
various Ivory Coast),
applications CNSL
in coatings, represents
laminates andan abundant
adhesives
non-edible
4.3.toCardanolby-product that has already found various applications in coatings, laminates
name a few. However, it also represents an interesting source of aromatic chemical building blocks. In and adhesives
to name a few.is However,
fact, CNSL it also represents
mainly composed of four majoran phenolic
interesting source ofanacardic
derivatives: aromaticacid,
chemical building
cardanol, cardolblocks.
and
Cashew nut shell liquid (CNSL) is a reddish-brown liquid that can be extracted from the soft
In 2-methyl
fact, CNSL
cardolis mainly
(Figure 9),composed of four
the percentage of major phenoliconderivatives:
which depends the extraction anacardic acid, cardanol,
method. Among these,
honeycomb structure located inside the cashew nut shell and constitutes from 30 to 35 wt % of it
cardanol
cardol and is often regarded
2-methyl cardolas the most
(Figure 9), interesting compound,
the percentage as itsdepends
of which percentageoncanthereach 60% inmethod.
extraction some
[16,91,104]. With approximately 2.1 millions of tons of cashew nuts produced every year, mainly from
Among these, cardanol is often regarded as the most interesting compound, as its percentage can
countries in Asia (India, Vietnam) and Africa (Nigeria, Ivory Coast), CNSL represents an abundant
reach 60% in some CNSL grades. Its structure is defined as a mono-aromatic phenol substituted in
non-edible by-product that has already found various applications in coatings, laminates and adhesives
meta-position by a C15 alkyl chain, on which none to three unsaturations in C8, C11 and C14 are
to name a few. However, it also represents an interesting source of aromatic chemical building blocks. In
possible [105–107]. Thanks to its hydroxyl function and carbon-carbon double bond(s), cardanol can
fact, CNSL is mainly composed of four major phenolic derivatives: anacardic acid, cardanol, cardol and
offer various functionalization opportunities, although its long aliphatic chain may severely impact
2-methyl cardol (Figure 9), the percentage of which depends on the extraction method. Among these,
materials in terms of thermo-mechanical properties.
cardanol is often regarded as the most interesting compound, as its percentage can reach 60% in some
 Molecules 2017, 22, 149 11 of 47

CNSL grades. Its structure is defined as a mono-aromatic phenol substituted in meta-position by a C15
alkyl chain, on which none to three unsaturations in C8, C11 and C14 are possible [105–107]. Thanks to
its hydroxyl function and carbon-carbon double bond(s), cardanol can offer various functionalization
Molecules opportunities,
2017, 22, 149 although its long aliphatic chain may severely impact materials in terms of 12 of 48
thermo-mechanical properties.

Figure 9. Main phenolic constituents of cashew nut shell liquid (from left to right): cardanol, anacardic
Figure 9. Main phenolic constituents of cashew nut shell liquid (from left to right): cardanol, anacardic
acid, cardol and 2-methyl cardol [104].
acid, cardol and 2-methyl cardol [104].
4.4. Cellulose and Hemi-Cellulose
4.4. CelluloseAsand Hemi-Cellulose
previously stated, cellulose is the most abundant naturally occurring polymer and accounts for
Asapproximately
previously stated,40–45 wt % of lignocellulosic biomass depending of wood species [108–111]. With an
cellulose is the most abundant naturally occurring polymer and accounts
annual production estimated around 100 billion tons, it is a remarkable feedstock for the synthesis of
for approximately 40–45 wt % of lignocellulosic biomass depending of wood species [108–111]. With
renewable chemical building blocks. Cellulose is a crystalline high molecular weight polysaccharide
an annual(7000production estimated
to 15,000 monomeric around
units) formed100of billion
D-glucosetons, it is
linked byaβ-1,4-glycosidic
remarkable feedstock
bonds. The for
highthe synthesis
chain
of renewable chemical
organization building
through blocks.
hydrogen Cellulose
bonding providesis cellulose
a crystalline high molecular
with interesting weight
mechanical polysaccharide
properties as
(7000 towell
15,000as poor solubilityunits)
monomeric in water and various
formed organic solvents.
of D-glucose linked by However, the several bonds.
β-1,4-glycosidic hydroxylThegroups
high chain
along its
organization backbone
through make cellulose
hydrogen highlyprovides
bonding hydrophilic. Althoughwith
cellulose it doesn’t exhibit an
interesting aromatic structure,
mechanical properties as
aromatic building blocks can be obtained from cellulose via depolymerization (Scheme 6) [112–114].
well as poor solubility in water and various organic solvents. However, the several hydroxyl groups
Through acid hydrolysis under harsh conditions or bacterial degradation [115] cellulose yields glucose
along itsthat
backbone make cellulose highly hydrophilic. Although it doesn’t exhibit an aromatic structure,
can further isomerize into fructose and then be dehydrated into 5-hydroxymethyl-2-furfural (HMF),
aromatic a building blocks can
furanic aldehyde. HMFbecanobtained
also be from cellulose
oxidized via depolymerization
into 2,5-furandicarboxylic (Scheme
acid or reduced6)into
[112–114].
Through2,5-furandimethanol,
acid hydrolysis under harsh conditions
two symmetric di-functionalor bacterial
aromatic degradation [115] cellulose yields glucose
moieties.
that can furtherThe other main component
isomerize of lignocellulosic
into fructose and thenbiomass, namely hemi-cellulose,
be dehydrated is an amorphous
into 5-hydroxymethyl-2-furfural
polysaccharide with short chains of 500 to 3000 monomer units with
(HMF), a furanic aldehyde. HMF can also be oxidized into 2,5-furandicarboxylic acid acidic groups. Similarly to or
cellulose,
reduced into
it can be depolymerized into pentose that can further be transformed into 2-furfural, 2-furanmethanol
2,5-furandimethanol,
Molecules 2017, 22, 149two symmetric di-functional aromatic moieties. 12 of 47
and 2-furancarboxylic acid. However, these derivatives are mono-functional, thus making them
unsuitable for the synthesis of di-epoxy monomers, only fit for reactive diluents. Finally, it is also worth
noting that cellulose can also be degraded into other interesting, although non aromatic, building blocks:
levulinic and lactic acid.

Scheme 6. Synthesis of furan derivatives from cellulose and hemi-cellulose [112–114].

Scheme 6. Synthesis of furan derivatives from cellulose and hemi-cellulose [112–114].
4.5. Other Natural Sources of Aromatic Moieties
Some other abundant biomasses are potential candidate to extract or synthesize phenolic
derivatives. For example, terpenes and terpenoids can be obtained from various plants’ essential oils or
as by-products of industrial processes and are largely available at reasonable prices [116–118]. For
example, 700 millions of kg of limonene are produced annually as a side-product of orange juice
production [117]. Terpenes form a large and diverse class of molecules based on repeating isoprene units
Molecules 2017, 22, 149 13 of 48

The other main component of lignocellulosic biomass, namely hemi-cellulose, is an amorphous

polysaccharide with short chains of 500 to 3000 monomer units with acidic groups. Similarly to
cellulose, it can be depolymerized into pentose that can further be transformed into 2-furfural,
2-furanmethanol and 2-furancarboxylic acid. However, these derivatives are mono-functional, thus
making them unsuitable for the synthesis of di-epoxy monomers, only fit for reactive diluents. Finally,
it is also worth noting that cellulose can also be degraded into other interesting, although non aromatic,
building blocks: levulinic and lactic acid.

4.5. Other Natural Sources of Aromatic Moieties

Some other abundant biomasses are potential candidate to extract or synthesize phenolic
derivatives. For example, terpenes and terpenoids can be obtained from various plants’ essential
oils or as by-products of industrial processes and are largely available at reasonable prices [116–118].
For example, 700 millions of kg of limonene are produced annually as a side-product of orange juice
production [117]. Terpenes form a large and diverse class of molecules based on repeating isoprene
units that can be linked head to tail or form cycloaliphatic or aromatic rings such as in α-pinene found
in pines, limonene from citrus fruits or p-cymene extracted from thyme, only to name a few. Some of
them may represent interesting candidates for the synthesis of epoxy monomers such as carvacrol,
which exhibits a phenol moiety and a carbon-carbon double bond (Scheme 7) and can be isolated
from oregano and thyme essential oils. However, not all terpenoids contain aromatic and/or phenolic
moieties, but these requirements can be reached via different synthesis steps. For example, carvacrol
can be obtained from other turpentine components such as limonene via an oxidation followed by an
isomerization with sulfated zirconia or from p-cymene by the action of concentrated sulfuric acid and
sodium hydroxide
Molecules 2017, 22, 149[117]. 13 of 47

Scheme 7. Synthesis of carvacrol from limonene or p-cymene according to Harvey et al. [117].
Scheme 7. Synthesis of carvacrol from limonene or p-cymene according to Harvey et al. [117].

Other phenolic compounds can be extracted from various plant essential oils such as
4-allyl-2-methoxyphenol, commonly known as eugenol (Figure 10), obtained from clove oil where
it accounts for 80% [119–122], Jamaican chili, cinnamon and bay leaves from California. It is a
renewable resource, but it is also considered safe, non-carcinogenic and non-mutagenic by the U.S.
Food and Drug Administration and used as a food flavoring agent. Furthermore, it exhibits several
pharmacological properties such as anesthetic, antioxidant, and antimicrobial activities. Apart from
extraction, eugenol can be synthesized by allylation of guaiacol, another bio-based phenolic derivative.
The main advantage of eugenol is that it exhibits a carbon-carbon double bond with fair reactivity and
Figure 10. Structures of eugenol and ferulic acid.
a phenolic group, thus allowing various functionalizations.
Lignocellulosic biomass may also contain p-coumaryl, coniferyl and sinapyl acids, depending on
the plant species, that act as crosslinkers between lignin and polysaccharides (cellulose and
hemi-cellulose) to increase the rigidity of the materials. Among these, 3-methoxy-4-hydroxycinnamic
acid (Figure 10), also known as ferulic acid, is an abundant derivative that can be extracted in good yields
from various non-food resources such as bagasse, rice, wheat and sugar beet roots [123–126] and has
Molecules 2017, 22, 149 14 of 48
Scheme 7. Synthesis of carvacrol from limonene or p-cymene according to Harvey et al. [117].

Figure10.
Figure 10.Structures
Structures of
of eugenol
eugenol and
and ferulic
ferulicacid.
acid.

Lignocellulosic biomass may also contain p-coumaryl, coniferyl and sinapyl acids, depending on
Lignocellulosic biomass may also contain p-coumaryl, coniferyl and sinapyl acids, depending
the plant species, that act as crosslinkers between lignin and polysaccharides (cellulose and
on the plant species, that act as crosslinkers between lignin and polysaccharides (cellulose and
hemi-cellulose) to increase the rigidity of the materials. Among these, 3-methoxy-4-hydroxycinnamic
hemi-cellulose) to increase the rigidity of the materials. Among these, 3-methoxy-4-hydroxycinnamic
acid (Figure 10), also known as ferulic acid, is an abundant derivative that can be extracted in good yields
acid (Figure 10), also known as ferulic acid, is an abundant derivative that can be extracted in good
from various non-food resources such as bagasse, rice, wheat and sugar beet roots [123–126] and has
yields from various non-food resources such as bagasse, rice, wheat and sugar beet roots [123–126] and
both a hydroxyl group and an aliphatic carboxylic acid, thus enabling functionalization. It also exhibits
has both a hydroxyl group and an aliphatic carboxylic acid, thus enabling functionalization. It also
antioxidative, anti-tumor, photoprotective and anti-hypertensive activities.
exhibits antioxidative, anti-tumor, photoprotective and anti-hypertensive activities.
5. Bio-Based Aromatic Epoxy Compounds
5. Bio-Based Aromatic Epoxy Compounds

5.1. Mono-Aromatic
5.1. Mono-AromaticEpoxy
EpoxyCompounds
Compounds
Mono-aromatic glycidyl
Mono-aromatic glycidyl compounds
compounds are defined by
are defined by having
having strictly
strictly one
one aromatic
aromatic ring
ring per
per molecule
molecule
and by having two or more epoxy groups per molecule. As previously stated, the characteristic
and by having two or more epoxy groups per molecule. As previously stated, the characteristic structure
of BPA, e.g., its length, its two aromatic rings and alcohols functions greatly influence its
structure of BPA, e.g., its length, its two aromatic rings and alcohols functions greatly influence its endocrine
disruptor activity.
endocrine disruptor Thus, mono-aromatic
activity. molecules with
Thus, mono-aromatic reduced
molecules hydrophobic
with skeleton may
reduced hydrophobic potentially
skeleton may
be less likely to bind with estrogen receptor, making their epoxy monomers interesting
potentially be less likely to bind with estrogen receptor, making their epoxy monomers interesting candidates for
BPA substitution,
candidates for BPA however, specific
substitution, studies
however, would
specific be would
studies necessary before these
be necessary beforecompounds can be
these compounds
proposed as BPA substitutes.
can be proposed as BPA substitutes.

5.1.1. Phenyl-Based
Phenyl-BasedDi-Functional
Di-FunctionalEpoxy
EpoxyMonomers
Monomers
mono-aromatic phenyl-based
Various mono-aromatic phenyl-based epoxy monomers have
epoxy monomers considered as
have been considered as potential
potential
candidates for
candidates forthe
thereplacement
replacementof DGEBA
of DGEBA(Figure 11). One
(Figure 11). ofOne
the simplest, diglycidyl
of the simplest, ether of resorcinol
diglycidyl ether of
(1), is obtained
resorcinol (1), isfrom resorcinol,
obtained a meta-substituted
from resorcinol, di-phenol that
a meta-substituted can be that
di-phenol obtained from
can be biomass
obtained fromby
biomass by fermentation [127] of catechins or by fermentation of glucose into inositol, chemical
conversion of the latter into 1,3,5-benzenetriol (or phloroglucinol) and finally reduction. As a part of
catechin’s skeleton structure, it has been used as model molecule for catechin characterization [128].
It is commercially available or can be prepared by direct O-glycidylation of resorcinol with good
yield (87%) [38]. Because of the resonance and inductive effects of the meta-substituted aromatic ring,
diglycidyl ether of resorcinol should be more reactive than its para-substituted analogue, diglycidyl
ether of hydroquinone (3) [129]. Its high toxicity may explain why this epoxy has not been much used
as material component. Similarly, a substituted resorcinol, methyl-2,4-dihydroxybenzoate has been
glycidylated with epibromohydrin (2) with a 78% yield but no materials have been developed from this
compound [24]. On the contrary, diglycidyl ether of hydroquinone, the para isomer or resorcinol can
be obtained via the microbial synthesis of phloroglucinol or quinic acid from glucose, converted into
hydroquinone (or resorcinol) [130]. This epoxy was cured with diethyl toluene diamine (EPIKURE W)
and the obtained materials exhibited slightly higher glass transition temperature (Tg ) than those based
on DGEBA (up to 8 ◦ C) [131], being the greatest data obtained with a di-functional epoxy. However,
contrary to resorcinol, hydroquinone is carcinogen (H351) and mutagen (H341).
 diglycidyl ether of hydroquinone, the para isomer or resorcinol can be obtained via the microbial
synthesis of phloroglucinol or quinic acid from glucose, converted into hydroquinone (or resorcinol)
[130]. This epoxy was cured with diethyl toluene diamine (EPIKURE W) and the obtained materials
exhibited slightly higher glass transition temperature (Tg) than those based on DGEBA (up to 8 °C) [131],
being 2017,
Molecules the greatest
22, 149 data obtained with a di-functional epoxy. However, contrary to resorcinol, 15 of 48
hydroquinone is carcinogen (H351) and mutagen (H341).

Figure11.
Figure 11.Mono-aromatic
Mono-aromatic phenyl-based
phenyl-based di-functional
di-functional epoxy
epoxy compounds.
compounds.

The same research team prepared the diglycidyl ether of p-xylene alcohol (5) by direct glycidylation
The same research team prepared the diglycidyl ether of p-xylene alcohol (5) by direct
of the non-toxic 1,4-benzenedimethanol with an overall yield of 90% and a purity of 99% assessed by 1H
glycidylation
NMR [131]. ofIt the hasnon-toxic
been cured 1,4-benzenedimethanol
with cycloaliphaticwith andanaromatic
overall yield of 90%4,4′-methylene
diamines, and a purity
ofbiscyclohexylamine
99% assessed by (PACM)1 H NMR [131]. It has been cured with cycloaliphatic and aromatic diamines,
and diethyl toluene diamine (EPIKURE W), respectively yielding materials
4,4 0 -methylene biscyclohexylamine (PACM) and diethyl toluene diamine (EPIKURE W), respectively
with Tg values up to 67 °C lower than those of DGEBA-based equivalents, because of the methylene
◦
linkages.materials with Tg values up to 67 C lower than those of DGEBA-based equivalents, because
yielding
of the The
methylene linkages.
ester form of the latter compound was prepared by direct glycidylation of the non-toxic
The ester
terephthalic form
acid of the
[132], latter
to form compound
diglycidyl esterwas prepared by
of terephthalic direct
acid glycidylation
(6) with of theThis
a yield of 80%. non-toxic
epoxy
terephthalic acid [132], to form diglycidyl ester of terephthalic acid (6) with
was cured with methylhexahydrophthalic anhydride and poly(propylene glycol) bis(2-aminopropyla yield of 80%. This epoxy
was cured with methylhexahydrophthalic anhydride and poly(propylene glycol)
ether). The materials showed similar Tg values as those based on DGEBA with both curing agents. bis(2-aminopropyl
ether). The materials
Furthermore, showed
terephthalic acidsimilar Tg values
is synthesized as those
from based
p-xylene thatoncan
DGEBA with both
be obtained fromcuring agents.
bio-mass by
Furthermore, terephthalic acid is synthesized from p-xylene that can be obtained
various processes [133]. Due to the large amount of by-products using both direct glycidylation and from bio-mass by
various processes
allylation methods, [133].
YouDue et al.to[134]
the large amount
prepared of by-products
diglycidyl using both direct
ester of terephthalic acid by glycidylation
esterificationand
of
allylation methods,
diacyl chloride You et al.
by glycidol, with[134] prepared
a 50% yield.diglycidyl
Diglycidyl ester
ester of
of terephthalic
terephthalic acid by wasesterification
cured with
ofcarboxylic
diacyl chloride by glycidol,
acid derivatives, and the with a 50% yield.materials
corresponding Diglycidyl
wereester
used of terephthalic acid
as biocompatible, was cured
biodegradable
with carboxylicpolymers
and functional acid derivatives,
for biomedicaland the corresponding
applications. materials
No thermal werewere
properties usedreported.
as biocompatible,
However,
biodegradable
the low hydrolyticand functional
stability of polymers for biomedical
aromatic ester applications.
groups is expected No thermal
to negatively impact properties were
the potential
reported. However,
materials [134]. the low hydrolytic stability of aromatic ester groups is expected to negatively
impactThe thedouble functionalization
potential materials [134]. of eugenol (7) requires a three-step route: (i) protection of the hydroxy
groupTheviadouble
an acetylation using aceticof
functionalization anhydride;
eugenol (ii)
(7) oxidation
requires of the double bond
a three-step route:using mCPBA and
(i) protection of(iii)
the
hydroxy group via an acetylation using acetic anhydride; (ii) oxidation of the double bond using
mCPBA and (iii) glycidylation by deacetylation using epichlorohydrin. The resulting solid was
obtained with an overall yield of 53% [119]. The epoxy was cured with anhydrides and the obtained
materials showed similar thermal and mechanical properties than those of DGEBA equivalents.
For example, when diglycidyl ether of eugenol was cured with hexahydrophtalic anhydride, the
obtained Tg reached 114 ◦ C, which was slightly higher than that of DGEBA counterparts (106 ◦ C).
Eugenol can be used as a precursor for vanillin synthesis. The latter is an important bio-based
phenolic aldehyde, which is the main component of vanilla bean extract, widely used as flavouring
in food, beverages and pharmaceuticals [135]. It is also a bio-sourced chemical derived from
lignin currently produced by Borregaard [123] that easily allows to lead to diepoxy compounds,
the structures of which are showed in Figure 12. All diglycidyl ethers deriving from vanillin can
be prepared by direct O-glycidylation of the corresponding alcohol derivatives, with good yield
(85%–89%) [27]. It is interesting to note that the alcohol derivatives, e.g., 4-hydroxy-3-methoxybenzyl
alcohol, 2-methoxyhydroquinone and 4-hydroxy-3-methoxybenzoic acid are all commercially available,
phenolic aldehyde, which is the main component of vanilla bean extract, widely used as flavouring in
food, beverages and pharmaceuticals [135]. It is also a bio-sourced chemical derived from lignin
currently produced by Borregaard [123] that easily allows to lead to diepoxy compounds, the structures
of which are showed in Figure 12. All diglycidyl ethers deriving from vanillin can be prepared by direct
O-glycidylation of the corresponding alcohol derivatives, with good yield (85%–89%) [27].16 It
Molecules 2017, 22, 149
is
of 48
interesting to note that the alcohol derivatives, e.g., 4-hydroxy-3-methoxybenzyl alcohol,
2-methoxyhydroquinone and 4-hydroxy-3-methoxybenzoic acid are all commercially available,
non-toxic
non-toxic and also used for for food
food flavouring.
flavouring. The three three diglycidyl
diglycidyl ether compounds
compounds were cured with with
isophorone diamine (IPDA) and showed
isophorone diamine (IPDA) and showed Tg values T g valueslower than that of DGEBA by 69 (9), 34 (8) and 14and
lower than that of DGEBA by 69 (9), 34 (8) °C
◦ ◦ and
14
(10).CThe
(10).authors
The authors considered
considered that thethat the presence
presence of a methylene
of a methylene spacerspacer Tg by T
decreased
decreased by 35
35g °C and Cwhen
when carbonyl
carbonyl groupgroup was used
was used as spacer,
as spacer, Tg increased
Tg increased by 20 20 ◦Additionally,
by°C. C. Additionally, when
when diglycidyl
diglycidyl ether
ether of
of hydroquinone and diglycidyl ether of methoxyhydroquinone were compared,
hydroquinone and diglycidyl ether of methoxyhydroquinone were compared, the presence of the the presence of the
methoxy group involved aa decrease
decreaseof ofTTggby ◦ C. Similarly, when comparing (8) and diglycidyl ether
by2525°C. Similarly, when comparing (8) and diglycidyl ether of
of eugenol (7), it seems that the loss of the
eugenol (7), it seems that the loss of the (CH2-O-) (CH -O-)
2 group group between
between the oxirane
the oxirane ring ring
and and the aromatic
the aromatic ring
ring
allowsallows to reach
to reach higherhigher glass transition
glass transition temperatures,
temperatures, closer
closer to thosetoofthose of DGEBA-based
DGEBA-based materials.
materials.

