Molecules: New Biosourced Flame Retardant Agents Based On Gallic and Ellagic Acids For Epoxy Resins

molecules
Article
New Biosourced Flame Retardant Agents Based on
Gallic and Ellagic Acids for Epoxy Resins
Valeriia Karaseva 1,2,3 , Anne Bergeret 2 , Clément Lacoste 2 , Hélène Fulcrand 4 and
Laurent Ferry 2, *
1 INRA, UMR 1083 SPO, 2 place Pierre Viala, 34060 Montpellier, France; valeriia.karaseva@supagro.inra.fr
2 Centre des Matériaux des Mines d’Alès (C2MA), IMT Mines Alès, Université de Montpellier, 6 avenue de
Clavières, 30319 Alès cedex, France; anne.bergeret@mines-ales.fr (A.B.); clement.lacoste@mines-ales.fr (C.L.)
3 French Environment and Energy Management Agency, 20 avenue du Grésillé, BP 90406, 49004 Angers cedex
01, France
4 INRA, UMR 1208 IATE, 2 Place Pierre Viala, 34060 Montpellier, France; helene.fulcrand@inra.fr
* Correspondence: laurent.ferry@mines-ales.fr
Academic Editor: Gaëlle Fontaine
Received: 30 September 2019; Accepted: 22 November 2019; Published: 26 November 2019
Abstract: The aim of this work was an investigation of the ability of gallic (GA) and ellagic (EA) acids,
which are phenolic compounds encountered in various plants, to act as flame retardants (FRs) for
epoxy resins. In order to improve their fireproofing properties, GA and EA were treated with boric
acid (to obtain gallic acid derivatives (GAD) and ellagic acid derivatives (EAD)) to introduce borate
ester moieties. Thermogravimetric analysis (TGA) highlighted the good charring ability of GA and
EA, which was enhanced by boration. The grafting of borate groups was also shown to increase
the thermal stability of GA and EA that goes up respectively from 269 to 528 ◦ C and from 496 to
628 ◦ C. The phenolic-based components were then incorporated into an epoxy resin formulated from
diglycidyl ether of bisphenol A (DGEBA) and isophorone diamine (IPDA) (72, 18, and 10 wt.% of
DGEBA, IPDA, and GA or EA, respectively). According to differential scanning calorimetry (DSC),
the glass transition temperature (Tg ) of the thermosets was decreased. Its values ranged from 137 up
to 108 ◦ C after adding the phenolic-based components. A cone calorimeter was used to evaluate the
burning behavior of the formulated thermosets. A significant reduction of the peak of heat release
rate (pHRR) for combustion was detected. Indeed, with 10 wt.% of GA and EA, pHRR was reduced
by 12 and 44%, respectively, compared to that for neat epoxy resin. GAD and EAD also induced
the decrease of pHRR values by 65 and 33%, respectively. In addition, a barrier effect was observed
for the resin containing GAD. These results show the important influence of the biobased phenolic
compounds and their boron derivatives on the fire behavior of a partially biobased epoxy resin.
Keywords: biobased flame retardant; ellagic acid; gallic acid; boration; epoxy resin
1. Introduction
Due to their intrinsic characteristics, such as mechanical and electrical insulating properties,
chemical resistance under both acidic and basic conditions, and adhesive properties, epoxy resins are
widely used for structural applications (in association with glass or carbon fibers), as well as in the
coating, electronic, and adhesive industries [1]. However, low thermal and fire resistance of epoxy
resins are drawbacks limiting their use in some applications. To improve these properties, the addition
of flame retardants (FRs) has been practiced for many years.
Among others, halogenated FRs have been extensively used [2,3]. But the harmful effects on
both environment and human beings are an impediment to their use [4]. Thus, the development of
Molecules 2019, 24, 4305; doi:10.3390/molecules24234305 www.mdpi.com/journal/molecules

Molecules 2019, 24, 4305 2 of 22
Molecules 2019,FRs,
halogen-free 24, x FOR PEER
ideally REVIEW from renewable resources, is a subject of extensive investigation2 of
extracted for22
Molecules 2019, 24, x FOR PEER REVIEW 2 of 22
epoxy resins [5–7].
Tanninsare
Tannins are a group of ofphenolic
phenolicbiopolymers and macromolecules widely distributed in plant
Tannins are aa groupgroup of phenolic biopolymers
biopolymers and
and macromolecules
macromolecules widely
widely distributed
distributed in
in plant
cells
plant [8,9].
cells There
[8,9]. are
There two
are main
two main classes of
classes oftannins:
tannins: hydrolysable
hydrolysable tannins,
tannins, based
based on
on gallic
gallic oror
cells [8,9]. There are two main classes of tannins: hydrolysable tannins, based on gallic or
hexahydroxyphenic acids
hexahydroxyphenic acids moieties connected
connected to a central polyol
polyol or osidic core
core (Figure1),1), and
hexahydroxyphenic acidsmoieties moieties connectedtotoaacentralcentral polyolororosidic
osidic core(Figure
(Figure 1),and and
condensed
condensed tannins,
tannins, polymers
polymers of
of flavonoid-based
flavonoid-based subunits
subunits (Figure
(Figure 2).
2). Considering
Considering their
their chemical
chemical
condensed tannins, polymers of flavonoid-based subunits (Figure 2). Considering their chemical
structuresand
structures and thermalproperties
properties providedby by thearomatic
aromatic rings,tannins
tannins presentan an interestfor
for the
structures andthermal
thermal propertiesprovided
provided bythe the aromaticrings,
rings, tanninspresent
present aninterest
interest forthethe
developmentofofFR
development FR additives.
development of FRadditives.
additives.
Figure 1. Typical molecules of hydrolysable tannins: (a) pentagalloyl glucose and (b) vescalagin.
Figure1.1.Typical
Figure Typicalmolecules
moleculesofofhydrolysable
hydrolysabletannins:
tannins:(a)(a)pentagalloyl
pentagalloylglucose
glucoseand
and(b)
(b)vescalagin.
vescalagin.
Figure 2. Typical constitutive units of condensed tannins: (a) (+)-catechin and (b) (+)-gallocatechin.
Figure 2. Typical constitutive units of condensed tannins: (a) (+)-catechin and (b) (+)-gallocatechin.
In Figure 2. ten
the last Typical constitutive
years, unitsfocus
a particular of condensed tannins:
has been (a) (+)-catechin
the development ofand (b) (+)-gallocatechin.
condensed tannins-based
FRs [10–12].
In the last Theten
efficiency
years, a of mimosafocus
particular tannins–boron
has been the preservatives
development forofwood buildings
condensed has been
tannins-based
In the last ten years, a particular focus has been the development of condensed tannins-based
studied [10,11]. It was found out that the use of tannins and tannins–boron
FRs [10–12]. The efficiency of mimosa tannins–boron preservatives for wood buildings has been additives provided
FRs [10–12]. The efficiency of mimosa tannins–boron preservatives for wood buildings has been
significant increaseIt ofwas
studied [10,11]. the found
time toout
ignition
that (TTI)
the use(from 12 s to >and
of tannins 120 s) with a decrease
tannins–boron of mass provided
additives loss rate
studied [10,11]. It was found out that the use of tannins and tannins–boron additives provided
ofsignificant
scots pinewood.
increaseThe application
of the of condensed
time to ignition tannins
(TTI) (from as >FRs
12 s to 120additives for silk textiles
s) with a decrease of masshas been
loss rate
significant increase of the time to ignition (TTI) (from 12 s to > 120 s) with a decrease of mass loss rate
previously reported [12]. The use of tannins allows flame retardancy of silk
of scots pinewood. The application of condensed tannins as FRs additives for silk textiles has been fabric to be improved.
of scots pinewood. The application of condensed tannins as FRs additives for silk textiles has been
The textile treated
previously with[12].
reported tannins
The exhibited a limiting
use of tannins allows oxygen
flameindex (LOI) above
retardancy of silk27.0%,
fabricwhereas the LOI
to be improved.
previously reported [12]. The use of tannins allows flame retardancy of silk fabric to be improved.
ofThe
thetextile
untreated fabric
treated was
with 24.7%. exhibited a limiting oxygen index (LOI) above 27.0%, whereas the
tannins
The textile treated with tannins exhibited a limiting oxygen index (LOI) above 27.0%, whereas the
LOITheof theeffectiveness
untreated fabricof hydrolysable
was 24.7%. tannins as FRs was not considerably investigated until
LOI of the untreated fabric was 24.7%.
recentlyThe[13,14]. The treatment
effectiveness with tannic
of hydrolysable tannins acid
asalone
FRs was changed the thermal
not considerably model of the
investigated pyrolysis
until recently
The effectiveness of hydrolysable tannins as FRs was not considerably investigated until recently
and
[13,14]. The treatment with tannic acid alone changed the thermal model of the pyrolysis(SH)
combustion of cotton and enhanced the char yield [13]. The addition of sodium hydroxide and
[13,14]. The treatment with tannic acid alone changed the thermal model of the pyrolysis and
during the treatment
combustion of cottoncontributed
and enhancedto thethe
adsorption
char yieldof[13].
tannic acid
The onto cotton.
addition It alsohydroxide
of sodium catalyzed (SH)
the
combustion of cotton and enhanced the char yield [13]. The addition of sodium hydroxide (SH)
decarboxylation
during the treatment of tannic acid and the
contributed dehydration
to the adsorptionofofcotton
tanniccellulose
acid ontoat lower
cotton.temperatures.
It also catalyzed Thesethe
during the treatment contributed to the adsorption of tannic acid onto cotton. It also catalyzed the
chemical modifications induced a reduction of heat release capacity (HRC) by
decarboxylation of tannic acid and the dehydration of cotton cellulose at lower temperatures. These 82% (from 278 to 51 J
decarboxylation
−1 of tannic acid and the dehydration of cotton cellulose at lower temperatures. These
(gchemical
K) ) and an increase of
modifications the LOIavalues
induced reductionfromof19.0
heattorelease
30.2% compared with that
capacity (HRC) of the(from
by 82% control
278cotton.
to 51 J
chemical modifications induced a reduction of heat release capacity (HRC) by 82% (from 278 to 51 J
However, more
(g K)−1−1) and attentionofshould
an increase bevalues
the LOI given to FRs19.0
from based on hydrolysable
to 30.2% tannins.
compared with thatTheir
of thearomatic rings
control cotton.
(g K) ) and an increase of the LOI values from 19.0 to 30.2% compared with that of the control cotton.
and hydroxyl
However, more functions
attentionavailable
should beforgiven
a chemical modification,
to FRs based as well as
on hydrolysable their abundance
tannins. Their aromaticin plant
rings
However, more attention should be given to FRs based on hydrolysable tannins. Their aromatic rings
and hydroxyl functions available for a chemical modification, as well as their abundance in plant
and hydroxyl functions available for a chemical modification, as well as their abundance in plant
biomass such as chestnut, tara, and oak trees [8], make them potential building blocks for bio-based
FR agents.
FR agents.
Hydrolysable tannins are usually subdivided in two groups: gallotannins and ellagitannins [8].
Gallotannins are polymers based on various numbers of galloyl units linked to a central polyol. Their
Molecules 2019, 24, 4305 3 of 22
FR agents.
acidic, alkali, or enzymatic hydrolysis leads to the release of gallic acid (GA) (Figure 3a). As for
acidic, alkali, or enzymatic hydrolysis leads to the release of gallic acid (GA) (Figure 3a). As for
ellagitannins, they contain various numbers of hexahydroxydiphenoyl (HHDP) units, which after
ellagitannins, they contain various numbers of hexahydroxydiphenoyl (HHDP) units, which after
hydrolysis spontaneously dehydrate to ellagic acid (EA) (Figure 3b) [15]. Due to their biological
hydrolysis spontaneously dehydrate to ellagic acid (EA) (Figure 3b) [15]. Due to their biological
activities in plants, investigation of their health properties and use as drugs, dietary supplements, or
activities in plants, investigation of their health properties and use as drugs, dietary supplements,
health care products has been undertaken. Nevertheless, both GA and EA can be employed for high
or health care products has been undertaken. Nevertheless, both GA and EA can be employed for
added-value applications in specialty chemistry and polymeric material sectors thanks to their
high added-value applications in specialty chemistry and polymeric material sectors thanks to their
particular chemical structures. Moreover, phosphorus derivatives of GA have already shown their
particular chemical structures. Moreover, phosphorus derivatives of GA have already shown their
efficiency as biobased FR agents for the formulation of epoxy resin based on diglycidyl ether of
efficiency as biobased FR agents for the formulation of epoxy resin based on diglycidyl ether of
bisphenol A (DGEBA) and 2-ethyl-4-methylimidazole [16]. Indeed, the incorporation of 15 wt.% of
bisphenol A (DGEBA) and 2-ethyl-4-methylimidazole [16]. Indeed, the incorporation of 15 wt.% of GA
GA modified with diethylphosphite (DEP) induced a reduction of peak of heat release rate (pHRR)
modified with diethylphosphite (DEP) induced a reduction of peak of heat release rate (pHRR) by 41%
by 41% (from 692 to 411 W g−1) and an increase of LOI value by 21% (from 19.0 to 23.0%) compared
(from 692 to 411 W g−1 ) and an increase of LOI value by 21% (from 19.0 to 23.0%) compared to the neat
to the neat epoxy resin.
epoxy resin.
Figure 3. Structure of (a) gallic and (b) ellagic acids.

