Tara tannins as phenolic precursors of thermosetting

epoxy resins
Chahinez Aouf
a,
, Soa Benyahya
b
, Antoine Esnouf
a
, Sylvain Caillol
b
,
Bernard Boutevin
b
, Hlne Fulcrand
a
a
UMR1083, INRA, Montpellier SupAgro, University Montpellier 1, 2 place Viala, 34060 Montpellier cedex 2, France
b
UMR CNRS 5253, Institut Charles Gerhardt, 8 rue de lcole normale, 34296 Montpellier cedex 5, France
a r t i c l e i n f o
Article history:
Received 25 February 2014
Received in revised form 28 March 2014
Accepted 31 March 2014
Available online 12 April 2014
Keywords:
Tara pods
Hydrolysable tannins
Functionalisation
Epoxy polymer
a b s t r a c t
Tara pods powder was used as a phenolic source in the synthesis of thermosetting epoxy
polymer. The tannase-assisted hydrolysis of galloylquinic acids contained in tara powder
allowed the determination of the tannins hydroxyl value (13.7 mmol/g powder). Then,
galloylquinic acids were reacted with epichlorohydrin and an aqueous solution of sodium
hydroxide in the presence of benzyltriethylammonium chloride as phase transfer catalyst
(PTC). The 1D and 2D NMR analyses of glycidylated products revealed the galloylquinic
esters hydrolysis and the dimerisation of the glycidylated gallic moities. The glycidylated
derivatives of tara tannins (GETT) were cured in epoxy polymer with isophorone diamine
(IPD). The glass transition temperature (T
g
= 129 C) and the thermal resistance
(T
d30
= 294 C) of the resulting network were determined. Preliminary results showed that
this new epoxy polymer based on GETT displayed interesting properties which are close to
those of the epoxy polymer formulated with commercial diglycidyl ether of bisphenol A
(DGEBA).
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Tannins are phenolic compounds of relative high
molecular weight. They are classied as condensed and
hydrolysable tannins. The hydrolysable tannins are readily
hydrolysed by acids, alkalis or enzymes into a sugar or a
related polyhydric alcohol (polyol) and a phenolic carbox-
ylic acid [1]. Depending on the nature of the phenolic
carboxylic acid, hydrolysable tannins are subdivided into
gallotannins and ellagitannins [1b,2]. They are biosynthes-
ised by galloyltransferases as defence compounds (against
Chinese gall and Turkey gall) and are accumulated in
mesophyl cell walls [3]. The simplest hydrolysable tannins
are gallotannins that are made up of gallic esters of
glucose, shikimic acid, quinic acid and quercitol among
others [4]. These tannins are found in various plants and
trees such as chestnut, oak, sumac, and tara [5]. Tara
(Caesalpinia spinosa) is a small leguminous tree native of
Peru and widely spread in Latin America, from Venezuela
to northern Chile [6]. The fruit of tara contains approxi-
mately 65% of pods [7] and 3238% of seeds. From the
pods, tara powder (100200 mesh) is obtained by simply
mechanically milling and sifting the gross powder. After-
ward, this powder is mixed with water (45 parts of its
weight) and heated at 6570 C for 3040 min. After
decantation and ltration, tara extract is obtained by
atomisation. This ecological and economical procedure
produces tara extract with high tannins content [8]. It
has been reported that 4065% of the fruit composition
of C. spinosa corresponds to gallotannins [7]. The chemical
structures of these gallotannins were widely investigated
http://dx.doi.org/10.1016/j.eurpolymj.2014.03.034
0014-3057/ 2014 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +33 499612454; fax: +33 499612857.

E-mail address: Chahinez.Aouf@supagro.inra.fr (C. Aouf).
European Polymer Journal 55 (2014) 186198
Contents lists available at ScienceDirect
European Polymer Journal
j our nal homepage: www. el sevi er . com/ l ocat e/ eur opol j
by Haslam et al. [9] and Horler et al. [10] who demon-
strated that the principal components of tara tannin were
based on a galloylated quinic acid structure (Scheme 1).
Thus, they differ from members of hydrolysable tannins
group which are based upon a galloylated or ellagoylated
hexose. In galloylquinic acids, not only may gallic acid moi-
eties be linked to each of the four hydroxyls carried by qui-
nic acid but these may form aryl ester(s) (depsides) with
one or more additional gallic acid moieties [9a,11]. Chains
of up to three gallic acid moieties, of which two are depsi-
dic, have been reported [9b], and a given quinic acid may
bear more than one depside chain [12]. In such structures,
depsidic linkages may be either meta or para.
Recently, Giovando et al. [13] reported the MALDI-TOF
structural analysis of a tara tannins extract. It has been
found that this extract is composed of a series of oligomers
of polygallic acid (depsidic bonds) attached by an ester link
to one quinic acid hydroxyl. Furthermore, other polygallic
chains linked to one or two repeating units such as caffeic
acid and methylated quinic, methylated gallic and methyl-
ated caffeic acids have been found in very small amounts
[13]. The same research group has also demonstrated that
tara tannins are constituted of a small amount of an ellagic
unit that is surrounded by several gallic acid units. In addi-
tion, the ellagic acid contains an ester group which could
be generated from hydrolysis reactions, during the extrac-
tion process [5].
Tara tannins nd valuable applications in the food and
beverage industries to clarify and give astringency to wine,
tea, coffee, cacao, and other food. Thanks to their astrin-
gent properties and very light colour, tara tannins are
particularly appreciated in the tannery industry [14].
Moreover, the alkaline hydrolysis of tara pods yields nearly
25% of gallic acid [15]. This phenolic acid and its decarbox-
ylated form (pyrogallol) are extensively used in straining
leather and hair and also as ingredients of developer in
photography and printing inks [16]. Furthermore, they
possess a large range of biological activities, including,
antioxidant, antibacterial, antiviral, analgesic etc. [17],
allowing them to act as precursors for the commercial pro-
duction of drugs [18]. However, little attention has been
given to the exploitation of these gallotannins as substi-
tutes of phenolic compounds in thermosetting polymers
manufacturing. Indeed, in 1973, as a consequence of the
rst oil crisis, Norsechem, a Norwegian paint group sub-
sidiary in Malaysia that produces phenol formaldehyde
resins, was forced to substitute 33 wt% of phenol with
chestnut tannins extract in their formulations [19]. Once
the rst oil crisis had passed and the price of phenol
became affordable again, the phenol formaldehydechest-
nut tannin resin production was stopped. Recently, pheno-
lic resin wood panel adhesive based on chestnut tannins
has been developed by Spina et al. [20]. In the same way,
Garro et al. have used tara pods as starting material to pro-
duce phenol formaldehyde adhesives [14a]. Our labora-
tory, interested in developing of thermosetting epoxy
resins from bio-sourced polyphenols [21] is considering
tara tannins extract as a potential substitute of petro-
leum-based phenols in the formulation of epoxy polymers.
Indeed, epoxy resins are the prime constituents in many
adhesives, paints, coating, sealants and electronic materi-
als [22]. Nevertheless, almost 90% of the world production
of epoxy resins involves the use of non-renewable hazard-
ous compounds such as bisphenol A. Meanwhile, there is a
lack on the studies devoted to the use of tannins in the pro-
duction of epoxy resins.
