1-s2.0-s0014305714001141-main tara
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Tara tannins as phenolic precursors of thermosettingepoxy resins
Chahinez Aoufa,, Sofia Benyahya b, Antoine Esnoufa, Sylvain Caillol b,Bernard Boutevin b, Hlne Fulcrand a
a UMR1083, INRA, Montpellier SupAgro, University Montpellier 1, 2 place Viala, 34060 Montpellier cedex 2, Franceb 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 (Tg= 129 C) and the thermal resistance
(Td30= 294 C) of the resulting network were determined. Preliminary results showed that
this new epoxy polymer based onGETTdisplayed 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 classified 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 thepods, 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 filtration, 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
ofC.spinosacorresponds 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: [email protected](C. Aouf).
European Polymer Journal 55 (2014) 186198
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European Polymer Journal
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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 metaor 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 find 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
first 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 first 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.
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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 ficuum
(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 aBrucker 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 flow rate of 550 lL/min. The mobile phase consisted of a combination of A
(H2O/HCOOH 99/1 v/v) and B (CH3CN/H2O/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 (kmax of phenolic compounds). Mass spectra were
acquired using electrospray ionisation in the positive mode
and recorded in the range 701500 amu. A drying gas flow
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 (MRRFx
) 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 (Cx) of gallic acid
andb-glucogallin can be computed as:
Cx Ax=MRRFx
whereAxis 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-d6. The chemical shifts were
reported on that of internal DMSO-d6
at 2.5 ppm for 1H and
39.5 ppm for 13C. Assignments of both proton and carbon
resonances, identification and structure characterisation
of products were performed using several NMR experi-
ments: homonuclear 1H and 13C 1D and 2D (COSY) and
heteronuclear 1H13C 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. ficuum 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 flask 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 transfercatalyst (BnEt3NCl) were added. The mixture was stirred
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vigorously for 90 min. The organic layer was separated,
dried over MgSO4 and concentrated under vacuum. The
crude product (5.8 g from gallic acid and 4.7 g from tara
tannins extract) was purified 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. 1H
NMR (500 MHz, DMSO-d6) d= 2.622.86 (m, 8H, H1, H11
and H14), 3.293.38 (m, 4H, H2, H12 and H15), 3.903.94
(m, 3H, H130, H160), 4.08 (dd, J= 12.4, 6.3 Hz, 1H, H30),
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. 13C NMR (125 MHz, DMSO-d6)
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
C19H23O9 [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. 1H NMR (600 MHz, DMSO-d6) 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, H60),4.31 (dd,
J= 11.5, 6.5 Hz, 1H, H25), 4.39 (m, 1H, H220), 4.42 (m, 1H,
H30), 4.56 (m, 1H, H250), 4.57 (d, J= 2.5 Hz, 2H, H27), 4.59
(m, 1H, H190), 4.65 (bs, 1H, H26), 7.16 (s, 1H, H15), 7.17
(s, 1H, H17), 7.27 (s, 2H, H8). 13C NMR (150 MHz, DMSO-
d6) 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 C32H36O16 [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. 1H NMR (600 MHz, DMSO-d6)
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, H60), 4.33 (m, 4H, H30 and H190), 4.39 (m, 1H,
H14), 4.44 (m, 1H, H140), 4.60 (d, J= 12.3 Hz, 1H, H230),
5.43 (m, 1H, H12), 7.14 (s, 1H, H8), 7.16 (s, 1H, H80), 7.22
(s, 1H, H17), 7.25 (s, 1H, H170). 13C NMR (150 MHz,
DMSO-d6) 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 C80), 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 C35H39O16Cl [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 reflux and subsequent back titration with standard
methanolic sodium hydroxide using phenolphthalein as
indicator[24].GETT(0.21 g) was placed in a 100 mL flask.
A volume of 25 mL of 0.2 N solution of hydrochloric acid
(37%) in pyridine was added. The mixture was heated at
reflux (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 CNaOH1
wherep 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 GETTand 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 agentwas isophorone diamine (IPD), a cycloaliphatic diamine,
with an amine equivalent weight (AEW) of 43 g/eq (techni-
cal data sheet).GETT-IPDsystem 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) ofIPD.
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 (Td5) and (Td30)
respectively, statistic heat-resistant index temperature
(Ts) 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 (E0
), andloss (E00) moduli as well as loss factory (tand) as a function
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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 6.3 105 and 1.5 104 for GETT-IPD and
DGEBA-IPD respectively at a fixed frequency of 1 Hz.
Experiments were carried out in triplicate. Temperatures
of the relaxation processes associated with glass transition
temperatures were determined through the inflexion point
of the storage modulus E0 curve as well as the maximum
peak in tandcurves[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 Cat a heating rate of 10 C/min. Three runs were recorded
and the glass transition temperature (Tg) values were
measured during the second run and confirmed by a third
run. Tgs were calculated at the inflexion 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 indistilled 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 kmax of phenolic compounds
(280 nm)[26]and mass spectra were acquired in positive
mode.
The UV profile and mass spectrum of the tara powder
are shown inFig. 1. The tara powder produced a relatively
complex UV chromatogram in which six oligomer groups
were identified by their pseudomolecular ions. Galloylqui-
nic acids (Q-G, m/z345), digalloylquinic acids (Q-2G, m/z
497), trigalloylquinic acids (Q-3G, m/z649), tetragalloyl-
quinic acids (Q-4G, m/z 801), pentagalloylquininc acids(Q-5G, m/z 953) and finally hexagalloylquininc acids
(Q-6G, m/z1105). All mass signals were separated from
Fig. 1. (a) UV profile at 280nm of tara tannins extract at 0.05 g/L in water and (b) ESI-MS positive ion mode spectrumof tara tannins extract in water in the3001200 Da mass range.