Figure 3. Structure of (a) gallic and (b) ellagic acids.
Boron-based FRs are considered as an efficient harmless alternative to halogen-containing FRs
Boron-based
in polymeric FRs are[17,18].
materials considered
They asactanasefficient harmless alternative
a multifunctional FRs providing to halogen-containing FRs
many useful properties:
inthe
polymeric
promotion materials [17,18].
of the char They act
formation, theasstabilization
a multifunctional FRs by
of the char providing
developing many useful
glass properties:
barriers, and the
the promotion of the char formation, the stabilization of the char by developing
suppression of smoke and carbon monoxide formation [19,20]. Usually, boric compounds are coated glass barriers, and
the suppression of smoke and carbon monoxide formation [19,20]. Usually,
onto cellulosic products but they can also be employed in epoxy resins for improving their thermal boric compounds are
coated onto cellulosic
properties. The use ofproducts
boric acidbut they
(BA) in can also be employed
epoxy-diamine in epoxy
resin cured with resins for improving their
hexamethylenediamine has
thermal properties. The use of boric acid (BA) in epoxy-diamine
been previously reported [21]. In this case, the temperature of 50 % weight loss resin
of thecured
epoxywith
resin
hexamethylenediamine
containing 10 wt.% of BA haswas
been previously
15.8% reported
higher than [21].
that for theIn this
neat case,polymer
epoxy the temperature
(425 ◦ C asof 50 %
opposed
weight loss
◦ of the epoxy resin containing 10 wt.% of BA was 15.8% higher than
to 367 C). It was also previously reported that BA and its derivatives may be used to improve firethat for the neat epoxy
polymer
retardancy(425of°C as opposed
phenolic to 367 °C).
compounds [19].ItTherefore,
was also previously
consideringreported that BA the
the advantages, andgrafting
its derivatives
of boron
may be used to improve fire retardancy of phenolic compounds [19]. Therefore,
on phenolic components should lead to an efficient biobased halogen-free FR for epoxy thermoset. considering the
advantages, the grafting of boron on phenolic components should lead
The present work reports the development of halogen-free FRs based on GA and EA phenolic to an efficient biobased
halogen-free
acids as well FRasfor epoxy
their thermoset.
borate forms, and a study of their impact on the thermal properties and fire
The present work reports
behavior of a model epoxy thermoset. the development
The resinofwashalogen-free
prepared by FRscrosslinking
based on GA and EA phenolic
of diglycidyl ether of
acids as well as their borate forms, and
bisphenol A (DGEBA) with isophorone diamine (IPDA).a study of their impact on the thermal properties and fire
behavior of a model epoxy thermoset. The resin was prepared by crosslinking of diglycidyl ether of
bisphenol
2. ResultsAand(DGEBA) with isophorone diamine (IPDA).
Discussion
2.2.1. Characterization
Results of the FRs
and Discussion
2.1.1.
2.1. Chemical Characterization
Characterization of the FRs of the FRs
Mass spectrometry (MS), 11 B solid-sate nuclear magnetic resonance (NMR) spectroscopy and
2.1.1. Chemical Characterization
inductively-coupled plasma–atomic of the FRs
emission spectrometer (ICP–AES) analyses of the FR agents were
performed. The results are reported in Figure
Mass spectrometry (MS), B solid-sate nuclear
11 4 and Table 1. resonance (NMR) spectroscopy and
magnetic
inductively-coupled plasma–atomic emission spectrometer (ICP–AES) analyses of the FR agents
were performed. The results are reported in Figure 4 and Table 1.
Gallic acid derivatives (GAD). Gallic acid derivatives (GAD) were prepared by treatment of GA
and BA at pH = 9 in the presence of SH. GAD were recovered by freeze-drying of the treatment
solution. A sample of freeze-dried GAD powder was dissolved in methanol prior to ESI–MS analysis.
The MS analysis showed the presence of various signals, of which two major ones were detected at
cycle bonds. The third signal at 1.9 ppm indicates the presence of four-coordinate boron, which
corresponds to the product of the reaction between BA and SH—sodium tetrahydroxyborate
Na[B(OH)4]—as it is shown in literature and confirmed by the laboratory tests [22]. From these
results, Figure 6 represents the potential main chemical structures of EAD. The boron and sodium
contents2019,
Molecules measured
24, 4305 by ICP–AES analysis were quite close to the theoretical ones (Table 1) and equal
4 of 22
to 3.51 ± 0.02 and 7.74 ± 0.03 wt.%.
11 NMR spectrum of boric

Figure 4. 11BB NMR
Figure 4. spectrum of boric acid (BA), gallic acid derivatives (GAD), and
and ellagic
ellagic acid
acid
derivatives
derivatives (EAD).
(EAD).
Table 1. MS, 11 B NMR and inductively-coupled plasma–atomic emission spectrometer (ICP–AES)
results of the flame retardant (FR) agents.
Molecular 11 B
Main MS Shifts BTh 1 BICP 2 NaTh 3 NaICP 4
Sample Weight (g
Signal (m/z) (ppm) (wt.%) (wt.%) (wt.%) (wt.%)
mol−1 )
GA 170 125, 169 - - - - -
EA 302 301 - - - - -
GAD - 241, 263 7.7, 13.9 4.23 3.69 ± 0.03 5.37 4.91 ± 0.02
EAD - 373, 413, 643 1.9, 8.1, 13.1 4.35 3.51 ± 0.02 9.09 7.74 ± 0.03
1BTh —theoretical boron content; 2 BICP —boron content measured by ICP–AES analysis; 3 NaTh -theoretical sodium
content; 4 NaICP —sodium content measured by ICP–AES analysis.
Gallic acid derivatives (GAD). Gallic acid derivatives (GAD) were prepared by treatment of GA
and BA at pH = 9 in the presence of SH. GAD were recovered by freeze-drying of the treatment solution.
A sample of freeze-dried GAD powder was dissolved in methanol prior to ESI–MS analysis. The MS
analysis showed the presence of various signals, of which two major ones were detected at m/z 241 and
263 in the negative ion mode (Table 1). The lowest m/z value was assigned to a gallic acid molecule
linked through an oxygen atom of the phenolic hydroxyls to B(OCH3 )2 , while m/z 263 was attributed
to the sodium adduct of the former molecule. The methylation of borate groups likely occurred in
methanol prior to MS analysis but GAD are not originally methylated and the borate groups should be
B(OH)2 in GAD. The 11 B NMR spectrum of GAD confirmed the treatment of GA with BA (Figure 4).
In fact, the spectrum displays a significant decrease of the signal at 13.9 ppm, which corresponds to
three-coordinate boron sites of unreacted BA [22]. The signal for boron at 7.7 ppm is associated with
a coordinate number of three, and it corresponds to the –B–O–aromatic cycle bonds. The putative
structures of GAD are shown in Figure 5. The theoretical boron and sodium contents of GAD were
calculated to be 4.23 and 5.37 wt.%, respectively (see the supplementary file). The boron and sodium
contents of GAD measured by ICP–AES were quite close to the theoretical values (Table 1) and were
equal to 3.69 ± 0.03 and 4.91 ± 0.02 wt.%, respectively.
GA 170 125, 169 - - - - -
EA 302 301 - - - - -
GAD - 241, 263 7.7, 13.9 4.23 3.69 ± 0.03 5.37 4.91 ± 0.02
EAD - 373, 413, 643 1.9, 8.1, 13.1 4.35 3.51 ± 0.02 9.09 7.74 ± 0.03
Molecules BTh—theoretical boron content; BICP—boron content measured by ICP–AES analysis; 53 of 22
1 2
2019, 24, 4305
NaTh-theoretical sodium content; NaICP —sodium content measured by ICP–AES analysis.
4
Table 1. MS, 11B NMR and inductively-coupled plasma–atomic emission spectrometer (ICP–AES)
results of the flame retardant (FR) agents.
Molecular Main MS 11B Shifts BTh 1 BICP 2 NaTh 3 NaICP 4

Sample Weight Signal
(ppm) (wt.%) (wt.%) (wt.%) (wt.%)
(g mol−1) (m/z)
GA 170 125, 169 - - - - -
EA 302 301 - - - - -
GAD -
Figure 241, 263
5. Putative structures7.7, 13.9deduced4.23
of GAD from MS3.69
and ±110.03 5.37
B NMR analyses. 4.91 ± 0.02
Figure 5. Putative structures of GAD deduced from MS and 11B NMR analyses.
EAD - 373, 413, 643 1.9, 8.1, 13.1 4.35 3.51 ± 0.02 9.09 7.74 ± 0.03
1Ellagic acid derivatives (EAD).
BTh—theoretical boron content; EA
2 was also borated by treatment with BA
BICP—boron content measured by ICP–AES analysis;at pH = 9 in3 the
presence of SH. As for
NaTh-theoretical GAD,
sodium the signals
content; 4 NaICPdetected
—sodium incontent
ESI–MSmeasured
analysisby
forICP–AES
EAD suggest the formation of
analysis.
methylated borate forms detected at m/z 373, 413, and 643 (Table 1). These m/z values were assigned
to ellagic acid linked to B(OCH3 )2 by one of the phenolic oxygen atoms, the same molecule containing
a second borate group BOCH3 twice linked to two phenolic adjacent oxygen atoms and a dimer of
ellagic acid linked by a borate group BOCH3 involving one phenolic oxygen atom of each ellagic acid
unit, respectively. The 11 B NMR analysis of EAD showed three different signals (Figure 4). The first
one in the 18-13 ppm spectral region corresponds to unreacted BA. Since the structures of GA and EA
are chemically close, the second signal at 8.1 ppm is associated with the -B-O–aromatic cycle bonds.
The third signal at 1.9 ppm indicates the presence of four-coordinate boron, which corresponds to the
product of the reaction between BA and SH—sodium tetrahydroxyborate Na[B(OH)4 ]—as it is shown
in literature and confirmed by the laboratory tests [22]. From these results, Figure 6 represents the
potential mainFigure
chemical structures of EAD. The boron and sodium contents measured by ICP–AES
5. Putative structures of GAD deduced from MS and 11B NMR analyses.
analysis were quite close to the theoretical ones (Table 1) and equal to 3.51 ± 0.02 and 7.74 ± 0.03 wt.%.
Figure 6. Putative structures of EAD deduced from MS and 11B NMR analyses.
2.1.2. Thermal Characterization of GA and EA and their Boron Modified Entities