Figure 12.
Figure 12. Diglycidyl
Diglycidyl ether compounds obtained
ether compounds obtained from vanillin: (8)
from vanillin: diglycidyl ether
(8) diglycidyl of vanillyl
ether of vanillyl alcohol,
alcohol,
(9) diglycidyl
(9) diglycidyl ether
etherof
ofmethoxyhydroquinone
methoxyhydroquinone and (10)
and diglycidyl
(10) ether
diglycidyl of vanillic
ether acidacid
of vanillic [135].
[135].

Recently, Hernandez et al. [17] continued the researches to determine the influence of the methoxy
Recently, Hernandez et al. [17] continued the researches to determine the influence of the methoxy
group of diglycidyl ether of vanillyl alcohol (DGEVA) (9) by comparing it with diglycidyl ether of
group of diglycidyl ether of vanillyl alcohol (DGEVA) (9) by comparing it with diglycidyl ether of
gastrodigenin (DGEGD) (4). When cured with 4,4′-methylbiscyclohexylamine, the DGEVA-based
gastrodigenin (DGEGD) (4). When cured with 4,40 -methylbiscyclohexylamine, the DGEVA-based
materials exhibited a lower Tg than the DGEGD ones due to the methoxy moiety, but it appears that it
materials exhibited a lower Tg than the DGEGD ones due to the methoxy moiety, but it appears that it
enables to obtain a higher rigidity in the glassy state, as observed via the higher storage modulus.
enables to obtain a higher rigidity in the glassy state, as observed via the higher storage modulus.
Following its previous work on lignin depolymerisation using hydrogenation in the presence of
Following its previous work on lignin depolymerisation using hydrogenation in the presence of
Zn/Pd catalysts [136,137] the team of Abu-Omar [138] synthesized di-epoxides from propylcatechol (11)
Zn/Pd catalysts [136,137] the team of Abu-Omar [138] synthesized di-epoxides from propylcatechol
(Scheme 8). As previously explained, the presence of hydroxyl groups in ortho position will yield
(11) (Scheme 8). As previously explained, the presence of hydroxyl groups in ortho position will yield
benzodioxane derivatives during the glycidylation step, but the authors claimed to have improved the
benzodioxane derivatives during the glycidylation step, but the authors claimed to have improved
synthesis conditions in terms of epoxy equivalent weight and mass ratio. The epoxy monomer was then
the synthesis conditions in terms of epoxy equivalent weight and mass ratio. The epoxy monomer
mixed with octadecylamine-modified nano-montmorillonite and cured with diethyl triamine. The
was then mixed with octadecylamine-modified nano-montmorillonite and cured with diethyl triamine.
bio-based polymers were characterized in terms of thermal stability and mechanical properties but no
The bio-based polymers were characterized in terms of thermal stability and mechanical properties but
possible leaching of the benzodioxane derivatives non-integrated in the network was discussed.
no possible leaching of the benzodioxane derivatives non-integrated in the network was discussed.
Another abundant and natural product is rosin. With a production of approximately 1.2 million
of tons per year [19], this compound is obtained by heating fresh tree resin to remove the volatile
liquid terpenes. It thus contains a mixture of isomerized acid with large hydrogenated phenanthrene
ring structures providing them with high rigidity. Most of them do not contain aromatic structures,
but Liu et Zhang [139] recently synthesized a mono-aromatic di-glycidyl ester based on rosin acid
(12) (Figure 13), cured it with 1,2-cyclohexanedicarboxylic anhydride and compared the results with
DER332, an epoxy resin from Dow Chemical Company cured in the same conditions. The resulting
material exhibited a Tg of 154 ◦ C slightly higher than its counterpart, and a good thermal stability with
a temperature of 5% weight loss of 311 ◦ C.
Molecules 2017, 22, 149 17 of 48
Molecules 2017, 22, 149 16 of 47

Scheme 8. Synthetic pathway to glycidylated propylcatechol as described by Zhao and Abu-Omar [138].

Another abundant and natural product is rosin. With a production of approximately 1.2 million of
tons per year [19], this compound is obtained by heating fresh tree resin to remove the volatile liquid
terpenes. It thus contains a mixture of isomerized acid with large hydrogenated phenanthrene ring
structures providing them with high rigidity. Most of them do not contain aromatic structures, but Liu et
Zhang [139] recently synthesized a mono-aromatic di-glycidyl ester based on rosin acid (12) (Figure 13),
cured it with 1,2-cyclohexanedicarboxylic anhydride and compared the results with DER332, an epoxy
resin from Dow Chemical Company cured in the same conditions. The resulting material exhibited a Tg
Scheme 8. Synthetic pathway to glycidylated propylcatechol as described by Zhao and Abu-Omar [138].
Scheme
of 154 8.
°C slightly Synthetic
higher pathway
than to glycidylated
its counterpart, propylcatechol
and a good as described
thermal stability by Zhao andof 5%
with a temperature
Abu-Omar [138].
weight loss of 311 °C.
Another abundant and natural product is rosin. With a production of approximately 1.2 million of
tons per year [19], this compound is obtained by heating fresh tree resin to remove the volatile liquid
terpenes. It thus contains a mixture of isomerized acid with large hydrogenated phenanthrene ring
structures providing them with high rigidity. Most of them do not contain aromatic structures, but Liu et
Zhang [139] recently synthesized a mono-aromatic di-glycidyl ester based on rosin acid (12) (Figure 13),
cured it with 1,2-cyclohexanedicarboxylic anhydride and compared the results with DER332, an epoxy
resin from Dow Chemical Company cured in the same conditions. The resulting material exhibited a Tg
of 154 °C slightly higher than its counterpart, and a good thermal stability with a temperature of 5%
weight loss of 311 °C.

Figure13.
Figure 13.Chemical
Chemicalstructure
structure of
of aa rosin-based
rosin-baseddiepoxy
diepoxycompound
compound[139].
[139].

5.1.2. Phenyl-Based Poly-Functional Epoxy Monomers

5.1.2. Phenyl-Based Poly-Functional Epoxy Monomers
Phloroglucinol is a bio-based tri-phenol and is used as an active ingredient in medicines
Phloroglucinol is a bio-based tri-phenol and is used as an active ingredient in medicines
(SPASFON). The glycidylated compound (13) (Figure 14) was prepared by direct glycidylation with a
(SPASFON). The glycidylated compound (13) (Figure 14) was prepared by direct glycidylation with
yield of 68%, leading to a mixture mainly containing triglycidyl ether of phloroglucinol [140]. Its
a yield of 68%, leading to a mixture mainly containing triglycidyl ether of phloroglucinol [140].
symmetric tridimensional and tri-functional meta-substituted structure makes it the most reactive epoxy
Its symmetric tridimensional and tri-functional meta-substituted structure makes it the most reactive
[129]. The reached materials exhibited much higher Tg than those of DGEBA, up to 60 °C for linear
epoxy [129]. The reached materials exhibited much higher Tg than those of DGEBA, up to 60 ◦ C for
aliphatic [141] and 20 °C for 13.cycloaliphatic diamines [142].
linear aliphatic [141]Figureand 20 ◦Chemical structure
C for cycloaliphatic of a rosin-based diepoxy compound [139].
diamines [142].
Another simple tri-functional glycidyl ether is based on pyrogallol (14), which is also a bio-based
Another simple tri-functional glycidyl ether is based on pyrogallol (14), which is also a
5.1.2. Phenyl-Based
molecule obtained Poly-Functional
from decarboxylation Epoxy Monomersof gallic acid extracted from hydrolysable tannins.
bio-based molecule obtained from decarboxylation of gallic acid extracted from hydrolysable tannins.
Unfortunately, it is mutagen (H341) and its structure produces more bulkiness than its meta-substituted
Phloroglucinol
Unfortunately, is a bio-based
it is mutagen (H341) and tri-phenol
its structureandproduces
is used moreas anbulkiness
active ingredient in medicines
than its meta-substituted
analogue. Moreover, as previously described, the ortho position of the phenol groups yields a 50:50
(SPASFON).
analogue. The glycidylated
Moreover, compound
as previously (13) (Figure
described, the ortho 14)position
was prepared by directgroups
of the phenol glycidylation
yields awith
50:50a
mixture of triglycidyl ether of pyrogallol and benzodioxane derivatives, with an overall yield of 66% [38].
mixture of triglycidyl ether of pyrogallol and benzodioxane derivatives, with an overall yield Its
yield of 68%, leading to a mixture mainly containing triglycidyl ether of phloroglucinol [140]. of
The low yield and by-products synthesis were likely the reason why no material has been prepared from
symmetric
66% tridimensional
[38]. The low yield and andby-products
tri-functionalsynthesis
meta-substituted
were likelystructure makeswhy
the reason it the
nomost reactive
material hasepoxy
been
this epoxy.
[129]. Thefrom
prepared reached materials exhibited much higher Tg than those of DGEBA, up to 60 °C for linear
this epoxy.
Similarly, protocatechuic acid, which is a relatively toxic (H315, H319, H335) major metabolite of
aliphatic [141] and
Similarly, 20 °C for cycloaliphatic
protocatechuic acid, whichdiamines [142].toxic (H315, H319, H335) major metabolite of
is a relatively
antioxidant and anti-inflammatory bio-based polyol found in green tea, yields a mixture of 60% of the
Another
antioxidant simple
and tri-functional glycidyl
anti-inflammatory bio-based ether
polyolis based
foundon inpyrogallol
green tea, (14),
yieldswhich is also
a mixture ofa60%
bio-based
of the
triglycidyl ether (15) and 9% of the benzodioxane derivative [38]. The presence of the carboxyl group in
molecule obtained from decarboxylation of gallic acid extracted from
triglycidyl ether (15) and 9% of the benzodioxane derivative [38]. The presence of the carboxyl group hydrolysable tannins.
meta-position apparently limited the cyclization compared to pyrogallol. Despite the good yield, no
Unfortunately,
in meta-position it is mutagen (H341)
apparently limitedand theits structure produces
cyclization comparedmore bulkiness than
to pyrogallol. its meta-substituted
Despite the good yield,
material has been reported.
analogue.
no materialMoreover, as previously described, the ortho position of the phenol groups yields a 50:50
has been reported.
mixture of triglycidyl
Another ether ofcompound
triglycidylated pyrogallol and wasbenzodioxane
synthesized from derivatives, with
trimellitic an(16),
acid overall yield
which is of 66% [38].
a relatively
The low
toxic yieldThe
triacid. andepoxy
by-products
form was synthesis
found were
at 25% likely
in athe reasonwith
mixture why75%no material has been
of diglycidyl prepared from
terephthalate acid
this epoxy.
ester, supplied by Vantico-Switzerland. This mixture was used as polyester curing agent for coating
Similarly,No
applications. protocatechuic
thermal propertiesacid, which
of theisintrinsic
a relatively toxic have
materials (H315,been
H319, H335) [143,144],
reported major metabolite of
but a low
antioxidantstability
hydrolytic and anti-inflammatory
is expected similarly bio-basedto thepolyol found ester
diglycidyl in green tea, yields aacid
of terephthalic mixture
(6). of 60% of the
triglycidyl ether (15) and 9% of the benzodioxane derivative [38]. The presence of the carboxyl group in
meta-position apparently limited the cyclization compared to pyrogallol. Despite the good yield, no
material has been reported.
 Another triglycidylated compound was synthesized from trimellitic acid (16), which is a relatively
toxic triacid. The epoxy form was found at 25% in a mixture with 75% of diglycidyl terephthalate acid
ester, supplied by Vantico-Switzerland. This mixture was used as polyester curing agent for coating
applications. No149thermal properties of the intrinsic materials have been reported [143,144], but 18
Molecules 2017, 22, a of
low
48
hydrolytic stability is expected similarly to the diglycidyl ester of terephthalic acid (6).

Figure
Figure 14.
14. Mono-aromatic
Mono-aromatic phenyl-based
phenyl-based poly-functional
poly-functional epoxy
epoxy compounds.
compounds.

Gallic acid is a bio-based, trihydroxybenzoic acid compound encountered in the plant hydrolysable
Gallic acid is a bio-based, trihydroxybenzoic acid compound encountered in the plant
tannins, as gallic acid derivatives (esters, glycosides) or as the acyl group of some polyols (glucose, quinic
hydrolysable tannins, as gallic acid derivatives (esters, glycosides) or as the acyl group of some
acid). It is as toxic as protocatechuic acid and is the only mono-aromatic compound with four functions
polyols (glucose, quinic acid). It is as toxic as protocatechuic acid and is the only mono-aromatic
that can be glycidylated. Tetraglycidyl ether of gallic acid (17) can be prepared by direct glycidylation or
compound with four functions that can be glycidylated. Tetraglycidyl ether of gallic acid (17) can be
allylation [22,145]. The direct glycidylation of gallic acid allowed to reach the targeted product with a
prepared by direct glycidylation or allylation [22,145]. The direct glycidylation of gallic acid allowed
yield of 68% [22,146,147], whereas, the allylation route led to a better control of the functionalization, but
to reach the targeted product with a yield of 68% [22,146,147], whereas, the allylation route led to a
a lower overall yield of tetraglycidyl derivative of 48%. The materials cured using isophorone diamine
better control of the functionalization, but a lower overall yield of tetraglycidyl derivative of 48%.
reached Tg values of 73 °C higher than that of DGEBA, which is the highest value obtained for
The materials cured using isophorone diamine reached Tg values of 73 ◦ C higher than that of DGEBA,
mono-aromatic epoxy compounds [22].
which is the highest value obtained for mono-aromatic epoxy compounds [22].
Cardanol has also been considered as a BPA substitute for epoxy monomer synthesis. The
Cardanol has also been considered as a BPA substitute for epoxy monomer synthesis.
conversion of the C=C double bonds to epoxide groups can be almost complete by reaction with
The conversion of the C=C double bonds to epoxide groups can be almost complete by reaction
hydrogen peroxide in the presence of formic acid and p-toluenesulfonic acid, with a yield of 82%. The
with hydrogen peroxide in the presence of formic acid and p-toluenesulfonic acid, with a yield of
resulting product is only glycidylated along the alkyl chain and is used for its antioxidative activity in
82%. The resulting product is only glycidylated along the alkyl chain and is used for its antioxidative
soybean oil [106].
activity in soybean oil [106].
Fully epoxidized cardanol (18) (Figure 15) was prepared by direct O-glycidylation of the phenol,
Fully epoxidized cardanol (18) (Figure 15) was prepared by direct O-glycidylation of the phenol,
followed by double bonds oxidation using mCPBA (78%) or perbenzoic acid and used as a natural
followed by double bonds oxidation using mCPBA (78%) or perbenzoic acid and used as a natural
plasticizer for PVC films [105] or as diluent to improve the mechanical properties of DGEBA cured by
plasticizer for PVC films [105] or as diluent to improve the mechanical properties of DGEBA cured by
phthalic anhydride for glass-fiber reinforcement applications. For this latter application, Tg increased
phthalic anhydride for glass-fiber reinforcement applications. For this latter application, Tg increased
with the amount of epoxidized cardanol, from 145 to 180 °C using 40% of diepoxy cardanol [107]. No
with the amount of epoxidized cardanol, from 145 to 180 ◦ C using 40% of diepoxy cardanol [107].
epoxy/amine-based material has been reported, likely because the epoxy groups along the alkyl chain
No epoxy/amine-based material has been reported, likely because the epoxy groups along the alkyl
exhibit a lower reactivity toward amines. In fact, glycidyl ether compounds are found to be the most
chain exhibit a lower reactivity toward amines. In fact, glycidyl ether compounds are found to be the
reactive species towards amine compounds because of the inductive effect of the oxygen on the
most reactive species towards amine compounds because of the inductive effect of the oxygen on the
epoxy-ring and the fact that the ether oxygen is able to form hydrogen bonds with the amine [129].
An interesting approach is thus to combine both characteristics in one molecule.
 Molecules 2017, 22, 149 18 of 47

Molecules epoxy-ring
2017, 22, 149and the fact that the ether oxygen is able to form hydrogen bonds with the amine [129]. An 19 of 48
Molecules 2017,
interesting 22, 149 is thus to combine both characteristics in one molecule.
approach 18 of 47

epoxy-ring and the fact that the ether oxygen is able to form hydrogen bonds with the amine [129]. An
interesting approach is thus to combine both characteristics in one molecule.

Figure 15. Theoretical structure of epoxidized cardanol.

Figure 15. Theoretical structure of epoxidized cardanol.
Triglycidyl ether of vanillylamine (19) (Figure 16) is the only tri-functional mono-phenolic
glycidylatedether
derivative Figure 15. Theoretical structure of epoxidized cardanol.
synthesized from(19) the bio-based
Triglycidyl of vanillylamine (Figure and
16) non-toxic vanillin
is the only reported in the mono-phenolic
tri-functional literature
[148]. It was prepared in a four-step synthesis from hydroxylamine hydrochloride: (i) aldoximation of
glycidylatedTriglycidyl
derivative ethersynthesized
of vanillylamine from(19)the(Figure
bio-based
16) is and non-toxic
the only vanillin
tri-functional reported in the
mono-phenolic
vanillin; (ii) reduction of the aldoxime using dihydrogen in the presence of Pd/C; (iii) neutralization in
literature [148].
glycidylated It was
derivativeprepared
synthesizedin a
from four-step
the bio-basedsynthesis
and non-toxicfrom hydroxylamine
vanillin hydrochloride:
reported in the literature
basic medium leading to a potential alkanolamine hardener; (iv) direct N-glycidylation of the resulting
[148].
(i) aldoximationIt was prepared
of with in
vanillin; a four-step synthesis
(ii) reduction from hydroxylamine hydrochloride: (i) aldoximation of
vanillylamine, an overall yield of 61%.ofThethematerials
aldoxime using
cured with dihydrogen
isophorone diamine in the presence
showed of
vanillin;
Pd/C; (iii) (ii) reduction
neutralization of the aldoxime
in basic medium using dihydrogen in the presence of Pd/C; (iii) neutralization
leading to a potential alkanolamine hardener; (iv) in direct
similar Tg than that of triglycidyl ether of phloroglucinol.
basic medium leading to a potential alkanolamine hardener; (iv) direct N-glycidylation of the resulting
N-glycidylation of the resulting vanillylamine, with an overall yield of 61%. The materials cured with
vanillylamine, with an overall yield of 61%. The materials cured with isophorone diamine showed
isophorone diamine
similar showed
Tg than that similar
of triglycidyl Tg of
ether than that of triglycidyl ether of phloroglucinol.
phloroglucinol.

Figure 16. Aromatic derivatives with epoxy groups grafted on nitrogen atoms.

5.1.3. Epoxy Monomers Based on Other Aromatic Rings

Figure 16. Aromatic derivatives with epoxy groups grafted on nitrogen atoms.
16. Aromatic
Figurediglycidyl
Furfuryl etherderivatives
(20) (Figure with17)
epoxy
wasgroups grafted
prepared by on nitrogen
direct atoms. of the
glycidylation
5-hydroxymethyl-2-furfural, with a yield
5.1.3. Epoxy Monomers Based on Other Aromatic Rings of 60% and a purity of 99%—however 5-hydroxymethyl-2-
furfural
5.1.3. Epoxy is a toxic substance.
Monomers Based on HuOther
et al. [149] found Rings
Aromatic that the overall reactivity of furan derivatives was
Furfuryl diglycidyl ether (20) (Figure 17) was prepared by direct glycidylation of the
significantly greater than that of the phenyl analogue and led to materials with a glass transition
5-hydroxymethyl-2-furfural,
Furfuryl diglycidyl ether with a yield of 60%17)and a purity of 99%—however direct5-hydroxymethyl-2-
temperature higher than their(20)
benzene(Figure
analogs. was
However, prepared
in a recently by corrected glycidylation
article [150], the of the
furfural is a toxic substance. Hu et al. [149] found that the overall reactivity of furan derivatives was
5-hydroxymethyl-2-furfural,
research group changed their with a yield of
observations and60% and a purity
conclusions of 99%—however
as the benzyl-based 5-hydroxymethyl-2
materials showed higher
significantly greater than that of the phenyl analogue and led to materials with a glass transition
-furfuralTtemperature
values
gis than
a toxic the furan-based
substance. Hu ones,
et al. due to afound
[149] higher that
freedom
the degree
overall of reactivity
the furan ring
higher than their benzene analogs. However, in a recently corrected article [150], the
of and
furanthe derivatives
hydrogen was
bonding between atoms in the furan rings and hydroxyl groups created by the epoxy opening.
significantly
research greater than that
group changed theirof the phenyl
observations andanalogue
conclusionsandas theled to materials
benzyl-based with
materials a glass
showed transition
higher
In another article, their further investigation on furfuryl diglycidyl ether cured with
temperature
Tg valueshigher
than the than their
furan-based benzene
ones, due to analogs. However,
a higher freedom degreeinof atherecently
furan ringcorrected
difurfurylamine led them to conclude that each methylene spacer per ring reduced the Tg by 32–34 °C
article
and the hydrogen [150],
bonding
the research between
group atoms
changed in the furan rings and hydroxyl groups created by the epoxy opening.
and that furanyl structuretheir
led toobservations
higher freedomand conclusions
degree, as theTgbenzyl-based
which decreased materials
[151]. When compared withshowed
In another
Tg values
higher those than article,furan-based
their further ones,investigation to on furfurylfreedom
diglycidyl ether of cured with
obtained fromtheDGEBA, the mono-aromatic due a higher
furan-based materials showed adegree
Tg in between the
66 furan
and ring
difurfurylamine led them to conclude that each methylene spacer per ring reduced the Tg by 32–34 °C
and the97hydrogen
°C lower. bonding between atoms in the furan rings and hydroxyl groups created by the
and that furanyl structure led to higher freedom degree, which decreased Tg [151]. When compared with
epoxy opening.
those obtained from DGEBA, the mono-aromatic furan-based materials showed a Tg in between 66 and
In 97another
°C lower. article, their further investigation on furfuryl diglycidyl ether cured with
difurfurylamine led them to conclude that each methylene spacer per ring reduced the Tg by 32–34 ◦ C
and that furanyl structure led to higher freedom degree, which decreased Tg [151]. When compared
with those obtained from DGEBA, the mono-aromatic furan-based materials showed a Tg in between
66 and 97 ◦ C lower.
Furfuryl diglycidyl ester (21) was prepared by allylation and epoxidation of the bio-based but
irritant 2,5-furandicarboxylic acid, in an overall yield of 59% [132]. The authors reported that the
furandicarboxylic-based materials displayed higher curing reactivity, higher Tg , similar mechanical
properties and thermal stability than those based on terephtalic derivatives. The freedom degree of
Molecules 2017, 22, 149 20 of 48

furandicarboxylic structure is lower than with a methylene spacer, which is consistent with previous
observations [135,151], but lower stability toward hydrolysis is expected.
Molecules 2017, 22, 149 19 of 47

Figure 17. Furan-based diglycidylated compounds.