Scheme 1. Supposed tara tannins chemical structure.
C. Aouf et al. / European Polymer Journal 55 (2014) 186198 187
In our previous works, one of the constitutive monomer
of condensed tannins, named catechin, was reacted with
epichlorohydrin to provide the corresponding glycidylated
ether derivative. The curing of this prepolymer in the pres-
ence of reactive diluent led to a crosslinking epoxy net-
work [21c]. More recently, the alkaline-assisted allylation
of gallic acid (a building block of gallotannins) followed
by the epoxidation of the resulting double bonds by
meta-chloroperbenzoic acid, provided the tri-glycidylated
ether derivative which was involved in the formulation
of a novel bio-based epoxy thermoset [23]. Having demon-
strated the feasibility of the synthesis of bio-based epoxy
polymers from these phenolic models; the ability of natu-
ral tannin extracts (generally occurring as polymers with a
large structural diversity) to produce epoxy networks was
evaluated. For this purpose, the commercially available
tara powder (kindly supplied by Silvateam) was selected
to react with epichlorohydrin.
The goal of the work reported herein was to extrapolate
the functionalisation processes developed for phenolic
models (within our previous work) for the synthesis of
epoxy prepolymer from tara gallotannins. Then, the bio-
based prepolymer was formulated into thermosetting
epoxy polymer. Some thermal and mechanical properties
of the resulting network were compared to those of
bisphenol A based epoxy polymer. The use of a natural
phenolic extract in the formulation of epoxy resins will
pave the way for numerous industrial applications.
2. Materials and methods
2.1. Materials
Tara powder: the tara powder from tara pods (C. spinosa)
were kindly supplied by Silvateam s.p.a (Italy).
Chemicals: gallic acid (97.5%), epichlorohydrin (99.0%),
benzyltriethylammonium chloride (P98.0%), sodium
hydroxide (P98.0%), tannase from Aspergillus cuum
(P150 U/g), isophorone diamine (IPD, P99.0%), HPLC
grade solvents (acetonitrile and methanol), formic acid
(P95.0%) were purchased from Sigma Aldrich (France).
DGEBA (D.E.R.352) (EEW = 5.66 mmol/g) (product reaction
of epichlorohydrin with bisphenol A and bisphenol F) was
supplied by Dow. UPLC water was prepared from distilled
water using a Milli-Q system (Merck-Millipore, France).
b-glucogallin (1-galloylglucose) was kindly provided by
Dr. G. Gross (ULM University, Germany). Gallic acid and
b-glucogallin were used as standards for the calibration.
Standard and tara tannins solutions: the tara tannins
solution was prepared by dissolving 5 mg of extract in
100 mL of distilled water (0.05 mg/mL). Standard solutions
of gallic acid and b-glucogallin were prepared with the
same mass concentration and injected in UPLC 7 times.
Each solution was prepared at 7 concentration levels
(initial concentration and diluted 1:2, 1:4, 1:10, 1:20,
1:40, and 1:100) to provide a range of signals suitable for
determining the molar relative response factor (MRRF).
UPLC-MS: the LC-DAD-ESI/MS consisted of an Acquity
UPLC (Waters, Milford, MA) coupled with a DAD and a
Brucker Daltonics Ion trap mass spectrometer. 2 lL of
standard and gallotannins extract solutions were injected
via the autosampler onto a Nucleosil 120-3 C18 encaped
column (100 2.1 mm, 5 lm particle size, Machery-Nagel,
Sweden), held at 38 C, with a constant ow rate of 550 lL/
min. The mobile phase consisted of a combination of A
(H
2
O/HCOOH 99/1 v/v) and B (CH
3
CN/H
2
O/HCOOH 80/19/
1 v/v/v); initial 0.1% B; 05 min, 40% B linear; 58 min,
99% B linear, 89 min 0.1% B linear. The DAD was set at
280 nm (k
max
of phenolic compounds). Mass spectra were
acquired using electrospray ionisation in the positive mode
and recorded in the range 701500 amu. A drying gas ow
of 12 L/min, a drying gas temperature of 200 C, a nebulizer
pressure of 44 psi, and capillary voltages of 5500 V were
used.
Concentration calculation by UPLC: it is well known that
the area of a spectral peak is proportional to the amount of
the substance that reaches the detector in LC instrument. A
response factor is obtained experimentally by analysing a
known concentration of the substance into the LC instru-
ment and measuring the area under the relevant peak.
The molar relative response factor (MRRF
x
) of each pheno-
lic standard equals the area of the spectral peak (mAu)
divided by the molar concentration of this compound.
Thus, for the quantitation of phenolic compounds in gallo-
tannins extract, the molar concentration (C
x
) of gallic acid
and b-glucogallin can be computed as:
C
x
A
x
=MRRF
x
where A
x
is the peak area of each phenolic compound cited
above.
NMR analyses: NMR spectra were acquired on VARIAN
Unity-Inova 500 MHz and Bruker 600 MHz liquid. All sam-
ples were dissolved in DMSO-d
6
. The chemical shifts were
reported on that of internal DMSO-d
6
at 2.5 ppm for
1
H and
39.5 ppm for
13
C. Assignments of both proton and carbon
resonances, identication and structure characterisation
of products were performed using several NMR experi-
ments: homonuclear
1
H and
13
C 1D and 2D (COSY) and
heteronuclear
1
H
13
C 2D (HSQC and HMBC).
2.2. Enzymatic hydrolysis of tara tannins
The tara tannins extract (0.5 mg) was dissolved in
100 mL of acetate buffer solution (200 mM, pH = 6.8).
Then, 1 mg of tannase from A. cuum was dissolved in
1 mL of the buffered gallotannins solution and the mixture
was incubated at 37 C for 90 min. The reaction products
were analysed by UPLC-MS combined system.
2.3. General procedure for the glycidylation of gallic acid and
tara tannins extract
A 250 mL two-necked ask equipped with a condenser,
a septum cap and a magnetic stirring bar was charged with
3 g of gallic acid or tara tannins extract in epichlorohydrin
(4 M eq/OH), the suspension was heated at 100 C and
benzyltriethylammonium chloride (0.012 M eq/OH) was
added. After 1 h, the resulting solution was cooled to
30 C and the aqueous solution of NaOH 20 wt% (2 M eq/
OH) with the same previous amount of phase transfer
catalyst (BnEt
3
NCl) were added. The mixture was stirred
188 C. Aouf et al. / European Polymer Journal 55 (2014) 186198
vigorously for 90 min. The organic layer was separated,
dried over MgSO
4
and concentrated under vacuum. The
crude product (5.8 g from gallic acid and 4.7 g from tara
tannins extract) was puried by silica gel chromatography
using petroleum ether/ethyl acetate (PE/EA) solvent sys-
tem to yield following products:
3,4,5-Triglycidylether glycidyl benzoate 1: (PE/EA, 30/70),
colourless oil, 60% yield (10.6 mmol) from gallic acid;
530 mg/g of prepolymer from tara tannins extract.