The thermal decomposition and thermal stability of the FR agents were assessed by coupling
thermogravimetric analysis with Fourier Transform InfraRed spectroscopy (TGA–FTIR). Figure 7
illustrates the thermogravimetric curves of the pure phenolic compounds and their synthesized
derivatives under nitrogen flow. The decomposition temperatures (T max) as well as the char yield
values at 600 °C (Char600) and 900 °C (Char900) are listed in Table 2.
Putative structures
Figure 6. Putative structures of
of EAD
EAD deduced
deduced from 11 B NMR analyses.
from MS and 11
Figure B NMR analyses.
2.1.2. Thermal
2.1.2. ThermalCharacterization
Characterization of of GA
GA andand EA
EA andand their
their Boron
Boron Modified
Modified Entities
Entities
The thermal
The thermal decomposition
decomposition and and thermal
thermal stability
stability ofof the
the FR
FR agents
agents were
were assessed
assessed byby coupling
coupling
thermogravimetric analysis
thermogravimetric analysis with
with Fourier
Fourier Transform
Transform InfraRed
InfraRed spectroscopy
spectroscopy (TGA–FTIR).
(TGA–FTIR). Figure
Figure 77
illustrates the thermogravimetric curves of the pure phenolic compounds
illustrates the thermogravimetric curves of the pure phenolic compounds and their synthesized and their synthesized
derivatives under
derivatives under nitrogen
nitrogen flow.
flow. The
The decomposition
decomposition temperatures
temperatures (T (Tmax
max) )as
aswell
wellas
as the
the char
char yield
yield
values at 600 ◦ C (Char ) and 900 ◦ C (Char ) are listed in Table 2.
600 900
values at 600 °C (Char600) and 900 °C (Char900) are listed in Table 2.
Molecules 2019,
Molecules 2019, 24,
24, 4305
x FOR PEER REVIEW 66 of
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22
Figure 7. Thermograms and the corresponding differential curves of the FR agents at 10 ◦ C min−1
Figurenitrogen
under 7. Thermograms
flow. and the corresponding differential curves of the FR agents at 10 °C min−1
under nitrogen flow.
Table 2. Thermal data of the FR agents obtained from thermogravimetric analysis (TGA).
Table 2. Thermal data(◦of
C)the FR agents obtained from thermogravimetric analysis
Char(TGA).
Sample Name Tmax1 Tmax2 (◦ C) Tmax3 (◦ C) Char600 (wt.%) 900 (wt.%)
Sample
GA Name Tmax1 269 (°C) Tmax2 327(°C) Tmax3 -(°C) Char60025.7 (wt.%) Char90019.3 (wt.%)
EAGA 496
269 528
327 630
- 52.9
25.7 31.7
19.3
GAD 528 - 53.1
EA 496 528 630- 60.7
52.9 31.7
EAD 628 - - 83.5 52.7
GAD 528 - - 60.7 53.1
EAD 628 - - 83.5 52.7
It was observed that both unmodified phenolic compounds (GA and EA) showed a multistep
degradation process. that both unmodified phenolic compounds (GA and EA) showed a multistep
It was observed
Gallic acid
degradation (GA). The thermal decomposition of GA was composed of two main steps. It was
process.
stableGallic
up to acid
around 230The◦ C at which point the first step of the thermal decomposition occurred with
(GA). thermal decomposition of GA was composed of two main steps. It was
the mass ◦ C (T ◦ C (T
stable up loss at 269 230
to around °Cmax1 ). The point
at which second theand major
first step degradation
of the thermal step occurred at 327
decomposition occurred with
max2 ).
Carbon
the mass dioxide
loss at(CO 2692 )°Cwas the ).main
(Tmax1 The component
second andofmajor the off-gases for these
degradation steptwo steps. It
occurred at corresponds
327 °C (Tmax2to).
the characteristic
Carbon dioxide (CO bands at 2359
2) was and 2323
the main cm−1 (stretching
component vibrations)
of the off-gases and 668
for these two
−1 (in-plane vibration).
cmsteps. It corresponds to
The
the formation
characteristic of CO 2 is principally
bands at 2359 and associated
2323 cm with the decarboxylation
−1 (stretching vibrations)of GAand[23,24].
668 cm As−1 described
(in-plane
by Rama Mohan Rao et al. [25], water is also released during these two
vibration). The formation of CO2 is principally associated with the decarboxylation of GA [23,24]. steps of decomposition. AboveAs
350 ◦ C, no other signals were detected. The char yield at 600 and 900 ◦ C were equal to 25.7 and
described by Rama Mohan Rao et al. [25], water is also released during these two steps of
19.3 wt.%, respectively.
decomposition. Above 350 °C, no other signals were detected. The char yield at 600 and 900 °C were
equal to 25.7 and (EA).
Ellagic acid EA exhibited
19.3 wt.%, a more remarkable thermal stability than GA. It could be due to
respectively.
its specific
Ellagicchemical
acid (EA). structure characterized
EA exhibited by relatively
a more remarkable stable stability
thermal central biphenyl
than GA. bond and
It could belactone
due to
groups (Figure
its specific 3b) [25,26].
chemical structureThecharacterized
TGA–FTIR analysis suggested
by relatively stablea central
three-step thermal
biphenyl decomposition
bond and lactone
process
groups of EA. The
(Figure 3b)weight
[25,26].loss about 100 ◦analysis
TheatTGA–FTIR C was mainly
suggested associated with the
a three-step evaporation
thermal of water
decomposition
attached toEA.
EA.The Theweight
first and major step started ◦
process of loss at about 100 °C at wasaround
mainly 400 C and showed
associated with the theevaporation
maximum signal of waterat
496 ◦ C (T ). The second and third steps were associated with the mass loss at 528 (T ) and 630 ◦C
attached max1to EA. The first and major step started at around 400 °C and showed the maximum max2 signal
(T 496 ),°Crespectively.
atmax3 (Tmax1). The These
secondsteps
and were
third mainly
steps were characterized
associatedby COthe
with 2 release, but carbon
mass loss at 528 (Tmonoxide
max2) and CO630
with −1 was also detected. These compounds are mainly
°C (Tthe characteristic
max3), respectively.bands Theseatsteps
2180were
and 2107
mainly cmcharacterized by CO 2 release, but carbon monoxide
ascribed ◦ C.
CO with to thethecharacteristic
pyrolysis of bandsthe lactone
at 2180 groups
and of EAcm
2107 [27,28].
−1 wasNo signal
also was observed
detected. above 650 are
These compounds
The charascribed
yield values ◦ C were more important than those of GA—52.9 and 31.7 wt.%,
mainly to theatpyrolysis
600 and 900 of the lactone groups of EA [27,28]. No signal was observed above
respectively.
650 °C. The char The yield
different
valuescharring
at 600abilities
and 900of°CGA andmore
were EA could be related
important than to their
those ofchemical
GA—52.9 structures.
and 31.7
In general, aromatic compounds show a formation of important carbon
wt.%, respectively. The different charring abilities GA and EA could be related to their chemical residue during the TGA test.
EA containsIntwo
structures. aromatic
general, rings incompounds
aromatic its structure, whilea GA
show has justofone.
formation Thus, it carbon
important could be assumed
residue that
during
EA better promotes the char formation than GA. In addition, EA shows
the TGA test. EA contains two aromatic rings in its structure, while GA has just one. Thus, it could more important carbon content
than GA—56 that
be assumed against
EA49 wt.%,promotes
better respectively. the char formation than GA. In addition, EA shows more
important carbon content than GA—56 against 49 wt.%, respectively.
Molecules 2019, 24, 4305 7 of 22
Boron derivatives of EA and GA (GAD and EAD). The boration of the phenolic compounds
allowed
Boron improving
derivativestheirofthermal
EA andstability.
GA (GAD Forand
bothEAD).
GADThe andboration
EAD a progressive
of the phenolic weight loss was
compounds
observed from 100 °C
allowed improving up thermal
their to their main decomposition
stability. For both GAD step.and
ThisEADphenomenon
a progressive was weight
associated
losswith
was
the dehydroxylation ◦ of boron derivatives [29]. It was confirmed by the
observed from 100 C up to their main decomposition step. This phenomenon was associated with the appearance of bands related
to water in FTIR spectra.
dehydroxylation of boronThe major decomposition
derivatives step occursbyatthe
[29]. It was confirmed 528appearance
°C (Tmax1) for of GAD
bandsand at 628
related to
°C (Tmax1
water in )FTIR
for EAD,
spectra.respectively. It was mainly ascribed
The major decomposition step occurs to the
at 528 ◦ C (T of)carboxylic
pyrolysis for GAD and
and atlactone
628 ◦C
max1
groups. TheEAD,
(Tmax1 ) for mainrespectively.
products relatedIt waswith thisascribed
mainly process,to COthe2 and CO, were
pyrolysis detected and
of carboxylic in the off-gasses
lactone groups.of
the
Theheating sample.related
main products No boron-withandthis sodium-containing
process, CO2 and CO, volatile compounds
were detected were
in the detected.
off-gasses Therefore,
of the heating
it may beNo
sample. assumed
boron- andthat sodium-containing
boron and sodium volatile atoms mainly
compounds remain werein the solid phase.
detected. In the
Therefore, case be
it may of
GAD,
assumed it isthat
noteworthy
boron andthat the formation
sodium atoms mainly of aremain
sodium in carboxylate
the solid phase. (see In
Figure
the case5) stabilizes
of GAD, itthe is
carboxylic
noteworthygroup thatformation
that the decomposes of a 200 °C higher
sodium compared
carboxylate with GA.
(see Figure The carboxylate
5) stabilizes form should
the carboxylic group
be
thatpredominant
decomposes in 200GAD◦ C higher
since compared
only a smallwith weight
GA. The losscarboxylate
was observed formatshould
300 °Cbe(decarboxylation
predominant in
temperature
GAD since only of GA). Theweight
a small boron loss
modification
was observedenhances ◦
at 300the C residue yield of the
(decarboxylation phenolic compounds.
temperature of GA). The
The
boronchar 600 and the char
modification 900 values
enhances were equal
the residue yieldtoof60.7
the and 53.1 wt.%
phenolic for GADThe
compounds. andchar to 83.5
600 and
and 52.7
the wt.%
char 900
for EAD,
values wererespectively.
equal to 60.7 and 53.1 wt.% for GAD and to 83.5 and 52.7 wt.% for EAD, respectively.
To
To assess
assess thetheflame
flameretardant
retardantpotential
potentialofofthethe
additives,
additives,purepurephenolic
phenoliccompounds
compounds (GA(GA and EA)
and
and their boron derivatives (GAD and EAD) were characterized
EA) and their boron derivatives (GAD and EAD) were characterized by pyrolysis/combustion flow by pyrolysis/combustion flow
calorimetry
calorimetry (PCFC).
(PCFC). The The heat
heat release
release rate
rate (HRR)
(HRR) curves
curves of of the
the FR
FR systems
systems are are shown
shown in in Figure
Figure 8. 8.
Table 3 summarizes the values of of pHRR,
pHRR, temperature
temperature of of pHRR
pHRR (T (Tpeak
peak),
), total
total heat
heat release
release (THR), and
theoretical and experimental
experimental effective
effectiveheat
heatof ofcombustion
combustion(EHC (EHCtheo and EHC
theo and EHCexpexp,, respectively).
respectively). AllAll the
results obtained by the PCFC analyses were in accordance with the TGA measurements measurements (Table (Table2).2).
Figure 8. Pyrolysis/combustion
Pyrolysis/combustion flowflowcalorimetry
calorimetry(PCFC)
(PCFC)curves
curvesofof
(a)(a)
thethe phenolic
phenolic compounds
compounds andand
(b)
(b) their
their boron
boron derivatives
derivatives ◦
at 1atC·s −1.
1°C∙s −1.
Table 3. Data from PCFC tests of the FR systems.

Table 3. Data from PCFC tests of the FR systems.
FRFR
systems
systems pHRR
pHRR g−1 )g−1) TTpeak
(W (W (◦ C)
peak (°
C) THR (kJgg−1−1
THR(kJ ) ) EHC
EHC (kJ(kJ
theo
theo
−1
g−1g) ) EHC
EHC exp (kJ
exp (kJ
−1
g−1)g )
GAGA 293293 276
276 12.4
12.4 14.814.8 15.915.9
EA EA 73 73 492
492 2.9
2.9 16.016.0 4.5 4.5
GAD 10 532 0.3 - 0.6
GAD 10 532 0.3 - 0.6
EAD 25 648 0.5 - 1.0
EAD 25 648 0.5 - 1.0
It was
It was confirmed
confirmed that
that GA
GA decomposes
decomposes in in two
two main
main steps,
steps, whereas
whereas EA
EA essentially
essentially does
does it
it in
in three
three
steps (the
(the one
one at
at about
about 100 ◦
100 °C C is
is not
not observed
observed onon the
the PCFC
PCFC curve
curve since
since itit is
is related
related to
to the
the release
release ofof
steps
water). It was observed that GA is the most exothermic compound with the pHRR
water). It was observed that GA is the most exothermic compound with the pHRR equal to 293 W g−1 equal to 293 W
g−1 and
and the THRthe THR
equalequal to 12.4
to 12.4 kJ g−1kJ g−1 , respectively,
, respectively, whilewhile EA shows
EA shows considerably
considerably lowerlower
pHRRpHRR
and THR and
values for an organic molecule (73 W g−1 and 2.9 kJ g−1, respectively). As is shown in Table 3, GA
Molecules 2019, 24, 4305 8 of 22
THR values for an organic molecule (73 W g−1 and 2.9 kJ g−1 , respectively). As is shown in Table 3,
GA exhibits similar EHCtheo and EHCexp values—14.8 and 15.9 kJ g−1 , respectively. Moreover, the
ratio THR/EHCtheo is approximately 80%, indicating that the THR decrease is almost proportional to
the char yield (circa 20%). As for EA, its EHCexp value is much lower than its EHCtheo —4.5 and 16.0 kJ
g-1 , respectively. The ratio THR/EHCtheo is 18%, meaning that the THR decrease is much higher that
the char yield. However, thermochemistry calculations do not take into account the energy stored in
the char. To correct this, the EHCtheo should be calculated again by considering the char composed
only of carbon (EHCchar char
theo ). The EHCtheo value of EA was calculated according to the method proposed
char
by Dorez et al. [30]. The EHCtheo value of EA was much closer to the EHCtheo one and equal to
15.7 kJ g−1 . Therefore, the low EHCexp and THR values of EA are mainly due to the charring ability of
the compound that enables storage of energy in the char [30].
The PCFC measurements also confirmed the improvement of GA and EA thermal characteristics
by their functionalization. In fact, GAD and EAD exhibited the pHRR equal to 10 and 25 W g−1 ,
respectively, while the THR values were equal to 0.3 kJ g−1 for GAD and 0.5 kJ g−1 for EAD, respectively.
In addition, GAD and EAD showed a decrease of the EHCexp values compared to the EHCexp of GA
and EA—0.6 and 1.0 kJ g−1 , respectively. The EHCtheo values of GAD and EAD cannot be calculated
because of their non-uniform chemical structure. That is why the EHCtheo and EHCexp values of GAD
and EAD cannot be compared.
2.2. Influence of FR Systems on Epoxy Properties