Figure 17. Furan-based diglycidylated compounds.
Furfuryl diglycidyl ester (21) was prepared by allylation and epoxidation of the bio-based but
irritant 2,5-furandicarboxylic acid, in an overall yield of 59% [132]. The authors reported that the
N,N 0 -Diglycidyl furfurylamine (22) was synthesized by double N-glycidylation of the relatively
furandicarboxylic-based materials displayed higher curing reactivity, higher Tg, similar mechanical
toxic 2-aminomethylfurfuran, with an
properties and thermal stability overall
than yieldon
those based of terephtalic
50% [152]. When the
derivatives. Theresulting multi-functional
freedom degree of
epoxy wasfurandicarboxylic
cured with maleimide and than
structure is lower anhydride species,spacer,
with a methylene stablewhich
thermally reversible
is consistent linkages were
with previous
observations
formed, leading [135,151], but lower
to self-healing stability toward
thermosetting hydrolysis is expected.
materials.
N,N′-Diglycidyl furfurylamine (22) was synthesized by double N-glycidylation of the relatively
Recently Liu et al. [153] developed a six-armed epoxy resin (23) based on linoleic acid and
toxic 2-aminomethylfurfuran, with an overall yield of 50% [152]. When the resulting multi-functional
hexamethylolepoxymelamine
was cured in a two-step
with maleimide process of esterification
and anhydride species, stableand epoxidation
thermally reversiblewith H2 O
linkages 2 (Figure 18).
were
Their goal formed,
was toleading
reduce to the high flexibility
self-healing thermosettinginduced
materials.by the long aliphatic chain of the vegetable oils by
introducing a Recently Liu et al.group.
rigid aromatic [153] developed
Resins werea six-armed
curedepoxy
usingresin (23) based
4-methyl on linoleic acid andanhydride
hexahydrophthalic
hexamethylol melamine in a two-step process of esterification and epoxidation with H2O2 (Figure 18).
and 1,8-diazabicyclo[5.4.0]undec-7-ene as a catalyst and exhibited high degrees of cure, Tg values
Their goal was to reduce the high flexibility induced by the long aliphatic chain of the vegetable oils by
and 42 ◦ C
between 28introducing higher
a rigid than group.
aromatic those Resins
observedwerewhen epoxidized
cured using 4-methylsucrose soyate was
hexahydrophthalic used. However,
anhydride
their temperature at 5% weight loss turned ◦ C lower, thus indicating a poorer
and 1,8-diazabicyclo[5.4.0]undec-7-ene as aout to beand
catalyst from 20–90high
exhibited degrees of cure, Tg values
between 28stability.
thermo-oxidative and 42 °C With
higher similar
than thosehardener
observed when epoxidized
content, sucrose
the resin soyate was used.
presented However,content of
a bio-based
their temperature at 5% weight loss turned out to be from 20–90 °C lower, thus indicating a poorer
70% vs. 80% for the sucrose soyate-based one.
thermo-oxidative
Molecules 2017, 22, stability.
149 With similar hardener content, the resin presented a bio-based content of4770%
20 of
vs. 80% for the sucrose soyate-based one.

5.1.4. Conclusions
Bio-based mono-aromatic epoxy materials show interesting properties in terms of Tg and thermal
stability. While cardanol-based materials exhibit flexibility and low Tg values, tri- and tetraglycidyl ether,
led to materials with higher Tg than DGEBA-based materials. Among the di-functional mono-aromatic
substances, only the materials based on epoxy with no spacer and separated by a carbonyl group
showed higher Tg. Unfortunately, since most of these epoxides are in development, their toxicity is not
known and at that moment, little information is available on the potential endocrine disruption of their
precursors. Tables 1 and 2 gather the known data on materials based-on mono-aromatic di- and
poly-epoxy monomers from renewable resources.

Figure 18. Structure of the glycidylated hexa(linoleoyl hydroxymethyl) melamine [153].

Figure 18. Structure of the glycidylated hexa(linoleoyl hydroxymethyl) melamine [153].
Table 1. Mono-aromatic, di-epoxy monomers and thermal properties of the cured materials. Tg
values are indicated in plain text, Tα are in italics.
5.1.4. Conclusions
Tg (°C) or Tα (°C)
Epoxy Curing Agent DGEBA T , (°C) Reference
Bio-based mono-aromatic epoxy materials Materials properties in terms of T g and thermal
show interesting d 5%

Comparison
stability. While cardanol-based materials exhibit flexibility and low Tg values, tri- and tetraglycidyl
2,5-difluoroterephthalic acid 69 66 242
[154]

2,5-difluoroterephthalic acid 74 66 305

Diethyl toluene diamine
193 a 185 /198
a b -
EPIKURE W
4,4′-methylene [150]
100 a/111 b 167 a/176 b -
biscyclohexylamine PACM
Molecules 2017, 22, 149 21 of 48

ether, led to materials with higher Tg than DGEBA-based materials. Among the di-functional
mono-aromatic
Table 1.
substances,
1. Mono-aromatic,
Mono-aromatic, di-epoxy
onlymonomers
di-epoxy monomers
the materials based
and thermal
on epoxy
thermal properties
properties of of the
withmaterials.
the cured
no spacer
cured materials.
and separated by
Table and TTgg
a carbonyl
values group
values are
are showed
indicated
indicated plainhigher
in plain
in Tgin
text, TTαα are
text, are . italics.
in Unfortunately,
italics. since most of these epoxides are in development,
Table
Table 1.
1. Mono-aromatic,
Mono-aromatic, di-epoxy
di-epoxy monomers
monomers and and thermal
thermal properties
properties of of the
the cured
cured materials.
materials. T Tggg
their values
toxicity
are is not
indicated inknown
plain and
text, T α are
α
at in that
italics. moment, little
Tg (°C) information
or Tor
Tg (°C) α (°C)
Tα (°C)
is available on the potential
values are indicated in plain text, T are in italics.
Table 1. Mono-aromatic, di-epoxy monomers and thermal properties of the cured materials. Tg
α
endocrine
values
disruption
Epoxy of their precursors.
Curing AgentTables 1 andT2gg (°C)
gather the known dataReference
Td,5%T(°C)
d,5% on materials based-on
Reference
Table are
1. indicated in plain
Epoxy
Mono-aromatic, text, Tα are
di-epoxy in italics.
Curing
monomers Agent Tg (°C) or
and thermal properties orofTαα (°C)
αthe
TDGEBA
(°C) cured materials.
DGEBA (°C) Tg
mono-aromatic
values are
di- and poly-epoxy
indicated in plain text, Tα are
Epoxy
monomers
in italics.
Curing Agent
from renewable
Materials
Materials Comparison resources.
Comparison Td,5% (°C) Reference
Epoxy Curing Agent Tg (°C) or Tα (°C) Td,5% (°C) Reference
Table 1.Epoxy Curing Agent
Mono-aromatic, di-epoxy monomers and thermal properties of DGEBA Td,5% (°C) TReference
the cured materials.
DGEBA g
Table 1. Mono-aromatic, di-epoxy monomers and thermalMaterials properties of
Materials the cured materials. Tg
Epoxy
values are Curing
indicated in plain text, Tα are Agent
in italics. Tg (°C) or TComparison
α (°C)
Comparison Td,5% (°C) Reference
Table 1. Mono-aromatic,
values are di-epoxy
indicated in plain text, Tα are inmonomers
italics. and Materials
thermal properties
DGEBA of the cured materials. Tg values
Epoxy Curing Agent Tg (°C) orComparison
Tα (°C) Td,5% (°C) Reference
T2,5-difluoroterephthalic
are indicated in plain text, 2,5-difluoroterephthalic
α are in italics. acid acid 69
MaterialsTg 69 (°C) or DGEBA
Tα (°C)66 66 242
242
Epoxy Curing Agent Comparison Td,5% (°C) [154]
Reference
[154]
Epoxy Curing Agent acid
2,5-difluoroterephthalic 69 DGEBA 66 Td,5%242 (°C) Reference
2,5-difluoroterephthalic acid 69
Materials DGEBA
◦ C) 66 ◦ C) 242
Materials T (
Comparison
g or T α ( [154]
Epoxy Curing Agent acid
2,5-difluoroterephthalic 69 66
Comparison 242 T d ,5% (◦ C)
[154] Reference
2,5-difluoroterephthalic
2,5-difluoroterephthalicacid acid Materials
74 74 DGEBA
66 66 Comparison
305
305 [154]
2,5-difluoroterephthalic acid 69 66 242
2,5-difluoroterephthalic
2,5-difluoroterephthalic acid
acid 74
74 a 66
66 a 305
305 [154]
Diethyl toluene diamine
2,5-difluoroterephthalic
Diethyl toluene diamine EPIKUREacid W 69 193193 a 18566185a/198/198
b b 242 - -
2,5-difluoroterephthalic
EPIKURE
2,5-difluoroterephthalic W
2,5-difluoroterephthalic acid acid
acid 74 6969 66 66 305
66 242 242
Diethyl [154] [154]
Diethyl toluene
toluene diamine
diamine 193 185 [154]
66aa/198 305--
aa a bb
2,5-difluoroterephthalic
EPIKURE
4,4′-methylene W acid
biscyclohexylamine 74
193 a 185 /198 b
Diethyl EPIKURE
4,4′-methylene W
toluene diamine 100a /111 167 b /176
[150]
- - -
a b a b
PACM 193
100 a/111 b 185167a/198a/176 b [150]
EPIKURE
biscyclohexylamine
2,5-difluoroterephthalicW PACM acid 74 74 66 305
2,5-difluoroterephthalic
Diethyl toluene diamine acid 66 305
4,4′-methylene
2,5-difluoroterephthalic acid 193 74 a 185 a/198 b -
4,4′-methylene
EPIKURE W PACM 100
100132
aa/111 bb
a/111 b 167 66 aa/176 bb 305
-- [150]
a/140 b 167185
a/176 b [150]
biscyclohexylamine
Diethyl Diethyl
toluene toluene
diamine
4,4′-methylene
biscyclohexylamine EPIKURE
PACM W a
a/198 b
a b-
Diethyl
Diethyl toluenediamine
toluene diamine 100 a193
a/111 b b 167 a/176 b b185 /198 -- - [150] -
diamine EPIKURE
biscyclohexylamine W 132
193 /140
a 185
185 a/198a/198
b
Diethyl tolueneW
EPIKURE
EPIKURE
4,4′-methylene WPACM
diamine
Diethyl toluene 193 a 185 a/198 b -
toluene diamine
0 -methylene
Methyhexahydrophthalic anhydride100 a/111 bbb b 167
b a/176 b - b [150]
4,4EPIKURE
Diethyl W
diamine 132
100aa/140 185
185 a/198 125bbb167 a /176--284
a a aa
biscyclohexylamine PACM 132 129
/140 /111 b /198 - [150]
Diethyl EPIKURE
biscyclohexylamine MHHPA
toluene
EPIKURE WW PACM
diamine
Methyhexahydrophthalic
4,4′-methylene 132 /140 185
167 a/198 -- 284
a b a b
EPIKURE W PACM 100 a129
/111b b 125 b
/176 [150]
[132]
4,4′-methylene
anhydride
biscyclohexylamine
Diethyl
Diethyl MHHPA
toluene
toluene diamine
Methyhexahydrophthalic
Poly(propylene glycol) 100
132132 a/111
a/140 a b b b 167
/140 185 a/198 a/176 b
b 185 a /198 - -
b [150] -
biscyclohexylamine
diamine
EPIKURE W PACM
Methyhexahydrophthalic
EPIKURE W 129 bb b 125 284 [132]
anhydride
bis(2-aminopropyl MHHPA
Methyhexahydrophthalic ether) D230 129 92 b 125 97 266
284
anhydride
Diethyl toluene
Poly(propylene MHHPA
diamine
glycol) 129 b 125 284
Methyhexahydrophthalic
anhydride MHHPA 132 a/140
92 b b
b 185 a/198 b
97 - 266 [132]
EPIKURE
Diethyl
bis(2-aminopropyltoluene W
Methyhexahydrophthalicdiamine
ether) D230 129 125 [132] 284
anhydride MHHPA 132
129/140 185125/198 284-
a b b a b
Poly(propylene
EPIKURE
Poly(propylene Wglycol)
glycol) [132] [132]
anhydride MHHPA 92 bb 97 266
Poly(propylene
bis(2-aminopropyl glycol)
ether)
Poly(propylene glycol) D230 92 b 97 266
Methyhexahydrophthalic
bis(2-aminopropyl ether) D230 92 bb92 b 97 97266 [132] 266
bis(2-aminopropyl
bis(2-aminopropyl ether)D230
ether) D230 129 125 284
anhydride MHHPA
4,4′-methylenebiscyclohexylamine
Methyhexahydrophthalic
Poly(propylene glycol) 100 a/107 b 149 a/158 b 341 [17]
129
92 b b
97125 266 284
anhydride MHHPA
bis(2-aminopropyl ether) D230
4,4′-methylenebiscyclohexylamine 100 a/107 b 149 a/158 b 341 [132][17]
Poly(propylene glycol) [132]
92 b 97 266
bis(2-aminopropyl
Poly(propylene ether)
4,4′-methylenebiscyclohexylamine D230
glycol)
0 -methylenebiscyclohexylamine 100 aa/107 bb
a a b b 149
aa/158 bb 341 [17]
4,4′-methylenebiscyclohexylamine
4,4 100
10092/107b /107 149 97 a/158 b
149 a /158 341b [17] 341 [17]
4,4′-methylenebiscyclohexylamine
bis(2-aminopropyl ether) D230 100 a/107 b 149 a/158 b 341266 [17]

4,4′-methylenebiscyclohexylamine 100 a/107 b 149 a/158 b 341 [17]

Isophorone Diamine 97/106 b 166/182 b 361 c
4,4′-methylenebiscyclohexylamine 100 a/107 b 149 a/158 b 341 [17]
Isophorone Diamine 97/106 b 166/182 b 361 c
4,4′-methylenebiscyclohexylamine 100 a/107 b 149 a/158 b 341 [17]
Isophorone
Isophorone Diamine
IsophoroneDiamine
Diamine 97/106
97/106
97/106
bb b
b 166/182
166/182
bb 361
b 166/182361
b ccc 361 c
Isophorone Diamine 97/106 b 166/182 b 361 c
[27,135]
Isophorone Diamine 97/106 b 166/182 b 361 c
[27,135]
Isophorone Diamine 152/166 b 166/182 b 315 c
Isophorone Diamine 97/106 b 166/182 b 361 c [27,135] [27,135]
Isophorone Diamine 152/166 b 166/182 b 315 c [27,135]
[27,135]
Isophorone Diamine 97/106 b 166/182 b 361 c
Isophorone
Isophorone Diamine
Diamine 152/166
152/166 bb b 166/182 bb 166/182315b ccc [27,135] 315 c
IsophoroneDiamine
Isophorone Diamine 152/166
152/166 b
b 166/182
166/182 b
b
315315
c

Isophorone Diamine 132/154 b 166/182 b 328

Isophorone Diamine 152/166 b 166/182 b 315 c [27,135]
Isophorone Diamine 132/154 b 166/182 b 328
Bisfurfurylamine A 85 111 312 [27,135]
Isophorone Diamine
Isophorone Diamine 152/166 b b 315 c b
166/182 b bb 166/182 328
Isophorone Diamine 132/154
132/154 bb 166/182 328
Isophorone Diamine
Bisfurfurylamine
Isophorone A
Diamine 132/154
85 b b
132/154 166/182
111b b
166/182 328
328312
Bisfurfurylamine
Isophorone A
Diamine
Vanillylamine 85
152/16664 b 166/18267b 111315262c
[148] 312
Isophorone Diamine
Bisfurfurylamine A 132/154
85 b 166/182
111 b 328
312
Bisfurfurylamine
Vanillylamine
Bisfurfurylamine
VanillylamineAA 8564
8564 111
11167 67 312
312262 [148] 262 [148]
1,10-diaminodecane 74 b98 328
Isophorone Diamine
1,10-diaminodecane
Bisfurfurylamine A 132/154
85 74
b 166/182
111 328
98
312 328
Vanillylamine
Vanillylamine
Vanillylamine 6464
64 6767
67 262262
262 [148]
[148]
[148]
1,10-diaminodecane 74 98 328
Isophorone Diamine
Hexahydrophthalic
Bisfurfurylamine anhydride
A 132/154
85 114
b 166/182
111 106
b
312328
321
Vanillylamine
Hexahydrophthalic anhydride
1,10-diaminodecane 6474114 6798 262
106 [148] 321
1,10-diaminodecane
1,10-diaminodecane
Hexahydrophthalic anhydride 74
74114 98
98106 328328
328
321 [119]
[119] [119]
Molecules 2017, 22, 149 Bisfurfurylamine
Vanillylamine A 85
64 111
67 312
262 2 of 7
[148]
1,10-diaminodecane
Maleopimaric
Hexahydrophthalic acid
anhydride 74
114155 98
106 - 328 317
Maleopimaricanhydride
Hexahydrophthalic
Hexahydrophthalic acid
anhydride 114 155
114 106
106 -321321
321 [119]
[119] 317
[119]
Vanillylamine
1,10-diaminodecane 7464 9867 328262 [148]
Hexahydrophthalic anhydride 114 106 321 [119]
Molecules 2017, 22, 149; doi:10.3390/molecules22010149
Molecules 2017, 22, 149; doi:10.3390/molecules22010149 www.mdpi.com/journal/molecules
www.mdpi.com/journal/molecules
1,10-diaminodecane
1,2-cyclohexanedicarboxylic
Hexahydrophthalic anhydride
1,2-cyclohexanedicarboxylic 74
114 10698 321328 [119]
154 154 144 144
311 [139] 311 [139]
Molecules
Molecules 2017,
Molecules 2017, 22,
2017, 22, 149;
22, 149; doi:10.3390/molecules22010149
anhydride
anhydride
149; doi:10.3390/molecules22010149
doi:10.3390/molecules22010149 www.mdpi.com/journal/molecules
www.mdpi.com/journal/molecules
www.mdpi.com/journal/molecules
Hexahydrophthalic anhydride 114 106 321 [119]
Molecules 2017, 22, 149; doi:10.3390/molecules22010149 www.mdpi.com/journal/molecules

aa T
T measured
ααmeasured by by
DMA DMA atpeak
at the the peak position
position of loss of loss modulus
modulus curve; b Tcurve; b T bymeasured
α measured by DMA at the maximum
Molecules 2017, 22, 149; doi:10.3390/molecules22010149 α DMA at the
www.mdpi.com/journal/molecules
of tan δ; cofTtan
maximum δ; c.Td,50%.
d,50%
Molecules 2017,2.22,
Table 149; doi:10.3390/molecules22010149
Mono-aromatic, poly-epoxy resins and thermal properties of the curedwww.mdpi.com/journal/molecules
materials. Tg values
are indicated in plain text, Tα are in italics.

Tg (°C) or Tα (°C)

Epoxy Curing Agent Td,5% (°C) Reference

DGEBA
Materials
Comparison

PE-C9-NH2 102 a 57 266 c

[141]
PE-C18-NH2 112 a 52 283 c
 anhydride 154 154
154 144 144
144 311 311
311 [139] [139]
[139]
1,2-cyclohexanedicarboxylic
anhydride
anhydride
154 144 311 [139]
anhydride
1,2-cyclohexanedicarboxylic
154 144 311 [139]
anhydride

T
T measured
aa α
a T measured by
measured
αα by DMA
by DMA
DMA at at the
at the peak
thepeak position
positionofof
peakposition loss
ofloss modulus
modulus
loss curve;
curve;
modulus
b Tα measured by DMA at the
curve;Tαb measured
b by DMA
Tα measured by DMA at theat the
a Tα measured by DMA at the peak position of loss modulus curve; b Tα measured by DMA at the
maximum
maximum of
maximum of tan
of tan δ; c T
tan δ; cc Td,50%
d,50%.
d,50%.
.
a maximum
Tα measured of tan Td,50%. at
byδ; DMA the peak position ofthermal
loss modulus curve; b Tα measured by DMA at the
Table
Table
Table
Molecules 2.2.Mono-aromatic,
2.
2017,
Mono-aromatic,
Mono-aromatic,
22, 149 c
poly-epoxy
poly-epoxyresins
poly-epoxy resinsand
resins and
and thermal
thermalproperties of the
properties
properties of cured
of the
the materials.
cured
cured Tg values
materials.
materials. T
Tgg values
values 22 of 48
Table
maximum
are 2. Mono-aromatic,
of
indicated tan
in δ;
plain T text,. poly-epoxy
T are in resins and thermal properties of the cured materials. Tg values
italics.
are
are indicated
indicated in
in plain
plain text,
d,50%
text, TT
αα are in italics.
α are in italics.
are indicated in plain text, T α are in italics.
Table 2. Mono-aromatic, poly-epoxy resins and thermal properties of the cured materials. Tg values
Tg (°C)
T or Tαor(°C)
are indicated in plain text, Tα are in italics. Tgg (°C)
Tg (°C) (°C) T
Tαα (°C)
or Tαor(°C) (°C)
Epoxy Curing Agent
Table Mono-aromatic,
2.Epoxy
Epoxy poly-epoxy
Curing
Curing resins
and thermal DGEBA
Agent
Agent propertiesTd,5%
of(°C)
TTthe
Reference
cured
d,5% (°C)
d,5% (°C)
materials. Tg values
Reference
Reference
Epoxy Curing Agent Tg (°C) or TDGEBA
Materials α (°C) Td,5% (°C) Reference
Materials DGEBADGEBA
Comparison
are indicated in plain text, Tα are in italics. Materials
Materials Comparison
Comparison
Comparison
Epoxy Curing Agent Td,5% (°C) Reference
PE-C9-NH2 102 a DGEBA 266 c
57
Materials
PE-C9-NH2
PE-C9-NH2
PE-C9-NH2 102102
102
a
a
a 57 57
Comparison
◦
57 266 c 266
◦ 266
c
c
T g ( C) or Tα ( C) [141]
◦
Epoxy Curing Agent
PE-C18-NH2 112 a 52 283 c [141] [141]
[141] T d,5% ( C) Reference
PE-C18-NH2
PE-C9-NH2 112Materials
a 52 DGEBA Comparison
283 c
PE-C18-NH2
PE-C18-NH2 112102
a a
112 a 52 5752 283 266
c c
283 c
PE-C9-NH2
Isophorone Diamine 177 102 a 157 306 (10%)57 [141] 266 c
Isophorone
Isophorone Diamine
Diamine
PE-C18-NH2 177
177112 a 157 157
52 306 306
(10%) (10%)
283 c [141]
Isophorone Diamine
PE-C18-NH2 177 a 157
112 306 (10%) c
52 283
Decane-1,10-diamine 137 - 300 (10%) [142]
Isophorone Diamine
Decane-1,10-diamine
Decane-1,10-diamine
Isophorone Diamine
Decane-1,10-diamine 137 177
137177
137
- 157
-- 157
300 (10%)
300
306
300 (10%)
(10%)
[142] [142] 306 (10%)
[142]
Difurfuryl amine 134 - 290 (10%) [142]
Decane-1,10-diamine 137 - 300 (10%)
Difurfuryl
Difurfurylamine 134137 - 290 (10%)
Difurfuryl amine
Decane-1,10-diamine
amine 134
134 - - 290 (10%)
300 290 (10%) [142]
Difurfuryl amine 134 - 290 (10%)
Difurfuryl amine 134 - 290 (10%)

