Fuel 235 (2019) 1010–1018

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Chemical transformations in technical cashew nut shell liquid and isolated T

mixture of cardanols, evaluation of the antioxidant activity and thermal
stability of the products for use in pure biodiesel
Kênia de P. Costaa, Bárbara M. de Viveirosa, Marco Aurelio S. Schmidt Juniora,
⁎
Paulo A.Z. Suarezb, Michelle J.C. Rezendea,
a
Universidade Federal do Rio de Janeiro, Instituto de Química, Cidade Universitária, CT, Bloco A, 21941-909 Rio de Janeiro, RJ, Brazil
b
Laboratório de Materiais e Combustíveis, Universidade de Brasília, Instituto de Química, 70910-970 Brasília, DF, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Biodiesel demand is increasing all over the world. The maintenance of oxidative stability is extremely important
Biodiesel to biodiesel market, from the point of view of the quality of the fuel as the economic amount involved. In the
Cardanol present work, we synthesized new antioxidant candidates for biodiesel from chemical transformations in alkyl
Cashew nut shell liquid phenols present in technical cashew nut shell liquid (t-CNSL) and, more specifically, in cardanols isolated from t-
t-CNSL
CNSL. This raw material is viable, easy accessed and low cost. Five chemical transformations were performed in
Oxidative stability
Thermal stability
both t-CNSL and cardanols with yields from 50% to 92%. The starting materials and their respective derivatives
were characterized by 1H NMR, 13C NMR and IR. Antioxidant activity and thermal stability of the products were
evaluated. The induction period for pure biodiesel was 6.35 h and the addition of 0.5% (w/w) of cardanols
increased to 7.37 h. Two products presented excellent antioxidant activity, epoxidized cardanols (4) and hy-
drolyzed cardanols (6). They increased the induction period to 15.05 h and 18.62 h, respectively. The oxyge-
nated derivatives also showed better thermal stability than the starting materials.

1. Introduction the chemical degradation of biodiesel (oxidation and hydrolysis pro-

Biodiesel has been used pure or blended to diesel in many countries,
including Brazil [1]. It is defined as a mixture of alkyl esters of long
chain fatty acids, obtained by transesterification or esterification of
vegetable or animal fats and oils, with short chain alcohols, like me-
thanol or ethanol [2–7]. Methanol is the most used industrially [8]. It is
a renewable, non-carcinogenic, sulfur-free fuel and also reduces emis-
sion of polluting gases. The only concerns regarding the use of biodiesel
are the increasing in NOx emissions and its low shelf life. The last one
has currently being one of the major problems, and this become more
evident with the increasing of the concentration of biodiesel in diesel
[9,10].
Deposits begin to appear in the tanks during transportation and
storage of biodiesel/diesel blends, which leads to clogging of filters,
valves and pipes, causing wear on the pumps. The formation of these
deposits is due to the chemical and physical differences between bio-
diesel and diesel. It consists of precipitated compounds due to the po-
larity difference in the blend, microorganisms that have proliferated
due to propitious conditions (biological degradation), and products of
cesses) [10]. Biodiesel is highly hygroscopic in comparison to diesel,
due to the presence of oxygen atoms in its structure which can form
hydrogen bonds with water. The presence of water leads to the growth
of bacteria and fungi and its removal is an alternative to prevent the
biological degradation, but it is not an easy strategy [11]. Another
possibility is the use of biocide additives but the studies on this topic is
still few [12–15]. Biodiesel and biodiesel/diesel blends are very sus-
ceptible to chemical degradation, mainly due to the composition of the
fatty acids of the raw materials used in the production of the biofuel.
Soybean oil is widely used as raw material for biodiesel production. It is
rich in unsaturated fatty acids, approximately 70% of the fatty acids
present in soybean oil has at least one double bond [16]. The presence
of unsaturations in the alkyl chain associated with the presence of
molecular oxygen in the environment lead to a series of oxidation re-
actions, which generate free radicals that can recombine and rearrange
giving compounds of high molecular mass that deposit in tanks, systems
of injection and other parts of the engine. Parts can also be worn and
aged by the volatile compounds from the oxidation processes [10].
Absorbed water also degrades biodiesel, increasing its oxidative

⁎
Corresponding author.
E-mail address: mjcrezende@gmail.com (M.J.C. Rezende).