The adhesion between the epoxy matrix and the FR additives as well as the influence of additives
on epoxy crosslinking are key factors that may affect the thermal and mechanical properties of FR/epoxy
systems. Therefore, dispersion within epoxy thermoset was studied through SEM observations, and
differential scanning calorimetry (DSC) experiments were carried on.
2.2.1. Dispersion of FR Agents within Epoxy Resin

The SEM observations of the formulated epoxy thermosets are illustrated in Figure 9.
Non-uniform dispersion of the pure phenolic components into the epoxy matrix was clearly
observed. The agglomeration process of acicular particles of GA and spherical particles of EA into
DGEBA/IPDA/GA and DGEBA/IPDA/EA thermosets, respectively, was noticed. This can be explained
by (1) mixing parameters such as speed and time of dispersion, (2) some adhesion forces (interlocking,
electrostatic, and/or van der Waals forces) holding the particles together [31], and (3) the low wettability
of the phenolic particles by the liquid epoxy resin, which induces the lack of interactions (observed
in the SEM images at 10 µm) [32]. Moreover, a sedimentation phenomenon was evidenced when
observing the sample cross sections especially for the DGEBA/IPDA/EA system. The EA content was
higher at the bottom area of the sample than at the top one (observed in the SEM image at 1 mm).
Sedimentation may occur during the early stage of curing when a decrease in epoxy resin viscosity is
occurring. At this moment, highly agglomerated particles of EA settle into the epoxy resin.
A chemical treatment is usually able to prevent such an agglomeration by changing interfacial
bondings with the epoxy matrix [32]. Nevertheless, it was not the case for GAD and EAD particles
in DGEBA/IPDA/GAD and DGEBA/IPDA/EAD resins, respectively. It is likely that aggregates were
formed during the freeze-drying step after chemical treatment. Further works are required to reduce
the particle size before incorporation into epoxy. Nevertheless, it can be noticed that GAD and EAD
particles exhibited better affinity with the epoxy matrix than GA and EA (observed in the SEM images
at 10 µm).
Molecules 2019, 24, 4305 9 of 22
Figure 9. The SEM images of the formulated epoxy resins.

Figure 9. The SEM images of the formulated epoxy resins.
Molecules 2019, 24, 4305 10 of 22
2.2.2. Thermal Properties of the FR Epoxy Resins

2.2.2.DSC
Thermal Properties
analyses of the FR Epoxy
were performed on theResins
non-cured epoxy resins to observe the influence of FR
systems
DSConanalyses
epoxy crosslinking. The glass
were performed transition
on the temperature
non-cured was determined
epoxy resins to observe after the resinsof
the influence were
FR
cured according
systems on epoxytocrosslinking.
the procedure
Thedescribed in section
glass transition 3.3. The results
temperature are reported
was determined afterinthe
Figure
resins10were
and
Table 4.
cured according to the procedure described in Section 3.3. The results are reported in Figure 10 and
Table 4.
Figure 10. Differential scanning calorimetry (DSC) thermograms at 10 ◦ C min−1 of uncured bisphenol
A diglycidyl
Figure ether and
10. Differential isophorone
scanning diamine(DSC)
calorimetry (DGEBA/IPDA) mixtures
thermograms at 10 in
°Cthe
minpresence or not bisphenol
−1 of uncured of FRs. A
diglycidyl ether and isophorone diamine (DGEBA/IPDA) mixtures in the presence or not of FRs.
Table 4. Data from DSC analyses of the thermosets.
◦ C) from DSC−1analyses
Thermoset TableTp4.(Data ∆H (J g ) % Reduction ∆H (kJ ee−1 )
of the thermosets. Tg (◦ C)
DGEBA/IPDA Tp (°C)
Thermoset 109 ∆𝐇 431(J g−1) -
% Reduction 96 ∆𝐇 (kJ ee144−1) Tg (°C)
DGEBA/IPDA/GA 107 382 11 94 127
DGEBA/IPDA 109 431 - 96 144
DGEBA/IPDA/EA 99 356 17 88 137
DGEBA/IPDA/GA
DGEBA/IPDA/GAD 107105 382
390 9 11 95 94 108 127
DGEBA/IPDA/EA
DGEBA/IPDA/EAD 99 108 356
391 9 17 96 88 110 137
DGEBA/IPDA/GAD 105 390 9 95 108
DGEBA/IPDA/EAD 108◦ −1 391 9
During a first heating at 10 C min , the neat epoxy resin showed an ideal exothermic peak 96 110(T )
p
at 109 ◦ C. Its total heat of reaction (∆H) was equal to 431 J g−1 corresponding to 96 kJ ee−1 . The cured
During a first
DGEBA/IPDA heatingexhibited
thermoset at 10 °C min −1, the neat epoxy resin showed an ideal exothermic peak (T p)
a glass transition temperature (Tg ) equal to 144 ◦ C. These results
at 109 °C. Its total heat of reaction (ΔH)
are consistent with those previously reported [33].
was equal to 431 J g−1 corresponding to 96 kJ ee−1. The cured
DGEBA/IPDA thermoset
The incorporation exhibited
of the a glass transition
phenolic-based additivestemperature (Tg) equal
such as GA, GAD, to 144into
and EAD °C.DGEBA/IPDA
These results
are consistent
resin withto
does not lead those previously
significant changesreported [33]. characteristics of the material (Table 4). No signal
in thermal
The incorporation of the phenolic-based
corresponding to the interaction between the additives additives such
and the as resins
epoxy GA, GAD, and EAD
was observed. Theinto
Tp
DGEBA/IPDA resin does not lead to significant changes in thermal characteristics
values of these resins were slightly reduced compared to the neat resin and ranged between 105 and
of the material
(Table 4). No signal corresponding to the interaction between the additives and the epoxy resins was
108 ◦ C. The lowest and the highest values correspond to DGEBA/IPDA/GAD and DGEBA/IPDA/EAD
observed. The
thermosets, Tp values ofThe
respectively. these∆Hresins
valueswere slightly by
calculated reduced
gram compared
of materialtowere
the neat resin reduced
logically and rangedby
between 105 and 108 °C. The lowest and the highest values correspond to DGEBA/IPDA/GAD
about 10% with the incorporation of 10 wt.% of the additives compared to the neat thermoset. The
and
DGEBA/IPDA/EAD thermosets, respectively. The ΔH values calculated by gram of material were
enthalpies of reaction calculated by epoxy equivalent (ee) were quite close to that of the neat resin
logically reduced by about 10% with the incorporation of 10 wt.% of the additives compared to the
except for DGEBA/IPDA/EA. It allows concluding that GA, GAD, and EAD do not influence the cure
neat thermoset.
kinetic The enthalpies
of the epoxy resin. On of thereaction
contrary,calculated
the use by epoxy
of EA as equivalent (ee) were
additive affects quiteproperties
thermal close to that
of
of the neat resin except for DGEBA/IPDA/EA. It allows concluding that
the epoxy thermoset. An exothermic peak at 99 C with a shoulder between 120 and 150 ◦ C was
◦ GA, GAD, and EAD do not
influence the cure kinetic of the epoxy resin. On the contrary, the use of EA as additive affects thermal
observed for the DGEBA/IPDA/EA thermoset (Figure 10). The enthalpy of reaction was decreased by
properties of the epoxy thermoset. An exothermic peak at 99 °C with a shoulder between 120 and 150
7 %, compared to the DGEBA/IPDA thermoset. Therefore, it could be assumed that EA affects the
°C was observed for the DGEBA/IPDA/EA thermoset (Figure 10). The enthalpy of reaction was
curing kinetic of the epoxy thermoset by reacting as a hardener [34]. It was noticed that the Tg values
decreased by 7 %, compared to the DGEBA/IPDA thermoset. Therefore, it could be assumed that EA
of the additive-containing resins were reduced compared to the neat epoxy resin (Table 4). The Tg
affects the curing kinetic of the epoxy thermoset by reacting as a hardener [34]. It was noticed that
Molecules2019,
Molecules 2019,24,
24,4305
x FOR PEER REVIEW 11ofof22
11 22
the Tg values of the additive-containing resins were reduced compared to the neat epoxy resin (Table
values
4). TheofTthe DGEBA/IPDA/GA,
g values DGEBA/IPDA/EA,
of the DGEBA/IPDA/GA, and DGEBA/IPDA/EAD
DGEBA/IPDA/EA, resins were equal
and DGEBA/IPDA/EAD towere
resins 127,
137, and
equal 127,◦ C,
to110 137,respectively,
and 110 °C,whereas DGEBA/IPDA/GAD
respectively, showed a Tg equal
whereas DGEBA/IPDA/GAD to 108a ◦TC.
showed The reduction
g equal to 108 °C.
of thereduction
The Tg valuesofcould
the Tbe due to
g values the non-uniform
could be due to thedispersion
non-uniform of dispersion
the additives within
of the the epoxy
additives withinresin
the
and the resin
epoxy important
and theagglomeration of the particles (the
important agglomeration of thecase of DGEBA/IPDA/GAD)
particles as already observed
(the case of DGEBA/IPDA/GAD) as
by the SEM analyses (Figure 9).
already observed by the SEM analyses (Figure 9).
TGA–FTIR
TGA–FTIRanalysisanalysiswas
wascarried
carriedout to to
out assess thethe
assess impact
impactof the purepure
of the phenolic compounds
phenolic compounds(EA and
(EA
GA)
andandGA)their
andderivatives (EAD and
their derivatives GAD)and
(EAD on the thermal
GAD) stability
on the thermaland stability
charring and
ability of DGEBA/IPDA
charring ability of
resin. TGA curves
DGEBA/IPDA underTGA
resin. nitrogen are illustrated
curves in Figure
under nitrogen are11.illustrated
The thermal in characteristics
Figure 11. The are listed
thermalin
Table 5.
characteristics are listed in Table 5.
Figure
Figure11.
11. Thermograms
Thermograms of
of epoxy resin and
epoxy resin andflame
flameretarded
retardedsystems
systemsatat1010
◦ C°C min
min undernitrogen
−1-1under nitrogenflow.
flow.
Table 5. Data from TGA analyses of the FR/epoxy systems