1
H
NMR (500 MHz, DMSO-d
6
) d = 2.622.86 (m, 8H, H1, H11
and H14), 3.293.38 (m, 4H, H2, H12 and H15), 3.903.94
(m, 3H, H13
0
, H16
0
), 4.08 (dd, J = 12.4, 6.3 Hz, 1H, H3
0
),
4.26 (qd, J = 11.7, 2.9 Hz, 1H, H16), 4.44 (dd, J = 11.3,
2.1 Hz, 2H, H13), 4.63 (dd, J = 12.4, 2.5 Hz, 1H, H3), 7.30
(s, 2H, H6 and H10) ppm.
13
C NMR (125 MHz, DMSO-d
6
)
d = 43.4 (C1), 43.6 (2C, C11), 43.8 (C14), 49.0 (C2), 49.7
(2C, C12), 50.1 (C15), 65.5 (C3), 70.0 (2C, C13), 74.0
(C16), 108.4 (2C, C6 and C10), 124.6 (C5), 141.6 (C8),
151.8 (2C, C7 and C9), 165.0 (C4) ppm. HRMS calc for
C
19
H
23
O
9
[M+H]
+
: 395.1342, found 395.1341.
Oxiran-2-ylmethyl4-(2,3-dihydroxypropoxy)-3-(oxiran-
2-ylmethoxy)-5-(3,4,5-tris(oxiran-2-ylmethoxy)benzoyloxy)
benzoate 2: (PE/EA, 10/90 to 0/100), pale yellow oil, 23%
yield (2 mmol) from gallic acid; 188 mg/g of prepolymer
from tara powder.
1
H NMR (600 MHz, DMSO-d
6
) d = 2.62
(dd, J = 4.5, 2.2 Hz, 1H, H4), 2.73 (m, 5H, H1, H4, H21 and
H24), 2.83 (dt, J = 9.3, 4.5 Hz, 4H, H1, H21 and H24), 3.30
(m, 1H, H5), 3.31 (m, 1H, H20), 3.33 (m, 1H, H23), 3.35
(m, 2H, H2), 3.85 (dd, J = 11.0, 5.7 Hz, 1H, H22), 3.92 (dd,
J = 11.5, 6.3 Hz, 2H, H3 and H6), 4.05 (dd, J = 12.3, 6.3 Hz,
1H, H19), 4.25 (dd, J = 11.7, 6.5 Hz, 1H, H6
0
),4.31 (dd,
J = 11.5, 6.5 Hz, 1H, H25), 4.39 (m, 1H, H22
0
), 4.42 (m, 1H,
H3
0
), 4.56 (m, 1H, H25
0
), 4.57 (d, J = 2.5 Hz, 2H, H27), 4.59
(m, 1H, H19
0
), 4.65 (bs, 1H, H26), 7.16 (s, 1H, H15), 7.17
(s, 1H, H17), 7.27 (s, 2H, H8).
13
C NMR (150 MHz, DMSO-
d
6
) d = 43.4 (C4), 43.5 (2C, C1), 43.6 (C24), 43.8 (C21),
49.0 (C5), 49.5 (C23), 49.6 (2C, C2), 50.1 (C20), 63.0
(C27), 64.7 (C25), 65.3 (C19), 70.0 (3C, C3 and C22), 70.7
(C26), 74.0 (C6), 106.6 (C15), 108.6 (2C, C8), 111.6 (C17),
121.2 (C16), 124.4 (C7), 137.4 (C13), 141.7 (C10), 142.9
(C12), 147.5 (C14), 151.8 (2C, C9),164.8 (2C, C18 and
C11). HRMS calc for C
32
H
36
O
16
[M+H]
+
: 677.2003, found
677.1992.
Oxiran-2-ylmethyl 4-(3-chloro-2-(3,4,5-tris(oxiran-2-
ylmethoxy) benzoyloxy)propoxy)-3,5-bis(oxiran-2-ylmeth-
oxy)benzoate 3: (PE/EA, 10/90 to 0/100), pale yellow oil,
2% yield (0.18 mmol) from gallic acid; 209 mg/g of pre-
polymer from tara powder.
1
H NMR (600 MHz, DMSO-d
6
)
d = 2.62 (m, 1H, H4), 2.702.77 (m, 5H, H1, H21 and
H25), 2.81 (m, 1H, H4), 2.84 (dd, J = 9.8, 5.1 Hz, 5H, H1,
H21 and H25), 3.33 (m, 5H, H2, H5 and H20), 3.34 (m,
1H, H24), 3.86 (m, 4H, H3 and H19), 3.91 (dd, J = 11.7,
6.1 Hz, 1H, H6), 4.06 (m, H, H23), 4.09 (bs, 2H, H13), 4.25
(m, 1H, H6
0
), 4.33 (m, 4H, H3
0
and H19
0
), 4.39 (m, 1H,
H14), 4.44 (m, 1H, H14
0
), 4.60 (d, J = 12.3 Hz, 1H, H23
0
),
5.43 (m, 1H, H12), 7.14 (s, 1H, H8), 7.16 (s, 1H, H8
0
), 7.22
(s, 1H, H17), 7.25 (s, 1H, H17
0
).
13
C NMR (150 MHz,
DMSO-d
6
) d = 43.0 (C13), 43.4 (C25), 43.5 (C21), 43.6 (3C,
C1 and C21), 43.8 (C4), 49.0 (C24), 49.6 (4C, C2 and C20),
50.1 (C5), 65.5 (C23), 70.1 (4C, C3 and C19), 71.2 (C14),
72.5 (C12), 74.0 (C6), 108.3 (2C, C17 and C17
0
), 108.7 (2C,
C8 and C8
0
), 124.4 (C7),124.5 (C18), 141.4 (C15), 141.9
(C10), 151.4 (2C, C16), 151.7 (2C, C9), 164.3 (C11),164.8
(C22). HRMS calc for C
35
H
39
O
16
Cl [M+H]
+
: 751.2027, found
751.2007.
2.4. Determination of the epoxy equivalent weight (EEW)
The epoxy equivalent of GETT prepolymer was deter-
mined by chemical assay based on the reaction with an ali-
quot of standard pyridine hydrochloride in excess pyridine
at reux and subsequent back titration with standard
methanolic sodium hydroxide using phenolphthalein as
indicator [24]. GETT (0.21 g) was placed in a 100 mL ask.
A volume of 25 mL of 0.2 N solution of hydrochloric acid
(37%) in pyridine was added. The mixture was heated at
reux (115 C) for 20 min. After cooling, the titration of
the excess of acid was carried out by a 0.6 N sodium
hydroxide solution in the presence of phenolphthalein (3
drops). A blank assay was performed under the same condi-
tions in the absence of pre-polymer. The epoxy equivalent
weight (EEW) was calculated by the following equation:
EEW
p 10
3
A B C
NaOH
1
where p is the prepolymer weight (g), A the NaOH volume
(mL) for blank, and B is the NaOH volume (mL) for
prepolymer.