https://doi.org/10.1016/j.fuel.2018.08.111
Received 1 July 2018; Received in revised form 22 August 2018; Accepted 24 August 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
K.d.P. Costa et al.
Table 1
Chemical composition of t-CNSL.
Phenolic compounds t-CNSL (%)
Anacardic acids 1.09–1.75
Cardanols 67.82–94.60
Cardols 3.80–18.86
2-Methylcardols 1.20–4.10
Minority components 3.05–3.98
Polymer material 0.34–21.63
Adapted from [32].
instability which is already quite pronounced by the presence of double
bonds in the chain of fatty acids alkyl esters. One way to minimize this
problem is the use of additives.
Indeed, antioxidant additives originally applied in the food industry
are currently being used for biodiesel. The chemicals used as additives
are preferentially oxidized, retarding or even extinguishing the pro-
cesses of oxidation of the biofuel. BHT (butylated hydroxytoluene),
TBHQ (tert-butylhydroxyquinone), PG (propyl gallate), PY (pyrogallol)
and BHA (butylated hydroxyanisole) are the most used [17–19]. More
recently, these phenolic compounds have also been evaluated as anti-
microbial agents in biodiesel [20,21]. Studies involving the use of
natural antioxidants as additives for biodiesel have been reported in the
literature. Some examples include the evaluation of phenolic acids [22],
carboxylic acids [23] and plant extracts [24].
Recent research on antioxidants derived from cardanols has been
reported [25–31]. Cardanols are the major constituents of technical
cashew nut shell liquid (t-CNSL), by-product obtained from thermo-
mechanical method used in the industrial processing of cashew nuts
[32]. The chemical composition of t-CNSL can be observed in Table 1
and the chemical structure of CNSL constituents can be seen in Fig. 1.
In 2009, Rodrigues et al. investigated the antioxidant activity of
hydrogenated cardanol by pressure differential scanning calorimetry
(PDSC) and UV/Vis spectrophotometer techniques. Hydrogenated car-
danol has improved cotton biodiesel oxidative stability, even after
heating process [25]. As far as we know it was the first study that
evaluated t-CNSL, more specifically cardanols, as antioxidant for bio-
diesel. In 2012, Lomonaco et al reported the synthesis of phosphory-
lated compounds by functionalization of the phenolic hydroxyl of
OH O OH
OH
R R
Anacardic acid Cardanol
Fig. 1. Chemical structure of CNSL constituents.
1011
Fuel 235 (2019) 1010–1018
cardanol; and the evaluation of the products as antioxidants for bio-
diesel using thermogravimetric analysis [26]. The results showed an
increase in the thermal stability of biodiesel, making it more resistant to
thermo-oxidative process. In 2013, the addition of hydrogenated car-
danol and tert-butylated hydrogenated cardanol in soybean biodiesel
influenced the biofuel stability with an increase of at least 70%, de-
termined by Rancimat method [27]. Maia et al (2015) evaluated the
antioxidant activity of buriti biodiesel added with both unsaturated and
saturated cardanol, cardol and tert-butylated cardanol. The Rancimat
method was used and it was also observed an increase in the value of
induction period (IP) for all phenolic compounds. The values of IP
obtained from analysis of unsaturated compounds were superior to that
obtained for the saturated compounds [28]. In the same year, the
electrochemical modification of t-CNSL led to the formation of a pro-
duct that increased the oxidative stability of soybean biodiesel. The
authors suggest that the electrolysis process produces dimers or oligo-
mers by reaction between phenols present in t-CNSL [29]. The first and
only antioxidant test involving a derivative from an effective chemical
transformation in the alkyl chain of cardanols was reported by Liu et al.
[30]. Until that moment, only the hydrogenation of the double bonds
had been mentioned for this purpose. Epoxidized cardanol was syn-
thesized and its effect on the oxidative stability of methyl oleate and
methyl linoleate was tested using Rancimat method. It was observed an
improvement in the oxidative stability of both methyl esters with the
addition of epoxidized cardanol. In 2017, Bastos and Tubino evaluated
the antioxidant activity of t-CNSL in biodiesels prepared from soybean
oil, corn oil, canola oil and sunflower oil using Rancimat method [9]. In
the same year, Kleinberg et al. verified the influence of the addition of
natural CNSL and t-CNSL on the stability oxidation of beef tallow [31].
Following, the authors determined the induction period for the bio-
diesel produced from the additive raw material. By both methods, the
addition of CNSL shows an increase in the oxidative stability of bio-
diesel.
Efforts to solve the low oxidative stability are an important step to
ensure the quality of biodiesel. Cardanols and other alkyl phenols
present in t-CNSL are characterized as chain breakers type antioxidants
as well as the commercially used phenolic antioxidants. The present
work reports the synthesis and evaluation of new t-CNSL and cardanols
derivatives as antioxidants for biodiesel. The strategy was to preserve
the phenolic structure and functionalize the double bonds of the alkyl
OH OH
H3C
HO R HO R
Cardol 2-Methylcardol
K.d.P. Costa et al.
chain. The allylic and bis-allylic sites susceptible to oxidation, equal to
those found in the unsaturated esters components of biodiesel, were
eliminated while groups capable of generating more stable radicals
were inserted.
2. Materials and methods
2.1. Biodiesel
Pure soybean biodiesel used in this work was kindly donated by
Granol Indústria, Comércio e Exportação S/A, a big Brazilian biodiesel
producer. The sample was from the biodiesel producing plant located in
Anápolis city, Goiás, Brazil. The content of methyl esters was de-
termined by 1H NMR as previously described [33,34] and the analysis
showed the conversion of 97.8% of vegetable oil in biodiesel. This value
is in accordance with the minimum percentage regulated by the Bra-
zilian National Agency of Petroleum, Natural Gas and Biofuels (ANP),
which is 96.5%. Its fatty acid composition was determined by GC–MS
using a method previously described by the group [35]. It is composed
by 11.4% palmitic acid, 36.0% oleic acid, 47.7% linoleic acid, 4.8%
stearic acid and 0.1% linolenic acid (% of area in the chromatogram).
2.2. t-CNSL
Technical cashew nut shell liquid was kindly donated by Iracema
Indústria e Comércio de Castanha de Cajú Ltda, a cashew nut processing
company located in Fortaleza city, Ceará, Brazil. The t-CNLS was ana-
lyzed by HPLC-DAD according to the method previously described by
Kumar et al. [36]. The analysis was performed on Shimadzu Promi-
nence HPLC System with automatic injector, using Phenomenex Luna
C18(2) column (5 μm, 100 Å, 250 × 4.6 mm) as stationary phase and
acetonitrile/milliQ water/glacial acetic acid (80:20:0.05% (v/v)) in
isocratic mode. All solvents used were chromatographic grade. The flow
used was 1.8 mL min−1 and the detection wavelength was set at 280 nm
[36]. The raw material was also characterized by 1H NMR, 13C NMR
and IR.
Experimental data of t-CNSL (1): 1H NMR (600 MHz, CDCl3) δ 0.92
(m, H-Csp3), 1.37 (m, H-Csp3), 1.61 (m, H-Csp3), 2.06 (m, H-Csp3), 2.57
(m, H-Csp3), 2.81 (m, H-Csp3), 5.01 (dd, J1 = 10.1 Hz, J2 = 1.3 Hz, H-
Csp2), 5.08 (dd, J1 = 17.2 Hz, J2 = 1.5 Hz, H-Csp2) 5.41 (m, H-Csp2),
5.84 (m, H-Csp2), 6.25 (ls, H-OH), 6.66 (m, H-Caromatic), 6.77 (d,
J = 7.3 Hz, H-Caromatic), 7.15 (t, J1 = 7.7 Hz, J2 = 7.7 Hz, H-Caromatic).
13
C NMR (150 MHz, CDCl3) δ 13.77 (Csp3), 14.08 (Csp3), 22.64 (Csp3),
22.78 (Csp3), 25.57 (Csp3), 25.64 (Csp3), 27.21 (Csp3), 28.97 (Csp3),
29.20 (Csp3), 29.37 (Csp3), 29.60 (Csp3), 29.73 (Csp3), 30.99 (Csp3),
31.23 (Csp3), 31.51 (Csp3), 31.77 (Csp3), 35.80 (Csp3), 108.02
(Caromatic), 112.48 (Caromatic), 114.70 (Caromatic), 115.31 (Caromatic),
120.96 (Caromatic), 126.83 (Csp2), 127.59 (Csp2), 128.01 (Csp2), 128.16
(Csp2), 129.30 (Csp2), 129.35 (Csp2), 129.83 (Csp2), 129.95 (Csp2),
130.12 (Caromatic), 130.39 (Caromatic), 136.83 (Csp2), 144.90 (Caromatic),
155.41 (Cphenolic), 156.58 (Cphenolic). IR (KBr, υmax, cm−1): 3355; 3008;
2925; 2852; 1589; 1485; 1456; 1349; 1268; 1157; 991; 910; 779; 694.
2.3. Cardanols