Table 5. Data from TGA analyses of the FR/epoxy systems
Theoretical Experimental
Thermoset
Theoretical ◦ Experimental
Char900 th Tmax ( C) Char600 (wt.%) Char900 (wt.%)
Thermoset Char600 Char900
DGEBA/IPDA - Char900 370 Tmax (°C) 11.3
th
9.8
(wt.%) (wt.%)
DGEBA/IPDA/GA 10.7 349 12.6 10.9
DGEBA/IPDA/EADGEBA/IPDA 12.0 - 338 370 11.3
20.7 9.8 18.6
DGEBA/IPDA/GA
DGEBA/IPDA/GAD 14.1 10.7 367 349 12.6
18.0 10.9 15.6
DGEBA/IPDA/EAD
DGEBA/IPDA/EA 14.1 12.0 371 338 18.0
20.7 18.6 15.8
DGEBA/IPDA/GAD 14.1 367 18.0 15.6
The GA- and DGEBA/IPDA/EAD
EA-containing epoxy thermosets 14.1 371 a premature
showed 18.0 15.8 of decomposition
onset
compared to the unfilled epoxy resin. The Tmax was reduced from 370 ◦ C for DGEBA/IPDA, to 349
and 338The◦ CGA-
for and EA-containing and
DGEBA/IPDA/GA epoxy thermosets showed
DGEBA/IPDA/EA, a premature
respectively. Twoonset of decomposition
phenomena could be
compared to
responsible forthe
thisunfilled
reduced epoxy resin.
thermal The T max
stability. Thewasfirstreduced from
one is the 370stage
early °C for DGEBA/IPDA, of
of decomposition to the
349
and 338 °C for DGEBA/IPDA/GA and DGEBA/IPDA/EA, respectively. Two
pure phenolic compounds. The effect is particularly noticeable for the GA-containing thermoset. Thephenomena could be
responsible for this reduced thermal
◦ stability. The first one is the early stage of decomposition
onset of weight loss at about 200 C corresponds to the beginning of thermal decomposition of the pure of the
pure phenolic
phenolic compounds.
additive (Figure 7). The effect phenomenon
A second is particularlyinfluencing
noticeable the
for thermal
the GA-containing thermoset.
stability of the The
thermosets
onset of weight loss at about 200 °C corresponds to the beginning of thermal
may be the pro-degradant effect of hydroxyl group bonds by the phenolic compounds. Such an decomposition of the
pure has
effect phenolic
already additive (Figure when
been observed 7). A incorporating
second phenomenon influencing
lignin into polylacticthe
acidthermal
(PLA), stability of the
leading to the
thermosetsdegradation
premature may be theof pro-degradant
the polymer matrixeffect of hydroxyl
[35]. group
The char yieldsbonds by the phenolic
of DGEBA/IPDA were compounds.
improved
Molecules 2019, 24, 4305 12 of 22
Such an effect has already been observed when incorporating lignin into polylactic acid (PLA),
leading to the premature degradation of the polymer matrix [35]. The char yields of DGEBA/IPDA
by
wereusing the pureby
improved phenolic
using the components
pure phenolic as additives.
componentsThe char 600 values The
as additives. increased
char 600from 11.3increased
values wt.% for
DGEBA/IPDA to 12.6 and 20.7 wt.% for DGEBA/IPDA/GA and DGEBA/IPDA/EA,
from 11.3 wt.% for DGEBA/IPDA to 12.6 and 20.7 wt.% for DGEBA/IPDA/GA and DGEBA/IPDA/EA, respectively. It was
observed thatItthe
respectively. theoretical
was observed(calculated using the(calculated
that the theoretical additive law) andthe
using experimental
additive law) charandyields at 900 ◦ C
experimental
of DGEBA/IPDA/GA
char yields at 900 °C thermoset were almostthermoset
of DGEBA/IPDA/GA the same were
- 10.7almost
and 10.9 thewt.%,
samerespectively.
- 10.7 and 10.9 Whereas
wt.%,
the theoretical char 900 value of DGEBA/IPDA/EA was lower than
respectively. Whereas the theoretical char 900 value of DGEBA/IPDA/EA was lower than the the experimental one—12.0 against
18.6 wt.%, respectively,
experimental one—12.0itagainst
could be18.6 explained by some reactions
wt.%, respectively, it could between the particles
be explained by some of EAreactions
and the
epoxy matrix (observed by the DSC analysis). The formed products
between the particles of EA and the epoxy matrix (observed by the DSC analysis). The formed seem to promote the charring
ability
productsof the
seemthermoset.
to promote the charring ability of the thermoset.
Concerning
Concerning the the GAD-
GAD- and and EAD-containing
EAD-containing epoxy epoxy thermosets,
thermosets, they they exhibited
exhibited similar
similar thermal
thermal
stability to the neat epoxy resin.
stability to the neat epoxy resin. The Tmax The T values of DGEBA/IPDA/GAD and DGEBA/IPDA/EAD
max values of DGEBA/IPDA/GAD and DGEBA/IPDA/EAD were
were
equal ◦
equal to
to 367
367 and
and 371371 °C, C, respectively.
respectively. It It is
is assumed
assumed that the pro-degradant
that the pro-degradant effect effect of
of hydroxyl
hydroxyl groups
groups
from GA and EA was screened after functionalization. An increase
from GA and EA was screened after functionalization. An increase of the char yield up of the char yield up toto 18.0
18.0 wt.%
wt.%
was ◦ C of the epoxy resins were close
was observed
observed for for both
both thermosets.
thermosets. The The theoretical
theoretical char
char yields
yields atat 900
900 °C of the epoxy resins were close
to
to the
the experimental
experimental ones: 14.1 against
ones: 14.1 against 15.615.6 wt.%
wt.% for
for DGEBA/IPDA/GAD
DGEBA/IPDA/GAD and and 14.1
14.1 against
against 15.8
15.8 wt.%
wt.%
for
for DGEBA/IPDA/EAD, respectively. These results allowed considering that GAD and EAD do
DGEBA/IPDA/EAD, respectively. These results allowed considering that GAD and EAD do not
not
promote additional charring of the DGEBA/IPDA
promote additional charring of the DGEBA/IPDA matrix. matrix.
The
The off-gases
off-gases of of the
the DGEBA/IPDA
DGEBA/IPDA thermosets thermosets analyzed
analyzed by by FTIR
FTIR correspond
correspond to to those
those previously
previously
reported [36]. The FTIR spectrums of the off-gases showed bands of C=O (1751 cm −1 ), C —O groups
reported [36]. The FTIR spectrums of the off-gases showed bands of C=O (1751 cm−1), CAr Ar—O groups
of −1 ), C =C −1 C –H (3057, 746, and 686 cm−1 ),
of phenol
phenol (1260
(1260 andand 1176
1176 cmcm−1 ), CArAr=CAr Ar (1603
(1603 and
and 15071507
cmcm−1), C), Ar (3057, 746, and 686 cm−1), and
Ar–H
and OH–phenolic groups of bisphenol A (3649 cm −1 ). The decomposition products as2 (2379
CO2 (2379 and
OH–phenolic groups of bisphenol A (3649 cm−1). The decomposition products as CO and 2311
2311 −1 −1 −1 −1 ),
cm−1),cmCO ), CO (2180
(2180 and 2107 andcm2107
−1), cm ), ammonia
ammonia NH3 (965NHand
3 (965
931and
cm931 cm ), methane
−1), methane CH4 (3018 CHcm4 (3018 cmfree
−1), and
and −1
H2Ofree
(3756H2and
O (3756
1595andcm−11595
) werecmalso ) were also detected.
detected.
2.2.3. Fire Behavior of the FR Epoxy Resins
2.2.3. Fire Behavior of the FR Epoxy Resins
Thermogravimetric analysis can be completed by the study of the fire behavior of the formulated
Thermogravimetric analysis can be completed by the study of the fire behavior of the formulated
FR epoxy thermosets using PCFC and cone calorimeter measurements. Figure 12 illustrates the HRR
FR epoxy thermosets using PCFC and cone calorimeter measurements. Figure 12 illustrates the HRR
curves of the epoxy thermosets obtained by PCFC measurements. The PCFC characteristics are listed
curves of the epoxy thermosets obtained by PCFC measurements. The PCFC characteristics are listed
in Table 6. The PCFC results are in accordance with the TGA measurements for all the studied samples
in Table 6. The PCFC results are in accordance with the TGA measurements for all the studied
(Table 5). Hence, GA and EA containing epoxies exhibit pHRR temperatures lower than those of the
samples (Table 5). Hence, GA and EA containing epoxies exhibit pHRR temperatures lower than
reference and the boron derivatives containing epoxies. This confirms the destabilizing effect of the
those of the reference and the boron derivatives containing epoxies. This confirms the destabilizing
pure phenolic compound onto the polymer matrix.
effect of the pure phenolic compound onto the polymer matrix.
Figure12.
Figure 12. PCFC
PCFC curves
curves of
of the
the DGEBA/IPDA
DGEBA/IPDAbased
basedflame
flameretarded systemsatat11◦°C
retardedsystems C ss−1.
−1.
Molecules 2019, 24, 4305 13 of 22