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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 thesegallotan-
nins by reaction with epichlorohydrin. Therefore, a deeper
characterisation of tara tannin structures to define 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 OH per gram of 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 theamount 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 fromA. ficuum. 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 thestructure 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 identified 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 quantified 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 quantification 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) UVprofile at280 nmof tannase hydrolysedtara tannins extract at0.05 g/L in water and (b) UVprofile at280 nmof gallic acid at0.05g/L inwater.
Table 1
The tara powder phenolic composition.
Phenolic
compound
[M+H]+
(m/z)
Phenolic
content (mg/g)
Hydroxyl valuea
(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.
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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 1H NMR spectrum, several aliphatic
signals arising from oxirane groups are identified. The
methylene and methyne ring proton signals appear in the
2.733.37 ppm range and the CH2O 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 from the ratio of
1
H surface signal integrations, wasequal 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 profile 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/z731). Then, the crude product was purified
by silica gel chromatography in order to isolate (quite labo-
riously) major compounds 1, 2and 3 (Scheme 2). This puri-
fication 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 1H 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 1H signal surface integrations counted five
Scheme 2. Glycidylation of gallic acid and tara powder in the presence of PTC followed by alkaline treatment.
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glycidyl groups. The linkage positions of these groups on
the aromatic rings were then determined using 1H13C
long range correlations between the CH2O protons of
the glycidyl groups and quaternary carbons of the aromatic
rings as shown inFig. 3. Thus, it was found that hydroxyls
carried by C9, C10, C14 and C18 are substituted by methyl
oxirane groups. However, the CH2O 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. Thisunshielding 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. 3was 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
of3 (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-d6 showing correlations between methylene protons of the substituent groups and quaternary
carbons of aromatic rings.
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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 inFig. 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 tetrafunctionalmolecule bearing three phenol-type hydroxyl groups and
a carboxyl group. Then, esterification reactions would be
very probable. Thus, product 3 could be generated by the
reaction of glycidylated gallic acid with a chlorohydrine
derivative as shown inScheme 3.
Concerning product2 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 esterifi-
cation reactions followed by the glycidylation of the result-ing dimers.
Fig. 4. A part of HMBC spectrum of compound 3 in DMSO-d6showing correlations between methylene protons of the substituent groups and quaternarycarbons of aromatic rings.
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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 and3 in 60%, 23% and 2% yields respectively. Conse-
quently, these results support the second hypothesis inthe 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 of13 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 (Tg) 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
Weight(%)
Temperature (C)
GETT-IPD
DGEBA-IPD
Fig. 5. Thermal decomposition of GETT-IPD and DGEBA-IPD undernitrogen.
Table 2
Weight loss temperatures under N2 and DMA data of GETT-IPDand DGEBA-IPD systems.
System Td5(C) Td30(C) %Res (575 C) Tg(C)a Tb(C) Ta (C) E0 (MPa)
At 30 C AtTg+ 30 C
GETT-IPD 256 294 12 129 50 139 5.28 103 116.0
DGEBA-IPD 328 353 9 149 50 140 1.29 103 13.8
a The glass transition temperature (Tg) 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
HeatFlow(mW/mg)
Temperature (C)
DGEBA-IPD
GETT-IPD
Tg = 149 C
Tg = 129 C
Fig. 6. DSC of GETT-IPD and DGEBA-IPD polymers.
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3.2. The epoxy polymers formulation
The glycidylether derivatives mixture (without silica gel
purification) 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 ofGETTwas first deter-
mined by chemical assay. The EEW value was estimatedat 8.48 103 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-IPD polymer 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
andDGEBA-IPD cured epoxy resins were investigated by
thermogravimetry analysis (TGA) from ambient tempera-
ture to 580
C. The thermograms obtained during TGAscans show the weight loss as a function of temperature
(Fig. 5). Temperatures at weight loss of 5% (Td5) and 30%
(Td30); were listed inTable 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 identification 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 fire resistance of the epoxy
polymers.
3.4. Differential scanning calorimetry (DSC)
Fig. 6shows 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. Tg 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
influence the polymer Tg. Despite the GETT-IPD lower Tg,
this polymer can keep it glassy state at high temperatures.
3.5. Thermo-mechanical properties of the networks
A plot of the storage modulus E0 and tandas a function
of temperature are reported in Figs. 7 and 8 respectively,
the values of Taand E0 are reported inTable 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 bothE0
and tand
as well as in DSC curves whichleft-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
Tandelta
Temperature (C)
GETT-IPD
DGEBA-IPD
Fig. 7. Tandversus 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
LogE'(MPa)
Temperature (C)
GETT-IPD
DGEBA-IPD
Fig. 8. Storage modulus versus temperature of GETT-IPD and DGEBA-IPD
systems.
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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 E0 of GETT-IPD is higher than that of
DGEBA-IPD material. This can be explained by the mul-
tifunctionality ofGETTprepolymer 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 significant 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 significantly to the higher glassy
modulus.
Finally, it is important to note that several factors influ-
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 and3. Consequently,
the number of aromatic groups and oxiran groups in the
prepolymer mixture will be modified. 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 first 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 reflect 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 aTgof 129 C.
These bio-based tara tannins epoxy thermosets are
expected to be environmentally benign materials for thereplacement 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 helpon NMR analyses. Thanks
to G. Gross (ULM University), Germany) and Nancy Terrier
(INRA Montpellier, France) for providingb-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.
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