Isolation of the mixture of cardanols was performed by open column
liquid chromatography (4.5 cm diameter × 22 cm height), packed with
silica gel 60 (70–230 mesh, Merck) and eluted with ethyl acetate in
hexane at concentrations 7% and 10% (v/v). 50 mL aliquots were col-
lected, which were pooled according to the thin layer chromatography
profile [37]. The isolated mixture of cardanols was analyzed by HPLC-
DAD using the same method described for t-CNSL. It was also char-
acterized by 1H NMR, 13C NMR and IR.
Experimental data of the mixture of cardanols (2): 1H NMR
(600 MHz, CDCl3) δ 0.93 (m, H-Csp3), 1.34 (m, H-Csp3), 1.62 (m, H-
Csp3), 2.06 (m, H-Csp3), 2.58 (m, H-Csp3), 2.82 (m, H-Csp3), 2.86 (m,
1012
Fuel 235 (2019) 1010–1018
H-Csp3), 5.03 (m, H-Csp2), 5.46 (m, H-Csp2), 5.85 (ls, Hphenolic), 6.68
(m, H-Caromatic), 6.78 (m, H-Caromatic), 7.16 (m, H-Caromatic). 13C NMR
(150 MHz, CDCl3) δ 13.77 (Csp3), 14.07 (Csp3), 22.63 (Csp3), 22.77
(Csp3), 25.55 (Csp3), 27.19 (Csp3), 28.96 (Csp3), 29.23 (Csp3), 29.36
(Csp3), 29.60 (Csp3), 29.71 (Csp3), 31.22 (Csp3), 31.49 (Csp3), 31.76
(Csp3), 35.79 (Csp3), 112.48 (Caromatic), 115.30 (Caromatic), 120.94
(Caromatic), 126.81 (Csp2), 127.57 (Csp2), 129.34 (Csp2), 129.94 (Csp2),
130.38 (Caromatic), 136.81 (Csp2), 144.88 (Caromatic), 155.38 (Cphenolic).
IR (KBr, υmax, cm−1): 3359; 3012; 2927; 2850; 1589; 1486; 1457; 1270;
1155; 1045; 993; 910; 875; 779; 694.
2.4. Chemical transformations in t-CNSL and in the mixture of cardanols
2.4.1. General procedure for epoxidation
Epoxidation reaction was performed in both t-CNSL and isolated
mixture of cardanols. The reaction was performed with 17 mmol of
cardanols/t-CNSL, 15 mmol of formic acid (85% aqueous solution),
0.58 mmol of p-toluenesulfonic acid and 54 mmol of toluene. The
mixture was heated to 50 °C and 51 mmol of hydrogen peroxide 30%
was added dropwise. Then, the system was maintained at 65 °C for 6 h.
After the reaction, the mixture was poured into 50 mL of ethyl acetate
and washed (4 × 25 mL) with 5% (w/v) sodium bicarbonate aqueous
solution. The organic layer was dried over anhydrous sodium sulphate,
and the solvent was removed by evaporation under reduced pressure
[30]. The obtained products were analyzed by IR, 1H NMR and 13C
NMR.
Experimental data of t-CNSL epoxidation product (3): 1H NMR
(600 MHz, CDCl3) δ 0.95 (m, H-Csp3), 1.35 (m, H-Csp3), 1.50 (m, H-
Csp3), 1.78 (m, H-Csp3), 2.26 (m, H-Csp3), 2.40 (m, H-Csp3), 2.53 (m,
H-Csp3), 2.83 (m, H-Coxirane ring), 2.97 (m, H-Coxirane ring), 3.10 (m, H-
Coxirane ring), 3.15 (m, H-Coxirane ring), 5.84 (ls, Hphenolic), 6.66 (m, H-
Caromatic), 6.73 (d, J = 7.3 Mz, H-Caromatic), 7.12 (m, H-Caromatic). 13C
NMR (150 MHz, CDCl3) δ 14.02 (Csp3), 22.52 (Csp3), 26.50 (Csp3),
27.69 (Csp3), 29.16 (Csp3), 29.25 (Csp3), 29.32 (Csp3), 31.06 (Csp3),
31.72 (Csp3), 35.68 (Csp3), 54.37 (Coxirane ring), 56.61 (Coxirane ring),
57.41 (Coxirane ring), 57.52 (Coxirane ring), 112.54 (Caromatic), 115.31
(Caromatic), 120.65 (Caromatic), 129.28 (Caromatic), 144.61 (Caromatic),
155.73 (Cphenolic). IR (KBr, υmax, cm−1): 3386; 2925; 2852; 1720; 1587;
1456; 1361; 1270; 1155; 1068; 917; 871; 779; 694.
Experimental data of cardanols epoxidation product (4): 1H NMR
(600 MHz, CDCl3) δ 0.89 (m, H-Csp3), 1.29 (m, H-Csp3), 1.51 (m, H-
Csp3), 1.78 (m, H-Csp3), 2.46 (m, H-Csp3), 2.95 (m, H-Coxirane ring), 3.01
(m, H-Coxirane ring), 3.10 (m, H-Coxirane ring), 3.15 (m, H-Coxirane ring),
5.88 (ls, Hphenolic), 6.70 (m, H-Caromatic), 7.12 (m, H-Caromatic). 13C NMR
(150 MHz, CDCl3) δ 14.01 (Csp3), 22.55 (Csp3), 26.48 (Csp3), 27.69
(Csp3), 28.93 (Csp3), 29.15 (Csp3), 29.23 (Csp3), 29.63 (Csp3), 31.03
(Csp3), 31.70 (Csp3), 35.66 (Csp3), 54.25 (Coxirane ring), 54.43 (Coxirane
ring), 57.21 (Coxirane ring), 57.57 (Coxirane ring), 112.55 (Caromatic), 115.31
(Caromatic), 120.58 (Caromatic), 129.26 (Caromatic), 144.59 (Caromatic),
155.76 (Cphenolic). IR (KBr, υmax, cm−1): 3374; 2929; 2854; 1714; 1645;
1589; 1486; 1456; 1361; 1276; 1187; 1155; 1078; 917; 873; 813; 781;
738; 696; 553.
2.4.2. General procedure for hydrolysis
In a round bottom flask containing 4.3080 g of the t-CNSL epoxides
(3) (or 2.9967 g of the mixture of cardanols epoxides (4)) was added
30 eq. of distilled water, 0.05 eq. of concentrated sulfuric acid and
20 eq. of 1,4-dioxane. The reaction mixture was kept under magnetic
stirring at 90 °C for 4 h. At the end of the reaction, the mixture was
solubilized in 60 mL of ethyl acetate and transferred to a separatory
funnel. The mixture was washed with 5% (w/v) sodium bicarbonate
solution (3 × 25 mL) and then with distilled water (3 × 25 mL). After
washing, the organic phase was dried with anhydrous sodium sulphate
and then the solvent was removed by evaporation under reduced
pressure. The obtained products were analyzed by IR, 1H NMR and 13C
NMR.
K.d.P. Costa et al.
Experimental data of t-CNSL hydrolysis product (5): 1H NMR
(600 MHz, DMSO) δ 0.85 (m, H-Csp3), 1.24 (m, H-Csp3), 1.38 (m, H-
Csp3), 1.50 (m, H-Csp3), 2.08 (s, Hhydroxyl group), 2.46 (m, H-Csp3), 3.20
(m, H-COH), 6.56 (m, H-Caromatic), 7.03 (m, H-Caromatic), 9.19 (ls,
Hphenolic). 13C NMR (150 MHz, DMSO) δ 13.94 (Csp3), 22.12 (Csp3),
25.65 (Csp3), 28.70 (Csp3), 29.04 (Csp3), 30.90 (Csp3), 32.34 (Csp3),
35.19 (Csp3), 39.01 (Csp3), 70.39 (C-OH), 73.17 (C-OH), 112.57
(Caromatic), 115.14 (Caromatic), 118.93 (Caromatic), 129.03 (Caromatic),
143.74 (Caromatic), 157.26 (Cphenolic). IR (KBr, υmax, cm−1): 3376; 2929;
2852; 1726; 1587; 1456; 1268; 1195; 1068; 784; 738; 696.
Experimental data of cardanols hydrolysis product (6): 1H NMR
(600 MHz, DMSO) δ 0.85 (m, H-Csp3), 1.22 (m, H-Csp3), 1.38 (m, H-
Csp3), 1.50 (m, H-Csp3), 2.08 (s, H-OHalcohol), 2.36 (m, H-Csp3), 2.45
(m, H-COH), 3.20 (ls, H-COH), 6.55 (m, H-Caromatic), 7.02 (m, H-
Caromatic), 9.19 (ls, Hphenolic). 13C NMR (150 MHz, DMSO) δ 14.61
(Csp3), 21.29 (Csp3), 22.66 (Csp3), 26.20 (Csp3), 29.23 (Csp3), 29.49
(Csp3), 29.58 (Csp3), 31.22 (Csp3), 31.46 (Csp3), 32.48 (Csp3), 35.71
(Csp3), 70.88 (C-OH), 73.67 (C-OH), 113.07 (Caromatic), 115.64
(Caromatic), 119.44 (Caromatic), 129.61 (Caromatic), 144.26 (Caromatic),
157.77 (Cphenolic). IR (KBr, υmax, cm−1): 3374; 2929; 2852; 1722; 1587;
1454; 1369; 1276; 1197; 1076; 865; 784; 727; 694.
2.4.3. General procedure for solvolysis with methanol
Epoxidation product was also submitted to solvolysis with me-
thanol. The methanol was previously dried with anhydrous Na2SO4 and
stored in molecular sieve, which was activated in an oven at 150 °C for
24 h. In the flask containing 4.1206 g of the t-CNSL epoxide (3) (or
4.1287 g of the cardanols epoxide (4)) were added 93.7 eq. of dry
methanol and 0.5 eq. of concentrated sulfuric acid. The system was held
under magnetic stirring at 70 °C for 12 h. At the end of the reaction, the
mixture was concentrated on a rotary evaporator. Then, 50 mL of ethyl
acetate were added; the mixture was transferred to a separatory funnel
and washed with 5% (w/v) aqueous sodium bicarbonate solution
(4 × 20 mL). Anhydrous sodium sulphate was added to the organic
phase and then the solvent was removed by evaporation under reduced
pressure. The obtained products were analyzed by IR, 1H NMR and 13C
NMR.
Experimental data of t-CNSL solvolysis product (7): 1H NMR
(600 MHz, DMSO) δ 0.85 (m, H-Csp3), 1.23 (m, H-Csp3), 1.42 (m, H-
Csp3), 1.98 (ls, Halcoholic), 2.42 (m, H-Csp3), 3.37 (m, H-C-OCH3), 3.34
(s, Hmethoxy group), 5.81 (ls, Hphenolic), 6.56 (m, H-Caromatic), 7.03 (m, H-
Caromatic). 13C NMR (150 MHz, DMSO) δ 13.89 (Csp3), 22.08 (Csp3),
25.61 (Csp3), 28.66 (Csp3), 28.92 (Csp3), 29.00 (Csp3), 30.85 (Csp3),
35.15 (Csp3), 57.52 (Cmethoxy group), 70.27 (C-OH), 73.13 (C-OH), 83.27
(C-OCH3), 83.97 (C-OCH3), 112.51 (Caromatic), 115.09 (Caromatic),
118.85 (Caromatic), 129.01 (Caromatic), 143.67 (Caromatic), 157.23
(Cphenolic). IR (KBr, υmax, cm−1): 3365; 2927; 2854; 1724; 1589; 1456;
1369; 1268; 1155; 1089; 1045; 782; 696.
Experimental data of cardanols solvolysis product (8): 1H NMR
(600 MHz, DMSO) δ 0.85 (m, H-Csp3), 1.26 (m, H-Csp3), 1.36 (m, H-
Csp3), 1.49 (m, H-Csp3), 2.37 (m, H-Csp3), 2.44 (m, H-Csp3), 3.24 (m,
H-C-OCH3), 3.41 (s, Hmethoxy group), 6.54 (d, J = 1.5 Hz, H-Caromatic),
6.57 (m, H-Caromatic), 7.03 (m, H-Caromatic). 13C NMR (150 MHz, DMSO)