Isophorone Diamine 233 a 160 300 [22]

Isophorone Diamine 233 a 160 300 [22]
Isophorone
Isophorone Diamine
Isophorone Diamine
Diamine 233 a
233 a233 a 160
160 300
160
300 [22]
[22] 300 [22]

Isophorone Diamine 233 a 160 300 [22]

Isophorone Diamine 176/194 b 166/182 b 308 [148]

Isophorone Diamine 176/194 b 166/182 b 308 [148]
Isophorone b 166/182 b b
Isophorone Diamine 176/194 308 [148]
b
Isophorone Diamine
Diamine 176/194
176/194 b 166/182 b 166/182
308 [148] 308 [148]

Isophorone Diamine
4,4′-metylene 176/194 b 166/182 b 308 [148]
71 a/80 b 167 a/176 b 303
4,4′-metylenePACM
biscyclohexylamine
71 a/80 b 167 a/176 b 303
4,40 -metylene
biscyclohexylamine PACM [[150]]
4,4′-metylene 71 ba /80 b 167 a/176 b 167 a303
/176 b[[150]] 303
Diethyl4,4′-metylene
biscyclohexylamine
toluene diaminePACM 71 aab/80
/94 /80
PACM 88 a71 185 a167
/198 b/176 303
b a b
biscyclohexylamine
biscyclohexylamine -
Diethyl W PACM
toluene diamine
EPIKURE [150]
Diethyl toluene
4,4′-metylenediamine 88 a/94 b 185 a/198 b - [[150]]
EPIKURE W
71 a/80 88ba /94 b 167 a/176 b 185 a303
/198 b [[150]] -
EPIKURE
Diethyl toluene W
Diethyl toluene diamine
biscyclohexylamine
5,5′-methylene PACM
diamine 88
/62 /94 b 121 a185
a/94 b
/128a/198 --
a b
EPIKURE W
0 -methylene 56 88
a ab 185 b/198 b 272 [[150]]
5,5
5,5′-methylene
EPIKURE
difurfurylamine W
56 a/62 b56 a /62
121b a/128 b 272 a /128 b
121 272
difurfurylamine
difurfurylamine
Diethyl toluene diamine [151]
88 /94
a b185 /198 a b - [151]
5,5′-methylene
EPIKURE W
5,5′-ethylidene
5,5′-methylene
0 -ethylidene [151]
5,5 /69aab/62
56 a56
56 /62 ba 128b a121
b
/142aa/128
121 b b
/128 b 272 a272
272
difurfurylamine
5,5′-ethylidene
difurfurylamine
difurfurylamine 56 /69 128 /142 b 272
difurfurylamine 56 a/69 b 128 a/142 b 272
difurfurylamine
5,5′-methylene [151]
56 a/62 b 121 a/128 b 272 [151]
methyhexahydrophthalic
methyhexahydrophthalic
5,5′-ethylidene
difurfurylamine b
5,5′-ethylidene 152
56ba 152 125 293 125 293
56b a/69 128
128 a/142 272
b a b
anhydride MHHPA
methyhexahydrophthalic
anhydride MHHPA
difurfurylamine /69 b /142 b 272
difurfurylamine 152 125 293 [151]
anhydride MHHPA [132] [132]
poly(propylene
5,5′-ethylideneglycol)
Molecules 2017, 22, 149 poly(propylene glycol)ether) 56 a/69 b b 128 a/142 b 272 [132] 3 of 7 267
bis(2-aminopropyl
methyhexahydrophthalic
difurfurylamine
methyhexahydrophthalic 101152
b 101 97 125 267 97
poly(propylene
bis(2-aminopropyl glycol)
ether) D230
b 293
D230 101 152 97 125 267 293
b
anhydride
anhydride MHHPA
MHHPA b
bis(2-aminopropyl ether) D230
methyhexahydrophthalic [132]
[132]
152 b 125 293
poly(propylene glycol)
anhydride MHHPA
poly(propylene glycol) 101 b
101 b 97
97 267
267
bis(2-aminopropyl
bis(2-aminopropyl ether)
ether) D230
D230 [132]
poly(propylene glycol)
101 b 97 267
bis(2-aminopropyl ether) D230
4-methyl hexahydrophthalic
4-methyl hexahydrophthalic
78–92
78–92 - -
246–316 [153] 246–316 [153]
anhydride
anhydride

aaTT measured
measured
α α byby DMA
DMA at at
thethe peak
peak position
position of loss
of loss modulus
modulus curve;
curve; b T measured
b Tα measured by at
by DMA DMAthe at the maximum of
α
tan δ; c T under air flow.
maximum of d tan δ; Td under air flow.
c

Table 3. Di-epoxy resins with two aromatic rings separated by one atom, and thermal properties of the
cured materials.
5.2. Di-Aromatic Epoxy Compounds
Tg (°C) or Tα (°C)
Its bisphenolic
Epoxy
structure provides BPA with high thermo-mechanical
Curing Agent T (°C)
properties
Reference
but also toxicity. d,5%
DGEBA
In an attempt to mimic but alter the BPA structure to match its
Materials qualities
Comparison
but not its defaults, researchers
have developed various di-aromatic derivatives based on bio-resources. The diaromatic glycidyl ether
compounds are defined as4,4′-methylene-biscyclohexylamine
having strictly two benzene 104 /111
rings149bearing
/158
two
363
or more
[17]
a
epoxy groups per
b a b

molecule. As the spacer between these two aromatic rings plays an important role in the estrogenic
disruption of BPA, the epoxy monomers will be presented in the following sections according to
the number of atoms between the two aromatic moieties: (i) two benzene rings without spacer;
(ii) separated by one atom; (iii)Isophorone
separated
Diamineby two atoms
158 and (iv) separated 361 by long spacers.

Isophorone Diamine 136 363

165 [157]
 an attempt to mimic but alter the BPA structure to match its qualities but not its defaults, researchers
have developed various di-aromatic derivatives based on bio-resources. The diaromatic glycidyl ether
compounds are defined as having strictly two benzene rings bearing two or more epoxy groups per
molecule. As the spacer between these two aromatic rings plays an important role in the estrogenic
disruption of BPA, the epoxy monomers will be presented in the following sections according to the
Molecules 2017, 22, 149 23 of 48
number of atoms between the two aromatic moieties: (i) two benzene rings without spacer; (ii) separated
by one atom; (iii) separated by two atoms and (iv) separated by long spacers.
5.2.1. Two Aromatic Rings without Spacer
5.2.1. Two Aromatic Rings without Spacer
Grelier et al. [155] synthesized a diglycidyl ether derivative (24) from the bio-based but highly
Grelier et al. [155] synthesized a diglycidyl ether derivative (24) from the bio-based but highly toxic
toxic for the environment (H411) 2,6-dimethoxyphenol using a three-steps pathway: (i) enzymatic
for the environment (H411) 2,6-dimethoxyphenol using a three-steps pathway: (i) enzymatic coupling
coupling using laccase from Tramates versicolor; (ii) reduction of the carbon-oxygen double bonds into
using laccase from Tramates versicolor; (ii) reduction of the carbon-oxygen double bonds into alcohols and
alcohols and (iii) O-glycidylation
(iii) O-glycidylation with epichlorohydrin
with epichlorohydrin (Scheme 9). The(Scheme
di-epoxy9). The di-epoxy
monomer obtainedmonomer obtained
was crosslinked
was crosslinked using isophorone diamine yielding a material that exhibits a T of 126 ◦ C and a good
using isophorone diamine yielding a material that exhibits a Tg of 126 °C and a good g thermal stability
thermal
with astability
Td,5% of 312with Td,5% of 312 ◦no
°C. aUnfortunately, C.DGEBA
Unfortunately, no DGEBA
comparison comparison was provided.
was provided.

Scheme
Scheme 9. 9. Syntheticpathway
Synthetic pathwaydeveloped
developed by
by Grelier
Grelier et
et al.
al. [155]
[155] to obtain diphenolic
to obtain diphenolicderivatives
derivativesfrom
from
2,6-dimethoxyphenol.
2,6-dimethoxyphenol.

Following this method, the same team synthesized di-phenols from vanillin [156] (Scheme 10). A
Followingstep
methylation this using
method, the same
methyl team
iodide can synthesized di-phenols
be applied prior to thefrom vanillin
reduction in [156]
order(Scheme
to obtain10).
A methylation
di-functional step using methyl
derivatives. iodide were
No epoxides can be applied prior
synthesized fromtothese
the reduction
compounds in order
but a to obtain
simple
di-functional derivatives. No epoxides were synthesized from
glycidylation step could easily lead to potential bio-based monomers. these compounds but a simple
glycidylation
Molecules 2017, 22,step
149 could easily lead to potential bio-based monomers. 23 of 47
5.2.2. Two Aromatic Rings Separated by One Atom
Hernandez et al. [17] recently synthesized epoxy resins by a two-steps pathway involving the
electrophilic condensation of vanillyl alcohol and guaiacol, a mono phenolic derivative that can be
obtained in large quantities when carrying out the pyrolysis of lignin. This original method is an
interesting alternative to the use of formaldehyde, especially for the synthesis of an analogue to
bisphenol F. The obtain bis-guaiacol was then glycidylated (25) (Figure 19) and cured with
4,4′-methylene-biscyclohexylamine (Amicure PACM), yielding a material with a Tg value of 111 °C
compared to 158 °C for the DGEBA-based material and a slightly lower thermal stability.

Scheme 10. Synthetic pathway developed by Grelier et al. [156] to obtain diphenolic derivatives from vanillin.
Scheme 10. Synthetic pathway developed by Grelier et al. [156] to obtain diphenolic derivatives
from vanillin.
N-alkyl diphenolate diglycidyl ethers (26) were synthesized by Maiorana et al. [157] in yields
ranging from 85% to 97% in a two-step pathway using diphenolic acid. First, it was esterified with
5.2.2. Two Aromatic Rings Separated by One Atom
various alcohols and then glycidylated using epichlorohydrin. The advantage of these epoxides is their
liquidHernandez
state at room et al. [17] recently
temperature andsynthesized epoxy
the possibility resins
to have by bio-based
fully a two-steps pathway
materials. Ininvolving the
fact, levulinic
electrophilic
acid is produced condensation
from cellulose of by
vanillyl alcohol
the acid and of
hydrolysis guaiacol,
C6 sugarsa at
mono phenolic
the pilot derivative
plant scale that[110]
by Biofine can
be obtained
and in large
Segetis [158]. The quantities whenwith
materials cured carrying out the
isophorone pyrolysis
diamine showedof lignin. This original
glass transition method in
temperatures is
an interesting alternative to the use of formaldehyde, especially for the synthesis
between 86 and 158 °C, depending of the alkyl chain, which is lower than that of DGEBA-based of an analogue
to bisphenol
equivalents (165F. °C).
TheTobtain bis-guaiacol
g decreases was then
with increasing alkylglycidylated
chain length.(25) (Figure
No trend was19) and cured
observed with
regarding
4,40 -methylene-biscyclohexylamine
storage modulus or tensile strength (Amicure PACM), yielding
but materials exhibiteda material
mechanical withproperties of 111 ◦to
a Tg valuesimilar C
compared to 158 ◦ C for the DGEBA-based material and a slightly lower thermal stability.
DGEBA-based materials and slightly lower thermal stability.
acid is produced from cellulose by the acid hydrolysis of C6 sugars at the pilot plant scale by Biofine [110]
and Segetis [158]. The materials cured with isophorone diamine showed glass transition temperatures in
between 86 and 158 °C, depending of the alkyl chain, which is lower than that of DGEBA-based
equivalents (165 °C). Tg decreases with increasing alkyl chain length. No trend was observed regarding
storage 2017,
Molecules modulus
22, 149 or tensile strength but materials exhibited mechanical properties similar 24 of to
48
DGEBA-based materials and slightly lower thermal stability.

Figure
Figure 19.
19. Bio-based
Bio-based di-aromatic
di-aromatic epoxy
epoxy derivatives
derivatives with
with aa single
single carbon atom spacer.
carbon atom spacer.

Harvey et al. [117] synthesized di-epoxides (27) through methylene bridging between two carvacrol
N-alkyl diphenolate diglycidyl ethers (26) were synthesized by Maiorana et al. [157] in yields
molecules with 1,3,5-trioxane in dilute HCl at elevated temperature (Figure 19) and O-glycidylation
ranging from 85% to 97% in a two-step pathway using diphenolic acid. First, it was esterified with
using epichlorohydrin, with an overall yield of 42%. The resulting monomer was cured with
various alcohols and then glycidylated using epichlorohydrin. The advantage of these epoxides is
4,4′-diaminodiphenyl methane and 4,4′-methylene bis(5-isopropyl-2-methylaniline), also prepared from
their liquid state at room temperature and the possibility to have fully bio-based materials. In fact,
levulinic acid is produced from cellulose by the acid hydrolysis of C6 sugars at the pilot plant scale by
Biofine [110] and Segetis [158]. The materials cured with isophorone diamine showed glass transition
temperatures in between 86 and 158 ◦ C, depending of the alkyl chain, which is lower than that of
DGEBA-based equivalents (165 ◦ C). Tg decreases with increasing alkyl chain length. No trend was
observed regarding storage modulus or tensile strength but materials exhibited mechanical properties
similar to DGEBA-based materials and slightly lower thermal stability.
Harvey et al. [117] synthesized di-epoxides (27) through methylene bridging between two
carvacrol molecules with 1,3,5-trioxane in dilute HCl at elevated temperature (Figure 19) and
O-glycidylation using epichlorohydrin, with an overall yield of 42%. The resulting monomer was
cured with 4,40 -diaminodiphenyl methane and 4,40 -methylene bis(5-isopropyl-2-methylaniline), also
prepared from p-cymene [116]. The ortho-methylene substituents led to lower degree of cure and
higher moisture resistance, and likely lower hydrolysis. The obtained materials showed glass transition
temperatures ranging from 143 to 161 ◦ C, which is slightly lower than DGEBA-based materials. When
this di-epoxide was cured with 4,40 -diaminodiphenyl methane and compared with diglycidyl ether of
tetramethylbisphenol F, the material based on the former showed lower Tg than the latter, up to 23 ◦ C.
Diglycidyl ether of tetramethylbisphenol F (28) was prepared in a two-step synthesis route
from 2,6-dimethylphenol and the mutagenic and carcinogenic (H341-350) formaldehyde: (i) aldol
condensation reaction between formaldehyde and two molecules of 2,6-dimethylphenol followed by
(ii) the direct O-glycidylation using epichlorohydrin, with an overall yield of 79% [159]; The Tg of the
material cured with 4,40 -diaminodiphenyl methane showed a high Tg value, up to 184 ◦ C. When this
epoxide was compared with its non-spacer analogue, 3,30 ,5,50 -tetramethyl-4,40 -biphenol, the additional
methylene spacer led to a slight decrease of the glass transition temperature, up to 15 ◦ C lower.
Diglycidyl ether of bisfuran (29) was prepared in a four-step synthesis from the bio-based 2-furoic
acid and acetone: (i) protection of the carboxylic groups using methanol; (ii) coupling of two resulting
molecules in the presence of acetone and concentrated sulfuric acid; (iii) reduction of the ester groups
 the direct O-glycidylation using epichlorohydrin, with an overall yield of 79% [159]; The Tg of the
material cured with 4,4′-diaminodiphenyl methane showed a high Tg value, up to 184 °C. When this
epoxide was compared with its non-spacer analogue, 3,3′,5,5′-tetramethyl-4,4′-biphenol, the additional
methylene spacer led to a slight decrease of the glass transition temperature, up to 15 °C lower.
Diglycidyl
Molecules ether of bisfuran (29) was prepared in a four-step synthesis from the bio-based 2-furoic
2017, 22, 149 25 of 48
acid and acetone: (i) protection of the carboxylic groups using methanol; (ii) coupling of two resulting
molecules in the presence of acetone and concentrated sulfuric acid; (iii) reduction of the ester groups
using
using lithium
lithium aluminum
aluminum hydride
hydride andand then;
then; (iv) direct O-glycidylation
(iv) direct O-glycidylation ofof the
the di-alcohol,
di-alcohol, with
with an
an overall
overall
yield of 48% [113]. However, no materials have been prepared from
yield of 48% [113]. However, no materials have been prepared from this epoxy resin. this epoxy resin.
Meylemans
Meylemans et et al. [160] proposed
proposed an an interesting
interestingstrategy
strategytotosynthesize
synthesizedi-phenols
di-phenolsfrom
fromcreosol,
creosol, a
aphenolic
phenolic derivative coming from the reduction of vanillin (Figure 20). Through
derivative coming from the reduction of vanillin (Figure 20). Through Zn(AcO)2 or 2acid Zn(AcO) or
acid catalyzed
catalyzed couplingcoupling with aldehydes,
with aldehydes, they obtained
they obtained two different
two different di-phenoldi-phenol suitable
suitable for epoxideforsynthesis.
epoxide
synthesis. Unfortunately,
Unfortunately, no glycidylation
no glycidylation step was
step was carried outcarried
on theseoutoriginal
on these original compounds,
compounds, although thealthough
use of
the
bio-based aldehydes such as benzaldehyde may produce highly bio-sourced monomers as well as
use of bio-based aldehydes such as benzaldehyde may produce highly bio-sourced monomers as
well as greatly
greatly influence influence the mechanical
the mechanical and thermal
and thermal properties.
properties. However,However,
despite the despite the presence
presence of methoxy of
methoxy
moieties andmoieties
a metaand a meta substitution,
substitution, the derivatives
the di-phenol di-phenol derivatives exhibit very
exhibit a structure a structure
close tovery close to
bisphenol E
bisphenol E and F, according to the aldehyde chosen, thus requiring toxicological studies
and F, according to the aldehyde chosen, thus requiring toxicological studies to determine their potential to determine
their potential dangerousness
dangerousness or estrogen
or estrogen disruptor disruptor behavior.
behavior.

Figure
Figure 20.20. Creosol-baseddi-phenolic
Creosol-based di-phenolicderivative
derivative synthesized
synthesizedby
byMeylemans
Meylemansetetal.al.[160].
[160].

5.2.3. Two Aromatic

AromaticRings
RingsSeparated
Separatedby
byTwo
TwoAtoms
Atoms
Duann et al. al. [161]
[161] prepared
preparedaabis-phenolic
bis-phenolicglycidylated
glycidylated derivative by by
derivative reacting p-aminophenol
reacting p-aminophenol and
p-hydroxybenzaldehyde
and p-hydroxybenzaldehyde prior prior
to ato direct epoxidation
a direct epoxidationwith withepichlorohydrin
epichlorohydrin(30) (30) (Figure 21).
(Figure 21).
p-hydroxybenzaldehyde can
p-hydroxybenzaldehyde can bebe obtained
obtained from
from biomass
biomass by depolymerizing lignin
by depolymerizing lignin [162]
[162] but to our
but to our
knowledge no bio-based commercial p-aminophenol is currently available. However,
knowledge no bio-based commercial p-aminophenol is currently available. However, Ng et al. [163] Ng et al. [163]
claimed in
claimed in aa patent
patent to to have
have developed
developed aa process
process for
for producing
producing this
this compound
compound using using genetically
genetically
engineered microorganisms and biomass-based sugars, possibly providing this resin with aa high
engineered microorganisms and biomass-based sugars, possibly providing this resin with high
renewability percentage. After curing with 0
4,4′-diamino diphenyl methane, they
renewability percentage. After curing with 4,4 -diamino diphenyl methane, they obtained a material obtained a material
with aa TTgg of
with 200 ◦°C
of 200 and aa temperature
C and temperature ofof 5%
5% weight
weight loss
loss under
under air
air of 342 ◦°C.
of 342 Unfortunately, no
C. Unfortunately, no
comparison with a DGEBA-based material was provided to determine the role
comparison with a DGEBA-based material was provided to determine the role of the carbon-nitrogenof the carbon-nitrogen
double-bond
double-bond
Molecules on the
on149
2017, 22, thethermal
thermalandandmechanical
mechanicalproperties.
properties. 25 of 47

Figure 21. Epoxy

Figure resin based
21. Epoxy resinon p-aminophenol
based and p-hydroxybenzaldehyde
on p-aminophenol synthesized bysynthesized
and p-hydroxybenzaldehyde Duann et al. by
[161].
Duann et al. [161].
Using vanillin as a starting material, Harvey et al. [164] synthesized a di-phenol stilbene using
titanium chloride and magnesium, and further hydrogenated it on platinum oxide (Scheme 11). These
Using vanillin as a starting material, Harvey et al. [164] synthesized a di-phenol stilbene using
compounds were turned into cyanates and used to obtain polycyanurates, but no glycidylation step has
titanium chloride and magnesium, and further hydrogenated it on platinum oxide (Scheme 11).
been considered by the authors despite the interesting potential of these molecules for di-epoxy
These compounds were turned into cyanates and used to obtain polycyanurates, but no glycidylation
monomers.
step has been considered by the authors despite the interesting potential of these molecules for
di-epoxy monomers.
 Figure 21. Epoxy resin based on p-aminophenol and p-hydroxybenzaldehyde synthesized by Duann et al. [161].
Using vanillin as a starting material, Harvey et al. [164] synthesized a di-phenol stilbene using
titanium
Usingchloride
vanillinandas magnesium, and further
a starting material, hydrogenated
Harvey et al. [164]itsynthesized
on platinuma oxide (Scheme
di-phenol 11). using
stilbene These
compounds
titanium were and
chloride turned into cyanates
magnesium, andand usedhydrogenated
further to obtain polycyanurates, butoxide
it on platinum no glycidylation
(Scheme 11).step has
These
been considered
compounds
Molecules were
2017, 22, by theinto
149 turned authors despite
cyanates the interesting
and used potential of these
to obtain polycyanurates, but nomolecules for di-epoxy
glycidylation step
26has
of 48
monomers.
been considered by the authors despite the interesting potential of these molecules for di-epoxy
monomers.