2.5. General procedure for the formulation of GETT and DGEBA
The glycidylated derivatives GETT and DGEBA are liquid
and were formulated at room temperature and cured in a
silicon mould at 100 C for 12 h followed by 2 h at 250 C
to ensure complete curing of networks. The curing agent
was isophorone diamine (IPD), a cycloaliphatic diamine,
with an amine equivalent weight (AEW) of 43 g/eq (techni-
cal data sheet). GETT-IPD system was obtained by the for-
mulation of 2 g (16.97 mmol) of glycidyl ether of tara
tannins with 0.73 g (16.97 mmol) of IPD. The reference
DGEBA-IPD network was produced from the curing of 2 g
(11.3 mmol) of DGEBA (DER352) (EEW = 5.66 mmol/g
based on Technical data sheet) by 0.5 g (11.3 mmol) of IPD.
2.6. Thermogravimetric analysis
TGA measurements were obtained on a TA Instruments
Q50 apparatus. The initial weight of each sample tested
was approximately 10 mg. Data were collected in nitrogen
atmosphere using a 10 C/min ramp from 20 to 580 C.
Experiments were carried out in triplicate. The tempera-
tures of 5% and 30% weight loss (T
d5
) and (T
d30
)
respectively, statistic heat-resistant index temperature
(T
s
) and the percentage of residue at 575 C (%res) were
determined.
2.7. Dynamic mechanical analysis
DMA was performed with a Metravib DMA 25 using the
uniaxial stretching mode to determine the storage (E
0
), and
loss (E
00
) moduli as well as loss factory (tand) as a function
C. Aouf et al. / European Polymer Journal 55 (2014) 186198 189
of temperature. Samples (30 10 2 mm) were heated
from 100 C to 250 C using a heating rate of 3 C/min
in a forced convection oven using a nitrogen stream. The
sample was deformed sinusoidally with controlled strain
amplitude of 6.3 10
5
and 1.5 10
4
for GETT-IPD and
DGEBA-IPD respectively at a xed frequency of 1 Hz.
Experiments were carried out in triplicate. Temperatures
of the relaxation processes associated with glass transition
temperatures were determined through the inexion point
of the storage modulus E
0
curve as well as the maximum
peak in tand curves [25].
2.8. Differential scanning calorimetry
DSC measurements were performed under inert atmo-
sphere with a calorimetric NETZSCH DSC 200 F3 calibrated
with an indium standard.
The polymer was weighted in an aluminium hermetic
pan and consecutively placed in the measurement heating
cell. An empty pan was used as reference. All the samples
were heated under inert atmosphere from 50 to 250 C
at a heating rate of 10 C/min. Three runs were recorded
and the glass transition temperature (T
g
) values were
measured during the second run and conrmed by a third
run. T
g
s were calculated at the inexion point of the heat
capacity jump. Experiments were carried out in triplicate.
3. Results and discussion
In order to determine the tannins composition of the
tara pods extract, the tara powder was dissolved in
distilled water (0.05 mg/mL) and analysed by UPLC
DADMS (Ultra Performance Liquid Chromatography
Diode Array DetectorMass Spectrometer) combined
system. The DAD was set at k
max
of phenolic compounds
(280 nm) [26] and mass spectra were acquired in positive
mode.
The UV prole and mass spectrum of the tara powder
are shown in Fig. 1. The tara powder produced a relatively
complex UV chromatogram in which six oligomer groups
were identied by their pseudomolecular ions. Galloylqui-
nic acids (Q-G, m/z 345), digalloylquinic acids (Q-2G, m/z
497), trigalloylquinic acids (Q-3G, m/z 649), tetragalloyl-
quinic acids (Q-4G, m/z 801), pentagalloylquininc acids
(Q-5G, m/z 953) and nally hexagalloylquininc acids
(Q-6G, m/z 1105). All mass signals were separated from
Fig. 1. (a) UV prole at 280 nm of tara tannins extract at 0.05 g/L in water and (b) ESI-MS positive ion mode spectrum of tara tannins extract in water in the
3001200 Da mass range.
190 C. Aouf et al. / European Polymer Journal 55 (2014) 186198
each other by 152 amu corresponding to a galloyl unit.
Beyond Q-G derivatives, the additional galloyl moiety
may be directly attached to a quinic acid molecule or
involved in depsidic bonds.
The aimof this work was to functionalise these gallotan-
nins by reaction with epichlorohydrin. Therefore, a deeper
characterisation of tara tannin structures to dene more
accurately the linkage of each galloyl group (ester bond
with quinic acid or depsidic bond) is not of great impor-
tance. However, it is important to determine the hydroxyl
value (mmol of free OHper gramof powder) of tara tannins.
Indeed, during the glycidylation process, the hydrolysis of
both ester and depsidic bonds was observed. Moreover,
the reaction of the hydrolysis products with epichlorohy-
drin involves only the carboxyl and phenolic hydroxyls.
The less acid hydroxyl groups from hydrolysed quinic acid
and other non-phenolic components are not reactive in
the glycidylation procedure (these two aspects will be dis-
cussed more accurately in next sections). Therefore, to
establish the amount of epichlorohydrin needed for the
reaction, it is necessary to determine the amount of free car-
boxyl and phenolic hydroxyls present in the tara powder.
To determine the hydroxyl value, the enzymatic hydro-
lysis of galloyquinic acids contained in the extract was car-
ried out. Thus, tara powder was dissolved in a acetate
buffer solution (200 mM, pH = 6.8) and the hydrolysis reac-
tion was catalysed by tannase from A. cuum. Indeed, tan-
nin acyl hydrolase, commonly known as tannase is widely
used to catalyse the hydrolysis of ester and depside link-
ages in hydrolysable tannins releasing gallic acid and the
structure core [27].
After 90 min of incubation at 37 C (which corresponds
to the optimised reaction conditions), the hydrolysed tara
tannins produced a simple chromatogram at 280 nm in
which gallic acid was identied as a main component
along with a small amount of Q-G derivatives (Fig. 2).
Based on this chromatogram, gallic acid and Q-G deriva-
tives were quantied in our tannins extract using stan-
dards. Since quinic acid and glucose do not absorb at
280 nm, the concentration of Q-G derivatives was esti-
mated with respect to the synthetised 1-galloylglucose.
The quantication results expressed in mg of phenolic
derivatives per gram of tannin extract are summarised in
Table 1. These results indicate that the overall content of
phenolic compounds present in the tara powder accounted
for 706 mg/g, that is nearly 70% of tannins.
Additionally, the hydroxyl value corresponding to the
number of reactive OH per gram of gallotannins extract
was calculated and a value of 13.7 mmol OH/g of powder
Fig. 2. (a) UV prole at 280 nm of tannase hydrolysed tara tannins extract at 0.05 g/L in water and (b) UV prole at 280 nm of gallic acid at 0.05 g/L in water.
Table 1
The tara powder phenolic composition.
Phenolic
compound
[M+H]
+
(m/z)
Phenolic
content (mg/g)
Hydroxyl value
a
(mmol OH/g extract)
Gallic acid 171.0 510.63 12.0
Q-G 345.0 195.11 1.7
Total 705.74 13.7
a
This value was calculated based on molecular weights of gallic acid
and Q-G associated to the number of reactive hydroxyl groups
attached to each phenolic derivative.
C. Aouf et al. / European Polymer Journal 55 (2014) 186198 191
was found. This value includes the carboxylic and phenolic
hydroxyls of gallic acid and Q-G.
