J. Coat. Technol. Res.

, 12 (2) 303311, 2015

DOI 10.1007/s11998-014-9630-7

Mechanical, chemical, and curing characteristics of cardanol

furfural-based novolac resin for application in green coatings
Riya Srivastava, Deepak Srivastava

American Coatings Association 2015

Abstract The present research work focuses on the
mechanical, chemical, and curing characteristics of
novolac resin based on renewable resource materials
such as cardanol and furfural. Cardanol, a metasubstituted phenol, is a renewable organic resource obtained
as a byproduct of the cashew industry. Furfural, an
aromatic aldehyde, is also a renewable resource
obtained as an agricultural waste product. Novolac
resin has been synthesized by the condensation of
cardanol with furfural in the presence of an oxalic acid
catalyst and using varied molar proportions of the
reacting monomers. The reaction was performed at
120C. The progress of the reaction was monitored by
determining the free formaldehyde and free phenol
content. The prepared cardanolfurfural-based novolac resins were further characterized by various techniques such as infrared and nuclear magnetic
resonance spectroscopic analysis. The resins were
cured using the most suitable agent, hexamethylenetetramine. The differential scanning calorimetric technique was used to investigate the curing behavior of
the prepared samples. The cured film samples were
used for the determination of mechanical properties
such as adhesion, flexibility, scratch hardness, gloss,
and impact resistance; these cured film samples were
also used to observe the effect of various chemicals and
solvents (chemical resistance properties) such as sulfuric acid, acetic acid, sodium hydroxide, sodium
carbonate and methanol, methyl ethyl ketone, xylene,
and deionized water, respectively, on the surface of the
film. The resulting coatings based on prepared carda-

R. Srivastava, D. Srivastava (&)

Department of Plastic Technology, H. B. Technological
Institute, Kanpur 208002, India
e-mail: dsri92@gmail.com
R. Srivastava
e-mail: riya.chem24@gmail.com

nolfurfural resin were found to have excellent

mechanical and chemical resistance properties.
Keywords Renewable resource, Cardanol, Furfural,
FTIR, NMR, DSC, Coatings

Introduction
Increasing environmental concerns have opened significant opportunities for polymers from renewable
resources. The utilization of renewable resources in
polymers and coating applications is receiving increasing attention and has been the subject of keen interest
among both academic and industrial researchers.13
The need to reduce the use of petrochemical-derived
monomers in the manufacture of polymers is evident as
a result of spiraling cost and the high rate of depletion
of petrochemical-derived stocks. This requires the
investigation and use of renewable resources which
can serve as alternative feedstocks of monomers for
the polymer industry.4 Among the renewable resources, cashew nut shell liquid (CNSL), an agricultural renewable resource material obtained as a
byproduct of the cashew processing industry, is unique
in that it possesses phenolic moiety with an unsaturated 15-carbon side chain, as shown in Scheme 1.5
Cardanol, a natural metasubstituted alkyl phenol from
CNSL, can be regarded as a versatile and valuable raw
material for polymer production,68 and like phenol, it
can be condensed with active hydrogen-containing
compounds to yield a series of phenolic resins, for
instance, base-catalyzed resoles and acid-catalyzed
novolacs.9 Resins derived from CNSL/cardanol are
widely employed in the field of surface coatings,
adhesives, and laminates, and have several miscellaneous applications.10
Furfural, the heteroaryl aldehyde, is obtained as an
agricultural waste product which has an extensive

303

J. Coat. Technol. Res., 12 (2) 303311, 2015

Methods

OH

Synthesis of cardanolfurfural-based novolac resin

(CH2)7(CH=CH)(CH2)5CH3
Structure of Cardanol

Scheme 1: Structure of cardanol

application in the formation of resins.11 Several resins

have been prepared by using cardanyl acrylate and
furfural in the presence of an acid catalyst and a
selective organic compound, and their thermal properties have been studied.12
Novolac resins based on phenolfurfural have
already been discussed in previous publications.9,10
The synthesis of cardanolformaldehyde resins have
been reported earlier.1315 However, these have some
limitations, like weak chemical stability, low flexibility,
and weak impact resistance.16 Therefore, the cardanol
formaldehyde resins may be further modified by
replacing formaldehyde with an aromatic aldehyde
such as furfural in the presence of a suitable catalyst to
improve the chemical and mechanical stability of such
cardanol-novolac resins. Since the study of mechanical,
chemical, and curing properties of cardanolfurfural
resins has hardly been investigated so far, the present
work is concerned with the mechanical, chemical, and
curing characteristics of cardanolfurfural resin for
application in green coatings, as these coatings are
derived from renewable resources (cardanol and furfural).