Table 6. Data from the PCFC tests of the formulated epoxy thermosets.
Table 6. Data from the PCFC tests of the formulated epoxy thermosets.
Thermoset pHRR (W g−1 ) % Reduction Tpeak (◦ C) THR (kJ g−1 ) EHCexp (kJ g−1 )
pHRR THR EHCexp
DGEBA/IPDA
Thermoset 525 %- Reduction 370Tpeak (°C) 28.4 31.8
DGEBA/IPDA/GA 292 (W g−1) 45 355 (kJ
25.8 g −1) (kJ g−129.3
)
DGEBA/IPDA 471
DGEBA/IPDA/EA 525 10 - 343 370 25.928.4 31.8 32.3
DGEBA/IPDA/GA451
DGEBA/IPDA/GAD 292 14 45 377 355 25.325.8 29.3 30.4
DGEBA/IPDA/EAD
DGEBA/IPDA/EA463 471 12 10 373 343 27.425.9 32.3 29.7
DGEBA/IPDA/GAD 451 14 377 25.3 30.4
DGEBA/IPDA/EAD 463 12
The neat epoxy resin shows high pHRR and THR values during PCFC test—525 373 27.4 29.7W g−1 and
28.4 kJ g−1 , respectively. Similar results were previously reported [37]. A decrease in these values was
The neat epoxy resin shows high pHRR and THR values during PCFC test—525 W g−1 and 28.4
observed after adding the pure phenolic compounds into the epoxy system. The pHRR values of the
kJ g , respectively. Similar results were previously reported [37]. A decrease in these values was
−1
GA- and EA-containing epoxy thermosets decreased respectively to 292 and 471 W g−1 . Regarding EA
observed after adding the pure phenolic compounds into the epoxy system. The pHRR values of the
containing epoxy, this corresponds to a 10% reduction in good agreement with an additive mixing law.
GA- and EA-containing epoxy thermosets decreased respectively to 292 and 471 W g −1. Regarding EA
Oncontaining
the opposite, the DGEBA/IPDA/GA resin exhibits a 45% pHRR reduction,
epoxy, this corresponds to a 10% reduction in good agreement with an additive mixing
i.e., much higher than
expected from the mixing law. It allows suggesting that this pure phenolic
law. On the opposite, the DGEBA/IPDA/GA resin exhibits a 45% pHRR reduction, i.e., much higher compound may influence
thethan
combustion
expected pathway
from the of the epoxy
mixing law. Itthermoset.
allows suggestingThe THR values
that of the
this pure GA- and
phenolic EA-containing
compound may
resins were reduced by about 10% compared to the uncharged
influence the combustion pathway of the epoxy thermoset. The THR values of the GA- epoxy thermoset and were andequal
EA- to
25.8 and 25.9 kJ g −1 , respectively. No significant variation was observed for the EHC
containing resins were reduced by about 10% compared to the uncharged epoxy thermoset and were of
exp values
theequal
formulated thermosets. −1
to 25.8 and 25.9 kJ g−1,They were equal
respectively. to 29.3 and
No significant 32.3 kJ was
variation g observed
for the GA- for and EA-containing
the EHC exp values
thermosets, respectively,
of the formulated compared
thermosets. Theytowere kJ g−1toof29.3
31.8equal theand
neat32.3epoxy
kJ g−1resin.
for the GA- and EA-containing
GAD andrespectively,
thermosets, EAD led to compared
the improvement
to 31.8 kJofgthe
−1 offire
the behavior
neat epoxy ofresin.
the epoxy resin. The pHRR, THR,
and EHC GADexp and EAD
values ofled to the improvementand
DGEBA/IPDA/GAD of the fire behavior of the were
DGEBA/IPDA/EAD epoxydecreased
resin. The in pHRR, THR,
proportions
and EHCwith
compliant exp values of DGEBA/IPDA/GAD
the mixing rule. Hence, no andspecific
DGEBA/IPDA/EAD
interactions were with decreased
the polymer in proportions
matrix were
compliantby
highlighted with
thisthe mixing rule. Hence, no specific interactions with the polymer matrix were
method.
highlighted by this method.
It is well known that the PCFC test is not sensitive to physical effects while both chemical and
physical It actions
is well known that theinPCFC
are effective cone test is not sensitive
calorimetry. to physical
Therefore, effects
the fire while both
behavior of thechemical and
epoxy resins
physical actions are effective in cone calorimetry. Therefore, the fire behavior
was also investigated using a cone calorimeter. It provides key information about flame retardant of the epoxy resins was
also investigated
properties of materials using
sucha ascone
timecalorimeter. It provides
to ignition (TTI), key information
HRR, pHRR, THR, and char aboutcontent.
flame retardant
The results
properties of materials such as time to ignition (TTI), HRR, pHRR, THR, and char content. The results
of cone calorimeter test are summarized in Figure 13 and Table 7. A sedimentation issue was observed
of cone calorimeter test are summarized in Figure 13 and Table 7. A sedimentation issue was observed
by SEM measurements for all the samples (Figure 9). In order to assess the fire behavior under the least
by SEM measurements for all the samples (Figure 9). In order to assess the fire behavior under the
favorable conditions, samples were exposed to the incident heat flux by the side with lower additive
least favorable conditions, samples were exposed to the incident heat flux by the side with lower
content, except DGEBA/IPDA/EA for which both sides were exposed.
additive content, except DGEBA/IPDA/EA for which both sides were exposed.
Figure 13. Heat release rate (HRR) curves of the formulated epoxy resin studied in a cone calorimeter
at 35 kW m−2. .
Molecules 2019, 24, 4305 14 of 22
Table 7. Data from the cone calorimeter (heat flux 35 kW m−2 ) test.
Thermoset TTI (s) pHRR (kW m−2 ) % Reduction THR (kJ g−1 ) Char (wt.%)
DGEBA/IPDA 90 1116 - 27.0 3.9
DGEBA/IPDA/GA 66 984 12 23.8 8.8
DGEBA/IPDA/EA 80 620 44 23.4 11.2
DGEBA/IPDA/EA*1 55 492 56 23.7 12.5
DGEBA/IPDA/GAD 69 394 65 23.8 13.7
DGEBA/IPDA/EAD 75 769 31 25.5 10.0
1 The sample DGEBA/IPDA/EA* was exposed to ignition by the side with higher EA content
According to the literature [36] and cone calorimeter tests, DGEBA/IPDA exhibits a high pHRR
and a low carbon residue content—1116 kW m−2 and 3.9 wt.%, respectively. The addition of the
phenolic compounds and their derivatives in DGEBA/IPDA leads to the evolution of its burning
behavior. The use of the pure phenolic additives induced a decrease of TTI values from 90 s for
DGEBA/IPDA to 66 and 80 s for the GA- and EA-containing epoxy resins, respectively. These variations
in TTI values are in good agreement with the lower thermal stability of these compositions as shown
by TGA and PCFC. It should be noted that a decrease of TTI was also observed in the presence of the
boron derivatives GAD or EAD despite their good thermal stability as observed in TGA. In a general
way, the incorporation of 10 wt.% of the phenolic compounds or their derivative in DGEBA/IPDA
allows reducing both the pHRR and THR. In the case of DGEBA/IPDA/GA, the pHRR value is reduced
only by 12% while for DGEBA/IPDA/EA, the decrease is much more significant (by 44%). The most
remarkable effect was obtained with GAD that induces a 65% reduction of pHRR while the results
for EAD were a little bit disappointing with only 31% reduction of pHRR. In order to evaluate the
influence of the additive dispersion in the epoxy matrix, the sample DGEBA/IPDA/EA was exposed to
the incident heat flux by the side with the higher EA content referred to as DGEBA/IPDA/EA*. It was
observed that TTI was decreased to 55 s. This result was associated with the early decomposition
of this composition as observed by TGA. Nevertheless, the pHRR value was significantly reduced
to 492 kW m−2 which corresponds to a decrease by 21 % compared to the DGEBA/IPDA/EA sample.
It leads to the conclusion that the non-uniform dispersion of additives in the epoxy matrix may affect
the fire behavior of material. A uniform dispersion of the additives in the epoxy matrix should be
achieved to ensure a better efficiency as FRs. Apart from the decrease of pHRR, it is noteworthy that the
use of phenolic compounds (GA, EA, EA*, and GAD) induces a change in the HRR curve shape. Hence,
for these compositions, the pHRR happens rapidly after ignition and then HRR tends to decrease. This
behavior is typical of thick charring materials according to the classification of Schartel and Hull [38].
It means that quickly after ignition a protective layer is formed at the sample surface that acts as heat
shield for the underlying polymer thus reducing its pyrolysis rate and consequently the heat release
rate as well. With a view to evaluate this barrier effect in the epoxy resin, PCFC and cone calorimeter
measurements can be used according to the method reported by Sonnier et al. [39]. This method
consists in plotting two parameters R1 (Y-axis) vs. R2 (X-axis), where R1 is the ratio between HRC in
PCFC of the additive-containing resin and HRC in PCFC of the neat resin and R2 is the ratio between
pHRR in the cone calorimeter of the additive-containing resin and the pHRR in the cone calorimeter of
the uncharged resin. At 1 K s−1 , the HRC is equal to the pHRR. The method relies on the assumption
that the barrier effect is only operative in the cone calorimeter but not in PCFC where samples are
supposed to be at a uniform temperature. Consequently, the occurrence of a barrier effect can be
evidenced by a deviation from the R1 = R2 line. As observed in Figure 14, the values corresponding
to epoxy containing EA, GAD, and EAD are located above the line R1 = R2 (which corresponds to a
similar decrease of pHRR in the cone calorimeter and of HRC in PCFC). It indicates that the decrease
of pHRR in the cone calorimeter is higher than the decrease of HRC in PCFC highlighting a significant
barrier effect. The strongest barrier effect was observed for DGEBA/IPDA/GAD. These results are
consistent with the residual mass after the flame out which is the highest for the GAD containing epoxy
(13.7 wt.%).
Molecules effect24,was
barrier 2019, 4305 observed 15 of 22
for DGEBA/IPDA/GAD. These results are consistent with the residual
mass after the flame out which is the highest for the GAD containing epoxy (13.7 wt.%).
Figure14.
Figure 14. R1
R1 vs.
vs. R2 plots for the DGEBA/IPDA
DGEBA/IPDA thermosets.
thermosets.
The
The barrier
barrier effect
effectcancanalso
alsobebegrasped
graspedby byobserving
observingthe thecone
conecalorimeter
calorimetertesttestresidues.
residues. Figure
Figure 1515
shows
shows that
that epoxies
epoxies containing
containingGA GA and and EA
EA exhibit
exhibit some
some charring,
charring, however
however in in both
both cases
cases the
the cohesion
cohesion
of residueseems
of the residue seemsvery very poor
poor which
which may may explain
explain thatthat
the heatthe release
heat release
rate israte is notunder
not really reallycontrol.
under
control.
On the opposite, GAD containing epoxy exhibits a cohesive residue. Moreover, this residue is
On the opposite, GAD containing epoxy exhibits a cohesive residue. Moreover, this residue is
significantly
significantly expanded
expanded (Figure
(Figure15) 15)which
whichemphasizes
emphasizesits its efficiency
efficiencyas asaaheat
heatshield.
shield. TheThe grey
grey color
color atat
the
the bottom
bottom of of the
the residue
residue maymay indicate
indicate that
that boron
boron plays
plays aa role
role in in its
its cohesion
cohesion asas aa glassy
glassybinder.
binder. This
This
assumption is corroborated by the fact that boron remains the residue as
assumption is corroborated by the fact that boron remains the residue as shown in Table 7. A similarshown in Table 7. A similar
behavior
behavior was
was expected
expected in in the
the case
case ofof EAD.
EAD. Figure
Figure 15
15 shows
shows that that the
the boron
boron derivative
derivativeseemsseems to to impart
impart
some
some cohesion
cohesion to to the
the residue.
residue. However, the the charring
charring effect
effect appears
appears as as negligible,
negligible, the the residue
residue being
being
almost
almost entirely grey. Moreover,
Moreover,no noexpansion
expansionofofthe thelayer
layerwas was observed
observed during
during thethe combustion.
combustion. In
In addition,
addition, results
results ofofICPICPanalysis
analysis(Table
(Table8),8),performed
performedon on thethe char
char formed during the the combustion
combustion
confirm
confirmthat
thatGADGADand andEAD EADact actininthe
thecondensed
condensed phase.
phase. In In
fact, thethe
fact, boron andand
boron sodium
sodium contents
contentsof the
of
epoxies char char
the epoxies residues measured
residues by ICP–AES
measured by ICP–AESanalysis were quite
analysis were closequiteto the theoretical
close ones, which
to the theoretical ones,
were
which calculated considering
were calculated the amount
considering the of the inorganic
amount components
of the inorganic in the GADinand
components theEAD
GADcontaining
and EAD
materials constant before and after fire testing. This result clearly indicates
containing materials constant before and after fire testing. This result clearly indicates that GAD that GAD and EADand act
mainly
EAD actinmainly
condensed phase. phase.
in condensed
Table8.8. ICP–AES
Table ICP–AES results
results of
of the
the char
char formed
formed during
during the
the combustion
combustion of
of DGEBA/IPDA/GAD
DGEBA/IPDA/GAD and
and
DGEBA/IPDA/EAD.
DGEBA/IPDA/EAD.
Sample Residue BTh 1 (wt.%) 2

BTh1 BICP (wt.%)
BICP2 NaTh 3 (wt.%)
NaTh3
4 (wt.%)
NaICPNa ICP4
Sample Residue
DGEBA/IPDA/GAD 3.84 (wt.%) 3.05 ± (wt.%)
0.02 (wt.%)
4.26 4.21(wt.%)
± 0.05
DGEBA/IPDA/EAD
DGEBA/IPDA/GAD 5.39 3.84 4.14 ± 0.20± 0.02
3.05 6.844.26 9.42 ±±
4.21 0.03
0.05
DGEBA/IPDA/EAD 5.39 4.14 ± 0.20 6.84 9.42 ± 0.03
Molecules 2019, 24, 4305 16 of 22
Figure 15. Cone calorimeter residues of the prepared thermosets.

Figure 15. Cone calorimeter residues of the prepared thermosets.
3. Materials and Methods
3.1. Materials
Ellagic acid labeled EA (purity 97%) was purchased (Alfa Aesar, Kandel, Germany). Gallic acid
labeled GA (purity 97.5%) was supplied (Sigma–Aldrich, Saint Louis, MO, USA). Boric acid labeled BA
(≥99%) was provided (GPR Rectapur, Leuven, Belgium). Sodium hydroxide abbreviated by SH (≥99%)
was supplied(Roth, Karlsruhe, Germany). The conventional petroleum-sourced epoxy monomer used
was diglycidyl ether of bisphenol A (DGEBA) (Figure 16a) and was supplied with an epoxy equivalent
3.1. Materials
Ellagic acid labeled EA (purity 97%) was purchased (Alfa Aesar, Kandel, Germany). Gallic acid
labeled GA (purity 97.5%) was supplied (Sigma–Aldrich, Saint Louis, MO, USA). Boric acid labeled
BA (≥99%) was provided (GPR Rectapur, Leuven, Belgium). Sodium hydroxide abbreviated by SH
Molecules 2019, 24, 4305 17 of 22
(≥99%) was supplied(Roth, Karlsruhe, Germany). The conventional petroleum-sourced epoxy
monomer used was diglycidyl ether of bisphenol A (DGEBA) (Figure 16a) and was supplied with an
epoxy
weightequivalent
(EEW) of 177 weight
g eq−1(EEW) of Aldrich,
(Sigma 177 g eq−1 (SigmaGermany).
Kandel, Aldrich, Kandel, Germany). cross-linking
The cycloaliphatic The cycloaliphatic
agent
cross-linking agent isophorone
isophorone diamine diamine
(IPDA) (Figure 16b)(IPDA) (Figure 16b)
was supplied withwas supplied
an amine with an amine
equivalent weightequivalent
(AEW) of
weight
42 g eq−1(AEW)
(Sigma of Aldrich,
42 g eq−1 Steinheim,
(Sigma Aldrich, Steinheim, Germany).
Germany).
Figure 16. Structure of (a) DGEBA and (b) IPDA.