3.1. The functionalisation of galloylquinic acids contained in
tara powder
Due to the structural complexity of the galloylquinic
acids contained in tara powder, it seems challenging to
understand their reactivity towards epichlorohydrin and
then to characterise their functionalised products. There-
fore, gallic acid was used as a representative model for
the glycidylation reaction with epichlorohydrin.
3.1.1. Gallic acid glycidylation
The glycidylation reaction of gallic acid was carried out
according to the experimental conditions disclosed in
Tomitas invention [28]. The tetraglycidylated product 1
was obtained in 72% yield.
The chemical structure of compound 1 was easily estab-
lished by HRMS and NMR analyses (see experimental sec-
tion). Indeed, from
1
H NMR spectrum, several aliphatic
signals arising from oxirane groups are identied. The
methylene and methyne ring proton signals appear in the
2.733.37 ppm range and the CH
2
O protons give reso-
nances signals in the 3.914.62 ppm spectral range. The
average number of oxirane groups per gallic acid ring, cal-
culated fromthe ratio of
1
H surface signal integrations, was
equal to 4. The hydroxyl groups (carboxylic and phenolic)
substitution occurred through a two steps mechanism
involving the ring opening of epichlorohydrin by the phe-
nolate anion giving the chlorohydrin derivative. The latter
was subsequently transformed into glycidylated derivative
by the alkaline assisted intramolecular cyclisation [21a].
3.1.2. Galloylquinic acids glycidylation
By relying on the calculated hydroxyl value (13.7 mmol
OH/g of powder), the tannins extract was glycidylated
according to the reported procedure [28]. The functionali-
sation reaction yielded 3.4 g of crude product. This latter
was analysed by UPLCDADMS system (data not shown)
to give a complex UV prole at 280 nm with tree main
compounds at 3.2 min (m/z 395), 4.2 min (m/z 659) and
4.6 min (m/z 731). Then, the crude product was puried
by silica gel chromatography in order to isolate (quite labo-
riously) major compounds 1, 2 and 3 (Scheme 2). This puri-
cation did not allow the isolation of the products present
in small quantities.
Detailed structure characterisation of product 2 was
performed by NMR spectroscopy. The disappearance of
hydroxyl protons associated to the aromatic proton signals
displayed in the
1
H NMR spectrum of 2 indicate the
presence of a symmetric aromatic ring (singlet at
7.27 ppm, 2 protons) and an asymmetric aromatic ring
(two singlets at 7.17 and 7.16 ppm, 1 proton) both substi-
tuted in their carboxylic and phenolic hydroxyls. More-
over, the
1
H signal surface integrations counted ve
Scheme 2. Glycidylation of gallic acid and tara powder in the presence of PTC followed by alkaline treatment.
192 C. Aouf et al. / European Polymer Journal 55 (2014) 186198
glycidyl groups. The linkage positions of these groups on
the aromatic rings were then determined using
1
H
13
C
long range correlations between the CH
2
O protons of
the glycidyl groups and quaternary carbons of the aromatic
rings as shown in Fig. 3. Thus, it was found that hydroxyls
carried by C9, C10, C14 and C18 are substituted by methyl
oxirane groups. However, the CH
2
O protons which cor-
relate with the quaternary carbon C13 are attached to an
unshielded CH (H26). This suggests the oxirane ring
opening of this substituent and the formation of a dihydr-
oxypropoxy group. Nevertheless, this proton (H26) dis-
plays a higher chemical shift (4.65 ppm) compared to the
methyne protons of classical dihydroxy groups. This
unshielding effect is probably due to the intramolecular
hydrogen bonding of the exchangeable hydroxyl group
linked to C26 [29]. Finally, no glycidyl nor dihydropropoxyl
substitutions were observed on OH (11) and OH (12) indi-
cating the linkage of C11 and OH (12) by a depside bond.
The postulated structure of compound 2 proposed in
Fig. 3 was supported by HRMS analysis.
Using the same analytical tools, detailed structure of
product 3 has been established. NMR analyses revealed
the presence of two symmetric phenolic rings substituted
by six methyl oxirane groups in hydroxyls OH (9), OH
(10), OH (16) and OH (18) as shown in the HMBC spectrum
of 3 (Fig. 4). Additionally, this 2D NMR method showed a
correlation between the carboxylic carbon C11 and meth-
yne proton H12 which correlated with methylene protons
Fig. 3. A part of HMBC spectrum of compound 2 in DMSO-d
6
showing correlations between methylene protons of the substituent groups and quaternary
carbons of aromatic rings.
C. Aouf et al. / European Polymer Journal 55 (2014) 186198 193
H13 and H14 (COSY spectrum is available in Supporting
data). Then, the heteronuclear correlation between C13
and H14 indicates that the two phenolic rings are linked
by an ester bond as displayed in Fig. 4. Chemical shifts of
H13/C13 (4.09 ppm and 43.0 ppm respectively) suggest
that C13 is linked to a chlorine atom.
Interestingly, the formation of compound 1 as main
product demonstrates unequivocally the hydrolysis of the
initial galloylquinic acids during the functionalisation reac-
tion, releasing free gallic acid which is then fully glycidy-
lated. On the other hand, gallic acid is a tetrafunctional
molecule bearing three phenol-type hydroxyl groups and
a carboxyl group. Then, esterication reactions would be
very probable. Thus, product 3 could be generated by the
reaction of glycidylated gallic acid with a chlorohydrine
derivative as shown in Scheme 3.
Concerning product 2 formation, two hypotheses could
be formulated: (i) the glycidylation of the remaining gallic
acid dimers generated by the partial hydrolysis of initial
galloylquinic acids (higher resistance of depside bonds)
and (ii) the dimerisation of free gallic acids (released by
the total hydrolysis of galloylquinic acids) through esteri-
cation reactions followed by the glycidylation of the result-
ing dimers.
Fig. 4. A part of HMBC spectrum of compound 3 in DMSO-d
6
showing correlations between methylene protons of the substituent groups and quaternary
carbons of aromatic rings.
194 C. Aouf et al. / European Polymer Journal 55 (2014) 186198
In order to verify the assumptions cited above, the gly-
cidylation reaction of tannins extract was repeated by
keeping epichlorohydrin, NaOH and PTC amounts and
replacing tara tannins by gallic acid. Thus, a large excess
of epichlorohydrin (13 M eq/OH) and higher amounts of
catalyst (0.04 M eq/OH) and NaOH (6.5 M eq/OH) were
used to perform this reaction. Surprisingly, under these
experimental conditions, gallic acid gave rise to products
1, 2 and 3 in 60%, 23% and 2% yields respectively. Conse-
quently, these results support the second hypothesis in
the sense that the formation of products 1, 2 and 3 can
stem from gallic acid released by a complete hydrolysis.
Therefore, it can be deduced from these experimental
observations that, three reactions took place during the
functionalisation reaction: the hydrolysis of galloylquinic
acids, the dimerisation of the resulting free gallic acids (in
two ways) and the glycidylation of galloyl derivatives. Nev-
ertheless, the sequence by which these reactions proceed
cannot be clearly established neither the actual role played
by both phase transfer catalyst and NaOH in the process.