δ 14.00 (Csp3), 22.16 (Csp3), 25.72 (Csp3), 28.74 (Csp3), 28.95 (Csp3),
29.00 (Csp3), 29.07 (Csp3), 30.95 (Csp3), 35.24 (Csp3), 57.61 (Cmethoxy
group), 70.35 (C-OH), 73.20 (C-OH), 84.04 (C-OCH3), 112.59 (Caromatic),
115.17 (Caromatic), 118.96 (Caromatic), 129.12 (Caromatic), 143.77
(Caromatic), 157.28 (Cphenolic). IR (KBr, υmax, cm−1): 3359, 2925, 2852,
1597, 1589, 1483, 1456, 1363, 1277, 1153, 1089, 951, 916, 874, 781,
748, 723, 696.
2.4.4. General procedure for hydrogenation
The hydrogenation reaction of cardanols and t-CNSL was performed
in a Parr reactor. The mixture of cardanols/t-CNSL (2.97 mmol) was
solubilized in 10 mL of ethanol. This solution was transferred to the
Parr reactor with Pd/C (10% (w/w)) and then the reactor was
1013
Fuel 235 (2019) 1010–1018
pressurized to 100 psi with hydrogen. The reaction system was kept
under magnetic stirring at room temperature for 5 h. The reaction
medium was filtered through a sintered plate funnel with celite to hold
the catalyst and the solvent was removed by evaporation under reduced
pressure [37]. A white solid was obtained as the product from cardanol
and a brown solid from t-CNSL. The obtained products were char-
acterized by IR, 1H NMR and 13C NMR.
Experimental data of t-CNSL hydrogenation product (9): 1H NMR
(600 MHz, CDCl3) δ 0.89 (m, 3H, H-Csp3), 1.30 (m, 26H, H-Csp3), 1.60
(m, 2H, H-Csp3), 2.48 (m, 1H, H-Csp3), 2.56 (m, 2H, H-Csp3), 6.25 (ls,
Hphenolic), 6.66 (m, 2H, H-Caromatic), 6.77 (d, J = 7.9 Hz, 1H, H-
Caromatic), 7.15 (t, J1 = 7.6 Hz, J2 = 7.6 Hz, 1H, H-Caromatic). 13C NMR
(150 MHz, CDCl3) δ 14.11 (Csp3), 22.68 (Csp3), 29.32 (Csp3), 29.35
(Csp3), 29.51 (Csp3), 29.58 (Csp3), 29.68 (Csp3), 31.29 (Csp3), 31.92
(Csp3), 35.82 (Csp3), 107.99 (Caromatic), 112.45 (Caromatic), 115.30
(Caromatic), 120.93 (Caromatic), 129.34 (Caromatic), 144.96 (Caromatic),
155.40 (Cphenolic). IR (KBr, υmax, cm−1): 3365; 2912; 2848; 1587; 1463;
1369; 1263; 1249; 1147; 1074; 991; 941; 865; 782; 748; 719; 694; 532.
Experimental data of cardanols hydrogenation product (10): 1H
NMR (600 MHz, CDCl3) δ 0.90 (m, 3H, H-Csp3), 1.30 (m, 26H, H-Csp3),
1.61 (m, 2H, H-Csp3), 2.57 (m, 2H, H-Csp3), 4.87 (s, 1H, Hphenolic), 6.66
(m, 2H, H-Caromatic), 6.77 (d, J1 = 7.3 Hz, 1H, H-Caromatic), 7.15 (t,
J1 = 7.9 Hz, J2 = 7.9 Hz, 1H, H-Caromatic). 13C NMR (150 MHz, CDCl3) δ
14.11 (Csp3), 22.68 (Csp3), 29.31 (Csp3), 29.35 (Csp3), 29.51 (Csp3),
31.28 (Csp3), 31.92 (Csp3), 35.81 (Csp3), 112.44 (Caromatic), 115.28
(Caromatic), 120.96 (Caromatic), 129.35 (Caromatic), 144.96 (Caromatic),
155.88 (Cphenolic). IR (KBr, υmax, cm−1): 3344; 2913; 2846; 1614; 1591;
1461; 1373; 1301; 1282; 1263; 1249; 1153; 1072; 1000; 941; 879; 865;
784; 748; 728; 719; 696; 572; 538.
2.4.5. General procedure for nitration
To obtain the nitro compounds, 2.0320 g of cardanols (or 2.1687 g
of t-CNSL) were solubilized in 70 mL of methanol. 6.5 eq. molar ratio of
concentrated sulfuric acid and 10.9 eq. of concentrated nitric acid were
added separately and dropwise. After complete addition of the re-
actants, the reaction system was kept under magnetic stirring at 45 °C
for 4 h [38]. At the end of the reaction, the mixture was solubilized in
110 mL of ethyl acetate and washed with 5% (w/v) aqueous sodium
carbonate solution until pH 5 (4 × 30 mL). The organic phase was dried
with anhydrous sodium sulphate and the solvent was removed by
evaporation under reduced pressure. The obtained products were ana-
lyzed by IR, 1H NMR and 13C NMR.
Experimental data of t-CNSL nitration product (11): 1H NMR
(600 MHz, CDCl3) δ 0.88 (m, H-Csp3), 1.32 (m, H-Csp3), 1.59 (m, H-
Csp3), 2.00 (m, H-Csp3), 2.63 (m, H-Csp3), 2.68 (d, J = 14.7 Hz, H-
Csp3), 2.74 (m, H-Csp3), 2.89 (m, H-Csp3), 5.00 (m, H-Csp2), 5.41 (m,
H-Csp2), 6.74 (ls, H-Caromatic), 6.80 (dd, J1 = 8.6 Hz, J2 = 1.7 Hz, H-
Caromatic), 6.95 (s, H-Caromatic), 7.96 (d, J = 8.8 Hz, H-Caromatic), 8.00 (d,
J = 8.4 Hz, H-Caromatic), 10.63 (s, H-Caromatic). 13C NMR (150 MHz,
CDCl3) δ 14.06 (Csp3), 22.60 (Csp3), 27.18 (Csp3), 28.79 (Csp3), 29.18
(Csp3), 29.56 (Csp3), 30.40 (Csp3), 31.70 (Csp3), 32.48 (Csp3), 32.56
(Csp3), 33.82 (Csp3), 36.01 (Csp3), 36.65 (Csp3), 113.47 (Caromatic),
114.82 (Caromatic), 117.98 (Caromatic), 118.92 (Caromatic), 120.90
(Caromatic), 123.29 (Caromatic), 124.91 (Caromatic), 127.89 (Csp2), 130.13
(Csp2), 130.20 (Csp2), 130.40 (Csp2), 130.48 (Csp2), 131.72 (Caromatic),
134.98 (Caromatic), 137.24 (Caromatic), 141.72 (Caromatic), 154.67
(Caromatic-NO2), 155.15 (Cphenolic), 160.01 (Caromatic-NO2). IR (KBr, υmax,
cm−1): 3273; 3077; 2931; 2852; 1620; 1579; 1533; 1468; 1437; 1323;
1271; 1084; 968; 910; 875; 841; 752; 729; 685; 619.
Experimental data of cardanols nitration product (12): 1H NMR
(600 MHz, CDCl3) δ 0.89 (m, H-Csp3), 1.32 (m, H-Csp3), 1.60 (m, H-
Csp3), 2.00 (m, H-Csp3), 2.64 (m, H-Csp3), 2.69 (m, H-Csp3), 2.75 (m,
H-Csp3), 2.90 (m, H-Csp3), 5.00 (m, H-Csp2), 5.41 (m, H-Csp2), 6.80
(dd, J1 = 8.8 Hz, J2 = 1.5 Hz, H- Caromatic), 6.95 (m, H-Caromatic), 7.97
(d, J = 9.3 Hz, H-Caromatic), 8.0 (d, J = 8.8 Hz, H-Caromatic), 10.63 (s, H-
Caromatic). 13C NMR (150 MHz, CDCl3) δ 14.07 (Csp3), 22.62 (Csp3),
K.d.P. Costa et al.
27.19 (Csp3), 28.81 (Csp3), 29.08 (Csp3), 29.20 (Csp3), 29.58 (Csp3),
30.43 (Csp3), 31.72 (Csp3), 32.50 (Csp3), 33.81 (Csp3), 34.63 (Csp3),
36.03 (Csp3), 36.67 (Csp3), 113.47 (Caromatic), 114.84 (Caromatic), 117.97
(Caromatic), 118.93 (Caromatic), 120.91 (Caromatic), 123.33 (Caromatic),
124.93 (Caromatic), 127.91 (Csp2), 130.21 (Csp2), 130.43 (Csp2), 135.03
(Caromatic), 137.26 (Caromatic), 141.76 (Caromatic), 142.12 (Caromatic),
154.68 (Caromatic-NO2), 155.17 (Cphenolic), 159.79 (Caromatic-NO2). IR
(KBr, υmax, cm−1): 3338; 3080; 2931; 2852; 1622; 1585; 1520; 1477;
1446; 1329; 1263; 1186; 1078; 966; 908; 874; 841; 760; 868; 623.
2.5. Characterization of the synthesized products
IR spectra were obtained on a spectrometer with Fourier transform
(FT-IR) from Thermo Scientific model Nicolet 6700, with a wave
number range from 400 to 4000 cm−1, a resolution of 4 cm−1 and each
spectrum was obtained from the average of 16 scans.
1
H NMR and 13C NMR spectroscopic measurements were carried out
at 298 K using a Bruker Magneto Ascend 600 Console Avance III HD
spectrometer. The sample was prepared by dissolving the sample in
0.6 mL CDCl3 or DMSO‑d6. The spectra were referenced to TMS.
2.6. Oxidative stability – Rancimat (EN 14112)
The antioxidant additive candidates were evaluated using the
EN14112 method [39]. The analyses were performed on the 873 Bio-
diesel Rancimat – Metrohm, which accelerates the oxidation of bio-
diesel. In the analysis, 3 g of biodiesel added with 0.5% (w/w) of the
products are subjected to 110 °C under constant bubbling of filtered
compressed air at a flow rate of 10 L h−1. The percentage of 0.5% (w/
w) is usually adopted by Brazilian biodiesel producers. All of the ana-
lyses were performed in triplicate and the standard deviation ranged
from 0.02 to 0.10.
2.7. Thermogravimetric analysis
The thermal stability of the products were evaluated on a Shimadzu
Thermogravimetric Analyzer, model DTG-60, under nitrogen atmo-
sphere (50 mL min−1 flow rate), from 30 °C to 700 °C, using
10 °C min−1 heating rate [30].
3. Results and discussion
t-CNSL was analyzed by HPLC-DAD and the chromatogram profile
was compared to the literature data [36]. Fig. 2A shows the chroma-
togram of the starting material used. Eleven constituents were observed
in the t-CNSL chromatogram, each color representing a different class of
alkyl phenols. The peaks 1, 4 and 8 correspond to the mixture of ana-
cardic acids (tri-, mono-unsaturated and saturated, respectively). Peaks
2, 3 and 5 refer to the mixture of cardols (tri-, di- and mono-un-
saturated, respectively). Peaks 6 and 9 are the mixture of 2-methyl-
cardols with mono- and di-unsaturated chain. Peaks 7, 10 and 11 re-
present the mixture of cardanols with the alkyl chain tri-, di- and mono-
unsaturated, respectively. The composition found matches the litera-
ture, thus confirming that the CNSL used in this work was the technical
CNSL, obtained by the mechanical thermal process, rich in cardanols
[32]. Table 2 presents the composition of the t-CNSL used in this work.