Figure 16. Structure of (a) DGEBA and (b) IPDA.
3.2. Boratation of Phenolic Compounds
3.2. Boratation of Phenolic Compounds
A two-step procedure was applied.
A two-step
The procedure
first step consisted wasin applied.
the preparation of BA and SH solution. Fifty milliliters of 0.2 M
The first step consisted
aqueous solution of BA and 21.4 in the
mL ofpreparation
0.2 M aqueousof BA and SH
solution of solution. Fifty milliliters
SH were mixed in a 100 mL of beaker.
0.2 M
aqueous
The mixturesolution of BA and
was stirred 21.4 mL for
vigorously of 0.2 M aqueous
5 min at roomsolution
temperatureof SHandwere mixed
then in aat100
stored 4 ◦mL beaker.
C until use.
The mixture was stirred
The pH of the solution was 9. vigorously for 5 min at room temperature and then stored at 4 °C until use.
The pH Theofsecond
the solution was 9.
step corresponded to the functionalization. A 25 mL single-necked round-bottomed
The second step corresponded
flask equipped with a magnetic stirring to the functionalization.
bar was charged A 25 mL
with single-necked
phenolic compound round-bottomed
and aqueous
flask equipped with a magnetic stirring bar was charged with phenolic
solution of BA and SH. The pH of the solution was adjusted to 9 with 0.2 M aqueous solution compound andofaqueous
SH and
solution of BA
then heated for and SH.
3 h at 50 The pH ofvigorous
◦ C under the solution was After
stirring. adjusted
that,tothe
9 with 0.2 M
solution wasaqueous solution
freeze-dried overof48
SHh.
and then heated for 3 h at 50 °C under vigorous stirring. After that, the solution
The formation of boron complexes of the phenolic compounds was supposed under the conditions was freeze-dried over
48 h.
described above. The hydroxyl groups of phenolic compounds in the ortho-position help a complex
The formation
formation with BA [40]. of boron
However,complexes of the
the presence of aphenolic
carboxylcompounds was supposed under
group (electron-withdrawing group) the
is
conditions described above. The hydroxyl groups of phenolic compounds in
expected to weaken the boron complex formation [40]. Freeze-drying was applied to the treatment the ortho-position help
asolution
complex in formation with BA
order to prevent [40]. However,
thermal decompositionthe presence of a carboxyl
of the synthesized group (electron-withdrawing
boron-based phenolic derivatives.
group) is expected to weaken the boron complex formation [40].
Table 9 summarizes information about the boration of the phenolic compounds. Freeze-drying was applied to the
treatment solution in order to prevent thermal decomposition of the synthesized boron-based
phenolic derivatives. Table 9. Boration data of the phenolic compounds.
Table 9 summarizes information about the boration of the phenolic compounds.
Sample Name Phenolic Compound Ph (mmol) BA (mmol) SH (mmol)
GAD Table 9. Boration
GA data of the phenolic
1.7 compounds.
1.7 1.0
EAD EA 0.5 1.0 1.0
Sample Name Phenolic Compound Ph (mmol) BA (mmol) SH (mmol)
GAD GA 1.7 1.7 1.0
3.3. Epoxy Resin Preparation
EAD EA 0.5 1.0 1.0
Different chemicals are under liquid forms (DGEBA and IPDA) while other are under solid forms
(FR systems). In order to obtain a homogeneous dispersion, GA and EA as well as GAD and EAD were
firstly introduced in DGEBA by manual stirring. The prepared mixture was then heated for 15 min
at 80 ◦ C. The curing agent–IPDA–was then added in a 1:1 molar ratio of epoxy group to active H of
amine. The system was stirred manually for 5 min. The mixture was cross-linked in a silicon mold to
the following temperature program: 4 h at 80 ◦ C and 1 h at 150 ◦ C under inert atmosphere.
Table 10 summarizes different epoxy resins formulated in this study.
Molecules 2019, 24, 4305 18 of 22
Table 10. Composition of the formulated epoxy thermosets.
Resin name DGEBA (wt.%) IPDA (wt.%) FR (wt.%)

DGEBA/IPDA 80 20 0
DGEBA/IPDA/GA
DGEBA/IPDA/EA
72 18 10
DGEBA/IPDA/GAD
DGEBA/IPDA/EAD
3.4. Chemical Characterization
3.4.1. Mass Spectrometry

Mass spectrometry (MS) analyses were performed on a Ion trap mass spectrometer with an
electrospray ionization (ESI) interface (Bruker Daltonics, Wissembourg, France) operating in negative
ion mode. The samples of additives were dissolved in methanol and then filtered through a polymer
membrane with a pore diameter of 0.45 µm. The injection of samples was made by syringe. The
following conditions of the ESI interface were used: drying gas flow, 8.0 L min−1 ; nebulize pressure,
3 bars; gas drying temperature, 200 ◦ C; capillary voltage, 5000 V; fragmentor voltage, 1 V.
3.4.2. 11 B solid-state Nuclear Magnetic Resonance Analysis

11 B
solid-state nuclear magnetic resonance (NMR) analyses were performed on an Avance III
600 MHz spectrometer (Bruker, Wissembourg, France) operating with 11 B frequency of 192.4 MHz.
A magic-angle spinning (MAS) rate of 20 kHz was used for all experiments. The samples were packed
into a 4 mm outer diameter ZrO2 rotor using a double resonance probe.
3.4.3. Elementary Analysis

Boron and sodium concentrations were determined by inductively-coupled plasma–atomic
emission spectrometer (ICP–AES, SGS Miltilab, France). Calibration curves were established by
employing the certified samples of known boron and sodium concentrations. Peak intensity was
converted into boron weight percentage using the calibration curves. All samples were analyzed three
times. The calculations were based on a dry weight of samples.
3.5. Thermal Characterization
3.5.1. Thermogravimetric Analysis Coupled with Infrared Spectroscopy

Thermogravimetric analysis (TGA) measurements were obtained on a thermal analysis system
Setsys Evolution (Setaram) (Setaram, Caluire, France). The initial weight of each tested sample was
about 10 mg. The samples were heated from 30 to 900 ◦ C at a heating rate of 10 ◦ C min−1 under
nitrogen atmosphere. The degradation temperatures (Tmax ) and the char yields at 600 ◦ C (Char600 ) and
900 ◦ C (Char900 ) were determined for each sample. The theoretical the char content at 900 ◦ C (Charth
900 )
for the thermosets was calculated according to the additive law of mixtures:
exp exp
Charth
900 = f Charad + (1 − f )Charep (1)
where Charth ◦
900 is the theoretical char yield of the additive-containing epoxy resin at 900 C, wt.%; f—the
exp
mass fraction of the additive (equal 0.1 for all formulated thermosets); Charad —the experimental char
exp
yield of the additive at 900 ◦ C, wt.%; Charep —the experimental char yield of the uncharged epoxy
resin at 900 ◦ C, wt.%.
A Fourier transform infrared spectrometer (FTIR) Antaris IGC (Thermo Fisher Scientific, Illkirch,
France) was connected to the previous thermal system. The temperatures of the transfer line and
the gas cell were fixed at 210 ◦ C. The FTIR spectrometer was settled to collect 8 interferograms at a
Molecules 2019, 24, 4305 19 of 22
resolution of 8 cm−1 in the spectral range of 4000–400 cm−1 . The evaluation of the gas concentration
during the test was measured using OMNIC© software (v. 9.2) from Thermo Fisher Scientific.
3.5.2. Differential Scanning Calorimetry Analysis

Differential scanning calorimetry (DSC) measurements of samples were carried out under nitrogen
atmosphere using a DSC Q200 (TA Instrument, Guyanourt, France). The thermal properties were
analyzed at 10 ◦ C min−1 between 30 ◦ C and 250 ◦ C to observe the exothermic temperature peak (Tp ),
the total heat of reaction (∆H), and the enthalpy of reaction of the uncured samples and the glass
transition temperature (Tg ) of the cross-linked thermosets determined as the inflexion value in the
heat capacity jump. The uncured samples were tested in duplicate, while the cures ones were tested
in triplicate.
3.6. Characterization of Fire Properties
3.6.1. Pyrolysis Combustion Flow Calorimetry

Pyrolysis combustion flow calorimetry (PCFC) analyses of materials were performed using
a FAA Micro Calorimeter from Fire Testing Technology (FTT, West Sussex, UK). About 2 mg of
sample was placed in the pyrolyzer, undergoing an increase of temperature from 100 to 750 ◦ C at
1 ◦ C s−1 under nitrogen flow. Then, decomposition gases were sent to a combustor where they were
heated at 900 ◦ C under air flow (N2 /O2 = 80/20). In these conditions, combustion was considered
to be complete. Heat release rate (HRR) value was calculated by oxygen depletion according to
Huggett’s relation [41]. The total heat released (THR) was determined by integration of PCFC curves.
The experimental effective heat of combustion (EHCexp ) represents the released heat by mass loss and
is calculated as a ratio between THR and mass loss measured using TGA. The theoretical effective heat
of combustion (EHCtheo ) of the pure phenolic compounds was also calculated [30]. For the case of
complete combustion, a chemical compound containing carbon, hydrogen, and oxygen undergoes
oxidation that leads to carbon dioxide and water release according to the following equation:
!
h − 2m h
Cc Hh Om + c + O2 → cCO2 + H2 O (2)
4 2
Conforming to Huggett’s relation, the heat released by the combustion is 13.1 kJ per gram of
consumed oxygen [41]. Therefore, EHCtheo of organic compounds can be calculated. All samples were
analyzed in duplicate.
3.6.2. Cone Calorimeter

Fire behavior of the epoxy resins was also studied using a cone calorimeter (Fire Testing Technology)
according to the standard ISO 5660 (sample dimensions 100 × 100 × 4 mm3 ). The samples were exposed
to an irradiance of 35 kW m−2 in the presence of a spark igniter to force the ignition. The peak of heat
release rate (pHRR), the time to ignition (TTI), the total heat release (THR), and the residue content
were measured. All blends were done in triplicate and results were averaged.
3.7. Morphological Characterization

