Progress in Organic Coatings 135 (2019) 608–612

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Review

Bio-epoxy resins with inherent flame retardancy T

a b,c,⁎ d b,c,⁎
Elaheh Rohani Rad , Henri Vahabi , Agustin Rios de Anda , Mohammad Reza Saeb ,
Sabu Thomase,
⁎⁎

a
Faculty of Health and Medical Sciences, The University of Adelaide, SA, Adelaide, Australia
b
Université de Lorraine, CentraleSupélec, LMOPS, F-57000 Metz, France
c
Laboratoire Matériaux Optiques, Photoniques et Systèmes, CentraleSupélec, Université Paris-Saclay, 57070, Metz, France
d
Institut de Chimie et des Matériaux Paris-Est, UMR 7182 CNRS – Université Paris-Est Créteil Val-de-Marne, 2, rue Henri Dunant, 94320 Thiais, France
e
School of Chemical Sciences, MG University, Kottayam 686560, Kerala, India

ARTICLE INFO ABSTRACT

Keywords: Nowadays, roughly 90% of worldwide epoxy resin materials are made from diglycidyl ether of bisphenol A
Bio-based epoxy resin (DGEBA). This resin offers unique features such as outstanding mechanical properties, chemical resistance, and
Flame retardancy shape stability. By contrast, the growing awareness of environmental issues, global warming, and depletion of
Thermoset composites petroleum reservoir suggest search for using bio-epoxy resin from sustainable resources. Indeed, DGEBA is a
Flame retardants
petroleum-based monomer obtained from bisphenol A and epichlorohydrin, two potential precursors harmful for
the environment and human health as well. The problem deepens when it comes to the high flammability of such
materials, which restricts their use in strategic applications. Although the introduction of flame retardant (FR)
additives to epoxy matrices has been a major strategy to induce flame retardancy, negative impact on me-
chanical properties and migration of FRs to the materials’ surface remained unresolved issues. Tailoring epoxy
chains with chemically bonded reactive flame retardants to epoxy resins would be the solution to avoid mi-
gration of FRs to surface, along with protecting mechanical properties of resin. With the rapid development of
reactive bio-based FRs and epoxy resins, production of flame retardant bio-epoxy with high biomass content has
become a promising strategy to address these issues. This conside review encompasses latest progress in flame
retardant bio-epoxy resins made of different resources, with inherent chemical structures of either epoxy
monomers or embedded reactive flame retardant elements.

1. Bio-epoxy versus conventional petroleum-based epoxy properties, the use of epoxy monomers brings about some problems [6]
summarized as follows:
Epoxy resins offer versatile integrated features such as outstanding
mechanical properties, chemical resistance, and shape integrity in (I) It has been proved that DGEBA has severed effects on living or-
harsh conditions. These properties are the result of a crosslinked 3D ganisms due to the toxicity of BPA [7]. Since BPA has been in-
network obtained by the chemical reaction between an epoxy monomer volved in the manufacture of many products, especially in epoxy
and a curing agent [1,2]. The use of epoxy thermosets has been surged resin thermosets, concerns about exposure to high dosages of BPA
over the last decade in a wide range of applications such as coatings, seems harmful for human life. Given this, legislation in many
adhesives, solar cells, electronic apparels, as well as in automotive and countries has banned the use of BPA in infant-related products [8].
aerospace industries [3,4]. Such applications are expected to receive (II) From an economic point of view, as DGEBA is derived from pet-
more attention in the near future. Petroleum-based diglycidyl ether roleum, it has experienced a rise in raw materials prices that have
bisphenol A (DGEBA) accounts for ca. 90% of the epoxy resin world- had a negative effect on the market.
wide usage. This monomer is produced from the reaction between bi- (III) CO2 emission from fossil fuels is the major suspect for recent global
sphenol A (BPA) and epichlorohydrin (ECH) in sodium hydroxide warming, which has encouraged researchers to substitute renew-
media (NaOH) [5]. Although DGEBA displays fascinating properties able green products by petroleum-based products. In addition,
such as chemical resistance, good adhesion, and superior mechanical unreacted BPA might be released during production and later due

⁎
Corresponding authors at: Université de Lorraine, CentraleSupélec, LMOPS, F-57000 Metz, France.
⁎⁎
Corresponding author at: School of Chemical Sciences, MG University, Kottayam 686560, Kerala, India.
E-mail addresses: [email protected] (H. Vahabi), [email protected] (M.R. Saeb), [email protected] (S. Thomas).

