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CNSL: An environment friendly alternative for the modern coating industry

Article  in  Journal of Coatings Technology and Research · March 2014


DOI: 10.1007/s11998-013-9521-3

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Dinesh Balgude Anagha Sabnis


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J. Coat. Technol. Res.
DOI 10.1007/s11998-013-9521-3

REVIEW ARTICLE

CNSL: an environment friendly alternative for the modern


coating industry
Dinesh Balgude, Anagha S. Sabnis

 American Coatings Association & Oil and Colour Chemists’ Association 2013

Abstract Considering ecological and economical industry, their uses have been overshadowed by eco-
issues in the new generation coating industries, the nomical and ecological aspects of the modern coating
maximum utilization of naturally occurring materials industry. These aspects involve exponentially rising
for polymer synthesis can be an obvious option. In the prices and high depletion rate, handling issues, toxicity
same line, one of the promising candidates for substi- and health hazards of material derived from petroleum
tuting partially, and to some extent totally, petroleum- stocks, and volatile organic compound (VOC) that are
based raw materials with an equivalent or even emitted in the environment during synthesis and
enhanced performance properties, is the Cashew Nut application of petroleum-derived chemistries as they
Shell Liquid (CNSL). This dark brown-colored viscous are volatile in nature. So, considering these issues, it is
liquid obtained from shells of the cashew nut can be necessary to search and explore the new sustainable,
utilized for a number of polymerization reactions due economical, nontoxic, and nonhazardous alternatives.
to its reactive phenolic structure and a meta-substi- One of the possible solutions is the use of bio-based
tuted unsaturated aliphatic chain. Therefore, a wide materials for polymer/resin synthesis. The increasing
variety of resins can be synthesized from CNSL, such worldwide interest in the use of biomaterials is mainly
as polyesters, phenolic resins, epoxy resins, polyure- due to the fact that these materials are derived from
thanes, acrylics, vinyl, alkyds, etc. The present article natural sources which are abundantly available and
discusses the potential of CNSL and its derivatives as their use would also contribute to global sustainability
an environment friendly alternative for petroleum- without depletion of scarce resources. Also, biomate-
based raw materials as far as polymer and coating rials are comparatively easy to handle with no or less
industries are concerned. toxicity and health-related issues. Unlike petroleum-
derived polymers, the polymers synthesized from such
Keywords CNSL, Renewable resources, Resins, bio-based materials can degrade in a controlled way
Functional chemicals, Coatings when they come in contact with the biological envi-
ronment due to the enzymatic action of some micro-
organisms, thus promoting the conversions to biomass,
Introduction methane, carbon dioxide, water, and other natural
substances.1,2 Thus, less environmental impact, ease of
Until now, a number of chemistries have been explored availability, more economical, and easy biodegradabil-
in the coatings industry, such as epoxy, alkyd, poly- ity makes bio-based material an attractive topic for
urethane, phenolic, acrylic, polyester, silicates, etc. academic as well as for industrial research on synthe-
Generally, these chemistries are derived from petro- sizing polymers and functional chemicals for the
leum-based stocks. Though these petroleum-derived coatings industry.3
polymers/resins have played a vital role in the coating The utilization of bio-based materials as such or by
chemical modifications for various applications like
resin synthesis, adhesives, paints, coatings, composites,
D. Balgude, A. S. Sabnis (&) etc., has been well reported.4–10 Such materials include
Department of Polymer & Surface Engineering, Institute cellulose, starch, sucrose, sugar, lignin, plant and
of Chemical Technology, Mumbai 400 019, India animal oils, etc. However, there exists a compound
e-mail: as.sabnis@ictmumbai.edu.in;
such as Cashew Nut Shell Liquid (CNSL), which can
anaghasabnis@rediffmail.com
J. Coat. Technol. Res.

be used as a possible substitute for petroleum-based production of cashew trees throughout the year. There
materials due to its availability, sustainability, cost are a number of other challenges like land preparation,
effectiveness, and reactive functionalities. spacing, fertilizer use, entomological/pathological
Physically CNSL appears as a reddish brown, problems, etc., that need to be taken care of in order
viscous fluid found in shells of cashew fruits of to have maximum production. Also, during processing,
Anacardium occidentale (as shown in Fig. 1) cultivated CNSL is difficult to remove from the shell with high
in a large number of tropical and subtropical countries. yields due to the hard outer shell, the intricate
The tree is native to Brazil and the coastal areas of honeycombed features of the pericarp and the ther-
Asia and Africa and is now being grown extensively in mally sensitive nature of the CNSL. Methods for
India, Vietnam, Mozambique, the Malagasy Republic, removing CNSL from the shell include roasting, hot-oil
Tanzania, Philippines, and other tropical countries.11,12 bath, steam processing at 270C, quick roasting at
In some of these regions, cashew is a popular 300C, cold methods, and the solvent extraction
plantation product, while some others import cashew method.16–18 Though commercially being used, these
nuts for processing. Figure 2 gives world production of methods have some constraints like low yield, poly-
cashew nuts showing the increasing trend in the merization of CNSL at processing temperature em-
production of CNSL from 1960 until now. Among ployed, long extraction times (22–336 h), large
the various countries mentioned above, Vietnam, amounts of solvent, harsh mechanical pretreatment,
India, Nigeria, Cote d\’Ivoire, and Brazil have become etc.19 To overcome these issues, supercritical fluids
the top five cashew nut producing countries all over the
world in 2010 with the production of 1,159,600, 613,000,
594,000, 370,000, and 174,300 metric tons (MT),
1,400,000
respectively.14 Thus considering the increasing produc-
tion of cashew nut from 1960 until now, across the 1,200,000
world, we can consider CNSL as a continuous source Production (tons)
1,000,000
available for industrial exploitation without depletion
of stocks which proves its sustainability. 800,000
Though having worldwide availability, there are
600,000
some challenges in CNSL. For example, the cashew
tree is usually grown from seeds placed directly in the 400,000
field. Seed nuts should be thoroughly dry, clean, and
free from insect or fungal attack. Cashew seeds should 200,000
be sown or planted during the rainy season. Once the 0
rainy season is over, seeds should be stored properly 1961 1965 1970 1975 1980 1985 1990 1995 1998 2000
until the next rainy season before they are planted in Years
the field. If not, they may lose their germination
capacity. As plantation of cashew seeds is seasonal, Fig. 2: World production of cashew nuts (from 1961 to
harvesting is another challenge in ensuring the continuous 2000)15