Experimental
Materials
Cardanol was procured from M/s Dheer Gramodyog
Ltd., Kanpur, India. Furfural (A.R. grade) was
obtained from Qualikems Fine Chemicals Pvt. Ltd.,
New Delhi, India, and was used for formylation.
Succinic acid and hexamethylenetetramine (HMTA)
were received from Central Drug House Ltd. (CDH),
Mumbai and New Delhi, India, respectively. Methanol
was used to dissolve the free catalyst and was received
from M/s Thomas Baker Chemicals Ltd., Mumbai,
India. Powdered soap was procured from the local
market.

Analysis of cardanol
Cardanol was subjected to extensive analysis for the
determination of iodine value, viscosity, and specific
gravity as per the procedures mentioned in IS-Standard
840-1964 (refer to Table 1).

304

Cardanolfurfural-based novolac resins were synthesized from cardanol and furfural in the mole ratios 1:0.5,
1:0.6, 1:0.7, and 1:0.8 using oxalic acid as a catalyst by a
method published in the literature for cardanolformaldehyde resin.16 Four samples of cardanolfurfural
novolacs were prepared using four different mole ratios
as mentioned earlier (refer to Table 2). Under warm
conditions, the catalyst (1% based on cardanol) was
dissolved in 5 mL methanol. In a three-necked roundbottomed flask containing cardanol, with a mechanical
stirrer and distillation unit attached, furfural was added
dropwise through a dropping funnel along with the
catalyst solution. The formation of multinuclear cardanolfurfural resin (Scheme 2) might occur when the
reaction mixture was heated under constant stirring at a
temperature of 120C. The reaction mixture was withdrawn after every 45 min to determine the free formaldehyde content (as per ASTM standard D1312-56)
and free phenol content (as per ISO standard 9397) for
checking the completion of the reaction. The pH of the
reaction mixture was found to be 2 at the end of the
reaction. The final resinous product was collected and
dried under vacuum at 60C overnight. Finally, the resin
was purified by column chromatography. A resin
solution prepared with n-hexane, charged to the silica
gel column chromatographic purification, was adopted
mainly to remove the unreacted components, impurities, etc., from the methylolated cardanol. Purification
was accomplished by using the eluent mixture of ethyl
acetatebenzene (60:40).
Curing of cardanolfurfural-based novolac resin
A process mentioned elsewhere17 was adopted for curing
of the cardanolfurfural-based novolac resin by using
HMTA. HMTA is the most widely used agent for curing
processes of novolac resins.18,19 Novolac resins made from
cardanol and furfural at four different mole ratios, viz. 1:0.5,
1:0.6, 1:0.7, and 1:0.8, were cured by the addition of 15%
HMTA. The mixtures of novolac resin and curing agent
were taken in small glass vials and mixed uniformly with the
help of a glass rod at room temperature. Thereafter, the
glass vials were kept in a preheated air oven.
Coating of panels
The prepared samples of cardanolfurfural novolac
resins were mixed with 15% HMTA and stirred well to
get a homogenous coating mixture. For the mechanical
properties of the films, the mild steel panels were
cleaned well with mineral turpentine oil (MTO) and
detergent such as powdered soap and finally with
methanol, and dried in an oven at 100C for 20 min.
Panels were then uniformly coated with the prepared

J. Coat. Technol. Res., 12 (2) 303311, 2015

Table 1: Physical characteristics of cardanol

Properties

Viscosity (cP)
Specific gravity (g/m3)
Iodine value (Wijs)
Moisture content at 100C (wt%)