https://doi.org/10.1016/j.porgcoat.2019.05.046
Received 24 March 2019; Received in revised form 5 May 2019; Accepted 29 May 2019
Available online 19 July 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
E.R. Rad, et al. Progress in Organic Coatings 135 (2019) 608–612

to ageing, and hence rejection by the environment [9]. from high flammability, which is a crucial prerequisite for transporta-
tion, construction, and electronic uses [29–33]. Overall, two strategies
In the light of above, taking into consideration the worldwide vo- can be used to achieve an adequate degree of flame retardancy per-
lume of DGEBA usage, a great deal of attention has been devoted to formance.
explore bio-based epoxy resins from renewable resources such as plant
oils [10,11], lignin [12], rosin acids [13], tannins [14], cardanol [15], (I) Development of char forming epoxy monomers with low combus-
and itaconic acid [16] instead of traditional petroleum-based DGEBA. tion energy, which can impart flame retardancy to the structure of
Rapid development in the synthesis of bio-epoxy resins and their out- epoxy building blocks [14].
standing characteristics nominated them as promising candidates to (II) The strategy of incorporation of flame retardant (FR) to the epoxy
overtake commercial DGEBA market [17,18]. In terms of curing po- matrix based on chemical bonding of FRs to epoxy monomers or
tential, substantial attempts have been made to define, quantify, and physical blending with epoxy resins [34]. Even if the physical
explain mechanism of network formation in thermoset systems blending of FRs is still a cheaper method from an industrial point of
[19–21]. However, potential curability of bio-epoxy resins is obviously view, it remains challenging due to the difference in chemical
lower than the commercial DGEBA. This must be overviewed because of structures of the FRs and the epoxy matrix. This leads to poor
the fact that almost the whole properties of thermoset systems depend miscibility and difficult handling of the epoxy filled with FR for-
on the epoxy curing state [22,23]. Analysis of mechanical properties mulations [35]. In addition, migration or leaching of FRs during life
revealed that bio-epoxy resins derived from rigid chemical structures cycle, as well as a negative effect of additives on the epoxies
such as diphenolic acid, rosin acid, and 2,5-furandicarboxylic acid crosslinking density [36] and consequently a loss of mechanical
(FDCA) have mechanical properties comparable to DGEBA [24,25]. properties remain unresolved issues. However, a means to over-
However, natural oil-based resins display inferior mechanical and come all these issues is to chemically bond FRs to epoxy monomers
thermal properties due to their long aliphatic chains, and because of so as to obtain captive FRs in the polymer network.
their lower crosslink density [25]. Furthermore, it was reported that the
analysis of kinetics of epoxy curing provides a practical tool to compare Development of the bio-based epoxy resins and bio-based flame
the reactivity of bio-epoxy monomers with flame retardant additives retardants are cutting edge strategies going forward concurrently. Both
[26]. Flame Retardancy Index was recently defined to qualitative study strategies benefit from the design of fully bio-epoxy resins with high
of flame retardancy potential of polymer composites, but not yet in- biomass content [37–41]. However, to the best of our knowledge, only
tended to inheren bio-epoxy systems [27]. Incorporation of flame re- few works reported the synthesis of fully bio-epoxy resins with flame
tardant additives impedes the curing reaction and consequently lowers retardancy properties. In this sense, this concise review aims to high-
the mechanical properties of matrix. Such an influence can also be light current developments in flame retardant bio-based epoxy resins.
detected by another newly defined criterion, namely Cure Index [28]. Even though several review papers have been published to cover the
Table 1 presents the main class of bio-based epoxy resins derived from bio-based epoxy resin [6,42] and bio-based flame retardants [43], the
sustainable resources. area of inherent FR epoxy resins from sustainable resources remains
Overall, epoxy resins derived from renewable resources benefit from largely intact.
properties, which are more or less identical to those of commercial
DGEBA. However, like petroleum-based epoxies, bio-epoxy resins suffer 2. Inherrently flame retardant bio-epoxy resins