Cashew apple
(pseudo-fruit)

Spongy
Shell
Cashew Nutshell Liquid
(CNSL)
Almond
OH Cardanol
OH
OH
Cashew Nut OH
(fruit)

Fig. 1: Cashew nut shell liquid origin13


J. Coat. Technol. Res.

have been suggested as an attractive alternative Also, chemically unmodified CNSL has been reported
method by Saito.20 So, with proper agricultural prac- to reduce the corrosion rate of carbon steel by over
tices and optimization of various process parameters 90% due to phenolic hydroxyl which gets adsorbed on
like extraction pressure, extraction temperature, and metal surface.24 This inhibitive property cannot be
mass flow rate of supercritical fluid in the advanced achieved with oils. Due to structural similarity, CNSL
extraction techniques, one can overcome all the chal- and their derivatives can easily replace toxic phenolic
lenges related to the production of cashew tree and compounds used in resin synthesis, like phenols in
CNSL extraction. phenolic resin synthesis, bisphenol-A in epoxy resin
Besides having processing constraints, CNSL and synthesis with improved properties. In some cases,
their derivatives possess a number of technical benefits epoxy resin derived from CNSL can replace conven-
over other renewable oils. Unlike oils, the extracted tional epoxy resin with equivalent or slightly higher
CNSL contains a number of useful phenolic derivatives performance properties. Also, chemically modified
with meta-substituted long chain saturated/unsaturated CNSL can replace hydroxyl functional resins derived
hydrocarbons which makes them suitable for a number from petroleum-based stocks which can be used in a
of polymerization reactions through addition as well as number of applications like polyurethane synthesis,
condensation mechanisms. Also, the combination of crosslinkers, etc., with better performance properties.
aromatic ring and long chain hydrocarbon helps to With esterification, CNSL can replace conventional
maintain the good balance between flexibility and toxic plasticizers like di-octylphthalate (DOP)/di-buty-
hardness properties of the coatings. On this basis they lphalate (DBP)/di-ethylhexylphthalate (DEHP) which
were used in a number of industrial applications, are used in polyvinyl chloride (PVC) processing.
including brake linings materials, laminating resins, Commercially used hindered phenols for antioxidant
adhesives, ion-exchange resins, paint and coating purpose can be replaced by chemically modified CNSL.
resins, foundry chemicals, lacquers, fine chemicals, These are all chemical modifications and their perfor-
hybrid materials, water proofing agents, surface active mance against conventional ones are covered in the
agents, synthetic rubber, wax compounding, etc., as subsequent sections.
shown in Fig. 3.
Due to reactive phenolic hydroxyl, one-step synthe-
sis of epoxy resin with 100% conversion can be Chemistry of CNSL and composition
possible, unlike epoxies derived from oil. Also, of its extraction
CNSL-based epoxy synthesis does not involve the use
of hazardous chemicals like peroxides which are used As an agricultural by-product of the cashew nut
in epoxidation of oils. Thus there are no handling or production, CNSL is one of the major economic
health-related issues in CNSL-based resin synthesis. sources of naturally occurring phenols and is regarded

Lacquers & Varnishes


– Decorative applications
– Protective applications
– Insulation Coatings Other Applications
– Buildings, Furnitures, &
Specialty Polymers & Coatings Automobiles – Foundary Chemicals
– Brake Lining & Clutch Facing
– Anti-biofilm Coating – Laminates
– Crosslinked Polymers – Cement Hardeners
– Molecularly Imprinted Polymers – Diesel Oil
– Fire Retardant Polymers – Adhesives
– Liquid Crystalline Polymers, etc. – Hybrid Materials
– Rubber Compounding
– Age Resistors (Prevent degradation)
Applications of – Vulcanizing Agent
CNSL

Resin Synthesis
Paints & Primers
– Alkyd
– Polyesters – Anticorrosive
– Epoxy – Heat Insulating
– Polyurethanes – Flame Resistant
– Acrylics Additives – Black Enamels
– Phenolics – Antioxidants
– Ion Exchange Resins, etc. – Corrosion Inhibitors
– Colorants & Dyes
– Coupling Agents
– Dispersants
– Bactericides
– Fungicides
– Emulsifying Agents
– Stabilizers
– Accelerators
– Plasticizers