Calculated
value

Literature
value

39.4
0.90
278.8
2.91

32.0
0.87
279.8
2.6

EVALUATION OF MECHANICAL PROPERTIES OF FILMS: All

the resin-coated panels were used for the evaluation of
cured film properties such as scratch hardness,
adhesion, flexibility, gloss, and impact resistance.
EVALUATION OF CHEMICAL RESISTANCE PROPERTIES OF
Each resin-coated panel was used for the
evaluation of chemical resistance properties of the cured
films such as acids, alkalis, deionized water, and solvents.
FILMS:

Table 2: Sample designation and reaction conditions

for synthesized novolac samples

Characterization of cardanolfurfural based

novolac resin

Reaction
S. Cardanol Furfural Sample Reaction
temperature
time
no.
(mol)
(mol) codes of
(C)
(min)
novolac
resin

Fourier-transform infrared (FTIR) spectroscopic

analysis

1
2
3
4

1.0
1.0
1.0
1.0

0.5
0.6
0.7
0.8

FFNR51
FFNR61
FFNR71
FFNR81

360
360
360
360

120
120
120
120

Furfural
(0.5 mol)

Cardanol
(1 mol)

The purified resin was subjected to Fourier transform

infrared (FTIR) spectroscopic analysis to monitor the
formation or disappearance of various functional
groups using a Perkin-Elmer (Model 843) infrared
spectrophotometer in the wavelength range of 500
4000 cm 1. Potassium bromide (KBr) pellets were
used to get the spectra of uncured material.
1

H-NMR spectroscopic analysis

Catalyst
Oxalic acid
(1% based on cardanol)

H-NMR (nuclear magnetic resonance) of the purified

cardanolfurfural-novolac resin was recorded using a JeolLA 500 NMR spectrophotometer. About 20 mg of the
sample, in a 10 mm diameter sample tube, was dissolved in
about 5 mL of chloroform-d1 (CDCl3), which was used a
solvent along with tetramethylsilane (TMS) as an internal
standard. Finally, the spectra were recorded on a computer.
Differential scanning calorimetry (DSC)

120 C
Cardanolfurfural novolac resin
160 C
Cured by addition of 15% HMTA

Scheme 2: Synthesis of cardanolfurfural-based novolac

resin

homogenous mixture by using a Bird Film Applicator

(M/s Sheen Instruments Ltd.). Resin-coated panels
were then subjected to the hot air oven for curing the
applied films. For chemical resistance of the films, glass
panels were used instead of mild steel panels. All of the
coating films were cured at 160C but at different time
intervals, as mentioned in Table 3.

Differential scanning calorimetric (DSC) analysis of the

prepared samples were carried out to investigate the
curing behavior of the cardanolfurfural novolac resins.
Cure temperatures of the prepared samples were
observed by taking a small amount of sample into a
shallow aluminium pan sealed by the aluminium cover
of a differential scanning calorimeter (TA instrument,
USA; modulated DSC-2920). This was placed in a
sample cell of the instrument; the starting temperature,
programmed rate, and final temperature were taken at a
heating rate of 10C/min. Dynamic scans were obtained
which were used for assuming the cure temperature.
Mechanical properties of the prepared films
Scratch hardness tester
The scratch hardness of the films of cardanolfurfural
novolac resins were checked by an automatic scratch
hardness tester (M/s Sheen Instruments Ltd., UK).

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J. Coat. Technol. Res., 12 (2) 303311, 2015

Table 3: Study of cure schedule

S. no.

Samples

Cardanol:furfural (mole ratio)

Cure time (min)

Cure temperature (C)

1
2
3
4

FFNR51
FFNR61
FFNR71
FFNR81

1.0:0.5
1.0:0.6
1.0:0.7
1.0:0.8

150
120
100
90

160
160
160
160

Impact hardness tester

The impact hardness of the films of the prepared
novolac resins were tested using a tubular impact
hardness tester (M/s Khusboo Scientific, Mumbai).
Cylindrical mandrel
The adhesion and flexibility of the cured films of
cardanolfurfural resins were tested using a cylindrical
mandrel (M/s Sheen Instruments Ltd., Model: 809),
with the mandrel of the diameters 1/12 to 1.3 of an
inch.
Gloss
Gloss was measured using a triglossometer (M/s Sheen
Instruments Ltd., UK). Watching the films from 60
angles, it was observed that all the coating films had
good gloss.
Chemical resistance of the prepared films
For chemical resistance testing, the panels were
prepared by applying the resin mixture to
150 9 50 9 1.25 mm glass panels by using a Bird Film
Applicator (Sheen Instruments Ltd., UK). A dry film
thickness of about 100 lm was maintained throughout
on all the panels.