Table 1 Synthesis of flame retardant bio-epoxy resins from renewable re-

Chemical structure and main sources of bio-epoxy resins [42]. sources capable of giving adequate mechanical properties, comparable
to that of DGEBA, is of a prime importance in developing bio-based
Class Chemical structure Main sources
formulations.
Isosorbide-based epoxy Starch Miao et al. [44] compared the flammability of bio-based bis(2-
methoxy-4-(oxiran-2-ylmethyl)phenyl)furan-2,5-dicarboxylate (EUFU-
EP) with the commercial DGEBA cured with methyl hexahydrophthalic
anhydride (MHHPA) in terms of time to ignition (TTI), peak of heat
Furan-based epoxy Corn cobs,
biomass wastes release rate (pHRR) and total heat release (THR). Aside from identical
TTI values of studied systems, EUFU-EP had lower pHRR and THR
Phenolic- and Black Mimosa values, which were indicative of its higher flame retardancy perfor-
polyphenolic-based Bark, Quebracho
mance. This was mainly explained by the presence of a packed aromatic
epoxy Wood
structure in EUFU-EP resin, which reflected in higher char content re-
sulting from higher glass transition temperature (Tg). Although the
crosslink density of EUFU-EP/MHHPA was lower than that of the
EUFU-EP/MHHPA system, the mechanical properties of EUFU-EP/
MHHPA were improved due to the presence of furan and aromatic
Lignin-based epoxy Wood
derivatives structures in the EUFU-EP backbone.
Likewise, Dai et al. [45] revealed that bio-based diglycidyl ether of
daidzein (DGED) cured with 4,4′-diaminodiphenylmethane (DDM) was
more reactive than the petroleum-based DGEBA. The higher reactivity
was attributed to the additional unsaturated double bonds in DGED
Rosin-based epoxy Pine resin structure involved in the course of curing reaction. Consequently, the
viscosity of DGED increased faster than that of DGEBA and; thus, the
thermo-mechanical properties of DGED/DDM stood over DGEBA/DDM
system. From the flammability point of view, DGED formed char at the
surface during combustion, which protected the bottom layers form
heat transfer leading to self-extinguishing behavior in just 3 s with a
very small flame. Since no complementary flame tests such as cone
calorimetry were conducted, it is difficult to understand the flame

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E.R. Rad, et al. Progress in Organic Coatings 135 (2019) 608–612

Table 2
Flame behaviour of reported bio-based epoxy resins.
Epoxy resin Curing agent FR Tg LOI Residue Cone calorimetry Ul-94 Ref.
(°C) (%) (%)
−2
TTI pHRR (kW·m ) THR
(s) (mJ·m−2)

EUFU-EP MHHPA – 153 – 10.9 200 291.3 20 – [44]

DGED DDM – 205 31.6 42.9 – – – V0 [45]
DEU-EP DDM – 114 – 38 – – – – [46]
TPEU-EP DDS – 168 26.8 31.7 33 860 50.1 – [47]
EPEU DDS Siloxane – 28 14.9 28 662 73.9 – [51]
P3EP DIFFA P2EP1P 124 – 43.5 – – – – [38]
DGEBA MHHPA EADI 109 31.4 5.55 – – – V0 [53]
UDTGE, UDBME BAMPO DOPO-III ≈80 > 28 > 18 – – – – [35]
ESO TA 57 8.7 – – – [54]