The isolation of cardanols was performed according to the method
described in Section 2.3. The mixture of cardanols was obtained with a
purity of 95%. The chromatogram can be seen in Fig. 2B.
t-CNSL and the isolated mixture of cardanols were characterized by
IR, 1H NMR and 13C NMR. IR spectrum of t-CNSL showed characteristic
absorption bands of alkyl phenols, also observed in the IR spectrum of
the mixture of cardanols. A band at 3359 cm−1 corresponds to the OeH
phenolic bond, the CeH stretch of alkenes in 3008 cm−1, and vibration
of methyl and methylene groups at 2925 and 2852 cm−1, respectively,
were observed. A band at 1589 cm−1 relative to C]C bond in the
1014
Fuel 235 (2019) 1010–1018
aromatic ring, symmetrical stretching and asymmetric C]C (1268 and
1157 cm−1), folding out of the plane of CeH in trans alkenes (991 and
910 cm−1) and vibration of CeH bond of disubstituted aromatic ring
(779 and 694 cm−1) were also present in the spectra. 1H NMR spectra
of t-CNSL and isolated cardanols are also similar. Both present char-
acteristic signals in the region of aromatic hydrogens (6.66–7.20 ppm),
in the region of olefinic hydrogens (5.01–5.84 ppm) and the hydrogens
bound to sp3 carbon between 0.90 and 2.90 ppm. 13C NMR spectra also
showed a very similar profile, with characteristic signals of alkyl phe-
nols: sp3 carbon signals between 13.77 and 35.80 ppm, signals between
108.02 and 120.96 ppm, 130.39 ppm and 144.90 ppm, related to aro-
matic carbons. The carbon bonded to the hydroxyl group at
155.41 ppm, and finally signals relative to the olefinic carbons
(126.81–129.94 ppm).
Fig. 3 illustrates the synthetic route to obtain the products from
transformations in unsaturated cardanols, but it is worth mentioning
that the same transformations were performed for t-CNSL.
The first transformation was the epoxidation of the double bonds, to
increase its reactivity, allowing the insertion of oxygenated groups in
the hydrocarbon chain. The epoxidation reaction was performed ac-
cording to the procedure described in Subsection 2.4.1, and the pro-
ducts (3) and (4) were characterized by IR, 1H and 13C NMR. The
formation of the epoxide group is indicated by the disappearance of the
band around 3008 cm−1 in the IR spectra of the products, characteristic
to the stretching of the CeH bond of alkenes, and the appearance of
bands in 914, 873 and 813 cm−1, characteristic of epoxide group. In the
1
H NMR spectra, the epoxidation is confirmed by disappearance of the
signals relative to the olefinic hydrogens, in the region between 5.0 and
6.0 ppm. In the 13C NMR spectra, the disappearance of the olefinic
carbon signals in the region of 130 ppm and the appearance of signals at
54 and 57 ppm characteristic of oxirane ring carbons confirm the for-
mation of the product.
Hydrolysis of the epoxides led to the formation of the mixture of
polyalcohols (5) and (6) as product. In the characterization of the
products by IR, the disappearance of the bands characteristic of the C-O
vibration of the oxirane ring (914, 873 and 813 cm−1) in the IR spectra
indicates that the hydrolysis of the epoxide was successful. In 13C NMR
spectra, characteristic signals of epoxide group carbons at 54 and
57 ppm disappeared, and chemical shifts appeared at 73.20, 70.40,
79.67 and 80.20 ppm, relative to the secondary alcohol carbons. The
characteristic signals of alkyl phenols were preserved.
The solvolysis of the epoxides with methanol was carried out as
described in Subsection 2.4.3. In the characterization of the products
(7) and (8) by IR, the main indication of product formation is the
disappearance of the characteristic bands of the epoxide ring at 917,
873 and 813 cm−1. In 13C NMR spectra, the signals relative to the
oxirane ring carbons disappear and a signal appear at approximately
84 ppm, relative to the carbon bound to the methoxyl group. Chemical
shifts at 70.20 and 73.13 ppm were also observed, relative to the carbon
bound to the hydroxyl groups, also formed in the solvolysis.
The hydrogenation of the double bonds present in the alkyl chain of
the phenols was carried out to analyze its effect on the antioxidant
activity. The products (9) and (10) were characterized by IR, 1H NMR
and 13C NMR. In the IR spectra, the main indication that the reaction
occurred was the disappearance of the CeH stretching band of alkenes
at 3008 cm−1. In the 1H NMR and 13C NMR spectra, the disappearance
of signals relative to the olefinic groups was observed around 5.5 ppm
and 130 ppm, respectively.
The t-CNSL (1) and cardanol (2) reacted with concentrated nitric
acid in the presence of sulfuric acid to obtain nitro compounds (11) and
(12). IR spectra of the products (11) and (12) showed intense absorp-
tion bands around 1533 cm−1 (11) and 1520 cm−1 (12), related to
asymmetrical stretching of the NO2 group. Absorption at 1323 cm−1
(11) and 1329 cm−1 (12) corresponds to the symmetrical stretching
and a band at 841 cm−1 is related to the axial deformation of the π
bond NeO. A low intensity band was observed in the region of
K.d.P. Costa et al.
Fig. 2. HPLC-DAD Chromatogram of: A) t-CNSL; B) isolated mixture of cardanols.
Table 2
Chemical composition of t-CNSL used in this work.
Percentual in area (%)
Cardanols mixture (blue) 75
Cardols mixture (green) 18
Anacardic acids mixture (red) 4
2-Methylcardols mixture (orange) 1
Not identified 2 w) of t-CNSL is in accordance with the result obtained by Bastos and
750–760 cm−1 related to the angular deflection of the nitro group. In
13
C NMR spectra, two new signals at 154 and 160 ppm were observed,
related to aromatic carbon bonded to NO2 groups.
The yields of the synthesized products are shown in Table 3.
3.1. Evaluation of the antioxidant activity of the products
The oxidative stability of biodiesel samples was evaluated pro-
moting an accelerated auto-oxidation and measuring the induction
period (IP), as described in the EN 14112 standard method. The IP
observed for biodiesel added with the synthesized candidates is shown
in Fig. 4. As can be depicted in Fig. 4, all products tested increased the
oxidative stability of biodiesel. Among the tested products, the ex-
cellent antioxidant activity of the products (4) and (6) was observed,
with an IP of 15.05 and 18.62 h, respectively.
The addition of 0.5% (w/w) of t-CNSL (1) or isolated mixture of
cardanols (2) to biodiesel increased the induction period. Alkyl chains
1015
Fuel 235 (2019) 1010–1018
of CNSL constituents have allylic and bis-allylic sites susceptible to
oxidation as well as the unsaturated esters components of biodiesel.
But, the abstraction of hydrogen from the phenolic hydroxyl group is
preferred because produces a more stable radical. The phenoxyl radical
is stabilized by resonance of the aromatic ring, inhibiting the propa-
gation of the radical reactions [30]. The enhance of the induction
period from 6.35 h (pure biodiesel) to 8.79 h with addition of 0.5% (w/
Tubino [9]. They evaluated the oxidative stability of soybean biodiesel
containing the same concentration of t-CNSL and the IP increased from
5.66 h (pure biodiesel) to 7.36 h (additive biodiesel).
A more pronounced oxidative stability was observed in biodiesel
added with pure t-CNSL (1) compared to the isolated mixture of car-
danols (2). This result can be explained by the presence of cardols in its
composition. Cardols possess two OH groups attached to the aromatic
ring, offering more sites for the formation of the complex between the
free radical and antioxidant radical [40]. Maia et al (2015) showed that
the class of cardols is more effective as inhibitor of oxidative process in
buriti biodiesel than cardanols [28].
The hydrogenation of double bonds of the alkyl chains of both t-
CNSL and isolated cardanols decreased the oxidative stability of bio-
diesel when compared to the corresponding unsaturated products.
These results are also in agreement with the work of Maia et al. [28].
Some radicals can be stabilized by the presence of electron-with-
drawing group. The nitration of the aromatic ring, however, led to re-
duced induction period compared to the starting materials. The nitra-
tion occurs in ortho and para position to hydroxyl group [38]. The nitro
K.d.P. Costa et al. Fuel 235 (2019) 1010–1018