A scanning electron microscope (FEI Quanta 200 ESEM, Felmi-Zfe, Graz, Austria) was used
to observe the dispersion of the FRs in the epoxy resin. Blended samples were prepared using
cryo-fractured cross-sections and analyzed under high vacuum at a 12.5 V with a working distance of
10 mm.
Molecules 2019, 24, 4305 20 of 22
4. Conclusions
This paper reported the alternative using of bio-sourced phenolic compounds such as gallic and
ellagic acids and their boron- and sodium-functionalized forms as FR agents in the epoxy resin. It was
observed that EA may influence the cure kinetic of the epoxy thermoset, whereas the other additives
act as invert additives. The incorporation of the FR agents caused the reduction of the glass transition
temperature from 144 ◦ C for the neat epoxy resin to 54 ◦ C for the GAD-containing thermoset. This
effect was mainly correlated to the low compatibility of the additives with the epoxy matrix as well as to
their non-uniform dispersion and agglomeration within the epoxy resin. These phenomena were also
confirmed by the SEM analysis. The TGA and PCFC measurements showed the decrease in the thermal
stability of the epoxy resins containing the pure phenolic components, and it was mainly attributed to
the early decomposition of the phenolic compounds. Nevertheless, this decrease in thermal stability
was accompanied by an increase in char yield and reduction of flammability. The THR was reduced
by 10% and the pHRR by 45% with 10 wt.% of gallic acid compared to that of the thermoset without
FR. The char content of the epoxy resin was doubled with the incorporation of 10 wt.% of ellagic acid.
It could be explained by the interaction of EA with the epoxy matrix as observed in the DSC analysis.
The derivatives of gallic and ellagic acids also showed the improvement of thermal characteristics.
The pHRR and the THR values were reduced by about 10% by using of 10 wt.% of the phenolic
derivatives. The combination of both PCFC and cone calorimeter analyses has highlighted that the
significant improvement of flame retardant properties was related to a physical barrier effect. These
results prove the potential of the bio-sourced phenolic compounds such as gallic and ellagic acid,
as well as their derivatives, as FRs for epoxy resin.
The development of bio-based FRs is still the main purpose of the FR field. In view of the obtained
results, the efficiency of the plant extracts (for example, chestnut wood extract) as FR agents for a
thermoset matrix should be investigated. The efficiency of its functionalized forms is also proposed
to be studied in following works. It is also suggested to investigate the influence of EA on the cure
kinetic of the epoxy thermoset by the other methods. The uniform dispersion of the additives in the
epoxy matrix should be achieved in order to better evaluate the influence of the phenolic additives on
the fire behavior of the epoxy thermosets.
Supplementary Materials: The calculation of BTh and NaTh contents of GAD and EAD are available online.
Author Contributions: All the authors conceived the experiments. V.K. performed the synthesis and characterization
experiments. V.K. wrote the manuscript. A.B., C.L., H.F., and L.F. corrected the manuscript. All the authors read
and accepted the final manuscript.
Funding: This work was supported by the French Environment and Energy Management Agency (ADEME),
Syndicat des Hautes Vallées Cévenoles (SHVC), and Centre d’Essais et de Recherche de l’Entente (CEREN). The
experiments and ACP were funded by Centre des Matériaux des Mines d’Alès and INRA, respectively.
Acknowledgments: The authors would like to acknowledge the technical support given by Romain Ravel and
Loic Dumazert from Centre des Matériaux des Mines d’Alès and Lucas Suc from INRA Montpellier.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Jin, F.-L.; Li, X.; Park, S.-J. Synthesis and application of epoxy resins: A review. J. Ind. Eng. Chem. 2015, 29,
1–11. [CrossRef]
2. Wang, C.-S.; Berman, J.R.; Walker, L.L.; Menzona, A. Meta-bromobiphenol epoxy resins: Applications in
electronic packaging and printed circuit board. J. Appl. Polym. Sci. 1991, 43, 1315–1321. [CrossRef]
3. Lo, J.; Pearce, E. Flame-retardant epoxy resins based on phthalide derivative. J. Polym. Sci. Polym. Chem. Ed.
1984, 22, 1707–1715. [CrossRef]
4. Shaw, S.D.; Blum, A.; Weber, R.; Kannan, K.; Rich, D.; Lucas, D.; Koshland, C.P.; Dobraca, D.; Hanson, S.;
Birnbaum, L.S. Halogenated flame retardants: Do the fire safety benefits justify the risks? Rev. Environ.
Health 2010, 25, 261–305. [CrossRef] [PubMed]
Molecules 2019, 24, 4305 21 of 22
5. Ecochard, Y.; Decostanzi, M.; Negrell, C.; Sonnier, R. Cardanol and eugenol based flame retardant epoxy
monomers for thermostable networks. Molecules 2019, 24, 1818. [CrossRef] [PubMed]
6. Ménard, R.; Negrell, C.; Fache, M.; Ferry, L.; Sonnier, R.; David, G. From a bio-based phosphorus-containing
epoxy monomer to fully bio-based flame-retardant thermosets. RSC Adv. 2015, 5, 70856–70867. [CrossRef]
7. Sonnier, R.; Taguet, A.; Ferry, L.; Lopez-cuesta, J.-M. Toward Bio-Based Flame Retardant Polymers; Springer:
Amsterdam, The Netherlands, 2017.
8. Pizzi, A. Chapter 8—Tannins: Major Sourced, Properties and Applications. In Monomers, Polymers and
Composites from Renewable Resources; Belgacem, M.N., Gandini, A., Eds.; Elsevier: Oxford, UK, 2008;
pp. 179–199.
9. Khanbabaee, K.; Ree, T. van Tannins: Classification and Definition. Nat. Prod. Rep. 2001, 18, 641–649.
10. Tondi, G.; Wieland, S.; Wimmer, T.; Thevenon, M.F.; Pizzi, A.; Petutschnigg, A. Tannin-boron preservatives
for wood buildings: Mechanical and fire properties. Eur. J. Wood Wood Prod. 2012, 70, 689–696. [CrossRef]
11. Tondi, G.; Haurie, L.; Wieland, S.; Petutshnigg, A.; Lacasta, A.; Monton, J. Comparison of disocium octaborate
tetrahydrate-based and tannin-boron-based formulations as fire retardant for wood structures. Fire Mater.
2014, 38, 381–390. [CrossRef]
12. Yang, T.-T.; Guan, J.-P.; Tang, R.-C.; Chen, G. Condensed tannin from Dioscorea cirrhosa tuber as an
eco-friendly and durable flame retardant for silk textile. Ind. Crops Prod. 2018, 115, 16–25. [CrossRef]
13. Nam, S.; Condon, B.D.; Xia, Z.; Nagarajan, R.; Hinchliffe, D.J.; Madison, C.A. Intumescent flame-retardant
cotton produced by tannic acid and sodium hydroxide. J. Anal. Appl. Pyrolysis 2017, 126, 239–246. [CrossRef]
14. Laoutid, F.; Karaseva, V.; Costes, L.; Brohez, S.; Mincheva, R. Novel bio-based flame retardant systems
derived from tannic acid. J. Renew. Mater. 2018, 6, 559–572. [CrossRef]
15. Aguilera-Carbo, A.; Augur, C.; Prado-Barragan, L.A.; Favela-Torres, E.; Aguilar, C.N. Microbial production
of ellagic acid and biodegradation of ellagitannins. Appl. Microbiol. Biotechnol. 2008, 78, 189–199. [CrossRef]
[PubMed]
16. Howell, B.A.; Oberdorfer, K.L.; Ostrander, E.A. Phosphorus flame retardants for polymeric materials from
gallic acid and other naturally occurring multihydroxybenzoic acids. Int. J. Polym. Sci. 2018, 2018. [CrossRef]
17. Shen, K.K.; O’Connor, R. Flame retardants: Borates. In Plastics Additives: An A-Z Reference; Pritchard, G., Ed.;
Chapman & Hall: London, UK, 1998.
18. Jadhav, S.D. A review of non-halogenated flame retardant. Pharma Innov. J. 2018, 7, 380–386.
19. Shen, K.K. Chapter 6—Boron-based flame retardants in non-halogen-based polymers. In Polymer Green Flame
Retardants; Papaspyrides, C.D., Kiliaris, P., Eds.; Elsevier: Amsterdam, The Netherlands, 2014; pp. 201–241.
ISBN 9781118939239.
20. Shen, K.K. Chapter 11—Review of recent advances on the use of boron-based Flame Retardants. In Polymer
Green Flame Retardants; Papaspyrides, C.D., Kiliaris, P., Eds.; Elsevier: Amsterdam, The Netherlands, 2014;
pp. 367–388. ISBN 9780444538093.
21. Visakh, P.M.; Nazarenko, O.B.; Amelkovich, Y.A.; Melnikova, T. V Thermal properties of epoxy composites
filled with boric acid. Mater. Sci. Eng. R Reports 2015, 81, 1–6. [CrossRef]
22. Yamada, K. Chapter 8—A solid-state NMR study of boric acid doped in poly (vinyl alcohol). In NMR
Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules; Series, A.S., Ed.; American Chemical
Society: Washington, DC ,USA, 2011; pp. 133–146.
23. Moldoveanu, S. Chapter 7—Analytical pyrolysis of natural organic polymers. In Techniques and Instrumentation
in Analytic Chemistry; Elsevier: Amsterdam, The Netherlands, 1998; pp. 217–315. ISBN 0444822038.
24. Rao, C.R.M.; Reddy, V.B.; Mehrotra, P.N. Derivatographic studies of gallic acid. Thermochim. Acta 1981, 46,
65–69. [CrossRef]
25. Coleman, D.J.; Pilcher, G. Heats of combustion of biphenyl, bibenzyl, naphthalene, anthracene and
phenanthrene. Trans. Faraday Soc. 1966, 62, 821–827. [CrossRef]
26. Bailey, W.J.; Bird, C.N. Pyrolysis of Esters. 27. Pyrolysis of Lactones. J. Org. Chem. 1977, 42, 3895–3899.
[CrossRef]
27. Brown, R.F.C. Pyrolytic methods in organic chemistry: Application of flow and flash vacuum pyrolytic techniques;
Academic Press: New York, NY, USA, 1980; ISBN 9780323154178.
28. Galletti, G.C.; Bocchini, P. Behaviour of catechin and ellagic acid subjected to therrnally-assisted hydrolysis
- methylation/gas chrornatography/mass spectrometry. Rapid Commun. Mass Spectrom. 1995, 9, 250–254.
[CrossRef]
Molecules 2019, 24, 4305 22 of 22
29. Greenwood, N.N.; Earnshaw, A. (Eds.) Chapter 6—Boron. In Chemistry of the Elements; Elsevier: Oxford, UK,
1984; pp. 139–215.
30. Dorez, G.; Ferry, L.; Sonnier, R.; Taguet, A.; Lopez-Cuesta, J.M. Effect of cellulose, hemicellulose and lignin
contents on pyrolysis and combustion of natural fibers. J. Anal. Appl. Pyrolysis 2014, 107, 323–331. [CrossRef]
31. Pritchard, G. Plastics Additives: An A-Z Reference; Springer: Amsterdam, The Netherlands, 1997;
ISBN 9401158622.
32. Whitaker, G. Overview of the technical compounder. In Proceedings of the Enhancing Polymers Using
Additives and Modifiers, Shrewsbury, UK, 14 November 1996; LTD, R.T., Ed.; p. 49.
33. Galy, J.; Sabra, A.; Pascault, J.-P. Characterization of epoxy thermosetting systems by differential scanning
calorimetry. Polym. Eng. Sci. 1986, 26, 1514–1523. [CrossRef]
34. Pham, M.P. Theoretical Studies of Mechanisms of Epoxy Curing Systems; The University of Utah: Utah, UT, USA,
2011.
35. Costes, L.; Laoutid, F.; Brohez, S.; Delvosalle, C.; Dubois, P. Phytic acid–lignin combination: A simple and
efficient route for enhancing thermal and flame retardant properties of polylactide. Eur. Polym. J. 2017, 94,
270–285. [CrossRef]
36. Müller, P.; Morys, M.; Sut, A.; Illerhaus, B.; Christian, J.; Schartel, B. Melamine poly (zinc phosphate) as fl
ame retardant in epoxy resin: Decomposition pathways, molecular mechanisms and morphology of fire
residues. Polym. Degrad. Stab. 2016, 130, 307–319. [CrossRef]
37. Schartel, B.; Patrick, M. Melamine poly (metal phosphates) as flame retardant in epoxy resin: Performance,
modes of action and synergy. J. Appl. Polym. Sci. 2016, 133, 1–14.
38. Schartel, B.; Hull, T.R. Development of fire-retarded materials - Interpretation of cone calorimeter data. Fire
Mater. 2007, 31, 327–354. [CrossRef]
39. Sonnier, R.; Ferry, L.; Longuet, C.; Laoutid, F.; Friederich, B. Combining cone calorimeter and PCFC to
determine the mode of action of flame-retardant additives. Polym. Adv. Technol. 2011, 22, 1091–1099.
[CrossRef]
40. Khan, I.A.; Sen, D. Studies on the complex formation of boron with aromatic hydroxy compounds. Indian
Acad. Sci. 1958, 49a, 226–233. [CrossRef]
41. Huggett, C. Estimation of rate of heat release by means of oxygen consumption measurements. Fire Mater.
1980, 4, 61–65. [CrossRef]
Sample Availability: Samples of the compounds GAD and EAD are available from the authors.
© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Molecules: New Biosourced Flame Retardant Agents Based On Gallic and Ellagic Acids For Epoxy Resins

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Molecules 2019, 24, 4305; doi:10.3390/molecules24234305 www.mdpi.com/journal/molecules

Figure 3. Structure of (a) gallic and (b) ellagic acids.

11 NMR spectrum of boric

Molecules 2019, 24, x FOR PEER REVIEW 5 of 22

Molecular Main MS 11B Shifts BTh 1 BICP 2 NaTh 3 NaICP 4

2.1.2. Thermal Characterization of GA and EA and their Boron Modified Entities

Table 3. Data from PCFC tests of the FR systems.

2.2. Influence of FR Systems on Epoxy Properties

2.2.1. Dispersion of FR Agents within Epoxy Resin

Figure 9. The SEM images of the formulated epoxy resins.

2.2.2. Thermal Properties of the FR Epoxy Resins

Table 5. Data from TGA analyses of the FR/epoxy systems

Molecules 2019, 24, x FOR PEER REVIEW 13 of 22

Sample Residue BTh 1 (wt.%) 2

Figure 15. Cone calorimeter residues of the prepared thermosets.

Figure 16. Structure of (a) DGEBA and (b) IPDA.

Table 10. Composition of the formulated epoxy thermosets.

Resin name DGEBA (wt.%) IPDA (wt.%) FR (wt.%)

3.4. Chemical Characterization

3.4.1. Mass Spectrometry

3.4.2. 11 B solid-state Nuclear Magnetic Resonance Analysis

3.4.3. Elementary Analysis

3.5. Thermal Characterization

3.5.1. Thermogravimetric Analysis Coupled with Infrared Spectroscopy

3.5.2. Differential Scanning Calorimetry Analysis

3.6. Characterization of Fire Properties

3.6.1. Pyrolysis Combustion Flow Calorimetry

3.6.2. Cone Calorimeter

3.7. Morphological Characterization

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