behaviour of the proposed system taking into account the resistance of decreased when the length of siloxane linker increased, which eased
materials from condensed phase that contributed to flame retardancy. epoxy curing reaction. The authors did not report on the mechanical
Wan et al. [46] synthesized bio-epoxy resins by making linked two and thermal properties of the prepared systems.
eugenol molecules together followed by epoxidation of terminal groups
(DEU-EP), which resulted in a product with very high bio-based content 3.2. Phosphorous-containing FR
of ca. 70 wt.%. This monomer was cured with DDM. The authors stu-
died cure kinetics mechanism of bio-epoxy using model-free iso- There are numerous works on the flame retardancy effect of phos-
conversional approach and reported that addition of eugenol building phorous-containing compounds, which mainly benefit from char for-
blocks in the chain backbone as well as and their arrangement greatly mation in the condensed phase [48,52].
affected cure behavior of DEU-EP/DDM systems. As a result, mechan- Menard et al. [38] embedded diglycidyl mono-phosphonated
ical properties and high-temperature charring ability and flammability phloroglucinol reactive flame retardant derived from renewable re-
resistance were enhanced. It was also reported that DEU-EP/DDM resin sources of phloroglucinol in triglycidyl phloroglucinol (P3EP), and re-
left 38% char at 800 °C, which was almost twice the amount left by the ported that the phosphorous flame retardant embedded in P3EP dete-
DGEBA/DDM system. Moreover, pHRR (201 kW/m2) and THR riorated thermal stability of epoxy resin; Such a behavior was explained
(16.3 kJ/m2) for DEU-EP were much lower than the values obtained for by the plasticizing role of the flame retardant. However, the flamm-
DGEBA. Eventually, self-extinguishing DEU-EP was attained in 10 s, ability of phosphorous flame retardants embedded in bio-epoxy was
which proved an inherent flame retardancy behavior. However, the improved significantly, as confirmed by pyrolysis combustion flow ca-
storage modulus of DEU-EP dropped suddenly at higher temperatures lorimetry (PCFC) data together with char content measurements.
where glass transition temperature occurred at 114 °C due to an in- Nevertheless, it should be noticed that the complementary flammability
crease in free volume and molecular mobility of DEU-EP polymer tests were principally needed to be conducted for this system to fully
chains. Later, this group [47] developed eugenol-based bifunctional comprehend the flame behaviour of system.
epoxy resins (TPEU-EP) with improved flame retardancy thanks to the Elsewhere [53], a phosphorus-containing bio-epoxy resin (EADI)
full aromatic ester backbone of TPEU-EP. Despite lower crosslinking was prepared based on itaconic acid (IA) and 9,10-dihydro-9-oxa-10-
density of TPEU-EP compared to commercial DGEBA, an enhanced phosphaphenanthrene 10-oxide (DOPO), then used as bio-based flame
mechanical property was observed, which was due to the aromatic retardant in DGEBA system. Mechanical and thermal properties of
structure of TPEU-EP. Cone calorimetry and burning analysis of TPEU- DGEBA/EADI were found to be similar to those of DGEBA systems, with
EP provided concrete evidence for potential application of TPEU-EP as a significant improvement in flame retardancy of bio-based system in
an alternative for DGEBA of the synthesis route of TPEU-EP was eco- terms of LOI, char content and burning time.
nomic-friendly for large scale production. Literature survey suggests In search for bio-epoxy resins, Lligadas et al. [35] synthesized two
that synthesis of flame retardant bio-epoxy experiences an early stage different epoxidized monomers including 10-undecenoyl triglyceride
flourishing period, while chemically embedded FR elements in bio- (UDTGE) and methyl 3,4,5-tris(10- undecenoyloxy) benzoate (UDBME)
epoxy were alternatives for inherent flame retardant bio-epoxy. from fatty acids. To improve their flame retardancy properties,10-
[2′,5′-bis(9-oxiranyl-nonayloxy)phenyl]-9,10-dihydro-9-oxa-10-phos-
3. FR elements chemically embedded in bio-epoxy backbone phaphenanthrene-10 oxide (DOPO-III) and bis(m-aminophenyl) me-
thylphosphine oxide (BAMPO) were added to the structure of epoxy
3.1. Silicon-containing FR resin as flame retardant and curing agent, respectively. It was found
that the Tg of UDBME-based resin was higher than that of UDTGE due to
Silicon compounds improve flame retardancy of epoxy resins as a the presence of aromatic groups in the chemical structure of UDBME.
result of formation of residue in the condensed phase as well as the However, Tg decreased upon addition of phosphorous-containing FR
presence of radicals in vapour phase [48–50]. Li et al. [51] linked due to a lower crosslink density. From a flammability point of view, LOI
epoxidized eugenol bio-epoxy (EPEU) with silicon-containing bridges values and charring residue were both improved upon addition of
with different lengths and chemical structures. It was found that the phosphorous-containing DOPO-III and BAMPO. However, more accu-
flammability of the prepared silicon-containing bio-epoxy resin was rate and reliable tests were required to fully analyze the flame behavior
significantly improved in comparison to the commercial DGEBA. The performance of the proposed system.
value of LOI reported for DGEBA was 22.8%, which was improved up to
31% for phenyl siloxane-containing bio-epoxy resins. This was ex- 4. Concluding remarks and recommendations for future works
plained by the carbonation of phenyl groups as well as the migration of
Si-O to the surface, which formed an ablative layer that avoided the DGEBA is the most sought epoxy resin in industrial applications
penetration of oxygen and fuel through the combustion layer. More- thanks to its remarkable features. However, high volume usage of this
over, the viscosity of the prepared silicon-containing bio-epoxy monomer in various applications has risen increasing environmental

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