Scheme 11. Synthesis of di-phenolic compounds from vanillin according to Harvey et al. [164]
Scheme 11. Synthesis of di-phenolic compounds from vanillin according to Harvey et al. [164].
Scheme 11. Synthesis of di-phenolic compounds from vanillin according to Harvey et al. [164]
5.2.4. Two Aromatic Rings Separated by More Than Two Atoms
5.2.4. Two Aromatic Rings Separated by More Than Two Atoms
5.2.4. The
Twosmall
Aromatic Rings
size of BPASeparated
allows it by More Than
to mimic Two Atoms
the natural estrogen 17β-estradiol and enter the estrogen
The small size of BPA allows it to mimic the natural estrogen 17β-estradiol and enter the estrogen
receptor pocket. Thus, by increasing the length of the spacer,
The small size of BPA allows it to mimic the natural estrogen it may be possible to and
17β-estradiol decrease
enterthe
theactivity
estrogenof
receptor pocket. Thus, by increasing the length of the spacer, it may be possible to decrease the activity
the epoxy monomer precursors. In this part, all monomers with long aliphatic or cycloaliphatic spacer
receptor pocket. Thus, by increasing the length of the spacer, it may be possible to decrease the activity of
of the epoxy monomer precursors. In this part, all monomers with long aliphatic or cycloaliphatic
willepoxy
the be presented,
monomer including bothIn
precursors. di-this
andpart,
poly-epoxy monomers.
all monomers with long aliphatic or cycloaliphatic spacer
spacer will be presented, including both di- and poly-epoxy monomers.
will be presented,
Di-Epoxy Monomers including both di- and poly-epoxy monomers.
Di-Epoxy
Di-Epoxy Monomers
Monomers
Recently, Zou et al. [165] synthesized bio-based epoxy monomers by coupling glycidylated eugenol
Recently, Zou
via photo-initiated
Recently, Zou et etal.al.[165]
thiol-ene [165] synthesized
reaction
synthesized bio-based
usingbio-based
three epoxyepoxy
different monomers
aliphatic
monomers di-thiols by coupling
(31)
by coupling (Figure glycidylated
22).
glycidylatedThe resins
eugenol
eugenol
were
via via photo-initiated
cured
photo-initiated thiol-ene thiol-ene
by 4,4′-diaminodiphenylmethane reaction
reaction using using
and
three three
the different
resulting
different aliphatic
materials
aliphatic di-thiols di-thiols
exhibited
(31) Tg (31)
(Figure and(Figure
22). Tα values
The 22).
resins
The resins
ranging were
from 39cured
to 60 by
°C 4,4
by 0 -diaminodiphenylmethane
DSC and 54 to 70 °C by DMA, and the resulting
respectively. As materials
expected, exhibited
the glass T and
transition
were cured by 4,4′-diaminodiphenylmethane and the resulting materials exhibited Tg and Tα values g
decreased when increasing ◦ C bychain ◦ C by DMA, respectively. As expected, the
Tranging
α values ranging
from 39 to from
60 °C 39 by the
to
DSC di-thiol
60 and to 70length.
54 DSC andby54DMA,
°C to 70respectively. As expected, the glass transition
glass transition
decreased whendecreased
increasingwhen increasing
the di-thiol chain the di-thiol chain length.
length.

Figure 22. Eugenol-based epoxy prepolymers synthesized by Zou et al. [165].

Figure 22. Eugenol-based epoxy prepolymers synthesized by Zou et al. [165].
Figure 22. Eugenol-based epoxy prepolymers synthesized by Zou et al. [165].
Following the same synthetic pathway, Maiorana et al. [123] and Menard et al. [166] synthesized
bio-based bis-ferulate
Following epoxy
the same monomers
synthetic (32) (33)
pathway, and (34)et(Scheme
Maiorana al. [123]12)
andviaMenard
a three step
et al.synthetic pathway:
[166] synthesized
(i) Following
synthesis of the
ethyl same
ferulatesynthetic
by pathway,
reacting with HCl Maiorana
and et al.
hydrogenating [123]
over and
Pd/C; Menard
(ii) et al. [166]
enzyme-catalyzed
bio-based bis-ferulate epoxy monomers (32) (33) and (34) (Scheme 12) via a three step synthetic pathway:
synthesized
(i) bio-based
transesterification
synthesis of ethylwith bis-ferulate
various
ferulate epoxy
bio-based
by reacting monomers
with HCl diols (32) (33) and
including n-alkyl
and hydrogenating (34) (Scheme
diols (ii)
over Pd/C; and 12) via a three
isosorbide
enzyme-catalyzed or
step synthetic pathway:
transamidification with
transesterification (i) synthesis
with1,4-diaminobutane; of
various bio-based ethyl ferulate
and (iii) by reacting
diolsO-glycidylation with HCl and
with epichlorohydrin
including n-alkyl hydrogenating
in high yields.
diols and isosorbide or
over Pd/C; (ii) enzyme-catalyzed
transamidification transesterification
with 1,4-diaminobutane; with variouswith
and (iii) O-glycidylation bio-based diols including
epichlorohydrin n-alkyl
in high yields.
diols and isosorbide or transamidification with 1,4-diaminobutane; and (iii) O-glycidylation with
epichlorohydrin in high yields. The epoxy monomers were cured by isophorone diamine,
1,10-diaminodecane and difurfurylamine. Regarding the thermosets based on the n-alkyl bis-ferulates
and IPDA, the Tα values ranged from 50 to 65 ◦ C and decreased while increasing the diol chain
length, compared to 170 ◦ C for DGEBA-based material. The change of ester to amide bonds lead
to higher Tg values thanks to the hydrogen bonding induced by the nitrogen atoms. These values
were roughly similar to those obtained with the isosorbide derivative, the cycloaliphatic structure
of which brought more rigidity to the polymeric network. However, none of these materials could
compete with DGEBA-based resources in terms of Tg /Tα . An interesting point to mention nonetheless
is that Maiorana et al. [123] also focused on the degradability of the obtained materials for thermosets
recyclability issues, and studied the estrogenic activity of bisferulates compared to bisphenol A and
17β-estradiol. The n-alkyl bis-ferulates derivatives showed no significant estrogenic activity for ER α
 The epoxy
Regarding the monomers
thermosets were basedcured
on theby isophorone
n-alkyl diamine,
bis-ferulates and1,10-diaminodecane
IPDA, the Tα valuesand difurfurylamine.
ranged from 50 to
Regarding the thermosets based on the n-alkyl bis-ferulates and IPDA,
65 °C and decreased while increasing the diol chain length, compared to 170 °C for DGEBA-based the Tα values ranged from 50 to

65 °C and
material. decreased
The change whiletoincreasing
of ester amide bonds the lead
diol to
chain
higherlength,
Tg valuescompared
thankstoto170 the °C for DGEBA-based
hydrogen bonding
material. The change of ester to amide bonds lead to higher T g values thanks to the hydrogen bonding
induced by the nitrogen atoms. These values were roughly similar to those obtained with the isosorbide
induced by
derivative, thethe nitrogen atoms.
cycloaliphatic These values
structure of which werebrought
roughlymore similar to those
rigidity toobtained with thenetwork.
the polymeric isosorbide
Molecules 2017, 22, 149 27 of 48
However, none of these materials could compete with DGEBA-based resources in terms of Tg/Tnetwork.
derivative, the cycloaliphatic structure of which brought more rigidity to the polymeric α. An
However,
interesting none
point to of these materials
mention nonetheless could compete
is that MaioranawithetDGEBA-based resources
al. [123] also focused on thein terms of Tg/Tαof
degradability . An
interesting point
the obtained materials
at concentrations to mention nonetheless
for thermosets
where bisphenol A does, is that Maiorana
recyclability
highlighting et
issues, al.
theand [123] also focused
studiedof the
potential these on the
estrogenic degradability
compounds activity as of of
a safer
the obtained
bisferulates compared to bisphenol A and 17β-estradiol. The n-alkyl bis-ferulates derivatives showed no of
materials for thermosets recyclability issues, and studied the estrogenic activity
substitute for BPA.
bisferulates
significant compared
estrogenic to bisphenol
activity Aα and 17β-estradiol. The n-alkyl bis-ferulates derivatives showed theno(35)
In a similar way, Aouf etfor
al.ER [40] at concentrations
synthesized where
glycidylated bisphenol A does,
bio-based highlighting
bis-vanillic acid
significant estrogenic activity for ER α at
potential of these compounds as a safer substitute for BPA. concentrations where bisphenol A does, highlighting the
in a three-steps
potential ofpathway:
these (i) synthesis
compounds as a safer of bis-vanillic
substitute for BPA.acid by reaction with 1,5-dibromopentane;
In a similar way, Aouf et al. [40] synthesized glycidylated bio-based bis-vanillic acid (35) in a
(ii) allylation In of the hydroxyl
apathway:
similar way, functions
Aouf etofal. with
[40] allyl bromide
synthesized and (iii)
glycidylated epoxidation
bio-based bis-vanillicof acid
the allyl
(35) inbond
a
three-steps (i) synthesis bis-vanillic acid by reaction with 1,5-dibromopentane; (ii) allylation
with ofanthree-steps
enzymatic catalyst
pathway: (i) (Figure
synthesis 23).
of Unfortunately,
bis-vanillic acid by no materials
reaction with were synthesized
1,5-dibromopentane;
the hydroxyl functions with allyl bromide and (iii) epoxidation of the allyl bond with an enzymatic (ii) with these
allylation
di-epoxy of monomers.
the(Figure
catalyst hydroxyl 23).functions with allyl
Unfortunately, bromidewere
no materials and (iii) epoxidation
synthesized withofthese
the allyl bondmonomers.
di-epoxy with an enzymatic
catalyst (Figure 23). Unfortunately, no materials were synthesized with these di-epoxy monomers.

Scheme 12. Synthetic pathway to obtain bio-based di-epoxy monomers from ferulic acid proposed
12. Synthetic pathway
SchemeScheme to obtain bio-based di-epoxy monomers from ferulic
ferulicacid
acidproposed
proposedby
by Maiorana12.etSynthetic pathway
al. [123] and Ménard to et
obtain bio-based
al. [166]. di-epoxy monomers from
Maiorana
by et al. [123]etand
Maiorana Ménard
al. [123] et al. [166].
and Ménard et al. [166].

Figure 23. Di-epoxy monomers with longer ester spacers between the aromatic rings.
Figure 23. Di-epoxy monomers with longer ester spacers between the aromatic rings.
Figure 23. Di-epoxy monomers with longer ester spacers between the aromatic rings.

Fourcade et al. [167] used 1,6-hexanediol to synthesize an epoxy resin using a two-steps synthetic
route: (i) phenolization of the 1,6-hexanediol using ethyl-4-hydroxybenzoate with 92% of yield; and
(ii) direct O-glycidylation using epichlorohydrin in the presence of sodium carbonate (36) (Figure 23).
The resulting epoxide was used as a DGEBA diluent and blended with 50%–90% of DGEBA and
then cured with dicyandiamide. The glass transition temperature of the blend materials ranged from
77 to 109 ◦ C, decreasing when increasing the amount of aliphatic epoxide. Materials exhibited high
thermal stabilities under air, but unfortunately no sample without DGEBA was mentioned. While
the 1,6-hexanediol used by the authors was oil-based, it can be obtained by hydrogenation of adipic
acid coming from different biomass such as glucose, lignin and fatty acids [168]. It is considered lowly
direct O-glycidylation using epichlorohydrin in the presence of sodium carbonate (36) (Figure 23). The
Fourcade et al. [167] used 1,6-hexanediol to synthesize an epoxy resin using a two-steps synthetic
resulting
route: (i) phenolization ofas
epoxide was used a 1,6-hexanediol
the DGEBA diluent andethyl-4-hydroxybenzoate
using blended with 50%–90% of 92%
with DGEBA andand
of yield; then (ii)cured
with direct
dicyandiamide.
O-glycidylationThe using
glass epichlorohydrin
transition temperature of the of
in the presence blend materials
sodium carbonateranged from 77
(36) (Figure 23).toThe
109 °C,
decreasing
resultingwhen increasing
epoxide was used theasamount
a DGEBA ofdiluent
aliphaticandepoxide.
blended withMaterials exhibited
50%–90% of DGEBA highand thermal stabilities
then cured
underwith
air,dicyandiamide.
but unfortunately no sample
The glass without
transition DGEBA
temperature wasblend
of the mentioned.
materialsWhile
ranged the 1,6-hexanediol
from 77 to 109 °C, used
Molecules 2017, 22, 149 28 of 48
decreasing when increasing the amount of aliphatic epoxide. Materials
by the authors was oil-based, it can be obtained by hydrogenation of adipic acid coming from exhibited high thermal stabilities
different
under
biomass air,as
such butglucose,
unfortunately
ligninno and sample
fatty without DGEBA
acids [168]. It iswas mentioned.
considered While
lowly the[169]
toxic 1,6-hexanediol
and is not used
labelled
by the authors was oil-based, it can be obtained by hydrogenation of adipic acid coming from different
as carcinogenic
toxic [169] and or mutagen.
is not labelled Ethyl-4-hydroxybenzoate
as carcinogenic or mutagen. is obtained by esterification of 4-hydroxybenzoic
Ethyl-4-hydroxybenzoate is obtained by
biomass such as glucose, lignin and fatty acids [168]. It is considered lowly toxic [169] and is not labelled
acid, a naturally
esterification of occurring product
4-hydroxybenzoic acid,synthesized
a naturally industrially
occurring from synthesized
product phenol, carbon dioxide from
industrially and
as carcinogenic or mutagen. Ethyl-4-hydroxybenzoate is obtained by esterification of 4-hydroxybenzoic
bio-ethanol.
phenol, Moreover,
acid,carbon dioxide
a naturally
the authors
and bio-ethanol.
occurring
used epichlorohydrin
Moreover, industrially
product synthesized
from glycerol
the authorsfrom (Epicerol
usedphenol,
epichlorohydrin® process) making the
carbon dioxide from andglycerol
(Epicerol ® process)
resinsbio-ethanol.
possibly highly renewable,
making the although
resins no
possibly value was
highly given.
renewable, although no value was given.
Moreover, the authors used epichlorohydrin from glycerol (Epicerol process) making the®

Diglycidyl
Diglycidyl
resins possiblyether
ether derivatives
highly derivatives
renewable, including
including
although spiro-ring
spiro-ring
no value wasasgiven.
spacer can becan
as spacer prepared in a two-step
be prepared pathway
in a two-step
from non-toxic,
pathway fromDiglycidyl bio-based reactants,
ether derivatives
non-toxic, bio-basedincluding e.g.,
reactants, vanillin
spiro-ring [27,135,170,171]
as spacer
e.g., vanillin and
can be preparedand
[27,135,170,171] pentaerythritol
in a pentaerythritol [167]:
two-step pathway[167]: (i)
condensation
(i) condensation of of
from non-toxic, both
both starting
bio-based
starting substances
reactants,
substances and
e.g.,
and (ii)
(ii)direct
vanillin O-glycidylation
[27,135,170,171]
direct and using
O-glycidylation epichlorohydrin
pentaerythritol
using [167]: (i)in the
epichlorohydrin
condensation
presence of sodium of both starting
hydroxide. substances
However, noand (ii)
other direct
detail, O-glycidylation
such as using
reaction
sodium hydroxide. However, no other detail, such as reaction yield could be found epichlorohydrin
yield could be found in the
[172]. In
[172].
1986 presence
and of
1987, sodium
Ochi hydroxide. However, no other detail, such as reaction yield could be found [172]. In
In 1986 and 1987, Ochietetal.al.[173]
[173]investigated
investigatedaaseries
seriesof of diglycidyl
diglycidyl ether containing spiro-ring building building
1986 and 1987, Ochi et al. [173] investigated a series of diglycidyl ether containing spiro-ring building
blocks (37) (38) (39), as shown in in Figure
Figure 24.24. Materials
Materials cured with with hexahydrophthalic
hexahydrophthalic anhydride showed
blocks (37) (38) (39), as shown in Figure 24. Materials cured with hexahydrophthalic anhydride showed
similar or
similar orhigher
higherglass
glasstransition
transition temperatures
temperatures than thatthat
than of their DGEBA
of their DGEBA counterparts.
counterparts. Curing with more
Curing with
similar or higher glass transition temperatures than that of their DGEBA counterparts. Curing with more
rigid rigid
more anhydrides,
rigid e.g., phthalic anhydride and nadic anhydride allowed to
anhydrides, e.g., phthalic anhydride and nadic anhydride allowed to slightly increase Tg, in Tg ,
anhydrides, e.g., phthalic anhydride and nadic anhydride allowed slightly
to increase
slightly increase Tg, in

comparison
in comparison to hexahydrophthalic
to hexahydrophthalic
comparison to hexahydrophthalic anhydride. anhydride.
anhydride.

Figure 24. Diglycidyl ether derivatives containing spiro rings.

Figure 24.Diglycidyl
Figure24. Diglycidylether
ether derivatives containingspiro
derivatives containing spirorings.
rings.
Rao and Samui [174] synthesized diepoxy monomers including bisbenzylidene segments by
Rao and
reaction Samui
andbetween [174]
[174] synthesized
Samuivanillin synthesized
or diepoxy
diepoxy
syringaldehyde monomers
monomers
with acetone including
(40) andincluding bisbenzylidene
ketones (41) segments
bisbenzylidene
cycloaliphatic segments by
followed
reaction between vanillin
by glycidylation or syringaldehyde
with epichlorohydrin
syringaldehyde with
(Scheme acetone
13). These (40) and
monomers cycloaliphatic
were
acetone (40) and cycloaliphatic used toketones (41)
synthesize followed
(41)linear
followed
polyesters
by glycidylationfor photoactive liquid
glycidylation with epichlorohydrin crystal applications
(Scheme 13).
epichlorohydrin (Scheme but
13). Thesealso reacted
These monomers with benzene-1,3,5-tricarboxylic
monomers were used to synthesize synthesize linear
linear
acid tofor
polyesters obtain dendrimers,
photoactive although
liquid their
crystal protocol
applications seems more
but also likely to
reacted yield
with crosslinked materials. No
benzene-1,3,5-tricarboxylic
photoactive liquid crystal applications but also reacted with benzene-1,3,5-tricarboxylic
data on potential thermo-mechanical properties is thus mentioned.
acid to obtain
obtain dendrimers,
dendrimers,although
althoughtheir
theirprotocol
protocol seems
seems more
more likely
likely to yield
to yield crosslinked
crosslinked materials.
materials. No
No
datadata on potential
on potential thermo-mechanical
thermo-mechanical properties
properties is thusismentioned.
thus mentioned.

Scheme 13. Synthesis of di-epoxy monomers from vanillin and syringaldehyde with acetone or
cycloaliphatic ketones according to Rao and Samui [174].

Scheme 13.
Scheme 13. Synthesis
Synthesis of
of di-epoxy
di-epoxy monomers
monomers from
from vanillin and syringaldehyde
vanillin and syringaldehyde with acetone or
with acetone or
cycloaliphatic ketones according to Rao and Samui [174].
cycloaliphatic ketones according to Rao and Samui [174].

Poly-Epoxy Monomers
Triglycidyl ether of polyphenol (42) (Figure 25) was synthesized in a two-steps pathway
from resorcinol and acetone: a coupling reaction followed by direct O-glycidylation using
epichlorohydrin [175]. The glass transition temperature of the resulting material cured with
diaminodiphenyl sulfone was not observed neither in DSC, nor in DMA, up to 300 ◦ C. The authors
concluded that the Tg was above 300 ◦ C, thus making it much higher than that of DGEBA-based
 Molecules 2017, 22, 149 28 of 47

Poly-Epoxy Monomers
Molecules 2017, 22,ether
Triglycidyl 149 of polyphenol (42) (Figure 25) was synthesized in a two-steps pathway 28 of from
47

resorcinol
Molecules 2017, 22,and acetone: a coupling reaction followed by direct O-glycidylation using epichlorohydrin
149Monomers 29 of 48
Poly-Epoxy
[175]. The glass transition temperature of the resulting material cured with diaminodiphenyl sulfone was
Triglycidyl
not observed ether
neither of polyphenol
in DSC, (42) (Figure
nor in DMA, 25)°C.
up to 300 wasThe
synthesized in a two-steps
authors concluded pathway
that the Tg wasfrom
above
material. resorcinol
300 °C, thus
The and
making
three acetone:
epoxy a
it much coupling reaction
higherand
groups thanthe followed
thatrigidity by
of DGEBA-baseddirect O-glycidylation
material.
of the cyclic using
The threemay
backbone epichlorohydrin
epoxyingroups and thesuch
fact explain
[175]. of
rigidity The glass
the transition
cyclic backbonetemperature of the
may in fact resulting
explain suchmaterial
a result.cured with diaminodiphenyl sulfone was
a result.
not observed neither in DSC, nor in DMA, up to 300 °C. The authors concluded that the Tg was above
300 °C, thus making it much higher than that of DGEBA-based material. The three epoxy groups and the
rigidity of the cyclic backbone may in fact explain such a result.

Figure
Figure 25. Triglycidyl
25. Triglycidyl etherderivative
ether derivative based
basedononresorcinol andand
resorcinol acetone.
acetone.

Aouf et al. [176] studied

Figure 25.hydrolysable tara
Triglycidyl ether tannins
derivative as potential
based candidates
on resorcinol for a source of phenolic
and acetone.
Aouf et al.
moieties. [176]
These studied hydrolysable
galloylquinic acid oligomers tara tannins
were as potential candidates
first depolymerized for a source
by tannase-assisted of phenolic
hydrolysis to
moieties. These
produceAouf galloylquinic
et al.gallic
mainly [176] acid acid
studied oligomers
andhydrolysable
galloylquinic were
tara first
tannins
acid. The as depolymerized by
potential candidates
epoxidation tannase-assisted
for a source
of this mixture hydrolysis
of phenolic
was carried out by
to produce
direct mainly
moieties. gallic
These acid
galloylquinic
O-glycidylation, and
leading togalloylquinic
acid oligomers were
galloylquinic acid. Theglycidylated
firstand
esters epoxidation
depolymerized of this gallic
bydimerized mixture
tannase-assisted was (Figure
hydrolysis
moieties carried
to out
26).produce
by direct The mainly gallic
O-glycidylation,
obtained monomer acid and
leading galloylquinic acid.
to galloylquinic
mixture was cured The
using epoxidation
esters of this mixture
and glycidylated
isophorone diamine wasresulting
anddimerized
the carried out
gallicbymoieties
material
(Figure direct
showed O-glycidylation,
a Tgobtained
26). The leading
up to 129monomer to galloylquinic
°C, which mixture esters
is 20 °C lower
was and glycidylated
than
cured that dimerizeddiamine
of isophorone
using DGEBA-based gallic moieties
materialsandin (Figure
the
the same
resulting
26). The obtained
conditions. The monomer
presence of mixture
◦
esters was cured
bonds may ◦using
however isophorone
make diamine
these and the resulting
thermosets more material to
sensitive
material showed a Tg up to 129 C, which is 20 C lower than that of DGEBA-based materials in the
showed anda Tg favour
up to 129 °C, of
which is 20 °Cinstead
lower of than that of DGEBA-based materials in the same
same hydrolysis
conditions.
conditions. The
the use
The presence
condensed
presence ofofesters
esters bonds
bonds maymay hydrolysable
however
however makemake tannins. thermosets
thesethese more sensitive
thermosets more sensitive to to
hydrolysis and favour
hydrolysis the the
and favour useuse
ofofcondensed instead
condensed instead of of hydrolysable
hydrolysable tannins.tannins.