Despite the very interesting aspect of the mechanism
investigations, this work aimed primarily to identify the
main glycidylation products of tara tannins in order to
exploit them in the synthesis of epoxy polymers. Thus,
the prepolymer composed of the mixture of 13 was for-
mulated as epoxy resin using isophorone diamine (IPD)
as curing agent. The thermal resistance of the resulting
network was evaluated and its glass transition tempera-
ture (T
g
) was determined by DSC. The diglycidyl ether of
bisphenol A (DGEBA) cured under the same conditions
was considered as reference.
Scheme 3. Probable mechanism of product 3 formation.
0 100 200 300 400 500 600
0
20
40
60
80
100
W
e
i
g
h
t

(
%
)
Temperature (C)
GETT-IPD
DGEBA-IPD
Fig. 5. Thermal decomposition of GETT-IPD and DGEBA-IPD under
nitrogen.
Table 2
Weight loss temperatures under N
2
and DMA data of GETT-IPD and DGEBA-IPD systems.
System T
d5
(C) T
d30
(C) %Res (575 C) T
g
(C)
a
Tb (C) Ta (C) E
0
(MPa)
At 30 C At T
g
+ 30 C
GETT-IPD 256 294 12 129 50 139 5.28 10
3
116.0
DGEBA-IPD 328 353 9 149 50 140 1.29 10
3
13.8
a
The glass transition temperature (T
g
) was determined by DSC.
-20 0 20 40 60 80 100 120 140 160 180
-0,45
-0,40
-0,35
-0,30
-0,25
-0,20
-0,15
-0,10
H
e
a
t

F
l
o
w

(
m
W
/
m
g
)
Temperature (C)
DGEBA-IPD
GETT-IPD
Tg = 149 C
Tg = 129 C
Fig. 6. DSC of GETT-IPD and DGEBA-IPD polymers.
C. Aouf et al. / European Polymer Journal 55 (2014) 186198 195
3.2. The epoxy polymers formulation
The glycidyl ether derivatives mixture (without silica gel
purication) obtained by reaction of tara tannins extract
with epichlorhydrin in alkaline medium is afterward
referred to as GETT. The epoxy network was built by curing
GETT with isophorone diamine (IPD) in 1:1 M ratio of
epoxy group to active H of amine [30]. To determine the
molar ratio, the epoxy equivalent weight (EEW), expressed
in mole of epoxy group per gram of GETT was rst deter-
mined by chemical assay. The EEW value was estimated
at 8.48 10
3
mol/g. Based on these results, GETT-IPD
mixture was cured at 100 C for 12 h followed by 2 h at
250 C and the thermo-mechanical properties of the result-
ing network were studied. DGEBA-IPDpolymer formulated
under the same conditions was used as reference.
3.3. Thermal stability of the networks
The thermal stability (under nitrogen) of the GETT-IPD
and DGEBA-IPD cured epoxy resins were investigated by
thermogravimetry analysis (TGA) from ambient tempera-
ture to 580 C. The thermograms obtained during TGA
scans show the weight loss as a function of temperature
(Fig. 5). Temperatures at weight loss of 5% (T
d5
) and 30%
(T
d30
); were listed in Table 2.
The two studied epoxy resins show a continuous single
step of degradation process which starts around 256 C for
GETT-IPD and at 328 C for DGEBA-IPD (Table 2) with a
slightly weight loss around 100 C in case of the bio-based
system.
Compared to the DGEBA-IPD network, the bio-based
network, exhibits a lower thermal stability. Three
assumptions may be proposed to explain this relatively
fast degradation: (i) Unlike bisphenol A, the tara tannins
powder is a natural extract which certainly contains other
components than tannins. Indeed, the UV analysis at
280 nm allowed the identication of phenolic compounds
only (about 70% of the tara powder composition). The pres-
ence of other natural components such as carbohydrates
and lignocellulose (10%) [14a], polyalcohols, proteins,
moisture and insoluble (which combined, represent 20%
of the tara powder composition) [8,31] necessarily deter-
mines the resulting polymer behaviour. (ii) The thermal
decarboxylation of ester bonds within the prepolymer
may also be implicated [32]. (iii) The evaporation of free
quinic acid which is not involved in the glycidylation reac-
tion constitutes another possibility.
Percentages of residue under nitrogen at 575 C are
presented in Table 2. It is shown that the non-oxidative
thermal decomposition of the two studied polymers
released approximately a similar char yield. Indeed,
GETT-IPD network exhibits an increase of only 3% in char
formation upon decomposition when compared with the
DGEBA-based polymer. In both cases, the presence of aro-
matic structures increases the re resistance of the epoxy
polymers.
3.4. Differential scanning calorimetry (DSC)
Fig. 6 shows DSC thermograms of the two studied sys-
tems obtained at 10 C/min heating rate. In order to ensure
the complete crosslinking of polymers, the glass transition
temperatures were determined in the second run of DSC
analyses. T
g
values are 129 C and 149 C for GETT-IPD
and DGEBA-IPD respectively (Table 2). Similarly, the
presence of non-phenolic compounds in the extract may
inuence the polymer T
g
. Despite the GETT-IPD lower T
g
,
this polymer can keep it glassy state at high temperatures.
3.5. Thermo-mechanical properties of the networks
A plot of the storage modulus E
0
and tand as a function
of temperature are reported in Figs. 7 and 8 respectively,
the values of Ta and E
0
are reported in Table 2.
The main transition, a in the high-temperature region,
is associated with the glass transition. The highly heteroge-
neous network structure can explain the high Ta relaxa-
tion spans of GETT-IPD system. The sub-transition b at
low temperature (50 C), assigned to short molecular
segment motion, hydroxyl ether groups in the particular
case of epoxy-amine is not very obvious. In contrary, a
sub-peak at the temperature from 50 to 100 C was
observed in both E
0
and tand as well as in DSC curves which
left-moved to the temperature range from 40 to 60 C. This
-150 -100 -50 0 50 100 150 200 250 300
-0,2
0,0
0,2
0,4
0,6
0,8
T
a
n

d
e
l
t
a

Temperature (C)
GETT-IPD
DGEBA-IPD
Fig. 7. Tand versus temperature of GETT-IPD and DGEBA-IPD systems.
-150 -100 -50 0 50 100 150 200 250 300
1,0
1,5
2,0
2,5
3,0
3,5
4,0
L
o
g

E
'

(
M
P
a
)

Temperature (C)
GETT-IPD
DGEBA-IPD
Fig. 8. Storage modulus versus temperature of GETT-IPD and DGEBA-IPD
systems.
196 C. Aouf et al. / European Polymer Journal 55 (2014) 186198
could be explained by the presence of free natural poly-
mers, which are not involved in the GETT-IPD network.
Indeed, it is important to recall that beside gallotannins,
tara powder contains polysaccharides and lignocellulose.
A recent study [33] demonstrated that some lignocellulosic
cell walls exhibit a glass transition temperature between
65 and 71 C which could be correlated to the GETT-IPD
behaviour under both DSC and DMA conditions.
The modulus E
0
of GETT-IPD is higher than that of
DGEBA-IPD material. This can be explained by the mul-
tifunctionality of GETT prepolymer inducing a more den-
sely cross-linked material compared to the DGEBA resin.