Fig. 3: Potential applications of CNSL and its derivatives21–23


J. Coat. Technol. Res.

Table 1: Physicochemical characteristics of Cashew OH OH


Nut Shell Liquid (CNSL)26 COOH

Parameter Observation
C15H31• C15H31•
Appearance and nature Reddish brown viscous liquid
(a) (b)
Refractive index 1.693–1.686
Specific gravity 0.941–0.924 OH OH
Viscosity (30C) (centripore) 41–56 H3C
Moisture (%) 3.9–6
Ash (%) 1.2
HO C15H31• HO C15H31•
Saponification value 47–58
(mgKOH/g) (c) (d)
Iodine value (mg/100 g) 215–235
Acid value (mgKOH/g) 12.1–15.4 C15H31• = (1)
Free fatty acid (mgKOH/g) 6.1–7.8 8'
(2)
8'
(3)
as a versatile and valuable raw material for polymer 11'
8' 14'
production. CNSL obtained from unroasted shells was
first found by Stadeler to consist chiefly of anacardic (4)
11'
acid which on heating decarboxylated to cardanol and
cardol. Since then, a number of authors have reported Fig. 4: Chemical composition of CNSL: (a) anacardic acid,
on the chemistry, method of extraction, refining, and (b) cardanol, (c) cardol, (d) 2-methylcardol
compositions of the extracted CNSL.25 The physico-
chemical properties of CNSL are stated in Table 1. Epoxidation of the phenolic group can be accom-
On thermal distillation, CNSL yields a number of plished by the reaction of CNSL with epichlorohy-
phenolic derivatives like anacardic acid (6-pentadece- drin.31 The chemical changes during this reaction are
nyl salicylic acid), cardol (5-pentadecenyl resorcinol), similar to those of conventional epoxy synthesis. In this
and 2-methylcardol (2-methyl 5-pentadecenyl resor- regard, Unnikrishnan et al. have studied the use of
cinol) whose main component is cardanol (3-pentade- cardanol in place of a phenol or diphenol, in the
cenyl phenol); a meta-substituted unsaturated synthesis of epoxy system and compared with the
hydrocarbon chain having a chain length of C-15,27 as conventional epoxy. Further, the combination of card-
shown in Fig. 4. anol and bisphenol-A have also been studied and it was
observed that introduction of 20 mol% cardanol into
bisphenol-A resulted in a resin having reduced tensile,
Possible reactions of CNSL and their derivatives impact, and compressive strengths upon curing by a
polyamine hardener but considerable improvement in
CNSL and their derivatives can undergo number of elongation-at-break without much decrease in energy
chemical reactions, some of them being sulfonation, absorption. All possible reactions are shown in Fig. 5.
nitration, esterification, halogenation, etherification,
epoxidation, etc.
CNSL was sulfonated28 to yield alkyl aryl sulfonic CNSL and its derivative-based polymers, resins,
acid or their metal salts. The reaction was carried out and functional chemicals
at 108C using concentrated H2SO4. To prevent
polymerization during sulfonation, an aryl or alkali CNSL, a naturally available material, undergoes similar
group was substituted for hydrogen and the double kinds of reactions as those of phenols due to its phenolic
bonds of the aliphatic side chain were saturated by structures. In addition, the presence of long chain
hydrogenation before treatment with the acid. unsaturated hydrocarbon chain provide additional
Direct nitration of cardanol leads to simultaneous reacting site. Therefore, a diverse range of resins/
oxidation and polymerization reactions. By nitration of polymers can be synthesized using CNSL. It includes
hydrogenated cardanol, 4-nitro and 6-nitro compounds epoxy, alkyd, polyurethane, phenolic resin, vinyl,
were obtained.29 Nitro-derivatives of cardanol are very acrylic, etc. Further, these synthesized resins can be
efficient antioxidants for gasoline, mineral hydrocar- formulated for different types of coatings like modified
bons, petroleum products, and lubricating oils. alkyd-based coatings, epoxy coatings, waterborne coat-
Cardanol esters can be synthesized by reacting ings, UV-curable coatings, modified polyurethane coat-
cardanol with acid chlorides in the presence of alkalis. ings, phenolic coatings, etc. (as shown in Fig. 6).
Thus benzoyl chloride gives benzoyl cardanol. Various Numerous authors have reported on the different
other esters of industrial importance have also been reaction conditions, number of reaction catalyst, and
reported.30 various process parameters to polymerized CNSL.32–35
J. Coat. Technol. Res.

Sulphonation

OR
SO3 +
M

C15H31

H2SO4, Zn, Ca –H2O

OR Es
te
rif
ica
tio
n
n

O
io

OCOC6H5
at

O C15H31
id
ox
Ep

+ HCI
+ NaCl RCl –HCl C15H31

I
C15H31

OC
EC

5C
H OH

6H
Na li
ka

C
OH Al

C15H31
HN
4
O

O
2S

–H 3
R

4
2S
O

2O
–H

OR OH OH

O2N
+
Et C15H31
he C15H31 C15H31
rif NO2
ica
tio

n
io
n

at
itr
N
Fig. 5: Possible reactions of CNSL and their derivatives

Epoxy resins compared to phenalkamine with a similar structure.


It was observed that etherification of phenolic hydroxyl
Aggarwal et al.36 have developed an epoxy-cardanol of cardanol improved the color stability and lowered
resin with better properties as compared to BPA-based the viscosity. However, etherified cardanol was found
epoxy resin in terms of an increase in tensile strength to be less reactive due to absences of phenolic hydroxyl
(31%), elongation (129%), and bond with steel (28%) group as compared to phenalkamine.
and reduced water vapor transmission of the film. Kim et al.38 have successfully synthesized an epoxide-
Further the synthesized resin was formulated for an containing polycardanol by enzymatic route using two
anticorrosive paint and cured with an aromatic poly- different enzymes, viz. lipase and peroxidase. Lipase
amine adduct hardener. The formulated paint was catalysis was used for the epoxidation of the unsatu-
tested for physico-mechanical properties, chemical rated alkyl chains of both cardanol and polycardanol,
resistance and corrosion protection efficiency and and peroxidase catalysis was used for the polymeriza-
compared with conventional epoxy resin-based anti- tion of both cardanol and epoxide-containing cardanol.
corrosive paint. It was found that the modified resin- The product was synthesized by two different routes
based paints exhibit about 25% higher tensile strength including synthesis of epoxide-containing cardanol in
and 15% more elongation than the paints made with presence of lipase, followed by the polymerization of
unmodified resin. Finally, authors have concluded that the phenolic functional groups of cardanol using
the developed resin performed better as binder media peroxidase. Another route involved a synthesis of
for the formulation of anticorrosion paints than the polymerized cardanol from cardanol in the presence
unmodified epoxy resin. of peroxidase and, subsequently, the epoxide-contain-
Huang et al.37 have synthesized a light color card- ing polycardanol from polycardanol in the presence of
anol-based epoxy curing agent from cardanol butyl lipase. The curing of the resulting polymers proceeded
ether, formaldehyde, and diethylenetriamine and thermally at 150C, and yielded a transparent polymeric
J. Coat. Technol. Res.

OH
OCH2CHCH2OH
MDI
P Polyurethane
Ad olya

sis
Epoxy Coating C15H31 Coatings

ly
du mi DBTDL

ro
ct ne O

yd
Modified

H
O
Polyol
Water Soluble Pd, Co Water Borne
C15H31
Binder Coatings
Driers
on
ti ine
iza lam
HO OH ECH NaOH
ral no
ut h a
OH
OH OH HO Ne iet
O O D
C15H31 HCHO Malenization
High Mol.Wt C15H31
Epoxy-Phenolic
180-200°C
Coating Epoxy, 180°C H+ C15H31
OH

C15H31 O O P
NaOh, Reflux Chlorohydrin OH HO Li htha
ns li
Gl eed c an
Modified Phenolic yc Oi hy
OH er l dr
Resin ol , id
OCH2CHCH2OH e ,
IP
DI Pd, Co Modified Alkyd
Hy ,
C15H31 m d Modified Alkyd based Coatings
et rox Driers
ha y Resin
cr eth
yl yl
at
e
UV-Curable Photoinitiator
Coating Material Modified Acrylic
Diluent Coating