Results and discussion

Analysis of cardanol
An analysis of cardanol is necessary to understand and
control the synthesis of phenolic resins. In this relation,
the iodine value is required to determine the presence
of a degree of unsaturation in the cardanol molecule.
Moreover, the viscosity and specific gravity is also
required for the synthesis of novolac resin. The
analytical data of cardanol was compared with standard technical CNSL. The lesser ash content and
nonself-polymerized fractions were indicated by the
relatively lesser viscosity (41.3 cP) of the cardanol, in
comparison with that of standard technical CNSL (552
cP). The specific gravity of cardanol (0.9 g/cm3) was

306

also relatively lower than standard CNSL (0.960

g/cm3), due to lower ash content and self-polymerized
fraction. The degree of unsaturation in cardanol is
determined experimentally by the iodine value, which
was found to be 278.8 Wijs. Wijs is the standard unit of
iodine value. These observations provided evidence
that cardanol is a monoene metasubstituted phenol and
its empirical formula is written as C21H34O. This was
also given in our earlier studies20,21 for different
systems. The structure of cardanol may be proposed
as shown in Scheme 1.

Synthesis of cardanolfurfural-based novolac resin

The methylolation of cardanol was carried out with
furfural in the presence of dicarboxylic acid, viz.
succinic acid using four different mole ratios. The
completion of the methylolation reaction was checked
by the periodic withdrawal of the reaction mixture to
analyze free formaldehyde content and free phenol
content.
The polymerization of cardanol can be accomplished in two ways: firstly, by the condensation of
furfural, and secondly, through the unsaturation present in the side chain. The side chain of cardanol
remained unaffected, because it is clear from the
measure of the iodine value.22 The iodine value of
cardanol before polymerization was 278.8 Wijs and
after polymerization the iodine value of the reaction
product was found to be 278.2 Wijs. Therefore, it was
concluded that the polymerization proceeded by the
first way, i.e., by the complicated step-growth polymerization reaction mechanism.23 The proposed mechanism of the reaction between cardanol and furfural
was based on the literature published earlier.24 The
mechanism of formation of novolac oligomers in acidic
media, using an excess of cardanol over furfural, might
proceed through the following steps. First, a furansubstituted methylene glycol is protonated by an acid
from the reaction medium, which then releases water
to form a furan-substituted hydroxyl methylene carbonium ion. This ion acts as a hydroxyalkylating agent by
reacting with the cardanol via electrophilic aromatic
substitution. A pair of electrons from the benzene ring
attacks the electrophilic element, forming a carbon
anion intermediate, followed by deprotonation. The
methylol group of the hydroxylmethylolated cardanol,
being unstable under acidic conditions, would lose
water readily to form a benzylic carbonium ion. The

J. Coat. Technol. Res., 12 (2) 303311, 2015

products formed would react with another cardanol

molecule to form a methylene bridge in another
electrophilic aromatic substitution. This process would
repeat until all of the furfural has been exhausted.25
The related reactions have been represented in
Scheme 3.
Evaluation of coating films for their curing
characteristics
The curing of all the prepared novolac resin samples
(FFNR51, FFNR61, FFNR71, and FFNR81) on mild
steel panels was completed in an air oven using HMTA
as the curing agent. The observations related to curing
conditions are presented in Table 3. The curing characteristics of the resin films show that the resin
FFNR81 prepared with mole ratio 1:0.8 has good
curing characteristics, as the films were cured in
90 min. However, the films of resins designated as
FFNR71, FFNR61, and FFNR51 with mole ratios 1:0.7,
1:0.6, and 1:0.5 were cured in 150, 120, and 100 min,
respectively, at 160C.
Fourier-transform infrared (FTIR) spectroscopic
analysis
The FTIR spectra of sample FFNR81 (Fig. 1) are
discussed here. IR spectral analysis of cardanolfurfural-based novolac resins reveals not only the condensation of methylolated cardanol, but also the degree of
ortho- and para-substitution. The band observed at
3472 cm 1 might be due to the presence of the
hydroxyl group in the methylolated cardanol. The
peaks that appear near 3011 and 2926 cm 1 in Fig. 1
might be due to the presence of aromatic CH stretching and aliphatic CH stretching, respectively, present in
the side chain of cardanol. The sharp band observed at
2854 cm 1 might be due to the CH structure in a
methylene bridge. The methylene bridge might form
due to the condensation reaction between cardanol and
furfural. The stretching vibrations near 2926 and
2854 cm 1 and deformative vibrations near 1464
1486 cm 1 indicate the presence of CH2 and CH3
groups, respectively. The sharp peaks near 722 and
884 cm 1 represent the ortho- and para-substitution in
benzene nuclei, respectively. A peak near 1266 cm 1
might correspond to phenol CO stretching. The
preceding spectral data were found to be identical to
those given in the literature.25
1