OH
R1

R2
(12)
R1 = H or NO 2
R2 = H or NO 2

2.4.5

OH OH

(2) 2.4.4 (10)

2.4.1

OH OH

O O 2.4.2 OH OH
(6)
(4)
OH OH

2.4.3

OH

(8) OCH3 OCH3

OH OH

Fig. 3. Synthetic route of products from cardanol (the correspondent experimental section number is indicated on the arrow).

Table 3 interaction between methyl esters peroxy radical (ROO%) and/or methyl
Yields of t-CNSL and cardanol derivatives. esters hydroperoxide (ROOH) and the oxygenated additives. It is known
Products Yields (%)
that hydrogen bonding interactions enhance the stability of radicals
[41]. Hydrogen bonding can even exert considerable effects on the
Epoxidized t-CNSL (3) 92 chemical properties of many radical species, such as bond dissociation
Epoxidized cardanols (4) 82 energies and reduction/oxidation potentials [42,43]. An interaction
Hydrolyzed t-CNSL (5) 70
Hydrolyzed cardanols (6) 50
between additive molecules and ROO% by hydrogen bonding could slow
Solvolyzed t-CNSL (7) 65 the propagation step, in other words, could prevent the peroxy radical
Solvolyzed cardanols (8) 77 to react with a new substrate (methyl esters) to form another methyl
Hydrogenated t-CNSL (9) 89 esters radical (R%) and ROOH. On the other hand, if the intermolecular
Hydrogenated cardanols (10) 61
interaction occurs between ROOH molecules and additive, it would
Nitro t-CNSL (11) 86
Nitro cardanols (12) 82 delay further oxidative degradation to secondary oxidation derivatives
such as aldehydes and carboxylic acids [44]. Both possibilities would
increase the induction period. The products of hydrolysis and solvolysis
group in the ortho position makes intramolecular interaction with the can perform intermolecular and intramolecular interactions by hy-
phenolic hydroxyl by hydrogen bond, hindering the abstraction of hy- drogen bonding. The addition of the solvolysis product (8) in biodiesel
drogen and, consequently, the formation of phenoxyl radical. The effect led to a lower induction period when compared to the products of
is more evident when biodiesel is added with nitro phenols from t-CNSL epoxidation (4) and hydrolysis (6). This result suggests a predominance
(11). The aromatic ring of cardols is even more reactive for aromatic of intramolecular interactions in the product of solvolysis. The poly-
electrophilic substitution. The formation of dinitrophenols allows in- alcohols (6) can do hydrogen bonding by the oxygen or the hydrogen
teraction by hydrogen bond with both phenolic hydroxyls, almost from the hydroxyl group being able to interact with both ROO% and
completely canceling the possibility of forming the radical. The in- ROOH. Based on this, the product (6) would present induction period
duction period was close to pure biodiesel. superior to the other oxygenated additives.
The functionalization of double bonds present in alkyl chain of the The second hypothesis is based on the existence of more easily ab-
phenols considerably increased the oxidative stability of biodiesel. The stracted hydrogen in the molecules of additive. Of course, the ab-
insertion of epoxide groups into the alkyl chain of cardanols increased straction of hydrogen from phenolic hydroxyl by ROO% generates more
by more than two times the induction period. The hydrolysis of the stable radical and because of this characteristic, phenols are used
epoxide groups led to the formation of a polyhydroxylated product (6), commercially as antioxidant additives. But this chain breaking me-
which presented even more potent antioxidant activity. As far as we chanism is equally possible for the three oxygenated additives in dis-
know there is no similar study in the literature to support the discussion cussion. Using bond dissociation energies as a guide to discuss the
of these results. Two hypotheses can be presented. formation of radicals [45], it is possible to say that the homolysis of
The first one is the possibility of occurrence of intermolecular CeH bond of alcohol (carbon also bonded to hydroxyl) exhibits

1016
K.d.P. Costa et al. Fuel 235 (2019) 1010–1018

Fig. 5. TGA curves of t-CNSL (A) and cardanol (B), and their derivatives, at
nitrogen atmosphere.

second phenolic hydroxyl associated to the formation of more hydro-

xyls from the hydrolysis of the epoxide makes solvation by biodiesel
difficult. The molecules of product preferred to maintain intermolecular
Fig. 4. Induction period (IP) in hours for biodiesel at 110 °C with 0.5% (w/w) of product-product interactions rather than product-biodiesel.
the additive candidates derived from t-CNSL (A) and cardanol (B).