Fig. 6: Coatings based on CNSL and its derivatives

film. The pencil scratch hardness of the films was mechanical thermal analysis (DMTA) and thermogravi-
improved compared with that of polycardanol. Owing metry analysis (TGA). The storage modulus (E¢) was
to the epoxide content in the polymerized cardanol, the found to be on the order of 109 Pa and tan d values were
film cured with phenalkamine showed a higher hardness around 90C. A reduction in storage modulus (E¢) and an
value after a relatively short curing time. increase in tan d values on postcuring were observed.
Longo and co-workers39 have synthesized two dif- TGA showed two-stage degradation above 250C; the
ferent novolac resins, named Nov-I and Nov-II, con- first stage being the decomposition of the aliphatic chain
taining an amount of unreacted cardanol of 35 and 20 of the Mannich base and the second stage due to cured
wt%, respectively, by the condensation reaction of epoxy polymer degradation.
cardanol and para formaldehyde using oxalic acid as Tan and Nieu41 have investigated the thermal,
catalyst. The cardanol-based novolacs were tested as dielectrical, chemical, and mechanical properties of a
curing agents for diglycidyl ether of bisphenol-A epoxy newly synthesized carbon fiber composite based on
resin employing 2-ethyl-4-methyl-imidazole as catalyst. tetrafunctional epoxy resin namely N,N,N,N-tetraglyc-
Differential scanning calorimeter (DSC) and thermo- idyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane modi-
gravimetric studies were performed to identify the fied with cardanol. It was observed that the use of
thermal properties of the cured resins. In addition, the cardanol in epoxy resins at cardanol/epoxy molar ratios
epoxy resins cured with the synthesized novolacs were less than 0.3/1 improved the chemical resistance as well
evaluated for tensile tests and synthesized novolacs as the mechanical properties of the composites, such as
and were shown to be worthy of consideration as flexural strength and modulus, tensile strength and
effective epoxy curing agents. modulus, and interlaminar shear strength. Higher
A new class of phenalkamine (Mannich reaction cardanol contents decreased such properties. The
product) from cardanol, formaldehyde, and polyamines maximum values of all properties of the composites
was successfully synthesized by Pathak and Rao.40 The were observed with the epoxy-cardanol resin having a
product was characterized by high-pressure liquid chro- cardanol/epoxy molar ratio of 0.3/1.
matography (HPLC), Fourier transform infrared spectro-
scopy (FTIR), and nuclear magnetic resonance
spectroscopy (1H-NMR). The presence of characteristic Alkyd resins
methylene linkages of Mannich bases at d 3.5–4.0 ppm
was observed by 1H-NMR. Further, the synthesized Madhusudhan and Murthy42 have synthesized a poly-
curing agent was used to cure diglycidyl ether of bisphe- functional compound from cardanol by reacting with
nol-A at room temperature and the curing times were maleic anhydride under various experimental condi-
optimized. The cured samples showed good adhesion tions to yield up to 70% conversion. Further, the
with different metal surfaces, in particular, higher values products were evaluated as intermediates for preparing
were observed with copper due to its high surface energy. water-soluble binders and as alkyd resin modifiers. It
Further, the coatings were analyzed for viscoelastic was concluded that the modification improved resis-
properties and thermal stability properties by dynamic tance to water and chemicals and showed high scratch
J. Coat. Technol. Res.

hardness values (1900 g for water-soluble binder and Especially in the field of polymers, CNSL has primarily
1100 g for modified alkyd compared to 800 g of neat been studied as a modifier of phenol–formaldehyde
alkyd). (PF) resins due to its structural similarity with phenol.
CNSL reacts with formaldehyde under a variety of
conditions, yielding both resole and novolac resins
Polyurethanes depending on the catalyst used. Figure 7 shows the
possible structure of crosslinked CNSL–formaldehyde
Tan et al.43 have investigated the synthesis of carda- resin where R represents the side chain.
nol–glycols (CGs) and polyurethane (CGPU) films The phenolic nature of the constituents of CNSL
thereof. The films were characterized for FTIR and 1H- along with varying degrees of unsaturation in the side
NMR spectroscopy, swelling test and DSC studies. The chain makes it a highly polymerizable substance
content of cardanol in CGPUs was found to be amenable to a variety of polymerization reactions.
inversely proportional to the molecular weight of The most obvious and common method of obtaining
glycols and affected the crosslinking density of the polymeric materials from CNSL is the condensation
films. The reduced crosslinking density strongly reaction with formaldehyde.
affected the swelling property and glass transition Mahanwar and Kale46 experimentally investigated
temperature. Further, the crosslinking of CGPUs was the effect of process condition during replacement of
improved by autooxidation–autopolymerization phenol with CNSL on the properties of novolac and
through the double bonds of the cardanol side chain, resole resins. The addition of CNSL into phenol seems
catalyzed by cobalt salt. to increase reaction times for the preparation of
A class of tough and crosslinked polyurethanes was phenolic resins. This increase in reaction time can be
successfully synthesized from a derivative of CNSL by due to the low reactivity of the CNSL, arising from the
Gopalakrishnan and co-workers.44 A three-stage syn- stearic hindrance caused by the side chain. Experi-
thesis of hydroxyl functional resins for polyurethane mental results revealed that an acid value of CNSL
involved a synthesis of novolac resin using cardanol and played an important role in resin synthesis. When
formaldehyde in three different molar ratios followed by CNSL with acid value more than 10 was used, only a
epoxidation and subsequent hydrolysis to obtain hy- viscous fluid with very low resin content was obtained.
droxyalkylated cardanol–formaldehyde resin. The syn- Finally, the authors concluded that only CNSL with an
thesized hydroxyl functional resin along with a acid value less than 10 was suitable for resin prepara-
commercial polyol (PPG-2000) was used to cure diph- tion; the addition of CNSL leads to a decrease in
enylmethane diisocyanate (MDI). Polyurethane pre- tensile strength but an improvement in the impact
pared using a higher mole ratio of cardanol/ strength and electrical properties of the resole resins.
formaldehyde of hydroxyalkylated cardanol–formalde- Similarly, the effect of partial replacement of phenol
hyde resin was found to possess better thermal and by CNSL in PF resin has studied by Papadopoulou and
mechanical properties than the polyurethane prepared Chrissafis.47 Further, the synthesized resin was com-
from a lower molar ratio. pared with a conventional petroleum-based PF resin.
Asha and co-workers45 have established a one-pot The resins were characterized for physicochemical and
synthetic step to prepare UV-curable urethane–meth- thermal properties. Wood panels impregnated with
acrylate crosslinkers from cardanol. The methodology these resins were also evaluated for thermal properties
involved an end capping of isophorone diisocyanate with by DSC from an end application point of view. The
one equivalent of hydroxyethyl methacrylate followed DSC measurements revealed that the wood reduces
by condensation with cardanol. The structures of the the curing temperature of both resins, but it has greater
resins were characterized by FTIR, 1H-NMR, 13C-
NMR, matrix-assisted laser desorption/ionization time
of flight (MALDI-TOF) spectroscopies, and size exclu- OH
OH
sion chromatography (SEC). Further, the synthesized H2 H2
C C
acrylate oligomer was formulated for UV-curable coat-
ings. The experimental results revealed that the hydro-
gen bonded crosslinkers based on cardanol and its
derivatives had higher double bond conversion when R R
compared to a nonhydrogen bonding standard such as H H
hexanediol diacrylate (HDDA) under identical condi- C C
tions. The temperature effects on the hydrogen bonding
and thereof on the curing process were also investigated.
HO R