Further, the presence of aromatic rings coming from
GETT, acting as 4-functional crosslinking junctions with
non-negligible mass, greatly reduces the network mobil-
ity thus imparting a signicant rigidity to the network in
the relaxed state. This constrained network structure
could also contribute to the higher glassy modulus.
However, enhanced intermolecular interactions (between
aromatics rings or H-bonding between OH groups com-
ing from the curing process and ether/carbonyl groups)
may also contribute signicantly to the higher glassy
modulus.
Finally, it is important to note that several factors inu-
ence the polyphenols composition in different plants.
Although the chemical structure of the polymer building
blocks do not change, the average polymerisation degree
as well as the phenolic concentration in the powder
depends on weather conditions, the degree of maturity in
plants, extraction processes. . . [34]. Therefore, by using
another batch of tara powder, the gallic acid amount (after
hydrolysis) may change. This will certainly affect the ratio
of the glycidylated compounds 1, 2 and 3. Consequently,
the number of aromatic groups and oxiran groups in the
prepolymer mixture will be modied. This will modify
the thermo-mechanical properties of the resulting resins
which strongly depend on the chemical structure of the
epoxy monomers [35].
4. Conclusions
In our on-going research program, the possibility to use
natural phenolic compounds in the synthesis of bio-based
epoxy resins is studied. Thus, the rst step was to func-
tionalise phenolic models such as catechin and gallic acid
in order to evaluate their reactivity towards glycidylation.
However, these monomers do not accurately reect the
structural complexity of natural polyphenols. Indeed, in
the plant kingdom, phenolic compounds mostly occur as
polymers with a large structural diversity. For this purpose,
we investigated the glycidylation of the tara tannins. Thus,
the reaction of tara powder with epichlorohydrin in the
presence of PTC and NaOH led to the hydrolysis of
galloylquinic acids along with the dimerisation of the
glycidylated gallic moieties through ester bonds. Then,
the glycidylated derivatives were formulated with IPD
producing a crosslinked network with good mechanical
characteristics and a T
g
of 129 C.
These bio-based tara tannins epoxy thermosets are
expected to be environmentally benign materials for the
replacement of petroleum-based epoxy resins.
In perspectives, a deeper characterisation of GETT-
based material, including impact strength and tensile
strength tests will be performed. In order to check the
functionalisation reproducibility, the use of different batch
of tara powder is envisioned.
Acknowledgements
The authors are grateful to Samuele Giovando
(Silvateam, Italy) for providing tara powder. Thanks also
to Pr. Antonio Pizzi (LERMAB, France) for helpful discus-
sions. We kindly acknowledge Aurlien Le Brun (UM2
Montpellier, France) and Christine Le Guernev (INRA
Montpellier, France) for their help on NMR analyses. Thanks
to G. Gross (ULM University), Germany) and Nancy Terrier
(INRA Montpellier, France) for providing b-glucogallin.
Appendix A. Supplementary material
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.eurpolymj.2014.03.034.
References
[1] (a) Hartzfeld PW, Forkner R, Hunter MD, Hagerman AE.
Determination of hydrolyzable tannins (gallotannins and
ellagitannins) after reaction with potassium iodate. J Agric Food
Chem 2002;50(7):178590;
(b) Santos-Buelga C, Scalbert A. Proanthocyanidins and tannin-like
compounds nature, occurrence, dietary intake and effects on
nutrition and health. J Sci Food Agric 2000;80(7):1094117;
(c) Sayago-Ayerdi SG, Moreno-Hernandez CL, Montalvo-Gonzalez E,
Garcia-Magana ML, Mata-Montes-de-Oca M, Torres JL, et al. Mexican
Ataulfo mango (Mangifera indica L.) as a source of hydrolyzable
tannins. Analysis by MALDI-TOF/TOF MS. Food Res Int
2013;51(1):18894.
[2] Schieber A, Ullrich W, Carle R. Characterization of polyphenols in
mango puree concentrate by HPLC with diode array and mass
spectrometric detection. Innov Food Sci Emerg 2000;1(2):1616.
[3] (a) Grundhofer P, Niemetz R, Schilling G, Gross GG. Biosynthesis and
subcellular distribution of hydrolyzable tannins. Phytochemistry
2001;57(6):91527;
(b) Tovar B, Garcia HS, Mata M. Physiology of pre-cut mango. I. ACC
and ACC oxidase activity of slices subjected to osmotic dehydration.
Food Res Int 2001;34(23):20715.
[4] Castaneda DM, Miguel Pombo L, Patricia Uruena C, Fredy Hernandez
J, Fiorentino S. A gallotannin-rich fraction from Caesalpinia spinosa
(Molina) Kuntze displays cytotoxic activity and raises sensitivity to
doxorubicin in a leukemia cell line. BMC Complem Altern Med
2012:12.
[5] Radebe N, Rode K, Pizzi A, Giovando S, Pasch H. MALDI-TOF-CID for
the microstructure elucidation of polymeric hydrolysable tannins. J
Appl Polym Sci 2013;128(1):97107.
[6] De la Cruz Lapa P. Aprovechamiento integral y racional de la tara
(Caesalpinia spinosa Caesalpinia tinctoria). Rev Inst Investig
FIGMMG 2004;7(14):6473.
[7] Chambi F, Chirinos R, Pedreschi R, Betalleluz-Pallardel I, Debaste F,
Campos D. Antioxidant potential of hydrolyzed polyphenolic
extracts from tara (Caesalpinia spinosa) pods. Ind Crop Prod
2013;47:16875.
[8] Castell J-C, Fabregat C, Sorollal S, Jorbal M, Bacarit A, Oll L.
Caesalpinia spinosa (tara): the sustainable source of tannins. J Aqeic
2012;63(2):2130.
[9] (a) Haslam E, Armitage R, Bayliss GS, Gramshaw JW, Haworth RD,
Jones K, et al. Gallotannins. Part III. The constitution of Chinese,
turkish, sumach and tara tannins. J Chem Soc 1961:184254;
(b) Haslam E, Haworth RD, Keen PC. Gallotannins. Part VII. Tara
gallotannin. J Chem Soc 1962:38148.
[10] Horler DF, Nursten HE. The tannins of tara. Caesalpinia spinosa (Mol.)
Kuntz. J Chem Soc 1961:378692.
C. Aouf et al. / European Polymer Journal 55 (2014) 186198 197
[11] Baratto MC, Tattini M, Galardi C, Pinelli P, Romani A, Visioli F, et al.
Antioxidant activity of galloyl quinic derivatives isolated from P-
lentiscus leaves. Free Radical Res 2003;37(4):40512.
[12] Nishizawa M, Yamagishi T, Dutschman GE, Parker WB, Bodner AJ,
Kilkuskie RE, et al. Anti-aids agents.1. Isolation and characterization
of 4 new tetragalloylquinic acids as a new class of HIV reverse-
transcriptase inhibitors from tannic-acid. J Nat Prod
1989;52(4):7628.
[13] Giovando S, Pizzi A, Pasch H, Pretorius N. Structure and oligomers
distribution of commercial Tara (Caesalpina spinosa) hydrolysable
tannin. Pro Ligno 2013;9(1):2231.