H-NMR spectroscopic analysis

Figure 2 shows the 1H-NMR spectrum of cardanol

furfural resins of samples FFNR81. The appearance of
a peak at 6.67.4 ppm is due to aromatic protons of
benzene and the furan ring. The peak around the
region 6.6 ppm might be due to the presence of the

phenolic hydroxyl group. The peak at 4.75.4 ppm

indicates the methylene (C=CH2) proton of a long
alkyl side chain originally present in cardanol, and the
peak at 0.82.9 ppm is due to a long aliphatic side
chain. The peak at 0.9 ppm might be due to a terminal
methyl group of the chain. The strong peak at 1.3 ppm
is attributed to the long chain (more than five methylene groups) of the side chain. The peak at 2.8 ppm
shows the methane proton of (C6H5)2CHC4H3O for
the bridge between two phenyl rings and one furan
ring. All these spectral data indicate that condensation
of methylolated cardanol with furfural has been completed under experimental conditions and was fully
consistent with the proposed structure (Scheme 3) due
to the reaction mechanism as discussed in our previous
publication.23

Differential scanning calorimetric analysis for

curing of FFNR
The temperature of onset (Ti), peak temperature (Tp),
and the temperature of completion of the exotherm
(Tstop) are noted in Fig. 3 (sample FFNR81), and the
data related to the dynamic DSC scans of FFNR51,
FFNR61, FFNR71, and FFNR81, respectively, are
summarized in Table 4. It is evident from the table
that the initiation of the crosslinking reaction lies in the
range of 64.1121C with peak maximum temperature
129, 140, 146, and 153C for samples FFNR51,
FFNR61, FFNR71, and FFNR81, respectively. The
completion of the exotherm was observed in the range
of 185165C. The DH values related to the cure
process were determined from the area of the exotherm peak obtained from DSC analysis taken in
dynamic mode. The preceding data and results of the
DSC scans were found to be in close agreement with
the values given in the literature for phenol formaldehyde resin.26 The peak exotherm (Tp) is shifted to a
higher temperature due to the increased reaction rate
with the higher molar ratio of cardanol and furfural.
Such a trend was observed by various authors during
the studies of the curing of epoxy and phenolic resins.27
The resins prepared by cardanolfurfural resin were
found to show high thermal stability, unlike phenol or
cardanolformaldehyde resins, which were thermally
less stable.16

Mechanical properties of the prepared films

The results on the mechanical properties of the cured
films are tabulated in Table 5. The table indicates that
films of resin FFNR81 were the hardest of all the films,
with a maximum value of 1500 g. The hardness of the
resins was indicative of the C15 long side chain of
cardanol that induced softness in the films, resulting in
an increase in flexibilty. Thus, it is clear now that all of
the films were found to possess good flexibility, which