Phenolic resins
H2C

CNSL has potential industrial applications such as for


resins, friction lining materials, and surface coatings. Fig. 7: Crosslinked structure of CNSL-formaldehyde resin
J. Coat. Technol. Res.

effect on the CNSL-modified PF resin (PCF) where it polymer blend was found to be composed of a soft solid
brings a reduction of 7C. In the case of the PF material and insoluble in ordinary solvents. Samples
standard resin this reduction corresponds to only 3.6C. were characterized through X-ray scattering, FTIR,
It was proven that, although the neat PCF cured at electrical conductivity, and pressure sensitivity mea-
longer time and higher temperature than a conven- surements. FTIR results indicated that the insertion of
tional PF resin, wood affects it more significantly, PANi into the blends did not change the chemical nature
resulting in the equalizing of their curing performance. of the resin. According to wide-angle X-ray scattering
Further, the adhesion strength of synthesized resins results, PANi was dispersed homogeneously in the final
was investigated by their application in plywood polymer samples which improved the sensitivity of the
production. The plywood panels were tested for their electrical conductivity to pressure variations. Pressure
shear strength and wood failure performance while sensitivity and electromechanical analysis indicated that
their free formaldehyde emissions were determined the produced blends could be used as pressure-sensing
with the desiccator method. This was a novel finding materials. Among the tested materials, the blend con-
that manifests the possibility of replacing a conven- taining 5 wt% PANi presented a larger variation of
tional PF resin with a CNSL-modified one in the conductivity (340%). The increase of the PANi concen-
plywood production, without changing any of their tration led to a decrease in the conductivity variation.
production conditions and with improvement to their This could be related to the increasing number of contact
overall properties. points among the PANi chains.
The various reaction parameters like reaction kinet- A number of researchers have reported on the
ics, reaction mechanism, composition of resin for acid synthesis of epoxidized cardanol-based novolac type
as well as alkali catalyzed cardanol-based phenolic phenolic resins.56–58 Though having several outstand-
resins have been extensively studied by a number of ing characteristics, epoxy resins exhibit a low impact
authors.48–52 resistance in their cured state which limits the appli-
Eswaran and co-workers53 have demonstrated a cations of epoxy resins. To alleviate this deficiency,
novel methodology for the synthesis of a new series of epoxy resins were modified by the incorporation of a
CNSL/cardanol-based ‘‘high ortho’’ novolac copoly- carboxyl-terminated copolymer of butadiene and acry-
mers, used as photoresists for microlithography. The lonitrile (CTBN).59–62 In this regard, Yadav et al.63
authors have used gel permeation chromatography have tried to produce the modified epoxy matrices
(GPC) and both 1-D and 2-D NMR spectroscopic based on cardanol and improved its impact resistance
techniques to elucidate the exact microstructure of by physical blending with CTBN. Further, CTBN
synthesized copolymer and to calculate the percentage blended epoxidized novolac resin was cured with a
incorporation of different monomers in the polymer stoichiometric amount of polyamine curing agent. The
microstructure. The lithographic performance of pho- formation of various products during the synthesis of
toresists using novolac resins based on cardanol (frac- cardanol-based novolac resin, epoxidized novolac
tionated CNSL) and diazonaphthoquinone ester was resin, and blending of epoxidized novolac resin with
also evaluated. CTBN has been studied by FTIR analysis. The number
A novel phenolic type of thermoset resin with average molecular weight was determined by GPC
improved mechanical and toughness properties was analysis. The blend sample, having 15 wt% CTBN
successfully synthesized by Cardona et al.54 The concentrations, showed minimum cure time and the
modification involved a copolymerization of phenol most thermally stable system.
with cardanol at different weight ratios. The modified
phenolic resins (CPF) were prepared at various molar
ratios of total phenol (phenol with cardanol) to
formaldehyde. CPF resins with maximum content of Miscellaneous coating materials
40 wt% of cardanol were synthesized and used. Both
resins (CPF/PF) were mixed in different proportions, ANTIBIOFILM COATINGS: Some species of natural
and their thermal and mechanical properties were then unsaturated hydrocarbon phenols such as cardanol and
established. An increase in the content of cardanol some component of lacquer tree sap (sap extracted from
resulted in a proportional increase of the flexural lacquer tree) have been reported to have an anti-
strength and fracture toughness together. The results biofouling effect. Kim et al. reported polymerization of
obtained by the DMA analysis of the post cured resin cardanol by enzymatic reaction and its potential
CPF/PF blends revealed a decrease in the crosslink application as antibiofilm coating material.64
density and Tg values with increasing cardanol content Choi et al.65 have studied an antifouling property of
and also with the decreasing total phenol/formalde- newly synthesized polydimethylsiloxane (PDMS) matri-
hyde molar ratio. This could be due to the flexibility ces impregnated with natural unsaturated hydrocarbon
enhancement by introduction of cardanol inside the phenols, i.e., urushiol from the sap of natural lacquer
phenolic molecular network. tree and a mixture of cardol and cardanol from refined
Souza et al.55 have developed cardanol-based pheno- CNSL. Incorporation of naturally available unsaturated
lic resins and blended them in situ with polyaniline phenols showed excellent antimicrobial property to
(PANi) for pressure-sensitive applications. The final both Escherichia coli and Saccharomyces cerevisiae.
J. Coat. Technol. Res.