[14] (a) Garro JM, Riedl B, Conner AH. Analytical studies on tara tannins.
Holzforschung 1997;51(3):23543;
(b) Glenz W. Renaissance of high quality vegetable-tanned leather
tanned with tara tannin agent. Przegl Skorzany 1991;46(12):2779.
[15] Raquez JM, Deleglise M, Lacrampe MF, Krawczak P. Thermosetting
(bio)materials derived from renewable resources: a critical review.
Prog Polym Sci 2010;35(4):487509.
[16] (a) Bajpai B, Patil S. A new approach to microbial production of gallic
acid. Braz J Microbiol 2008;39(4):70811;
(b) Manish S, Sharma KP, Sanket K, John PJ. Purication and
characterization of gallic acid decarboxylase from Enterobacter
spp. isolated from a region in Rajasthan, India. Int J Biosci (IJB)
2012;2(12):97104.
[17] Beena PS, Basheer SM, Bhat SG, Bahkali AH, Chandrasekaran M.
Propyl gallate synthesis using acidophilic tannase and simultaneous
production of tannase and gallic acid by marine Aspergillus awamori
BTMFW032. Appl Biochem Biotechnol 2011;164(5):61228.
[18] Pourrat H, Regerat F, Morvan P, Pourrat A. Microbiological
production of gallic acid from Rhus-coriaria L.. Biotechnol Lett
1987;9(10):7314.
[19] Kulvik E. Chestnut wood tannin extract in plywood adhesives. Adhes
Age 1976;19(3):1921.
[20] Spina S, Zhou X, Segovia C, Pizzi A, Romagnoli M, Giovando S, et al.
Phenolic resin wood panel adhesives based on chestnut (Castanea
sativa) hydrolysable tannins. Int Wood Prod J 2013;4(2):95100.
[21] (a) Aouf C, Le Guerneve C, Caillol S, Fulcrand H. Study of the O-
glycidylation of natural phenolic compounds. The relationship
between the phenolic structure and the reaction mechanism.
Tetrahedron Lett 2012;
(b) Aouf C, Lecomte J, Villeneuve P, Dubreucq E, Fulcrand H. Chemo-
enzymatic functionalization of gallic and vanillic acids: synthesis of
bio-based epoxy resins prepolymers. Green Chem
2012;14(8):232836;
(c) Nouailhas H, Aouf C, Le Guerneve C, Caillol S, Boutevin B,
Fulcrand H. Synthesis and properties of biobased epoxy resins. Part
1. Glycidylation of avonoids by epichlorohydrin. J Polym Sci A
Polym Chem 2011;49(10):226170.
[22] (a) Bauer RS. Epoxy resin chemistry, advances in chemistry
series. Washington, DC: American Chemical Society; 1979;
(b) May CA. Epoxy resins, chemistry and technology. New York/
Basel: Marcel Dekker; 1988. p. 1.
[23] Aouf C, Nouailhas H, fache M, Caillol S, Boutevin B, Fulcrand H.
Multi-functionalization of gallic acid. Synthesis of a novel bio-based
epoxy resin. Eur Polym J 2012.
[24] Lee H, Neville K. Handbook of epoxy resins. New York: Mc Graw-
Hill; 1967.
[25] (a) Psomiadou E, Arvanitoyannis I, Yamamoto N. Edible lms made
from natural resources; microcrystalline cellulose (MCC),
methylcellulose (MC) and corn starch and polyols. Part 2.
Carbohydr Polym 1997;31:193204 [Copyright (C) 2013 American
Chemical Society (ACS). All Rights Reserved];
(b) Lopez OV, Lecot CJ, Zaritzky NE, Garcia MA. Biodegradable
packages development from starch based heat sealable lms. J Food
Eng 2011;105:25463 [Copyright (C) 2013 American Chemical
Society (ACS). All Rights Reserved].
[26] Anouar EH, Gierschner J, Duroux J-L, Trouillas P. UV/Visible spectra
of natural polyphenols: a time-dependent density functional theory
study. Food Chem 2012;131(1):7989.
[27] (a) Belmares R, Contreras-Esquivel JC, Rodriguez-Herrera R, Coronel
AR, Aguilar CN. Microbial production of tannase: an enzyme with
potential use in food industry. Lebensmittel-Wiss Technol Food Sci
Technol 2004;37(8):85764;
(b) Bhat TK, Singh B, Sharma OP. Microbial degradation of tannins
a current perspective. Biodegradation 1998;9(5):34357;
(c) Sariozlu NY, Kivanc M. Isolation of gallic acid-producing
microorganisms and their use in the production of gallic acid from
gall nuts and sumac. Afr J Biotechnol 2009;8(6):11105.
[28] Tomita H, Yonezawa K. Epoxy resin and process for preparing the
same; 1985.
[29] (a) Dolensy B, Konvalinka R, Jakubek M, Kral V. Identication of
intramolecular hydrogen bonds as the origin of malfunctioning of
multitopic receptors. J Mol Struct 2013;1035:1248;
(b) Tayyari SF, Laleh S, Zahedi-Tabrizi M, Vakili M. Structure,
vibrational assignment, and NMR spectroscopy of 1,2-bis
(dichloroacetyl) cyclopentadiene. J Mol Struct 2013;1036:15160.
[30] Galy J, Sabra A, Pascault JP. Characterization of epoxy thermosetting
systems by differential scanning calorimetry. Polym Eng Sci
1986;26:151423 [Copyright (C) 2012 American Chemical Society
(ACS). All Rights Reserved].
[31] Luz Sanz M, Martinez-Castro I, Victoria Moreno-Arribas M.
Identication of the origin of commercial enological tannins by the
analysis of monosaccharides and polyalcohols. Food Chem
2008;111(3):77883.
[32] Bertero M, de la Puente G, Sedran U. Products and coke from the
conversion of bio-oil acids, esters, aldehydes and ketones over
equilibrium FCC catalysts. Renew Energy 2013;60:34954.
[33] Antoniow J, Maigret J, Chirtoc M, Beaugrand J, Dpole P. In: Bataille F,
Flamant G, editors. Mise en vidence par micro-analyse thermique
balayage (SThM) de gradients de temprature de transitions
vitreuses dans les parois lignocellulosiques. Perpignan,
France: Socit Franaise de Thermique (SFT); 2011. p. 7782.
[34] (a) Cheynier V. Polyphenols in foods are more complex than often
thought. Am J Clin Nutr 2005;81(1):223S9S;
(b) Morison JIL, Lawlor DW. Interactions between increasing CO
2
concentration and temperature on plant growth. Plant Cell Environ
1999;22(6):65982.
[35] (a) Su WFA, Chen KC, Tseng SY. Effects of chemical structure changes
on thermal, mechanical, and crystalline properties of rigid rod epoxy
resins. J Appl Polym Sci 2000;78(2):44651;
(b) Mujtaba Ellahi YG, Yang Huai. Effects of di and tetra functional
epoxy monomers structure on the morphology and the electro-
optical properties of polymer-dispersed liquid crystal lms. Int J Sci
Technol Res 2013;2(3):12731.
198 C. Aouf et al. / European Polymer Journal 55 (2014) 186198