Figure 26. Main oligomers obtained from the glycidylation of depolymerized tara tannins by Aouf et al. [176].
Figure 26. Main oligomers obtained from the glycidylation of depolymerized tara tannins by Aouf et al. [176].
Figure 26. Main oligomers obtained from the glycidylation of depolymerized tara tannins by
Aouf For this
et For
al. reason, Nouailhas et al. [128,177] focused their research on catechin, one of the constitutive
[176].
this reason, Nouailhas et al. [128,177] focused their research on catechin, one of the constitutive
units of condensed tannins. Although it is not yet bio-based, it can be obtained by acid-depolymerization
units of condensed tannins. Although it is not yet bio-based, it can be obtained by acid-depolymerization
as previously described (Section
(Section4.2.). The direct
direct O-glycidylation ofofcatechin
catechin(Figure
(Figure
27)27)ledled mainly to the
Forasthis
previously
reason,described
Nouailhas 4.2.).
et al. The[128,177]
O-glycidylation
focused their research on mainly
catechin, toone
the of the
tetraglycidylated
tetraglycidylated catechin (45) (46%) and to two di-glycidylated benzodioxane derivatives (46), with a a
catechin (45) (46%) and to two di-glycidylated benzodioxane derivatives (46), with
constitutive
yield units
of of
18% and of15%,
condensed tannins. Although was ait is not yet bio-based, it itcan be obtained
with by
yield 18% and 15%,respectively.
respectively.AsAs the
the mixture
mixture was asolid
solidatatroom
room temperature,
temperature, it was was mixed
mixed with
acid-depolymerization
25 25
and 50% ofof
DGEBA as previously described (Section 4.2.). The direct O-glycidylation of catechin
and 50% DGEBAasasa areactive
reactivediluent
diluent and
and cured withEpamine
cured with EpaminePC PC19,
19,which
whichis is composed
composed of benzyl
of benzyl
(Figure 27)
alcohol, led mainly to the tetraglycidylated
alcohol,1,3-bis(aminomethyl)benzene, catechin (45) (46%)
1,3-bis(aminomethyl)benzene, 3-amino-methyl-3,5,5-trimethylcyclohexylamine and to
3-amino-methyl-3,5,5-trimethylcyclohexylamine and two di-glycidylated
andBPA- BPA-
benzodioxane derivatives (46), with a yield of 18% and 15%, respectively. As the mixture was a
solid at room temperature, it was mixed with 25 and 50% of DGEBA as a reactive diluent and
cured with Epamine PC 19, which is composed of benzyl alcohol, 1,3-bis(aminomethyl)benzene,
3-amino-methyl-3,5,5-trimethylcyclohexylamine and BPA-epichlorohydrin polymer. The materials
based on the 50% and 75% blends of glycidylated catechin exhibited slightly lower and 10 ◦ C higher
Tg than DGEBA-based materials, respectively. These results may seem surprising as the introduction
of tetra-epoxy monomers with the catechin rigid structure was expected to increase glass transition
temperature. However, the role of the di-epoxy benzodioxane derivative is not elucidated and may
explain these results.
 Molecules 2017, 22, 149 29 of 47

epichlorohydrin polymer. The materials based on the 50% and 75% blends of glycidylated catechin
exhibited slightly lower and 10 °C higher Tg than DGEBA-based materials, respectively. These results
may seem surprising as the introduction of tetra-epoxy monomers with the catechin rigid structure was
expected
Molecules to149
2017, 22, increase glass transition temperature. However, the role of the di-epoxy benzodioxane 30 of 48
derivative is not elucidated and may explain these results.

Molecules 2017,
Molecules 2017, 22,
22, 149
149 33 of
of 77
Molecules
Molecules 2017,
2017, 22,
22, 149
149 33 of
of 77
Molecules 2017,
Figure 27. Epoxy monomers obtained by glycidylation of catechin according to Nouailhas7et al. [128].
22, 149 3 of
Figure 27. Epoxy monomers obtained by glycidylation of catechin according to Nouailhas et al. [128].
Molecules 2017, 22, 149 3 of 7
5.2.5. Conclusions
5.2.5. Conclusions
A wide range of di-aromatic
4-methylbio-based epoxy monomers has been synthesized and cured over the
hexahydrophthalic
4-methyl hexahydrophthalic 78–92 - 246–316 [153]
4-methyl hexahydrophthalic 78–92 - been246–316 [153] and cured over the
A
past wide yearsrange
withof most di-aromatic
of them bio-based
exhibiting
4-methyl epoxy monomers
anhydrideinteresting
hexahydrophthalic
anhydride
4-methylanhydride
hexahydrophthalic
and variedhas
78–92
78–92 --properties synthesized
in terms
246–316
246–316 of glass transition
[153]
[153]
anhydride 78–92 - 246–316 [153]
temperature
past years with most and thermal of themstability.exhibiting Shrewd
anhydride strategies
interesting
4-methyl hexahydrophthalic
have
and been
varied developed
properties toin slightly
terms or
of largely step
glass transition
78–92 - 246–316 [153]
away from the detrimental structure of BPA, but similarly
temperature and thermal stability. Shrewd strategies have been developed to slightly or largely step
anhydride to mono-aromatic compounds, very few were
awaystudied
from the for detrimental
their estrogen structure activity. The of following
BPA, buttables similarly(Tables to 3–5) gather the known
mono-aromatic data on cured
compounds, very few
materials
T
aaa T α based
measured
measured by
by on DMA
DMA the di-aromatic
at
at the
the peak
peak di-
position
positionandof
of poly-epoxy
loss
loss modulus
modulus monomers.
curve;
curve;
b Tα measured by DMA at the
b Tα
b measured by DMA at the
were studied
a
a T
α
α for by
Tαα measured
measured their
by DMA
DMA estrogen
at
at the
the peak
peak activity.
position
position ofofThe
loss following
loss modulus
modulus curve;tables
curve; b T
b α (Tables
Tαα measured
measured by 3–5)
by DMA gather
DMA at
at the
the the known data on
maximum
amaximum
Tα measured of tan
of tan
by δ;cDMA
δ; Tddd under
ccc T under
at the airpeak
air flow.position
flow. of loss modulus curve; b Tα measured by DMA at the
cured maximum
materials
maximum
aTable 3.
Tα Table
Table
of
of
measured
tan
tan
Di-epoxy
δ;
based
δ;
3. Di-epoxy
by DMA
3. Di-epoxy
cT Td under air flow.
on
d under
resins
cresinsatresins
the
with air
the peak
with two
di-aromatic
flow.
two aromatic
with rings
two aromatic
position
aromatic of
di- and
separated poly-epoxy
by one
rings separated
lossseparated
rings modulus curve;
by batom, and
byand
Tα measured
one atom,
monomers.
thermal
onethermal
atom,
by DMAproperties
andatthermalof the
the of the
properties properties of the
Table3.3.Di-epoxy
maximum
Table Di-epoxy resins withair
Td under
of tan δ;resins with two
two aromatic ringsseparated
flow.
aromatic separated byone
one atom,and and thermalproperties
properties ofthe the
Table
cured 3. Di-epoxy
materials.
maximum resins
ofmaterials. with
Td under
tan δ; cresins two
airtwo aromatic rings
flow.aromatic rings separated by
by one atom,
atom, and thermal
thermal properties of of the
cured
Table
cured materials.
cured
3. Di-epoxy
materials. with rings separated by one atom, and thermal properties of the
cured materials.
Table3.
3. Di-epoxy
Di-epoxy resins with two
resins with aromatic rings separated
two aromatic by one
rings atom, andby
separated thermal properties of the
Table
cured materials. Tgg (°C)
T (°C) or Tααone
or T (°C) atom, and thermal
(°C)
properties of the
cured materials. TTg g(°C)
(°C)or
orTTαα(°C)
(°C)Tg (°C) or Tα (°C)
cured materials. Tg (°C) or Tα (°C)
EpoxyEpoxy
Epoxy Curing Agent
Curing Agent
Curing Agent Tg (°C) or Tα (°C) Td,5%
T (°C)
DGEBA
d,5% Reference
Td,5% (°C) Reference
Epoxy d,5% (°C) Reference
Epoxy Curing Agent Tg (°C) or Tα (°C) DGEBA
Materials
DGEBA Td,5% (°C) Reference
Epoxy Curing Agent Materials DGEBA d,5% (°C)
TComparison Reference
Epoxy Curing Agent Materials
Materials Comparison
DGEBA T d,5% (°C) Reference
Materials Comparison ◦
Epoxy Curing Agent
Materials DGEBA (◦DGEBA
T gComparison
C) or TTα
Comparison
d,5% (°C)
( C) Reference
Epoxy Curing Agent Materials Comparison T d,5% (◦ C) Reference
4,4′-methylene-biscyclohexylamine 104 /111
Comparison
Materials 149 /158
a b
DGEBA Comparison
a b 363 [17]
4,4′-methylene-biscyclohexylamine 104 /111 bbb
104 aaa/111 149 aaa/158
149 /158 bbb 363
363 [17]
4,4′-methylene-biscyclohexylamine
4,4′-methylene-biscyclohexylamine 104 aa/111 bb 149 aa/158 bb 363 [17]
[17]
4,4′-methylene-biscyclohexylamine 104 /111 149 /158 363 [17]
4,4′-methylene-biscyclohexylamine
0 -methylene-biscyclohexylamine 104 a104
a
b/111a
b 149b /158 363a 363 b [17]
b a/158
a b [17]
4,4
4,4′-methylene-biscyclohexylamine /111
104 /111149 149 /158 363 [17]

Isophorone Diamine 158 361

Isophorone Diamine
Isophorone Diamine 158
158 361
361
Isophorone Diamine 158 361
Isophorone Diamine 158 361
Isophorone
Isophorone Diamine
Diamine
Isophorone Diamine 158 158158 361 361 361

Isophorone Diamine 136 363

Isophorone Diamine
Isophorone Diamine 136
136 363
363
Isophorone Diamine 136 363165 [157]
Isophorone
Isophorone
Isophorone Diamine
Diamine
Diamine 136 136136 363 363 363
Isophorone Diamine 136 363
165
165 [157]
[157]
165
165 [157] 363
Isophorone Diamine 165 96
165 [157] [157]
165 165 [157] [157]

Isophorone Diamine 96 363

Isophorone Diamine
Isophorone Diamine 96 96
96
96 363
363
Isophorone
Isophorone Diamine
Diamine
Isophorone Diamine 96 96 363 363 363
Isophorone Diamine 96 363

Isophorone Diamine 86 362

Isophorone
Isophorone Diamine
Diamine
4,4′-diaminodiphenyl methane86
86 161 362
362
Isophorone
IsophoroneDiamine
Isophorone Diamine
Diamine 86 86 86 362 362179 367/368
362 c [116]
Isophorone Diamine 86 362
Isophorone Diamine 86 362

4,4′-diaminodiphenyl
4,4′-diaminodiphenyl methane
methane
4,4′-diaminodiphenyl methane 161
161 161 179 179 367/368367/368
179 367/368
c c
cc
4,4 0 -diaminodiphenyl
4,4′-diaminodiphenyl methane
methane 161 161 179 367/368 cc
179 367/368 c
4,4′-diaminodiphenyl methane 161 179 367/368
4,4′-diaminodiphenyl methane 161 179 367/368 [116]
c
[116] [116]
4,4′-methylene
4,4′-methylene [116]
[116]
4,4′-methylene
0 -methylene 143 143 154 154 363/360363/360
c
363/360 c [116]
4,4′-methylene
4,4
bis(5-isopropyl-2-methylaniline)
bis(5-isopropyl-2-methylaniline) 143
143 154 cc
[116]363/360 c
4,4′-methylene 143 154 363/360 cc
bis(5-isopropyl-2-methylaniline)
4,4′-methylene
bis(5-isopropyl-2-methylaniline)
bis(5-isopropyl-2-methylaniline) 143143 154 154
363/360
bis(5-isopropyl-2-methylaniline) 143 154 363/360 c
bis(5-isopropyl-2-methylaniline)

4,4′-diaminodiphenyl methane
0 -diaminodiphenyl 184/183 b - 346/355 c [159]
4,44,4′-diaminodiphenyl
4,4′-diaminodiphenyl methane
methane
methane 184/183
184/183
184/183
b
b
b
b
-- -346/355
346/355 ccc 346/355 c
[159]
[159] [159]
4,4′-diaminodiphenyl methane 184/183 bb - 346/355 cc [159]
4,4′-diaminodiphenyl methane 184/183 - 346/355 [159]
4,4′-diaminodiphenyl methane 184/183 b - 346/355 c [159]
a
aa αTα measured by DMA at the peak position of loss modulus curve; b Tα measured by DMA at the
b T measured
T measured
T
aa measuredby
measured
αα
α
amaximum
byDMA
by DMAat
DMA atatthe
thepeak
the peakposition
peak position
position of of
of loss
loss
loss modulus
modulus
modulus curve;
curve;
curve; b Tα
b
b TT
b α measured
α measured
α by DMA
by DMA
by DMA theat the maximum of
at the
at
T of tanbyδ; cDMA
Tc d under air flow.
T measured
a αα
tan δ;
maximum
c
measured
T of by
under
tan
dof tan δ;DMA air
T d
at
at
flow.
under
the
theair
peak
peak
flow.
position
position of
of loss
loss modulus
modulus curve;
curve; b Tαα measured
measured byby DMA
DMA at at the
the
amaximum
T measured
Table 4. Di-epoxy
α
maximum of by δ;DMAc Td
c
monomers d under
at theair flow.
peak
withflow. position of loss modulus curve; b Tα measured by DMA at the
two aromatic rings separated by more than one atom exhibiting ester
of tan
tan δ; TTdd under
under air
c
maximum
Table 4.4. Di-epoxy
Di-epoxy δ; ccmonomers air flow.
with two aromatic
aromatic rings
rings separated
separated by
by more
more than
than one
one atom
atom exhibiting
exhibiting ester
ester
Table
maximum
or amide
Table 4. of tanand
bonds,
Di-epoxy monomers
δ;monomers
Td under
thermal with
air
properties
with two
flow.
twoof the curedrings
materials.
Table 4.
or amide
amide Di-epoxy
bonds, and monomers
and with
thermal propertiestwo aromatic
properties aromatic
of the rings
the cured
cured
separated
separated by
materials. by more
more than
than one
one atom
atom exhibiting
exhibiting ester
ester
or
Table
or 4. bonds,
Di-epoxy thermal
monomers with two of
aromatic ringsmaterials.
separated by more than one atom exhibiting ester
or amide
amide bonds,
bonds, andand thermal
thermal properties
properties ofof the
the cured
cured materials.
materials.
or amide bonds, and thermal properties of the cured materials.
Molecules 2017,
Molecules 22,22,149
2017, 149 4 of 7 31 of 48
Molecules 2017, 22, 149 4 of 7
Molecules 2017, 22, 149 4 of 7

Tg (°C) or Tα (°C)
Molecules 2017, 22, 149 Tg (°C) or Tα (°C) 4 of 7
Molecules 2017, 22, 149 T (°C) or T (°C) T44 of
of 77 Reference
Table
Molecules 4. Di-epoxy
Molecules 2017,
2017, 22,
22, 149
149
Molecules 2017, 22, 149
monomers with two aromatic
Epoxy Curing Agent rings separated by more T4 of 7 than one atom exhibiting
g α d,5%
d,5%
Epoxy Curing Agent DGEBA T4 of 7 Reference
(°C) d,5%
Epoxy Curing Agent Materials DGEBA (°C) Reference
ester or amide bonds, and thermal properties of the T
T cured
Materials
(°C)
T (°C)
(°C) or
or T
T (°C)
materials.
or T (°C) Comparison
DGEBA
(°C) Comparison
Materials
(°C)
g
g
α
α

Tgg (°C) or Tαα (°C) Td,5%

Epoxy Curing Agent Tg (°C) or Tα (°C) Comparison
T
T d,5% Reference
Epoxy
Epoxy Curing
Curing Agent DGEBA Td,5%
(°C) Reference
Curing Agent Reference
d,5%
Epoxy Agent Materials DGEBA
DGEBA (°C)
T
(°C)
d,5% Reference
Epoxy Curing Agent Materials Comparison
DGEBA ◦ (°C) (◦ C)
or Tα Reference
T ( C)(°C)
Materials
DGEBA g
Materials Comparison
Comparison
Epoxy Curing AgentMaterials Comparison
Isophorone T d,5% (◦ C) Reference
Comparison
Isophorone b Materials
66 b b DGEBA
170 Comparison
300 [123]
diamine
Isophorone 66 170 b 300 [123]
diamine 66 b 170 b 300 [123]
diamine
Isophorone
Isophorone
Isophorone 66bb b 170bb b 300 [123]
Isophorone
diamine 66
66 170
170 300
300 [123]
[123]
Isophorone
diamine
Isophorone
diamine 66 b b b 170 b 300 [123]
b
diamine
diamine
66 b 66 170 300 [123]
170 300 [123]
diamine
Isophorone
Isophorone 51/61 bb 150/174 bb 314
diamine
Isophorone 51/61 150/174 314
diamine 51/61 b 150/174 b 314
Isophoronediamine
Isophorone
Isophorone 51/61bb b 150/174b b 314 [166]
Isophorone
diamine 51/61
1,10-diaminodecane
51/61 150/174
33/33
150/174
b b 314
98/97
314
b 314 [166]
diamine
Isophorone
Isophorone
diamine 51/61 b
1,10-diaminodecane 150/174
33/33 b
b 314
98/97 b 314 b
diamine 51/61 b b b
150/174
51/61 314 150/174 [166] 314
1,10-diaminodecane
diamine
diamine 33/33 b 98/97 b 314
[166]
[166]
1,10-diaminodecane
Difurfurylamine
1,10-diaminodecane 33/33bb b
33/33 98/97bb
32/4198/97
b b
92/110314
314b [166]
306
[166]
1,10-diaminodecane 33/33
Difurfurylamine
1,10-diaminodecane 33/33 b 32/4198/97
b
98/97 b 314
92/110
314b 306 b
[166] [166]
1,10-diaminodecane
1,10-diaminodecane 33/33 b
Difurfurylamine 33/33 b bb
32/4198/97 314b
92/110 98/97
306 314
Difurfurylamine
Difurfurylamine 32/41bb b
32/41 92/110bb b
92/110 306
306
Difurfurylamine
Difurfurylamine 32/41
32/41 bb 92/110
b b
92/110 306
306 b
Difurfurylamine32/41
Difurfurylamine 32/41
92/110 b 306 92/110 306
Isophorone
Isophorone 50 bb 170 bb 331 [123]
diamine
Isophorone 50 170 331 [123]
diamine
Isophorone
Isophorone
Isophorone 50 b 170b b 170 b331 331 [123]
Isophorone
Isophorone 5050bb
diamine 50 bb 170
b b
170 331
331 [123]
[123]
b
[123]
diamine
diamine
Isophorone
diamine 50 50 170 bb 331 170
[123] 331 [123]
diamine
diamine 50 b 170 331 [123]
diamine

Isophorone
Isophorone 85/99 b 150/174 b 295
diamine
Isophorone
Isophorone
Isophorone 85/99 b 150/174 b 295
Isophorone
Isophoronediamine 85/99
85/99bb b 85/99150/174
b
150/174 295
bb b 150/174
295 b 295
diamine
diamine
Isophorone
diamine diamine 85/99
Isophorone 85/99 b 150/174
150/174 bb 295
295
diamine 85/99 b 150/174
b 295 b
diamine
1,10-diaminodecane 85/99
54/68 b 98/97 b 150/174
292 295
diamine
1,10-diaminodecane
54/68bb b 54/6898/97 98/97 292
b b
1,10-diaminodecane
1,10-diaminodecane
1,10-diaminodecane 54/68
54/68 98/97bb b 292
292
54/68 b 54/6898/97
1,10-diaminodecane 292
98/97 292
b b
1,10-diaminodecane 98/97 b 292
1,10-diaminodecane 54/68 b 98/97 b 292
Difurfurylamine 63/85 b b 92/110 b 304
b
1,10-diaminodecane
Difurfurylamine
Difurfurylamine
Difurfurylamine 63/85bb b 54/68
Difurfurylamine
63/85
63/85 63/85 b
92/110
92/110
92/110
bb b 92/110 b
304
304
304
98/97
304 292
Difurfurylamine
Difurfurylamine 63/85 b 63/85 b
92/110 b 92/110
304b 304 [166]
Difurfurylamine 63/85 b 92/110
b
b 304 [166]b
[166]
[166] [166] [166]
Difurfurylamine 63/85 92/110
[166] [166] 304
Isophorone [166]
Isophorone
Isophorone
Isophorone
Isophorone 75 150 150 282
Isophorone
Isophorone
diamine
Isophorone 75
75
75 75 150
150 282
150 282
282 282
diamine
diamine
Isophorone
diaminediamine 75 75150
75 150 282
150 150
282 282
diamine
diamine
diaminediamine 75 282

1,10-diaminodecane
1,10-diaminodecane
1,10-diaminodecane
1,10-diaminodecane
1,10-diaminodecane 6969 98
69
69
69 98 98297
297 297
98 297
1,10-diaminodecane 69 98
1,10-diaminodecane
69 98 98297
297 297
1,10-diaminodecane 69
69 98
1,10-diaminodecane 98297 297
Difurfurylamine
Difurfurylamine
Difurfurylamine74
Difurfurylamine
Difurfurylamine 74
74 7474 92
92
92 92271
271
271 92
271 271
Difurfurylamine
Difurfurylamine74 74 92 92271 271
a Difurfurylamine 74 92 271
Taaa aαTTTααmeasured
measured byby DMA
DMA DMA at positionDifurfurylamine
at theatthe
the thepeak
peak
peak peak
of loss modulus
position
position of
of loss
b curve; b T92 measured
74
ofmodulus
loss modulus curve;
271
bTT
α measured
curve;bbcurve; measuredby
byDMA
DMAat the bythe
DMA at the maximum of
measured
measured by
byby DMA DMA at the
at peak position of
positionloss modulus curve;
loss modulus T
Tαααmeasured by DMA atatthe
at the at
b Tα measured
α by DMA
TT α αmeasured DMA at the peak position of loss modulus curve; measured by DMA the
tan a aT cmeasured
α αmeasured
Tdofunderby byDMA air DMA at the
flow. at the
peak peak position
position of lossofmodulus
loss modulus
curve; bcurve; b Tα measured
Tα measured by DMA by DMA at the
at the
a δ;
maximum
maximum of
Tα measured tan
tan δ;
δ; ccc T
Td under
under
under air
air flow.
airthe
flow.
flow.
maximum
maximum ofof δ;by
tantan cδ;TdddcDMA
Td under
under at
air peak position of loss modulus curve; b Tα measured by DMA at the
air flow.
flow.
maximum
maximum
Table 5. of of
tantan
Di-epoxy
cδ; Td under
Tdcc under
δ; monomers air airtwo
flow. flow.
Table 5.
maximum
Table
Table of tanmonomers
5.5.Di-epoxy
Di-epoxy
Di-epoxy monomers with
Td under
δ; monomers
monomers with
with
with air two
two
with
aromatic
aromatic
aromatic
flow.
two two
rings
ringsseparated
rings
aromatic
aromatic rings separated
separated
rings
by
bymore
by more
more
separated
separated by more
than
than
bythan
one
more
than one
one
one
atom,
atom,
atom,
than
and
and
and
one
atom, and
thermal
thermal
thermal
atom, and thermal
thermal
Table
Table5.5.Di-epoxy
properties
properties Di-epoxy
of
of the
the monomers
cured
cured
cured monomers withwith
materials.
materials.
materials. two aromatic rings separated
two aromatic by moreby
rings separated than onethan
more atom,one
andatom,
thermal
and thermal
Table
Table 5. 5. Di-epoxy
Di-epoxy
properties
properties of the
of cured
the monomers
curedmonomers with two aromatic rings separated by
materials. with two aromatic rings separated by more
materials. more than one atom, and thermal
than one atom, and thermal
properties of the cured materials.
properties of the cured materials.
properties of the cured materials. T
T g (°C)
(°C)or TTα (°C)
TTgg g(°C)
(°C) or
ororT
Tαα α(°C)
(°C)
(°C)
properties of Epoxy
the cured materials.
Curing Agent
Tg (°C) orTTgα(°C)
T
(°C) or Tα (°C)
g (°C) or Tα (°C)Td,5% (°C) Reference
Epoxy
Epoxy
Epoxy Curing
CuringAgent
Curing Agent
Agent TgDGEBA
(°C) or Tα (°C)T
TT
d,5% (°C)
d,5% (°C)
d,5% (°C)
Reference
Reference
Reference
Epoxy
Epoxy CuringCuring
Agent AgentMaterials DGEBA
DGEBA
DGEBA Td,5% (°C) Td,5% (°C)
Reference Reference
Epoxy Curing AgentMaterials
Materials Comparison
Materials DGEBA DGEBA
Comparison
Comparison Td,5% (°C) Reference
Epoxy Curing AgentMaterialsMaterialsComparisonDGEBA ◦
Comparison
Materials Comparison
DGEBA
T
T g ( C) or Tα (◦ C) Reference
d,5% (°C)