3.2. Thermal stability of products

Table 4
Bond dissociation energies (BDE) in kcal mol−1 at 25 °C.
Fig. 5 shows TGA data of t-CNSL (A) and cardanol (B), and their
BDE Reference derivatives. From the curves, it was observed that, except for hydro-
genation, the other transformations increased the thermal stability of
H-CH2CHCH2 89 [45,46]
the starting materials, and the epoxides (3) and (4) were more ther-
H-OC6H5 90 [46]
H-CH3 105 [45,46] mally stable. In addition, the nitro derivatives (11) and (12) presented
H-OCH3 104 [45,46] a thermal decomposition profile different from the other compounds,
H-CH2OH 96 [46] with two stages of mass loss, starting with the loss of the nitro group
HO-CH3 92 [45,47]
followed by a possible polymerization, which is evidenced mainly by
H-OCH(CH3)2 106 [46]
H-CH(CH3)2 99 [45,46] the high amount of carbon residue, approximately 30%. These results
HO-CH(CH3)2 96 [47] indicate that t-CNSL and cardanol derivatives, except for products (9)
and (10), are suitable for applications at high temperatures, being in
consensus for application as fuel additives.
dissociation energy value not so different to the required for homolytic
cleavage of the CeH bond next to conjugating groups (generating allyl
4. Conclusions
radicals). This could also explain the greater induction period when
biodiesel is added with the product (6) since the probability of ab-
The use of a low cost renewable source such as CNSL is in ac-
straction of that hydrogen by the radical ROO% is higher. Table 4 shows
cordance with the concept of sustainable chemistry. The alkyl phenols
some bond dissociation energies data for comparison.
present in t-CNSL have great chemical versatility since several trans-
The antioxidant capacity of the product of t-CNSL epoxide hydro-
formations are possible in strategic positions. Among the products
lysis (5) was not evaluated because it was not soluble in biodiesel. The
synthesized in this work, epoxidized cardanols (4) and hydrolyzed
t-CNSL used in this work contains about 18% of cardols where tri-un-
cardanols (6) showed excellent antioxidant activity. The mixture of
saturated cardol is the majority (peak 2 in Fig. 2A). The presence of a
polyols (6), especially, showed to be a promising antioxidant additive