PROCESSABLE AROMATIC DIAMINE: More and co- 100


workers66 have synthesized a processable aromatic
diamine monomer, viz., 4-(4¢-aminophenoxy)-2- 90
pentadecylbenzenamine containing pendant pentadecyl
80
chain from CNSL for electronic applications. A series of
new polyazomethines containing flexibilizing ether 70
linkages was synthesized by polycondensation of 60
synthesized diamine monomer with commercially

Wt%
available aromatic dialdehydes viz., terephthaldehyde 50
(TPA), isophthaldehyde (IPA), and varying mixtures of
40
TPA and IPA. Inherent viscosities and number average
molecular weights of (co) polyazomethines were in the 30
range 0.50–0.70 dL/g and 10,490–40,800 (GPC, b
20
polystyrene standard), respectively, indicating the
a
formation of medium to reasonably high molecular 10
weight polymers. Polyazomethines containing pendant
100 200 300 400 500
pentadecyl chains were found to be soluble in common
organic solvents such as chloroform, dichloromethane, Temperature (°C)
tetrahydrofuran, pyridine, m-cresol and could be cast into Fig. 8: TG curves of the polycardanol by solvent-free
transparent and stretchable films from their solution in polymerization (a) and by liquid-phase polymerization (b)
chloroform. Polyazomethines exhibited glass transition
temperatures (Tg) in the range 21–48C. The observed
depression of Tg could be ascribed to the ‘‘internal MICROBIAL CATALYZED POLYMER: Kim et al.69 have
plasticization’’ effect of pentadecyl chains. The successfully carried out an oxidative polymerization of
temperature at 10 wt% loss (T10), determined from cardanol in water–organic solvent mixtures using a
TGA in nitrogen atmosphere of polyazomethines was in fungal peroxidase from Coprinus cinereus (CiP). So far,
the range 434–441C indicating their good thermal only uneconomic plant peroxidases, such as soybean
stability. peroxidase (SBP), have been used to polymerize
cardanol. The fungal peroxidase used was easily
FIRE RETARDANT MATERIAL: The recognition of produced by cultivating C. cinereus, and was purified
toxicity and environmental persistence of halogenated by ultrafiltration and size exclusion chromatography.
flame retardant (FR) materials has prompted the Microbial CiP-catalyzed the cardanol polymerization
reduction in their usage across the globe. There is an as efficiently as SBP. The effects of reaction
immediate need for new types of nontoxic and temperature and peroxide concentration on the CiP-
effective FR produced preferably through sustainable catalyzed polymerization of cardanol were investigated
routes. In this regard, Ravichandran et al.67 have in aqueous 2-propanol. It was found that a low reaction
reported the synthesis and characterization of a new temperature of 10 and 15C increased the polycardanol
polyphenolic FR material-based cardanol. Cardanol yield (to 91%) and the hydrogen peroxide feed rate
was polymerized in aqueous media using various types was found to affect the initial reaction rate and the final
of oxidants. The thermal properties of the resulting conversion. Finally it was concluded that the microbial
polymers were investigated. Polycardanol synthesized CiP could be more useful for the synthesis of a range of
using a specific type of oxidant exhibited good thermal polyphenols from renewable resources than plant
stability and low heat release capacity. Finally, authors peroxidases.
concluded that the preliminary results obtained from
the study were quite promising and indicated the COPOLYMER CURING SYSTEM: Rao et al.70 have
possibility of synthesizing new types of FR materials developed a new copolymer curing system based on
from bio-based phenols. newly synthesized monofunctional benzoxazine (CBO)
and hydroxyl functionalized benzoxazoline monomer
CROSSLINKED POLYMER: A novel crosslinked polymer (HBO), 2-(4-hydroxy phenyl)-2-oxazoline from
from cardanol was synthesized easily by Bai et al.68 cardanol derivatives. Further, the curing system was
through solvent-free polymerization with FeCl3. The evaluated for thermal and mechanical properties by
methodology involved grinding of cardanol and varying proportions of CBO and HBO in copolymer
anhydrous FeCl3 powder using a glass pestle in a system. A significant reduction in curing temperature
mortar at ambient temperature and solvent-free was observed from thermal studies and an increase in
condition, yielded up to 80% in 5 min. It was heat of polymerization value with incorporation of
concluded that the rigid structure of conjugated HBO was also noted. The activation energy of
condense rings improved the thermal stability of the cardanol benzoxazine was found to reduce with
polymer which was in good agreement with incorporation of 25 mol% of hydroxy benzoxazoline
thermogravimetric graphs as shown in Fig. 8. due to the catalytic effect of OH group lowering the
J. Coat. Technol. Res.

activation energy. The flexible cardanol benzoxazine polycondensation in N,N-dimethylacetamide. The