Epoxy Materials
Curing Agent Comparison
Comparison
Td,5% (◦ C) Reference
4,4′-Diamino
4,4′-Diamino
4,4′-Diamino
4,4′-Diamino 60/70
Materials
- -
DGEBA Comparison
diphenyl methane
4,4′-Diamino 60/70
60/70
60/70 -- - -- -
diphenyl
diphenyl
diphenyl methane
methane
4,4′-Diamino
methane 60/70 - -
diphenyl
4,40 -Diamino 60/70
diphenyl 4,4′-Diamino
methane
methane 60/70
-
-
-
-
4,4′-Diamino
diphenyl
diphenyl methane 60/70 60/70 - - - -
diphenyl methane
4,4′-Diamino
4,4′-Diamino
methane
4,4′-Diamino
4,4′-Diamino 45/58
45/58 -- -- [165]
diphenyl methane
4,4′-Diamino
diphenyl methane 45/58
45/58 -- -- [165]
[165]
[165]
diphenyl
diphenyl methane0
methane 45/58 - - [165]
diphenyl 4,4′-Diamino
4,4 -Diamino
methane
4,4′-Diamino 45/58 - - [165]
diphenyl methane
diphenyl
4,4′-Diamino 45/58 45/58 - - - [165] -
diphenyl methane 45/58 - - [165] [165]
methane
diphenyl methane
4,4′-Diamino
4,4′-Diamino
4,4′-Diamino
4,4′-Diamino 39/54 -- --
diphenyl methane
4,4′-Diamino 39/54
39/54
39/54 -- --
Molecules 2017, 22, 149 diphenyl
diphenylmethane
diphenyl methane0
methane 5 of 7
39/54
4,4 -Diamino - -
Molecules 2017, 22, 149 diphenyl 4,4′-Diamino
methane 5 of 7
Molecules 2017, 22, 149 diphenyl 39/54
4,4′-Diamino 39/54 - - - 5 of 7 -
Molecules 2017, 22, 149 diphenyl methane
4,4′-Diamino 39/54 - - 5 of 7
methane 39/54
diphenyl methane - -
diphenyl methane
4,4′-Diamino
4,4′-Diamino
0 -Diamino 200 - 341/342 cc [16]]
diphenyl 4,4
methane
4,4′-Diamino
200 - 341/342 [16]]
diphenyl methane
4,4′-Diamino
diphenyl diphenyl200 200
methane 200
- - 341/342 341/342 [16]]
c
c- [16]] 341/342 c [16]
diphenyl methane
methane
Hexahydrophthalic
Hexahydrophthalic 134 bb 132 bb -
anhydride
Hexahydrophthalic
Hexahydrophthalic 134 132 -
Hexahydrophthalic
anhydride 134 b 134b b132 b
132 - 132 b -
anhydride 134 b
anhydride
anhydride
-
Phthalic anhydride 138 b - -
Phthalic138 b 138 b
Phthalic anhydride b - -
Phthalic anhydride
Phthalic anhydride
-
138 - - -
anhydride 138 bb - -
Nadic anhydride 147 - -
Nadic
Nadic anhydride 147 b 147 b
anhydride - b - - -
Nadic anhydride
Nadic anhydride 147 b 147 - -
- -
Hexahydrophthalic [173] [173]
Hexahydrophthalic
Hexahydrophthalic
Hexahydrophthalic 170 b 132 b - [173] [173]
anhydride
Hexahydrophthalic
anhydride
anhydride
170 b 170 b 170b b132
132 b - - 132 b [173] -
anhydride 170 b 132 b -
anhydride

Hexahydrophthalic
Hexahydrophthalic
Hexahydrophthalic
Hexahydrophthalic 149 b 149 bb 149b b132 bb
132 - - 132 b -
anhydride 149
anhydride
anhydride
Hexahydrophthalic
anhydride
132 -
149 b 132 b -
anhydride

a Tαaa aTmeasured b by
TαDMA
α measuredby
T α measured by DMA atthe
the peak position of loss modulus curve; measured bythe
DMA at the maximum of
by DMA
DMAatat peak position of loss modulus curve; b Tα measured
the peak position of loss modulus curve; b Tα measured by atDMA
the at
Tαc measured
maximum of tanby cDMA
δ;air at air
Tdflow.
under theflow.
peak position of loss modulus curve; b Tα measured by DMA at the
tanmaximum
aδ; T under
d of tanby
Tα measured c Td under
δ; DMA
c air flow.
at the peak position of loss modulus curve; Tα measured by DMA at the
b
maximum of tan δ; Tepoxy
Table 6. Poly-aromatic d under air flow.from crude bio-mass and thermal properties of the cured materials.
monomers
Table 6. Poly-aromatic
maximum of tan δ; c Tepoxy monomers
d under air flow. from crude bio-mass and thermal properties of the cured materials.
Table 6. Poly-aromatic epoxy monomers from crude bio-mass and thermal properties of the cured materials.
Table 6. Poly-aromatic epoxy monomers from crude bio-mass Tand g (°C) or Tα (°C)
thermal
Tg (°C) orproperties
Tα (°C) of the cured materials.
Epoxy Curing Agent Tg (°C) or Tα (°C) Td,5% (°C) Reference
DGEBA
Tg (°C) or Tα (°C)
Epoxy Curing Agent Materials Td,5% (°C) Reference
Epoxy Curing Agent DGEBA
Comparison Td,5% (°C) Reference
Epoxy Curing Agent Materials DGEBA T (°C) Reference
Materials Comparison d,5%
DGEBA
Comparison d
Diethylenetriamine -Materials - 252
Comparison
Epoxidized depolymerized kraft lignin Diethylenetriamine - - 252 dd
Diethylenetriamine
4,4-diaminodiphenyl - - 252
d
Molecules 2017, 22, 149 32 of 48

5.3. Polyaromatic Epoxy Compounds

As observed in the previous parts, it is hard to match up with the properties of DGEBA-based
materials, especially in term of glass transition temperature, thus making the use of polyaromatic
and possibly poly-epoxy derivatives a viable alternative. Moreover, the direct use of the biomass
would avoid the costly and time-consuming depolymerization and purification steps. The next part
will present the epoxy prepolymers containing at least three aromatic moieties and two or more
epoxy rings.

5.3.1. Glycidylated Lignin

Chemical modifications of lignin functional groups were carried out to increase its solubility
and chemical reactivity, and thus its range of applications. Among the possible functionalizations,
modification of the hydroxyl groups is the most versatile since phenolic hydroxyl groups are the most
reactive groups and can significantly affect the chemical reactivity of the materials. Allylation [178],
esterification [179,180], phenolation [181] or etherification [172,182–184] of lignin have been widely
investigated. However, only few research groups attempted to epoxidize raw depolymerized lignin by
direct O-glycidylation.
As the isolation of pure building blocks from lignin is both economically and environmentally
costly, Fache et al. [185] developed model mixtures of depolymerization products of lignin from both
hardwood and softwood, including for example vanillin, syringaldehyde and their acid equivalents.
After a Dakin oxidation to increase the number of reactive hydroxyl groups and an O-glycidylation
step, the materials cured with IPDA showed interesting thermo-mechanical properties, with Tg values
of 99 ◦ C and 113 ◦ C for hardwood and softwood model mixtures, respectively. These temperatures
remain lower than that of DGEBA-based materials synthesized by the same authors in fairly similar
conditions [135], probably due to the mono-epoxy derivatives included in the mixtures. Both materials
exhibited a good thermal stability with onset degradation temperatures above 250 ◦ C under nitrogen
atmosphere and high char yields of 20%–23% at 600 ◦ C. This study demonstrated that purification
steps are not necessarily required to achieve high-performance epoxy thermosets from biomass.
Ferdosian et al. [186] carried out the glycidylation of de-polymerized organosolv or Kraft lignin
with epichlorohydrin and highlighted the presence of epoxy by normalized FTIR. Then, they prepared
materials of the resulting epoxidized lignin by curing with aromatic and aliphatic amines to show the
influence of the curing agent on the thermal stability. Despite the good thermal stability and very high
char rate at 800 ◦ C, no glass transition temperature or mechanical properties were given.
Following the work of Zhao et al. [187], Sun et al. [188] prepared a liquid epoxy resin from
phenolated lignosulfonate and focused their study on its curing kinetics with maleic anhydride. No
data on the material properties were given.
Kaiho et al. [189] used a three-steps pathway to synthesize lignin-based epoxy resins (Figure 28):
(i) selective β-O-4 bond cleavage of eucalyptus globulus lignin, (ii) transacetalization for the synthesis of
spiro rings (47) or annulation to form a phenyl-naphthalene derivative (48) and (iii) O-glycidylation
with epichlorohydrin. The obtained resins were cured with phenol novolac yielding materials with
glass transition temperatures ranging from 67 to 134 ◦ C and of 95 ◦ C for an epoxy/bisphenol A system.
As expected from the structures, the more rigid structure of the phenyl-naphthalene lignin epoxy
prepolymers lead to higher Tg values and higher flexural strength.
Similarly, Asada et al. [190] used various low molecular weight lignins extracted with methanol
to synthesized bio-based epoxy resins. The glycidylation was assessed by FTIR and 1 H NMR
spectroscopies and four sets of materials were cured using two epoxy resins: glycidylated lignin
and an oil-based commercial Epikote 828 (EP828, DGEBA from Japan Epoxy Resins Co. Ltd., Nagoya,
Japan) and two phenolic hardeners: non-glycidylated lignin and TD2131 (a phenol novolac from DIC
Corp., Tokyo, Japan). The materials exhibited high thermal stabilities with Td,5% ranging from 259 to
326 ◦ C, still lower than the fully oil-based material (361 ◦ C) but with higher char rates, up to 41% at
800 ◦ C. Unfortunately, no glass transition temperatures or mechanical properties were provided. It is
phenolated lignosulfonate and focused their study on its curing kinetics with maleic anhydride. No data
on the material properties were given.
Kaiho et al. [189] used a three-steps pathway to synthesize lignin-based epoxy resins (Figure 28): (i)
selective β-O-4 bond cleavage of eucalyptus globulus lignin, (ii) transacetalization for the synthesis of spiro
rings (47) or annulation to form a phenyl-naphthalene derivative (48) and (iii) O-glycidylation33with
Molecules 2017, 22, 149 of 48
epichlorohydrin. The obtained resins were cured with phenol novolac yielding materials with glass
transition temperatures ranging from 67 to 134 °C and of 95 °C for an epoxy/bisphenol A system. As
worth
expectednoting
fromthatthethestructures,
lignin extract
theinsoluble in methanol
more rigid structurewas
of enzymatically transformedlignin
the phenyl-naphthalene into glucose,
epoxy
increasing the biomass promotion.
prepolymers lead to higher Tg values and higher flexural strength.

Figure28.
Figure 28.Lignin-based
Lignin-basedepoxy
epoxy resins
resins synthesized
synthesized by
byKaiho
Kaihoetetal.
al.[189].
[189].

Similarly, Asada et al. [190] used various low molecular weight lignins extracted with methanol to
Other uses have been found to lignin for the improvement of epoxy resins. Lignin functionalized
synthesized bio-based epoxy resins. The glycidylation was assessed by FTIR and 1H NMR spectroscopies
by a dicarboxylic acid prepared by dimerizing unsaturated fatty acids was considered as a phenolic
and four sets of materials were cured using two epoxy resins: glycidylated lignin and an oil-based
aldehyde amine curing agent by Fang et al. [191]. Similarly, Engelmann et Ganster [192] blended a low
commercial Epikote 828 (EP828, DGEBA from Japan Epoxy Resins Co. Ltd., Nagoya, Japan) and two
molecular weight lignin fraction with the bio-based tri-glycidylated glycerol for the preparation of
phenolic hardeners: non-glycidylated lignin and TD2131 (a phenol novolac from DIC Corp., Tokyo,
composites reinforced with cellulosic fibers.
Japan). The materials exhibited high thermal stabilities with Td,5% ranging from 259 to 326 °C, still lower
5.3.2.the
than fully oil-based
Glycidylated material (361 °C) but with higher char rates, up to 41% at 800 °C. Unfortunately,
Tannins
no glass transition temperatures or mechanical properties were provided. It is worth noting that the
ligninFew research
extract papers
insoluble are devoted
in methanol to the use of tannins
was enzymatically transformedand tannin-based moleculesthe
into glucose, increasing forbiomass
epoxy
materials
promotion. synthesis compared to lignin ones. Maybe the reduced availability of the former is a key
factorOther
in this
usesresult,
have as thefound
been complexity
to ligninand for the variability of of
the improvement both these
epoxy bio-resources
resins. seem similar.
Lignin functionalized by
As
a dicarboxylic acid prepared by dimerizing unsaturated fatty acids was considered asfrom
previously mentioned before, Aouf et al. [176] considered the hydrolysable tannins tara as
a phenolic
potential
aldehyde precursor
amine curing for epoxy
agent byprepolymer
Fang et al.synthesis, but they
[191]. Similarly, first carried
Engelmann out a depolymerization
et Ganster [192] blended a low to
obtain
moleculargallic acid mixtures
weight prior with
lignin fraction to glycidylation.
the bio-basedBenyahya et al. [193]
tri-glycidylated focused
glycerol theirpreparation
for the work on the of
inexpensive green tea (Camellia sinensis)
composites reinforced with cellulosic fibers. tannins, which are condensed tannins mainly composed of
epicatechin, catechin dimers and their galloylated equivalents. The tannins extracts were glycidylated
with
5.3.2. epichlorohydrin
Glycidylated Tannins and cured with isophorone diamine. The obtained materials exhibited a Tα of
142 ◦ C, a value similar to the 140 ◦ C of the material from IPDA and DER352 (a mixture of DGEBA and
DGEBF Few researchbypapers
supplied are devoted
Dow (France)). to the
Swelling use and
ratios of tannins
soluble and tannin-based
fractions moleculesalso
of these materials forproved
epoxy
materials
to be verysynthesis comparedettoal.
low. Jahanshahi lignin ones. recently
[194,195] Maybe the reduced availability
published two papersofon thethe
former is acondensed
use of key factor
in this result, as the complexity and the variability of both these bio-resources
tannins for the synthesis of bio-based materials. In the first one [194], Mimosa (Acacia mearnsii) bark seem similar. As
previously
tannins werementioned before,
glycidylated Aouf
with et al. [176] considered
epichlorohydrin but thethe hydrolysable
epoxy rings weretannins
then from tarawith
reacted as potential
acrylic
precursor for epoxy prepolymer synthesis, but they first carried out a depolymerization
acid for adhesive synthesis. On the contrary, in their second paper, they focused their efforts on to obtain gallic
the
acid mixtures prior to glycidylation. Benyahya et al. [193] focused their work
glycidylation optimal parameters and characterization of the epoxy prepolymers, thus very brief on the inexpensive green
tea (Camellia
results sinensis)
on tensile sheartannins,
tests ofwhich are condensed
glycidylated tannins tannins
mixed withmainly composed
DGEBA were of epicatechin, catechin
mentioned.
dimers and their galloylated equivalents. The tannins extracts were glycidylated with epichlorohydrin
and cured
5.3.3. with isophorone
Glycidylated Cardanol diamine. The obtained materials exhibited a Tα of 142 °C, a value similar to
the 140 °C of the material from IPDA and DER352 (a mixture of DGEBA and DGEBF supplied by Dow
To increase the low glass transition temperatures obtained with materials based on glycidylated
(France)). Swelling ratios and soluble fractions of these materials also proved to be very low. Jahanshahi
cardanol, a polyaromatic derivative of it can be designed by a two-steps synthesis, beginning by
et al. [194,195] recently published two papers on the use of condensed tannins for the synthesis of
a phenolation step and followed by direct O-glycidylation. The resulting product is idealized by
bio-based materials. In the first one [194], Mimosa (Acacia mearnsii) bark tannins were glycidylated with
a diepoxidized diaromatic cardanol structure and marketed with the name NC514 by Cardolite.
epichlorohydrin but the epoxy rings were then reacted with acrylic acid for adhesive synthesis. On the
However, Jaillet et al. [196] showed that the commercial product is a mixture (49), in which chains
contrary, in their second paper, they focused their efforts on the glycidylation optimal parameters and
are crosslinked and some epoxy rings are opened, as shown in Figure 29. This product may cause an
characterization of the epoxy prepolymers, thus very brief results on tensile shear tests of glycidylated
allergic skin reaction (H317), but can be used as food contact material, according to the supplier.
tannins mixed with DGEBA were mentioned.
Epoxy-amine based materials showed moderate glass transition temperature, from 13 to
◦
30 C with linear aliphatic diamines [197–199]. The highest Tg was reached when epoxidized
cardanol was cured with isophorone diamine, up to 50 ◦ C, which is still 100 ◦ C lower than that
of DGEBA-based material [196]. Nevertheless, the fatty chain of the epoxidized cardanol allows more
flexibility, conferring mechanical properties suitable for particular coating applications. Glycidyl ether
5.3.3. Glycidylated Cardanol
To increase the low glass transition temperatures obtained with materials based on glycidylated
cardanol, a polyaromatic derivative of it can be designed by a two-steps synthesis, beginning by a
phenolation
Molecules step
2017, 22, 149 and followed by direct O-glycidylation. The resulting product is idealized34by a
of 48
diepoxidized diaromatic cardanol structure and marketed with the name NC514 by Cardolite. However,
Jaillet et al. [196] showed that the commercial product is a mixture (49), in which chains are crosslinked
groups
and some have also rings
epoxy been converted to as
are opened, methacrylate, allowing
shown in Figure radical
29. This polymerization
product may causefor
another coating
allergic skin
applications [200,201].
reaction (H317), but can be used as food contact material, according to the supplier.

Figure 29.
Figure 29.Idealized structure
Idealized of phenolated
structure cardanol
of phenolated (left) and
cardanol real
(left) structure
and (49) of NC514
real structure byNC514
(49) of Cardolite.
by
Cardolite. The numbers between brackets indicate the locations of the phenol moieties alongalkyl
The numbers between brackets indicate the locations of the phenol moieties along the aliphatic the
chain. alkyl chain.
aliphatic

Epoxy-amine based materials showed moderate glass transition temperature, from 13 to 30 °C with
5.3.4. Other Bio-Based Poly-Aromatic Monomers
linear aliphatic diamines [197–199]. The highest Tg was reached when epoxidized cardanol was cured
with Fourcade
isophorone etdiamine,
al. [167] upapplied
to 50 the
°C, same
whichstrategy as °C
is still 100 previously
lower thandescribed (see Section 5.2.2.)
that of DGEBA-based on
material
various aliphatic polyols
[196]. Nevertheless, (Scheme
the fatty chain 14). Glycerol
of the (50) and
epoxidized sorbitol
cardanol (51)more
allows are bio-based
flexibility,precursors,
conferring
pentaerythritol (52), di-pentaerythritol
mechanical properties (53) and
suitable for particular trimethylolpropane
coating (54) areether
applications. Glycidyl obtained via have
groups formaldehyde
also been
and acetaldehyde
converted from allowing
to methacrylate, syngas of the polymerization
radical Biomass-to-Liquid (BtL)
for other process
coating or carbon
applications monoxide
[200,201].
hydrogenation. Moreover, according to their corresponding MSDS files, these polyols and
ethyl-4-hydroxybenzoate show no toxic
5.3.4. Other Bio-Based Poly-Aromatic risk. Only the dibutyltin dilaurate (DBTDL), which is used as
Monomers
catalyst 2017,
Molecules in the
22,phenolation
149 step and the unavoidable epichlorohydrin present safety risks. 34 of 47
Fourcade et al. [167] applied the same strategy as previously described (see Section 5.2.2.) on
various aliphatic polyols (Scheme 14). Glycerol (50) and sorbitol (51) are bio-based precursors,
pentaerythritol (52), di-pentaerythritol (53) and trimethylolpropane (54) are obtained via formaldehyde
and acetaldehyde from syngas of the Biomass-to-Liquid (BtL) process or carbon monoxide
hydrogenation. Moreover, according to their corresponding MSDS files, these polyols and
ethyl-4-hydroxybenzoate show no toxic risk. Only the dibutyltin dilaurate (DBTDL), which is used as
catalyst in the phenolation step and the unavoidable epichlorohydrin present safety risks.
The phenolation step allowed 75% to 100% of conversion and the glycidylation of the resulting
phenolic compounds led to an overall functionality ranging between 2 and 5. The synthesized
polyaromatic glycidyl epoxides were blended with DGEBA and cured with dicyandiamide. From a
general point of view, the addition of these new resins decreased the glass transition temperature of the
blend materials, up to 24% when 25% are used. Glycidyl ether of trimethylolpropane-tris
(4-hydroxybenzoate) was cured with dicyandiamide in the absence of DGEBA and the corresponding
material showed a Tg of 105 °C, slightly lower than that of DGEBA-based material (119 °C). This result is
very promising since materials can be prepared from non-toxic hydroxyl compounds and almost meet
the thermal properties of the harmful DGEBA-based materials.