307

J. Coat. Technol. Res., 12 (2) 303311, 2015

OH

OH
+
Slow
+ CHR-OH

H
CHROH

OH
Fast

CHROH +
+H
C15H29

C15H29

C15H29
OH

OH

OH
+
Slow
+ CHR-OH

C15H29
H

OH +
CH-R

Fast
+H

C15H29
CHROH

C15H29
CHROH

OH

OH

R
CH

+
C15H29

C15H29

C15H29

C15H29

+
+ H

+
C15H29

C15H29

C15H29

OH
+
+ H

OH

OH

OH

OH

RCH

RCH
+

C15H29

OH

R
CH OH

R
+
CH OH2

OH
+
+H

C15H29

CHR

C15H29

+ H2O

C15H29

C15H29

+
H2OH2C R

C15H29

C15H29
CH R
+

+ H2O

OH

O
CH

R
CH

CH

HC

CH

CH

CH

OH

OH

CH

+
+H
CHR OH

OH

OH

OH

CH

HC

OR
OH

OH

OH

CH
OH

Structure of cardanol furfural resin

Scheme 3: Reactions involved during the synthesis of cardanolfurfural-based novolac resin

balances the rigid nature of the cured films by

introducing this chain in the crosslinked structure, thus
increasing the intermolecular spacing. Adhesion of the
films was measured by a crosshatch tape test, and all
the fims showed 100% adhesion, i.e., no square was
lifted by the crosshatch test. The presence of the
hydroxyl groups (OH) in the cardanolfurfural resin
might be responsible for the adhesion property of
cardanolfurfural novolac resins and this could also be
attributed to the high crosslink density and increased
crystallinity due to the aromatic backbone of the
furfural moiety used. All of the films were found to
possess good flexibility due to the presence of C15 long
side chain in the cardanol, and they passed the 1/8-in.
mandrel bend test successfully. All the cured films were
found to be smooth and uniform with good gloss.

308

Impact resistance of all the films was found to be

excellent. Overall, the mechanical properties of the
cured films of the prepared novolac resins showed
promising results for nearly all the samples of novolac
resin for application in surface coatings, as opposed to
phenol or cardanolformaldehyde resins that were
found to have low flexiblity and weak impact resistance.16
Chemical resistance of the prepared films
Table 6 shows the comparative acids, alkalies, and
solvents resistance of the cured films of cardanol
furfural-based novolac resin. A quick perusal of Table 6
clearly illustrates that the films of coatings prepared

J. Coat. Technol. Res., 12 (2) 303311, 2015

from resins FFNR71 and FFNR81 (i.e., mole ratios 1:0.7

and 1:0.8) have offered maximum resistance towards
different solvents, deionized water, and different concentrations of alkalis and acids as compared to the films
from other resin samples. The chemical resistance was
evaluated by solvents such as methyl ethyl ketone
(MEK), xylene, and methanol, and showed no visible
effect on cured films in all cases, irrespective of the
hardener system employed. This could be due to the
increasing polarity of the cured backbone, as discussed
above. This was further supported by increasing the
aromatic content from the furfural moiety and highly
crosslinked structure of prepared novolac resin, as
opposed to phenolformaldehyde or cardanolformaldehyde resin, which were found to exhibit weak
chemical stability.16 The deionized water resistance of
the cured films showed no effect, and maintained

homogeneity even after 6 months of dipping. This could

be attributed to the hydrophobic nature of the novolac
resin backbone, which resisted any possible interaction
between the crosslinked backbone and water. The
novolac resin backbone was further responsible for
giving excellent alkali (5% sodium carbonate) and weak
acid (5% acetic acid) resistance. But the films immersed
in strong acid (2% HCl) and strong base (2% NaOH)
were affected to a large extent. These coated films
showed either dissolution or blistering during the first
3 months and were further affected afterward. This was
evident from the fact that the resultant novolac resin
structure was found to be highly crosslinked, which
would lead to increasing polarity of the system, which is
one of the deciding parameters for adhesion of coating
on the metallic panels and its solvent compatibility.
Thus, the prepared novolac resin system possessed poor

110
100
129.23 C

Heat flow (W/g)

Transmittance (%)

0.2

90
80
70
60
50

0.0
0.2
0.4
0.6

40
0.8

30
4000

71.62 C

3500

3000

2500

2000

1500

1000

500

1.0
40

Wavenumber (cm1)

60

80

100

120

140

160

180

200

Temperature (C)

Fig. 1: FTIR spectrum of cardanolfurfural-based novolac

resin FFNR81

11.0

Fig. 2:

10.0

9.0

8.0

7.0

6.0

Fig. 3: Dynamic DSC scan of sample FFNR81

5.0

4.0

3.0

2.0

1.0

H-NMR spectrum of cardanolfurfural-based novolac resin FFNR81

309

J. Coat. Technol. Res., 12 (2) 303311, 2015

Table 4: Results obtained from dynamic DSC scan

S. no.

Samples

Ti (C)a

Tp (C)b

Tstop (C)c

DH (J/g)

1
2
3
4

FFNR51
FFNR61
FFNR71
FFNR81

64.1
87.2
111
121

129
140
146
153

165
174
181
185

96.2
107
121
83.8

Ti represents temperature of onset, Tp peak temperature, Tstop temperature of completion of the exotherm
a
Temperature of cure initiation
b
Temperature of cure maximum
c
Temperature of end of cure
Table 5: Mechanical properties of the cured films
S. no.
1.
2.
3.
4.
5.

Properties of films

FFNR51

FFNR61

FFNR71

FFNR81

Adhesion (crosshatch test) (%)

Flexibility (mandrel bend test)
Scratch hardness (g)
Gloss (60C angle)
Impact resistance (kg cm)

100
Pass
900
80.9
30

100
Pass
1150
86.8
35

100
Pass
1400
92.5
40

100
Pass
1500
94.9
40

Table 6: Chemical resistance properties of the cured films after 6 months

S. no.
1.
2.
3.
4.
5.
6.
7.
8.

Chemicals

FFNR51

FFNR61

FFNR71

FFNR81

Deionized water
Methyl ethyl ketone
Xylene
Methanol
Sulfuric acid 2%
Acetic acid 5%
Sodium hydroxide 2%
Sodium carbonate 5%

1
2
1
2
6
4
3
4

1
2
1
2
6
4
3
3

1
2
1
1
5
3
2
2

1
1
1
1
5
3
2
1

1 unaffected, 2 loss in gloss, 3 softening observed, 4 slight loss in adhesion, 5 film partially removed, 6 film completely
removed

strong acid and strong base resistance, irrespective of

excellent solvent, weak acid, alkali, and deionized water
resistance. Moreover, the cured film of FFNR81 was
found to exhibit excellent and remarkable chemical
resistance properties compared to the other film samples (see Table 6), except for the strong acid and the
strong base. The results obtained from chemical resistance after 6 months are given in Table 6.

Conclusions
The following conclusions seem to be warranted from
the present findings of the study on the performance
properties of cardanolfurfural-based novolac resins
and their films.
(1)

310

The proposed research might prove to be a

milestone in the field of resins based on renew-

able resources. The synthesized cardanolfurfural-based novolac resin has the potential to
minimize the use of phenol resin based on
petrochemical derivatives like phenolformaldehyde resin because, unlike phenolformaldehyde
resin, these cured cardanolfurfural resins have
better mechanical properties, heat resistance, and
especially chemical resistance, particularly to
alkalies, solvents, and water. Moreover, furfural,
being a product of vegetable origin and available
in virtually unlimited quantities, is a much more
economical aldehyde than formaldehyde. In these
many respects, cardanolfurfural resins are similar to, but superior to, phenolformaldehyde
resins as well as cardanolformaldehyde resins.
Hence, the work is novel. The mechanical and
thermal properties of cardanolfurfural resins
were found to be better when compared with
the literature28,29 on phenolformaldehyde resins.

J. Coat. Technol. Res., 12 (2) 303311, 2015

(2)

(3)

(4)

(5)

Utilization of the prepared cardanolfurfuralbased novolac resin from renewable resources in

the green coatings can thus contribute to sustainable development and will help in realizing the
principles of green chemistry. Thus, the use of
cardanol and furfural in the synthesis of novolac
resin is attractive in view of its low price and
renewable nature.
The mechanical properties of the films of cardanolfurfural novolac resin, such as adhesion,
flexibility, gloss, and impact resistance, were
found to be good, though these films lacked in
hardness.
The chemical resistance properties of the films of
the cardanolfurfural novolacs were found to be
excellent, except in resistance to acids, such as
sulfuric acid in particular.
DSC results showed that the synthesized novolac
resins showed high thermal stability.

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