polymer displayed a lower storage modulus of 2.7 9 solubility of poly(amideimide)s in N,N-dimethylacet-
108 (Pa) and a tan d of 104C, with incorporation of amide, 1-methyl-2-pyrrolidinone, pyridine, and m-cresol
rigid hydroxy benzoxazoline monomer in the at room temperature was found to be significantly
copolymers exhibiting significant enhancement of improved by incorporation of pendant pentadecyl chains.
these values. The width of tan d peak of copolymers In addition, the synthesized polymer was characterized for
was found to increase, suggesting an enhancement of wide-angle X-ray diffraction, while thermal stability was
toughness value. determined by TGA in nitrogen atmosphere. From the
experimental results, the authors concluded that the
WATER-SOLUBLE MANNICH BASES: Ramasri et al.71 thermal stability of poly(amideimide)s was excellent.
have synthesized water-soluble Mannich bases from Also, a glass transition temperature of poly(amideimide)
cardbisphenol, a reaction product of distilled cardanol was in the range 162–198C. It was observed that the
and phenol by Mannich reaction, as shown in Fig. 9. plasticization effect of attached pentadecyl side chains
The effect of electrodeposition parameters on the induced the depression of Tg.
film formation from synthesized binders and from the
pigmented composition was studied. It was found that MOLECULARLY IMPRINTED POLYMER: Recently, Philip
the polymers gave uniform coatings with good mechan- et al.73 have used monomers from CNSL to develop
ical properties and the pigmented systems exhibited molecularly imprinted polymers. The extracted CNSL
high resistance to organic solvents and excellent was used to synthesize anacardanyl acrylate (AnAcr)
corrosion resistance properties. and anacardanyl methacrylate (AnMcr) monomers and
were characterized by FTIR and 1H-NMR. Different
POLY(AMIDEIMIDE): A novel class of aromatic diacy- imprinted bulk polymers based on AnAc, AnAcr, and
lhydrazide monomer was successfully synthesized from AnMcr functional monomers were separately
cardanol by More et al.72 The synthesized monomer was copolymerized in toluene with ethylene glycol
used to developed a new series of poly(amideimide)s dimethacrylate and divinylbenzene as crosslinkers,
containing flexibilizing ether linkages and using racemic propranolol as a model template. The
pendant pentadecyl chains by a two-step solution experimental results showed that the AnAc-based
polymer revealed a meager rebinding ability, the
imprinted polymers made from AnAcr and AnMcr
OH displayed highly specific propranolol binding. At a
polymer concentration of 2 mg/mL, AnAcr- and
AnMcr-based imprinted polymers were able to bind
H over 50% of trace propranolol. Under the same
(CH2)7 C (CH2)6CH3 condition propranolol uptake by the two nonimprinted
OH control polymers was less than 20%.

Cardbisphenol Adhesives

Kim74 developed CNSL–formaldehyde (CF)-based


2-ethylaminoethanol
0 to –5°C
resin and its alloy with polyvinyl acetate (PVAc) resin
HCHO for the maple face of the veneer bonding on plywood.
The CF resin was used to replace urea–formaldehyde
HO (UF) resin in the formaldehyde-based resin system in
OH order to reduce formaldehyde and VOCs emissions
from the adhesives used between plywoods and fancy
N
veneers. The use of PVAc was found to introduce
reactive sites in the CF resin. The green adhesives with
(CH2)7
H
C (CH2)6CH3
varying percentages of PVAc resins such as 5, 10, 20, and
30% were evaluated for surface bonding strength by
OH
Universal Testing Machine (UTM) in the tensile mode,
light microscopy, scanning electron microscopy, form-
aldehyde emission test, and a VOC analyzer test. The
CF/PVAc resins showed better bonding than the com-
N mercial natural tannin adhesive with a higher level of
HO
Mannich base wood penetration, as shown in Fig. 10.
The bonding strengths of the nontreated (before
Fig. 9: Mannich Bases from cardanol for cathodically boiling), engineered flooring samples made using CF/
electrodepositable system PVAc hybrid adhesives were considerably higher than
J. Coat. Technol. Res.

Non-treated styrene and methyl ethyl ketone peroxide (MEKP)


After bonding have shown low impact resistance and flexibility in the
final cured state. In this regard, some of the researchers
20 have reported the use of cardanol derivatives as
Bonding strength (kgf/cm2)

renewable plasticizers/flexibilizers to achieve the re-


quired properties.
15 Greco et al.77 have studied two different plasticizers
obtained by esterification of the cardanol hydroxyl
group (cardanol acetate) and further epoxidation of
10 the side chain double bonds (epoxidated cardanol
acetate). The synthesized renewable plasticizer was
characterized for DSC to study the miscibility with
5
PVC. The miscibility was correlated to the chemical
structure of plasticizer by means of the Hansen
0 5 10 15 20 25 30 solubility parameter analysis. Results obtained indi-
PVAc content in CNSL–formaldehyde/PVAc green adhesive cated that esterification of cardanol yields a partial
miscibility with PVC, whereas esterification and sub-
Fig. 10: Bonding strength between the face of the fancy sequent epoxidation yield a complete miscibility with
veneer and plywood substrate in engineered flooring: PVC. Therefore cardanol acetate, obtained by solvent-
CNSL–formaldehyde (CF) resin and CF/PVAc green adhe- free esterification of cardanol, was used as a secondary
sives
plasticizer of PVC. Mechanical and rheological anal-
ysis showed that the cardanol acetate can partially
replace commercially used di-ethyl-hexyl-phthalate
those of the CF resin. With increasing PVAc content, (DEHP) plasticizer in PVC formulation.
the bonding strength was increased up to 20% of PVAc
content.
Lee et al.75 have studied the properties of green Coating additives
adhesives based on tannin (a naturally occurring
phenolic compound) and CNSL for the replacement ANTIOXIDANT AGENT: Dantas et al.78 have synthesized
of conventional formaldehyde-based toxic and hazard- novel tert-butyl substituted phenolic compounds from
ous adhesives in indoor environments. CNSL at ortho and para position, through simple and
low cost methodology. The electron donor character of
the substituent increased the electronic density of the
Laminating resins phenolic oxygen atom, and hence, yielded a good
proportion between the captive and the captor radicals
Sridhar et al.76 have synthesized a series of resole which helped to retard/inhibit the oxidative
resins from distilled multivalent phenol obtained dur- degradation as compared to commercially available
ing the carbonization process of a lignite source, along additives.
with other phenolic derivatives like cardanol. They Additionally, an antioxidant property of newly
established a low cost method for making electrical- synthesized phosphorated cardanol on the mineral oils
grade laminate from the synthesized resin on a NH10 and NH20 was investigated by Facanha et al.79
laboratory scale. The properties of the resoles were using TGA. It was found that the addition of 1.2–
evaluated and found to be similar to that of pure 2.0 wt% of phosphorated cardanol compound to the
phenol (C6H5OH) resins. The resole varnishes pre- mineral oils improved their thermal oxidative stability
pared were used for making cotton paper phenolic on 14–18C, respectively. The occurrence of major
laminates by hand impregnation and the compression thermal degradation events at higher temperatures
molding technique. The paper laminates were evalu- (Tmax) on additivated oils confirmed an antioxidant
ated for physical, chemical, mechanical, and electrical property of phosphorated cardanol compound.
properties. The experimental investigations indicated Lomonaco et al.80 reported on the synthesis of
that the distillate of multivalent phenol can be a useful phosphorylated compounds derived from cardanol and
inexpensive substitute for conventionally used phenols its application as antioxidants for biodiesel. These
in the manufacture of P3 grade laminates. compounds were added in biodiesel samples in three
different concentrations (500, 1000, and 2000 ppm) and
their antioxidants activities were tested by TGA by
Modifying agents for resins and plastics evaluating their integral procedure degradation tem-
peratures (IPDTs). The results showed that the addi-
Although providing excellent application properties, tion of new antioxidants increased the thermal stability
some of the resins like PVC, low molecular weight of biodiesel, making this biofuel more resistant to the
epoxies, and unsaturated polyesters when cured with thermo-oxidative process.
J. Coat. Technol. Res.