Scheme
Scheme 14. 14.Synthetic pathway
Synthetic to obtain
pathway poly-aromatic
to obtain poly-glycidyl
poly-aromatic ethers developed
poly-glycidyl by Fourcade
ethers developed by
et al. [167].
Fourcade et al. [167].

Similarly, Ménard et al. [166] synthesized a tri-aromatic tri-epoxy monomer based on glycerol and
ferulic acid (55) (Figure 30), although the esterification step was carried out with an enzymatic catalyst.
After curing with IPDA, difurfurylamine and 1,10-diaminodecane, the thermosets showed Tg and Tα
values ranging from 54 to 73 °C and 67 to 92 °C, respectively, with lowest values observed for the
aliphatic diamine. These values remain significantly lower than those observed for DGEBA-based
materials, as the increased functionality does not compensate the effect of the long aliphatic segments.
Molecules 2017, 22, 149 35 of 48

The phenolation step allowed 75% to 100% of conversion and the glycidylation of the resulting
phenolic compounds led to an overall functionality ranging between 2 and 5. The synthesized
polyaromatic glycidyl epoxides were blended with DGEBA and cured with dicyandiamide. From
a general point of view, the addition of these new resins decreased the glass transition temperature
of the blend materials, up to 24% when 25% are used. Glycidyl ether of trimethylolpropane-tris
(4-hydroxybenzoate) was cured with dicyandiamide in the absence of DGEBA and the corresponding
material showed a Tg of 105 ◦ C, slightly lower than that of DGEBA-based material (119 ◦ C). This result
Scheme 14. Synthetic pathway to obtain poly-aromatic poly-glycidyl ethers developed by Fourcade
is very promising since materials can be prepared from non-toxic hydroxyl compounds and almost
et al. [167].
meet the thermal properties of the harmful DGEBA-based materials.
Similarly, Ménardetetal.
Similarly, Ménard al.[166]
[166]synthesized
synthesized a tri-aromatic
a tri-aromatic tri-epoxy
tri-epoxy monomer
monomer based
based on glycerol
on glycerol and
and ferulic
ferulic acid(Figure
acid (55) (55) (Figure 30), although
30), although the esterification
the esterification step
step was was carried
carried out withoutan with an enzymatic
enzymatic catalyst.
catalyst. Afterwith
After curing curing withdifurfurylamine
IPDA, IPDA, difurfurylamine and 1,10-diaminodecane,
and 1,10-diaminodecane, the thermosets
the thermosets Tg and TTgα
showedshowed
and T values ranging from 54 to 73 ◦ C and 67 to 92 ◦ C, respectively, with lowest values observed for
valuesαranging from 54 to 73 °C and 67 to 92 °C, respectively, with lowest values observed for the
the aliphatic
aliphatic diamine.
diamine. These
These values
values remain
remain significantly
significantly lowerthan
lower thanthose
those observed
observed for
for DGEBA-based
DGEBA-based
materials, as the increased functionality does not compensate the effect of the long aliphatic
materials, as the increased functionality does not compensate the effect of the long aliphatic segments. segments.

Figure
Figure 30.30.Tri-epoxy
Tri-epoxymonomer
monomerbased
basedon
onferulic
ferulic acid
acid and
and glycerol
glycerolsynthesized
synthesizedby
byMénard
Ménardetet
al.al.
[166].
[166].

Very recently, Wan et al. [121,202] prepared two eugenol-based di-epoxy compounds, using a
Very recently, Wan et al. [121,202] prepared two eugenol-based di-epoxy compounds, using
two-steps synthesis. The first step consisted in a Williamson etherification reaction between the hydroxyl
a two-steps synthesis. The first step consisted in a Williamson etherification reaction between the
group of eugenol and chloride aromatic derivatives, α,α′-dichloro-p-xylene [202] or cyanuric chloride
hydroxyl group of eugenol and chloride aromatic derivatives, α,α0 -dichloro-p-xylene [202] or cyanuric
[121]. The resulting allylated intermediate was achieved with an almost quantitative yield. Then, the
chloride [121]. The resulting allylated intermediate was achieved with an almost quantitative yield.
carbon-carbon double bonds were oxidized using mCPBA with a moderate yield (44%–70%), yielding
Then, the carbon-carbon double bonds were oxidized using mCPBA with a moderate yield (44%–70%),
di- (56) and tri-glycidylated (57) derivatives (Figure 31). Despite a high net bio-based content (70%) of
yielding di- (56) and tri-glycidylated (57) derivatives (Figure 31). Despite a high net bio-based content
these new epoxy resins, the chosen synthetic pathway requires the use of mCPBA, which is known to be
(70%) of these new epoxy resins, the chosen synthetic pathway requires the use of mCPBA, which is
dangerous, and chlorinated derivatives, which are highly toxic (H302-H314-H330) for cyaniric chloride
known to be dangerous, and chlorinated derivatives, which are highly toxic (H302-H314-H330) for
and detrimental for the environment (H400) for α,α′-dichloro-p-xylene.
cyaniric chloride and detrimental for the environment (H400) for α,α0 -dichloro-p-xylene.
Both eugenol-based epoxies showed lower reactivity towards amine than DGEBA, due to the
lower electron withdrawing effect of the -CH2 Ph epoxy-ring, compared to the usual -CH2 OPh in
BPA, but they avoid the use of epichlorohydrin and still, eugenol-based materials were successfully
prepared by curing with aromatic diamines. The material based on the diglycidyl ether compounds
prepared from α,α0 -dichloro-p-xylene showed a Tg 40 ◦ C lower than for DGEBA-based materials,
probably due to the methoxy groups on the aromatic rings and the -CH2 O linkages between them.
For the material obtained from cyanuric chloride, the glass transition temperature proved to be 33 ◦ C
higher despite the methoxy moieties, probably thanks to the tri-functional nature of the prepolymer.
Molecules 2017, 22, 149 36 of 48
Molecules 2017, 22, 149 35 of 47

Figure 31. Eugenol-based poly-aromatic epoxy monomers.

Both eugenol-based epoxies showed lower reactivity towards amine than DGEBA, due to the lower
electron withdrawing effect of the -CH2Ph epoxy-ring, compared to the usual -CH2OPh in BPA, but they
avoid the use of epichlorohydrin and still, eugenol-based materials were successfully prepared by curing
with aromatic diamines. The material based on the diglycidyl ether compounds prepared from
α,α′-dichloro-p-xylene showed a Tg 40 °C lower than for DGEBA-based materials, probably due to the
methoxy groups on the aromatic rings and the -CH2O linkages between them. For the material obtained
Figure 31. Eugenol-based poly-aromatic epoxy monomers.
from cyanuric chloride, the Figure
glass Eugenol-based
31.transition poly-aromatic
temperature proved epoxy
to bemonomers.
33 °C higher despite the methoxy
moieties, probably thanks to the tri-functional nature of the prepolymer.
Both eugenol-based epoxies showed lower reactivity towards amine than DGEBA, due to the lower
et
et al.
al. [120]
Wanwithdrawing [120] also
also prepared
prepared a bio-based epoxy building
buildingtoblock in a two-step synthesis
synthesis from
electron effect of the -CHa2Ph bio-based
epoxy-ring, epoxy compared block
the usuala-CH two-step
2OPh in BPA, but they
eugenol and terephthaloyl chloride: (i) (i) aa coupling
coupling reaction
reaction between
between eugenol and terephthaloyl
terephthaloyl chloride,
chloride,
avoid the use of epichlorohydrin and still, eugenol-based materials were successfully prepared by curing
followed by
followed by(ii)
(ii)ananepoxidation
epoxidation by oxidation of the C=C double bonds (58). The coupling step
with aromatic diamines. The by oxidation
material based of the
on C=Cthe double
diglycidyl bonds (58).compounds
ether The coupling step allowed
prepared from
allowed
93% 93% of yield
of yield and the final and the
product final product was a white solid. However, the high toxicity of the
α,α′-dichloro-p-xylene showed a Tg was
40 °Ca lower
white thansolid.forHowever,
DGEBA-based the high toxicity of
materials, the commercially
probably due to the
commercially
available available chloride
terephthaloyl terephthaloyl has toandchloride
bethetaken has toaccount.
be takenThe in account.
material The materialby obtained by
methoxy groups on the aromatic rings -CHin obtained
2O linkages between them. For the material obtained
curing with
curing with 3,30 -diaminodiphenyl
3,3′-diaminodiphenyl sulfone showed sulfone
lower showed
Tg and lower
thermalTg and thermal
stability and stability
slightly and slightly
higher higher
mechanical
from cyanuric chloride, the glass transition temperature proved to be 33 °C higher despite the methoxy
mechanicalthan
properties properties
the than
one the one
based on based
DGEBA. on DGEBA.
Furthermore,Furthermore, it exhibited
it exhibited interesting
interesting intrinsic
intrinsic flame
moieties, probably thanks to the tri-functional nature of the prepolymer.
flame retardancy.
retardancy.
Wan et al. [120] also prepared a bio-based epoxy building block in a two-step synthesis from
Czub [203] considered recycling polyethylene terephthalate terephthalate (PET) wastes, especially coming from
eugenol and terephthaloyl chloride: (i) a coupling reaction between eugenol and terephthaloyl chloride,
bottles,
bottles, for the synthesis of epoxy resins (59). The
The precursor
precursor of PET, terephtalic acid, is mostly produced
followed by (ii) an epoxidation by oxidation of the C=C double bonds (58). The coupling step allowed
by air oxidation of oil-based p-xylene [204]. However, as previously stated, p-xylene be obtained
93% ofoxidation
yield and the oil-based
final product was a white solid. However,previously p-xylene
the high toxicity cancommercially
of the obtained
from cellulosic
cellulosic biomass,
biomass, for example via dehydration
dehydration of iso-butanol
iso-butanol into
into iso-butene,
iso-butene, dimerization
dimerization into
available terephthaloyl chloride has to be taken in account. The material obtained by curing with
iso-octene and catalytic conversion.
iso-octene conversion. ItIt can can also
also be synthesized by dehydrogenation of 3-carene extracted
3,3′-diaminodiphenyl sulfone showed lower T g and thermal stability and slightly higher mechanical
from pine tree or limonene
limonene extracted
extracted from citrus
citrus fruits into p-xylene. Thus, the author degraded PET
properties than the one based on DGEBA. Furthermore,p-xylene. it exhibited interesting intrinsic flame
waste by glycolysis
glycolysis reaction into small
small aromatic
aromatic hydroxy
hydroxy telechelic
telechelic oligomers.
oligomers. Using epichlorohydrin,
epichlorohydrin,
retardancy.
these polyhydroxyl
these derivatives were were glycidylated
glycidylatedand and mixed
mixed with with DGEBA
DGEBA oligomers
oligomers leading
leading to an
Czub [203] considered recycling polyethylene terephthalate (PET) wastes, especially comingto
polyhydroxyl derivatives from
improved water absorption and
absorption and resistance
resistanceto toHNO
HNO3,3 ,HH2SO 2 SO
4 andand ethyl
ethyl acetate
acetate (Figure
(Figure 32).
32).
4of PET, terephtalic acid, is mostly The The addition
addition of
bottles, for the synthesis of epoxy resins (59). The precursor produced
of 5%–20%
5%–20% of glycidylated
of glycidylated PET-wastes
PET-wastes in oligo(DGEBA)
in oligo(DGEBA) curedcured with isophorone
with isophorone diamine led to similar
by air oxidation of oil-based p-xylene [204]. However, as previously
◦ C to 53–63 ◦ C measured in DMTA.
stated,diamine
p-xyleneled canto be
similar and
obtained
and slightly
slightly higher higher
T Tg values,
g values, from from
56 °C 5653–63
to °C measured in DMTA.
from cellulosic biomass, for example via dehydration of iso-butanol into iso-butene, dimerization into
iso-octene and catalytic conversion. It can also be synthesized by dehydrogenation of 3-carene extracted
from pine tree or limonene extracted from citrus fruits into p-xylene. Thus, the author degraded PET
waste by glycolysis reaction into small aromatic hydroxy telechelic oligomers. Using epichlorohydrin,
these polyhydroxyl derivatives were glycidylated and mixed with DGEBA oligomers leading to an
improved water absorption and resistance to HNO3, H2SO4 and ethyl acetate (Figure 32). The addition of
5%–20% of glycidylated PET-wastes in oligo(DGEBA) cured with isophorone diamine led to similar and
slightly higher Tg values, from 56 °C to 53–63 °C measured in DMTA.

Figure32.
Figure 32.Epoxy
Epoxymonomers
monomers obtained
obtained from
from glycolyzed
glycolyzedPET
PETwaste
wasteby
byCzub
Czub[203].
[203].

5.3.5. Conclusions
Due to their complexity and variability, bio-mass resources such as lignin or tannins have not
received as much attention as smaller molecules for BPA substitution. However, as observed in
the previous parts, they have been successfully turned into poly-epoxy monomers and used for the
synthesis of materials exhibiting interesting properties. Similarly, smaller bio-based molecules such
Figure 32. Epoxy monomers obtained from glycolyzed PET waste by Czub [203].
 anhydride 170 b 132 b -
anhydride

Hexahydrophthalic
Hexahydrophthalic 149 b b 132 b b -
anhydride 149 132 -
anhydride
Molecules 2017, 22, 149 37 of 48

TTαα measured
a
measured by
a by DMADMA atat the
the peak
peak position
position of
of loss
loss modulus
modulus curve;
curve; b TTαα measured
b
measured byby DMA
DMA atat the
the
maximum
maximum of
oftan
tanδ;δ; cTTddunder
c
underair
airflow.
flow.
as eugenol and ferulic acid were turned into poly-aromatic epoxy monomers, but still few materials
Table 6.6.Poly-aromatic
Poly-aromaticepoxy epoxymonomers from
fromcrude
crudebio-mass
bio-massand
andthermal
thermalproperties of the
thecured
curedmaterials.
reachedTable
the high Tg values ofmonomers
their DGEBA counterparts. Theseproperties
resultsofare materials.
gathered in Tables 6 and 7.
TTgg(°C)
(°C)or
orTTαα(°C)
(°C)
Epoxy
Table 6. Poly-aromatic
Epoxy Curing
CuringAgent
epoxy monomers from crude bio-mass
Agent TTd,5%
and thermal (°C) Reference
d,5% (°C) properties
Reference of the
DGEBA
DGEBA
Materials
Materials
cured materials. Comparison
Comparison

Diethylenetriamine
Diethylenetriamine -- ◦ - 252 d
T g ( C) or T α -(◦ C) 252 d
Epoxy Curing Agent T d,5% (◦ C) Reference
Epoxidized
Epoxidizeddepolymerized
depolymerizedkraft
kraftlignin
lignin Materials DGEBA Comparison
4,4-diaminodiphenyl
4,4-diaminodiphenyl -- -- 290 d
290 d
methane
Diethylenetriamine
methane - - 252 d
Epoxidized depolymerized [186]
[186]
kraft lignin 4,4-diaminodiphenyl
Diethylenetriamine - -- -- - 228 d 290 d
methane
Diethylenetriamine 228 d [186]
Epoxidized
Epoxidizeddepolymerized
depolymerized
organosolv lignin Diethylenetriamine
4,4-diaminodiphenyl
- - 228 d
organosolv
Epoxidized lignin
depolymerized 4,4-diaminodiphenyl -- -- 257 d
methane
4,4-diaminodiphenyl 257 d
organosolv lignin methane - - 257 d
methane

94
94 --
94 -

Phenol
PhenolNovolac
Novolac 95
95 95 [189]
[189]
Phenol Novolac [189]

134 134
134 -- -

Phenol Novolac
Phenol
PhenolNovolac
Novolac(TD2131)
(TD2131)
- -- -- - 293
293
293
Epoxidized lignin (Cedar) (TD2131)
Epoxidized
Epoxidizedlignin
lignin(Cedar)
(Cedar)
Lignin (Cedar)
Lignin - -- - 296
Lignin(Cedar)
(Cedar) -- 296
296
Phenol Novolac
- - 275
Epoxidized lignin (Eucalyptus) Phenol(TD2131)
PhenolNovolac
Novolac(TD2131)
(TD2131) -- -- 275
275 [190]
[190] [190]
Epoxidized
Epoxidizedlignin
lignin(Eucalyptus)
(Eucalyptus) Lignin
- - 274
(Eucalyptus)
Lignin
Lignin(Eucalyptus)
(Eucalyptus) -- -- 274
274
Phenol Novolac
- - 266
Epoxidized
Epoxidized lignin(Bamboo)
(Bamboo) (TD2131) (TD2131)
Epoxidizedlignin
lignin (Bamboo) Phenol
PhenolNovolac
Novolac (TD2131) -- -- 266
266
Lignin (Bamboo) - - 259
Isophorone
Epoxidized green tea extract 142 a,b
140 a,b 256/267 c [193]
Diamine
Isophorone
50 a,b 155 a,b 350 [205]
Diamine
Jeffamine T403 23 70 352 e
[198]
41 121 350 e
Isophorone
366 e /363
Diamine 50/59 b 158/158 b c,e

[196]
Epoxidized cardanol (NC514) 362 e /361
Jeffamine D400 15/9 b - c,e

PE-C9-NH2 13 279 -
[141]
PE-C18-NH2 14 284 -
Phenalkamine 325 f /322
30/38 a,b - c,f
NX5454
[206]
Cardanol 328 f /311
19/21 a,b - c,f
cysteamine
a Tα measured by DMA at the peak position of loss modulus curve; b Tα measured by DMA at the maximum of
tan δ; c Td under air flow; d IDT = initial decomposition temperature; e Td,30% ; f Td,10% .
 [141]
PE-C18-NH2
PE-C18-NH2 14
14 284
284 --

a,b
Phenalkamine NX5454 30/38 a,b
a,b - 325 fff/322 c,f
c,f
c,f

[206]
Cardanol
Cardanol cysteamine
cysteamine 19/21 a,b
19/21 a,b
a,b -- 328
328 ff/311
f c,f
/311 c,fc,f
Molecules 2017,
aaa Tα
22, 149
α measured by DMA at the peak position of loss modulus curve; bbb Tα
α measured by DMA at the
38 of 48
α α
ccc d
maximum of tan δ; Tddd under air flow; IDT = initial decomposition temperature; T
d
d ; Td,10%
d,10%. eee d,30% fff
d,30%
d,10% d,30%

Table 7. Poly-aromatic di- and tri-epoxy monomers and thermal properties of the cured materials.
Table 7. Poly-aromatic di- and tri-epoxy monomers and thermal properties of the cured materials.
Tgg (°C) or Tαα (°C) Tgg (°C) or Tαα (°C)

Epoxy Curing Agent Td,5%

d,5% (°C)
d,5% Reference
T g (◦ C) or T α (◦ C)
DGEBA
Epoxy Curing AgentMaterials T d,5% (◦ C) Reference
Comparison
Materials DGEBA Comparison

4,40 -diaminodiphenyl bbb

4,4′-diaminodiphenyl
114 114 b 154 bbb 154 b
341 [202] 341 [202]
methanemethane

1,10-diaminodecane 54/70 bbb 293

1,10-diaminodecane 54/70 b 293
Isophorone
Isophorone Diamine
Diamine 73/92 b
73/92 bb 294
294
bbb b
150/174 150/174 [166] [166]
Isophorone
73/92 b 294
Diamine
Difurfurylamine 58/67 bbb 284

Difurfurylamine b 284
58/67

3,30 -diaminodiphenyl
3,3′-diaminodiphenyl
168 bbb b c
[120] 338/337 c
sulfone 168 b 174 bb 174 ccb
338/337 [120]
sulfone

Dicyandiamide 105 bbb

Dicyandiamide 105 b 119 bbb ccc b
119
305 [167] 305 c [167]
Molecules 2017, 22, 149 7 of 7

3,30 -diaminodiphenyl
3,3′-diaminodiphenyl
207 b
sulfone 207 b 174 b 326
174 b [121] 326 [121]
sulfone

a Taα Tmeasured
α measuredbybyDMADMA at at the
the peak
peak position
positionofofloss modulus
loss curve;
modulus b Tα bmeasured by DMA at the
curve; Tα measured by DMA at the maximum of
δ; c Td under
tanmaximum air
of tan δ; c Tflow.
d under air flow.

6. General Conclusions
Biorefinery processes and retreatment of biomass was out of our scope. However, it is clear that
the future of bio-based polymers, including building blocks for thermosetting epoxies is strongly
dependent on the future of biorefinery. The goal of a biorefinery is to produce high quality
chemicals for fuels, monomers, and finally polymers and materials. New screening techniques
like “Green Chemistry” and techno-economic and Life Cycle Assessment (LCA) indicators can help
chemical-based biorefinery project developments. But efficient, economical, and large-scale synthesis
of monomers is crucial, and the first key parameter remains a resource pool that should be abundant
and easily accessed.
At first glance, there are a lot of opportunities to develop molecular biomass and monomers for
preparation of renewable epoxy formulations and materials. But, the biggest changes for thermosetting
epoxy formulations in the near future will certainly come from the regulation changes like the
environmental directives for reducing Volatile Organic Constituents (VOC), the “Restriction of certain
Hazardous Substances” (RoHS), or the “Registration, Evaluation and Authorisation of Chemicals”,
(REACh). Bio-based compounds will not be the only solution for these policy pressures but will be
an opportunity.
There are many different routes to synthesize bio-based aromatic epoxy monomers and hence
to replace DGEBA. However, we have to take into account several parameters such as the epoxy
functionality; the different applications—for example coatings are totally different from composites
and the adaptation of properties to applications. Hence, even if DGEBA is very interesting since it
allows to cover all applications, it seems difficult to imagine to replace DGEBA by the same bio-based
epoxy monomer in all applications. Currently, only a handful of patents led to commercialization
of products, such as epoxided cardanol or vegetable oils. However, these epoxide monomers led to
Molecules 2017, 22, 149 39 of 48

low Tg polyepoxide networks for low Tg applications. Epoxy aromatic monomers leading to high Tg
polyepoxide are desired and correspond to an important challenge. Some industrial countries have
declared bisphenol A (BPA) to be a toxic substance that causes risks to human health as well as to
the environment; thus it has to be banned for all food contact applications in the next coming years,
and in the immediate future the pressure is on its replacement. BPA is industrially produced from
condensation of acetone with phenols. Therefore, bio-based aromatic/rigid epoxy monomers are still
needed in order to fulfil good compromise between processing and properties, and able to enable
replacement of BPA.
Developing highly efficient, safe, low waste, low toxicity and atom economy processes are the
key words for green chemistry. Chemistry has to be simple, practical, and operational, and catalysts
are expected to play an important role. Epichlorohydrin is the preferred way to prepare epoxy
monomers; but epichlorohydrin is a toxic molecule which has to be manipulated in a safe environment.
Epoxidation without the use of epichlorohydrin is a key challenge. Even if allylation or crotonization
of alcohols can be a first step for epoxydation, the second step, i.e., double bond oxidation, requires the
use of hazardous catalysts. Therefore, the oxidation of terminal double bonds is an interesting route
but still needs research to propose industrial routes.

Conflicts of Interest: The authors declare no conflict of interest.

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