1017
K.d.P. Costa et al.
for biodiesel, increasing the induction period to 18.62 h.
Thermogravimetric analysis of the oxygenated derivatives from both t-
CNSL and cardanols showed that the chemical modifications enhanced
the thermal stability of the products compared to the starting materials.
Acknowledgements
The authors would like to thank CNPq (Brazilian Research Council,
UNIVERSAL 421590/2016-5), FAPERJ (Rio de Janeiro State Research
Sponsor Foundation, E-26/200.976/2016), FAPDF (Federal District
Research Sponsor Foundation) and ANP (Brazilian National Agency of
Petroleum, Natural Gas and Biofuels) for financial support.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.fuel.2018.08.111.
References
[1] ANP – Agência Nacional do Petróleo Gás Natural e Biocombustíveis. Dados
estatísticos – Produção de biodiesel (metros cúbicos) 2017. http://www.anp.gov.
br/wwwanp/dados-estatisticos; 2017 [accessed 5 september 2017].
[2] Pinto AC, Guarieiro LLN, Rezende MJC, Ribeiro NM, Torres EA, Lopes WA, et al.
Biodiesel: an overview. J Braz Chem Soc 2005;16:1313–30. https://doi.org/10.
1590/S0103-50532005000800003.
[3] Lois E. Definition of biodiesel. Fuel 2007;86:1212–3. https://doi.org/10.1016/j.
fuel.2006.09.028.
[4] Rico JAP, Sauer IL. A review of Brazilian biodiesel experiences. Renewable
Sustainable Energy Rev 2015;45:513–29. https://doi.org/10.1016/j.rser.2015.01.
028.
[5] Hoekman SK, Broch A, Robbins C, Ceniceros E, Natarajan M. Review of biodiesel
composition, properties, and specifications. Renewable Sustainable Energy Rev
2012;16:143–69. https://doi.org/10.1016/j.rser.2011.07.143.
[6] Suarez P, Meneghetti S. Transformation of triglycerides into fuels, polymers and
chemicals: some applications of catalysis in oleochemistry. Quim Nova
2007;30:667–76. https://doi.org/10.1590/S0100-40422007000300028.
[7] Sharma YC, Singh B, Upadhyay SN. Advancements in development and character-
ization of biodiesel: a review. Fuel 2008;87:2355–73. https://doi.org/10.1016/j.
fuel.2008.01.014.
[8] ANP – Agência Nacional do Petróleo Gás Natural e Biocombustíveis. Percentual de
consumo de cada matéria-prima para produção de biodiesel nacional e por região
2017. http://www.anp.gov.br/wwwanp/producao-de-biocombustiveis/biodiesel/
informacoes-de-mercado; 2017 [accessed 18 september 2017].
[9] Bastos FA, Tubino M. The use of the liquid from cashew nut shells as an antioxidant
in biodiesel. J Braz Chem Soc 2017;28:747–55.
[10] Pinho DMM, Suarez PAZ. Armazenagem e uso de biodiesel: problemas associado e
formas de controle. Brasília – DF: Centro de Apoio ao Desenvolvimento Tecnológico
– CDT – UnB; 2016.
[11] Cazarolli JC, Boelter G, de Lima AMDL, Hengles T, Correa C, Peralba MCR, et al.
Nature of insoluble material found in the bottom of soybean biodiesel storage tank:
chemical and microbiological approach. J Braz Chem Soc 2018.
[12] Passman FJ. Microbial contamination and its control in fuels and fuel systems since
1980 – a review. Int Biodeterior Biodegrad 2013;81:88–104.
[13] Ramalho HF, Ferreira KMC, Machado PMA, Silva TB, Rangel ET, Prauchner MJ,
et al. Production of additives with antimicrobial activity via tandem hydro-
formylation – amine condensation of soybean FAME using an ionic liquid-based
biphasic catalytic system. J Braz Chem Soc 2016;27:321–33.
[14] Zimmer AR, Oliboni A, Viscardi SLC, Teixeira RM, Ferrao MF, Bento FM. Biodiesel
blend (B10) treated with a multifunctional additive (biocide) under simulated
stored conditions: a field and lab scale monitoring. Biofuel Res J 2017;14:627–36.
https://doi.org/10.18331/BRJ2017.4.2.7.
[15] Costa KP, do Valle SF, dos Santos TFL, Rangel ET, Pinto AC, Suarez PAZ, et al.
Synthesis and evaluation of biocide and cetane number improver additives for
biodiesel from chemical changes in triacylglycerides. J Braz Chem Soc 2018.
[16] Qi DH, Lee CF. Influence of soybean biodiesel content on basic properties of bio-
diesel-diesel blends. J Taiwan Inst Chem Eng 2014;45:504–7. https://doi.org/10.
1016/j.jtice.2013.06.021.
[17] Schober S, Mittelbach M. The impact of antioxidants on biodiesel oxidation stabi-
lity. Eur J Lipid Sci Technol 2004;106:382–9. https://doi.org/10.1002/ejlt.
200400954.
[18] Knothe G, Van Gerpen J, Krahl J, Ramos LP. Manual de biodiesel. São Paulo:
Blucher; 2006.
[19] Jain S, Sharma MP. Stability of biodiesel and its blends: a review. Renewable
Sustainable Energy Rev 2010;14:667–78. https://doi.org/10.1016/J.RSER.2009.
10.011.
[20] Beker SA, da Silva YP, Bücker F, Cazarolli JC, de Quadros PD, Peralba MCR, et al.
Effect of different concentrations of tert-butylhydroquinone (TBHQ) on microbial
growth and chemical stability of soybean biodiesel during simulated storage. Fuel
2016;184:701–7.
1018
Fuel 235 (2019) 1010–1018
[21] Dodos GS, Tsesmeli CE, Zannikos F. Evaluation of the antimicrobial activity of
synthetic and natural phenolic type antioxidants in biodiesel fuel. Fuel
2017;209:150–61.
[22] Damasceno SS, Santos NA, Santos IMG, Souza AL, Souza AG, Queiroz N. Caffeic and
ferulic acids: an investigation of the effect of antioxidants on the stability of soybean
biodiesel during storage. Fuel 2013;107:641–6.
[23] Medeiros ML, Cordeiro AMMT, Queiroz N, Soledade LEB, Souza AL, Souza AG.
Efficient antioxidant formulations for use in biodiesel. Energy Fuels
2014;1074–80:28. https://doi.org/10.1021/ef402009e.
[24] Buosi GM, da Silva ET, Spacino K, Silva LRC, Ferreira BAD, Borsato D. Oxidative
stability of biodiesel from soybean oil: comparison between synthetic and natural
antioxidants. Fuel 2016;181:759–64.
[25] Rodrigues FMG, Souza AG, Santos IMG, Bicudo TC, Silva MCD, Sinfrônio FSM, et al.
Antioxidative properties of hydrogenated cardanol for cotton biodiesel by PDSC and
UV/VIS. J Therm Anal Calorim 2009;97:605–9. https://doi.org/10.1007/s10973-
008-9600-3.
[26] Lomonaco D, Maia FJN, Clemente CS, Mota JPF, Costa AE, Mazzetto SE. Thermal
studies of new biodiesel antioxidants synthesized from a natural occurring phenolic
lipid. Fuel 2012;97:552–9. https://doi.org/10.1016/j.fuel.2012.01.059.
[27] Rios MAS, Santos FFP, Maia FJN, Mazzetto SE. Evaluation of antioxidants on the
thermo-oxidative stability of soybean biodiesel. J Therm Anal Calorim
2013;112:921–7. https://doi.org/10.1007/s10973-012-2650-6.
[28] Maia FJN, Ribeiro FWP, Rangel JHG, Lomonaco D, Luna FMT, de Lima-Neto P, et al.
Evaluation of antioxidant action by electrochemical and accelerated oxidation ex-
periments of phenolic compounds derived from cashew nut shell liquid. Ind Crops
Prod 2015;67:281–6. https://doi.org/10.1016/j.indcrop.2015.01.034.
[29] Dos Santos RC, Amorim ADGN, Thomasi SS, Figueiredo FC, Carneiro CS, Da Silva
PRP, et al. Development of an electrolytic method to obtain antioxidant for bio-
diesel from cashew nut shell liquid. Fuel 2015;144:415–22. https://doi.org/10.
1016/j.fuel.2014.11.082.
[30] Liu Z, Chen J, Knothe G, Nie X, Jiang J. Synthesis of epoxidized cardanol and its
antioxidative properties for vegetable oils and biodiesel. ACS Sustain Chem Eng
2016;4:901–6. https://doi.org/10.1021/acssuschemeng.5b00991.
[31] Kleinberg MN, Rios MAS, Buarque HLB, Parente MMV, Cavalcante Jr. CL, Luna
FMT. Influence of synthetic and natural antioxidants on the oxidation stability of
beef tallow before biodiesel production. Waste Biomass Valorization 2017. https://
doi.org/10.1007/s12649-017-0120-x.
[32] Mazzetto SE, Lomonaco D, Mele G. Oleo da castanha de caju: oportunidades e de-
safios no contexto do desenvolvimento e sustentabilidade industrial. Quim Nova
2009;32:732–41. https://doi.org/10.1590/S0100-40422009000300017.
[33] Gelbard G, Brès O, Vargas RM, Vielfaure F, Schuchardt UF. 1H nuclear magnetic
resonance determination of the yield of the transesterification of rapeseed oil with
methanol. J Am Oil Chem Soc 1995;72:1239–41. https://doi.org/10.1007/
BF02540998.
[34] Rezende M, Vale D, Aguiar P, Riehl C, Azevedo D. Application of full factorial
design to evaluate the effect of different variables on the stability of biodiesel:diesel
blends under storage conditions. J Braz Chem Soc 2017;28:1966–74. https://doi.
org/10.21577/0103-5053.20170041.
[35] Pinho D, Oliveira R, dos Santos V, Marques W, Pinto A, Rezende M, et al. Evaluating
the potential of biodiesel production through microalgae farming in photo-
bioreactor and high rate ponds from wastewater treatment. J Braz Chem Soc
2017;28:2429–37. https://doi.org/10.21577/0103-5053.20170097.
[36] Phani Kumar P, Paramashivappa R, Vithayathil PJ, Subba Rao PV, Srinivasa Rao A.
Process for isolation of cardanol from technical cashew (Anacardium occidentale L.)
nut shell liquid. J Agric Food Chem 2002;50:4705–8. https://doi.org/10.1021/
jf020224w.
[37] Souza Filho RY. Estudos visando à síntese de heterociclos de 5- membros a partir
dos lipídeos fenólicos do lcc: isobenzofuranonas e indolinonas em foco.
Universidade de Brasília; 2013.
[38] Attanasi OA, Berretta S, Fiani C, Filippone P, Mele G, Saladino R. Synthesis and
reactions of nitro derivatives of hydrogenated cardanol. Tetrahedron
2006;62:6113–20. https://doi.org/10.1016/j.tet.2006.03.105.
[39] European Committee for Standardization. Determination of oxidation stability
(accelerated oxidation test) – EN 14112, 2003.
[40] Jakeria MR, Fazal MA, Haseeb ASMA. Influence of different factors on the stability
of biodiesel: a review. Renewable Sustainable Energy Rev 2014;30:154–63. https://
doi.org/10.1016/j.rser.2013.09.024.
[41] Hernández-Soto H, Weinhold F, Francisco JS. Radical hydrogen bonding: origin of
stability of radical-molecule complexes. J Chem Phys 2007;127:1–11. https://doi.
org/10.1063/1.2784558.
[42] Qi X-J, Liu L, Fu Y, Guo Q-X. Hydrogen bonding interactions of radicals. Struct
Chem 2005;16:347–53. https://doi.org/10.1007/s11224-005-4465-6.
[43] Johnson ER, Dilabio GA. Radicals as hydrogen bond donors and acceptors.
Interdiscip Sci Comput Life Sci 2009;1:133–40. https://doi.org/10.1007/s12539-
009-0024-3.
[44] Pullen J, Saeed K. An overview of biodiesel oxidation stability. Renewable
Sustainable Energy Rev 2012;16:5924–50. https://doi.org/10.1016/j.rser.2012.06.
024.
[45] Carey FA, Sundberg RJ. Advanced Organic Chemistry: Structure and mechanisms.
fifth ed. New York: Springer Science+Business Media, LLC; 2007. doi:10.1007/
978-0-387-44899-2.
[46] Blanksby SJ, Ellison GB. Bond dissociation energies of organic molecules. Acc Chem
Res 2003;36:255–63. https://doi.org/10.1021/ar020230d.
[47] Matsunaga N, Rogers DW, Zavitsas AA. Pauling’s electronegativity equation and a
new corollary accurately predict bond dissociation enthalpies and enhance current
understanding of the nature of the chemical bond. J Org Chem 2003;68:3158–72.
https://doi.org/10.1021/jo020650g.