COLORANTS AND DYES: CNSL and its derivatives have Chemical dispersant serves to aid in the wetting of the
been found to be excellent raw materials for the pigment particles, adjust the surface charges of the
preparation of colorants and dyes. A number of azo pigment particle to prevent flocculation, and reduce
compound-modified cardanol-based dyes have been the viscosity. In this regard, Suryanarayan et al.85 have
well reported as a colorant for polymer/plastic and studied the sodium salt of sulfonated CNSL as a
coatings.81,82 dispersant for china clay and calcium carbonate and
Similarly, Thamyongkit and co-workers83 success- compared it with the conventional dispersant
fully synthesized a novel bis (azo) dye from the (polyacrylate) used in paper mills. Finally, the
coupling of cardanol with a series of diazotized properties of coated papers were studied and it was
aromatic amines and diamines. The dyes were highly found that the bio-based dispersant gave better results
soluble in a variety of common organic solvents and compared to conventional one at an optimum dose of
gasoline as a consequence of the cardanol unit. Based 0.8%.
on the colorimetric analysis, the practical concentra-
tion of the synthesized dye that gives the most similar COUPLING AGENT: The term coupling agent generally
gasoline color compared to that of the commercial one applies to silicon-containing species capable of forming
was 6 or 18 ppm. Further from experimental results of chemical linkages between dissimilar materials. The
stability and solubility of synthesized dye in gasoline materials to be linked are often organic polymers and
91, authors concluded that the synthesized dye can be inorganic fillers, as in pigmented coatings, although
successfully used as a coloring agent in gasoline 91. silane coupling agents can also be useful with other
kinds of fillers and polymers. Small amounts of silane
CORROSION INHIBITOR: Philip et al.84 have reported a coupling agents, used at an interface, can greatly
mechanism of interaction of CNSL with metallic improve the mechanical properties of the coating.
substrate and their effect on the dissolution rate of Silane coupling agents are found in a broad range of
SAE 1008 carbon steel in CO2 saturated NaCl applications as varied as metal coatings, dental
solution. It was observed that CNSL acts as an materials, and contact lenses.86
anionic inhibitor at higher solution pH (i.e., a basic In this regards, Tanaka et al.87 have developed a
type inhibitor). The phenoxide ions, R–C6H4–O , of cardanol-modified silane coupling agent, by reacting
the CNSL inhibitor was adsorbed on SAE 1008 carbon cardanol or a derivative thereof with an epoxy silane
steel surface in aqueous CO2 saturated 3% NaCl coupling agent (3-glycidoxypropyl trimethoxy silane)
solution by electrostatic interaction as shown in or an isocyanate silane coupling agent (c-isocyanato-
Fig. 11. propyl trimethoxy silane/c-isocyanatopropyl triethoxy
silane/c-isocyanatopropyl methyl diethoxy silane/c-iso-
DISPERSANT: The principal reasons for applying cyanatopropyl methyl dimethoxy silane) which can
pigmented coating to paper and paperboard are to improve strength and toughness by improving adhesion
improve printability and appearance. The simplest at an interface between a filler and a cellulose resin
form of coatings contains a pigment and a binder to when being used as an surface treatment agent
bind the pigment particles both to one another and to
the base sheet of paper. It is very important that the
pigment be fully dispersed to ensure satisfactory Conclusion
performance and to fully contribute to the properties
of the coated paper. A number of systems are used for CNSL, one of the major sustainable resources, mainly
pigment dispersion, all of which involve the addition of extracted by hot-oil and roasting process, contains
chemical dispersant and the use of mixing equipment. number of useful phenolic derivatives like cardol,
cardanol, 2-methyl cardol, and anacardic acid with
meta-substituted unsaturated hydrocarbon chain
(chain length of C15). The combination of reactive
R R R phenolic structure and unsaturated hydrocarbon chain
makes CNSL a suitable starting material to synthesize
various resins like epoxy, alkyd, polyurethanes, acryl-
ics, phenolic resins, etc. In addition, a number of other
useful products, such as modifiers like flexibilizer and
- - - reactive diluents, adhesives, laminating resins, antiox-
0
0
0

idants, colorants and dyes, etc., have also been


+ + + developed from CNSL and its derivatives. So, consid-
ering the high depletion rate of petroleum-based
Metal
stocks and the range of possible applications, CNSL
Fig. 11: Electrostatic adsorption of the anionic corrosion can be accepted as a greener and sustainable
inhibiting CNSL to positively charged SAE 1008 carbon approach for future expansion in the modern coating
steel surface industry.
J. Coat. Technol. Res.

Future trends 6. Ferrer, CB, Hablot, E, Garrigos, MC, Bocchini, S, Averous,


L, Jimenez, A, ‘‘Relationship Between Morphology, Prop-
Due to availability of unsaturation in the long chain erties and Degradation Parameters of Novative Biobased
Thermoplastic Polyurethanes Obtained from Dimer Fatty
and reactive phenolic hydroxyl group of CNSL and
Acids.’’ Polym. Degrad. Stab., 97 1964–1969 (2012)
their derivatives, a number of functional groups like 7. Oliveira, WD, Glasser, WG, ‘‘Multiphase Materials with
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Benzene Polyols Synthesized from Vegetable Oils: Depen-
solid coating formulations as it can act as a reactive dence of Physical Properties on Structure.’’ J. Appl. Polym.
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