International Journal of Trend in Scientific Research and Development (IJTSRD)

Volume 8 Issue 3, May-June 2024 Available Online: www.ijtsrd.com e-ISSN: 2456 – 6470

Study on Oxirane Cleavage (Oxirane Ring Opening) of

Epoxidized Cardanol by Methanol and Characterization of Polyols
Bach Trong Phuc, Nguyen Thanh Liem
School of Materials Science and Engineering, Hanoi University of Science and Technology, Hanoi, Vietnam

ABSTRACT How to cite this paper: Bach Trong

The impact of the main process variables (temperature, catalyst Phuc | Nguyen Thanh Liem "Study on
concentration, agitation, ratio of content, time of reaction) on the Oxirane Cleavage (Oxirane Ring
degration of the oxirane ring of epoxidizedcardanol by hydrogen Opening) of Epoxidized Cardanol by
Methanol and Characterization of
active compound (methanol) when a homogeneous acid catalyst used,
Polyols" Published
is analyzed in detail. Cashew Nut Shell Liquid (CNSL), an in International
agricultural by-product abundantly available in tropical countries Journal of Trend in
such as Vietnam, India, is one of the major and economical resources Scientific Research
of naturally occurring phenols. Cardanol a by product of CNSL could and Development
be epoxidized by reacting carbon-carbon double bonds of long (ijtsrd), ISSN: 2456-
unsaturated chain with peracids via the Prileshajev-epoxidation 6470, Volume-8 | IJTSRD64848
process or the conventional process. This paper presents a simple and Issue-3, June 2024,
convenient method to oxirane ring opening of epoxidizedcardanol by pp.306-311, URL:
methanol with preservation of p-toluenesulfonic acid catalyst. The www.ijtsrd.com/papers/ijtsrd64848.pdf
method uses mild reaction conditions: low temperature of 400C –
Copyright © 2024 by author (s) and
500C and low pressure (air pressure). The results shown that the
International Journal of Trend in
oxirane ring opening of epoxidizedcardanol efficiency reacheres 76% Scientific Research and Development
at 500C, stirring rates 1500 rpm, 6% p-toluenesulfonic acid catalyst Journal. This is an
and time of reaction 3h. The product of polyolcardanol is also Open Access article
characterized by FT-IR, 1H-NMR and 13C-NMR. distributed under the
terms of the Creative Commons
KEYWORDS: epoxidizedcardanol, oxirane ring openning, methanol, Attribution License (CC BY 4.0)
polyolcardanol, p-toluenesulfonic acid catalyst (http://creativecommons.org/licenses/by/4.0)

INTRODUCTION:
Polyurethanes (PU) represent an important class of precursor to develop new materials to be used in eco-
polymeric material. It has versatile properties and is friendly process. Cardanol is unique since it contains
suitable for foams, thermoplastic elastomers, a phenolic moiety with an unsaturated 15-carbon side
adhesives, coatings, sealants, and fibers [1]. Most chain having 1 to 3 double bonds. The long chain in
PUs is derived from petroleum resources. However, the cardanol imparts flexibility due to internal
using fossil resources is causing increasingly plasticizing and the reactivity of the hydroxyl phenyl
prominent environmental issues. Therefore, using group of cardanol can be taken advantage of to
renewable monomers and PUs to replace traditional develop a variety of structurally diverse funtional
petrochemical–based monomers and PUs have molecules [11-14]. In recent years, there are many
attracted significant attention [2-4]. Vegetable oils are studies about the chemical modification of cardanol
one of the cheapest and most abundant biological to diol or polyol compounds. For instance, cardanol-
resources; they are a bio-renewable material that has based polyols were prepared by modifying the
many advantages such as low toxicity, inherent unsaturation sites on the 15-carbon side chain with a
biodegradability, and high purity [5]. Among all two-step procedure reported by Suresh of
vegetable oils, cardanol is an agricultural by-product epoxidation, followed by hydrolysis [15]. In this
abundantly obtained from the complete distillation of study, we report synthesis cardanol-based polyol
Cashew Nut Shell Liquid (CNSL), and stands out for (polyolcardanol) from epoxidizedcardanol which is
preparing cost effective materials [6-10]. Cardanol synthesized Vietnamese cardanol with methnol (Me)
extracted from CNSL by via vacuum distillation is an as a ring opener [16, 17].
agricultural byproduct considered very attractive

@ IJTSRD | Unique Paper ID – IJTSRD64848 | Volume – 8 | Issue – 3 | May-June 2024 Page 306
 International Journal of Trend in Scientific Research and Development @ www.ijtsrd.com eISSN: 2456-6470
Experimental
Materials
Epoxidizedcarrdanol (ECD) was synthesized by
reaction of cardanol with glacial acetic acid and
hydrogen peroxide using p-toluenesulfonic acid as a
catalyst, toluene as a solvent [16]. The physico- Fig.1: Scheme of the idealized synthesis route
chemical properties of the ECD are shown in Table of polyolcardanol based on epoxidizedcardanol
1. Characterization of the compounds
Table 1: Physico-chemical properties of The density was determined by Erichsen
epoxidizedcarrdanol (ECD) Pycnometer Model 290 according to the standard
Parameters Value ISO 2611. The viscosity of the compounds was
0 determined at room temperature with a Brookfield
Viscosity (25 C), Cps 30.34 RVT viscometer. The hydroxyl values were
0
Density (25 C) 0.956 determined according to the standard ASTM
Hydroxyl value, mgKOH/g 150.7 D1957-86. The epoxy group content was
Epoxy group content, % 21.45 determined by the direct titation of the compounds
with HBr according to the standard method for oils
Oxirane index, % 7.98 and fats [18]. The Iodine index was determined
Iodine index, mg/g 30.78 according to the stabdard ASTM D5768-02 (Wijs
Humidity, % 2.5 method). Fuorier transform infrared (FT-IR)
spectroscopy was performed on a FT/IR Affinity-IS
Ash, % 2.6
(Shimadzu-Japan) spectometer using NaCl plate at
Methanol (99.5%) from Xilong (China); p- 230C ± 10C. The sample was scaned from 4000 to
toluenesulfonic acid was obtained from Merck 400 cm-1. Proton and carbon NMR (1H-NMR and
13
(Germany); solvent ether and toluene from Xilong C-NMR) spectra of compounds in deuteatred
(Chiana). chloroform (CDCl3) were recorded with a Bruker
400 MHz spectometer (Bruker, Rheinstetten
Methods
Germany) at room temperature.
Synthesis of polyolcarrdanol (PCD)
In a four-necked a round-bottomed reaction flash Results and discussion
equipped with a mechanical stirrer, thermometer Synthesis of the polyolcardanol
sensor, and reflux condenser, epoxidizedcarrdanol The effect of temperature on the oxirane ring
(ECD), p-toluenesulfonic acid and toluene were opening reaction of the epoxidizedcardanol
charged. The mixture was heated to the desired The oxirane ring opening reaction of the ECD was
temperature and time in a constant-temperature water carried out over a temperature range of 400C to
bath. Methanol, was pre-warmed to the same 700C with a step change of 100C. Molar ratio of the
temperature and then quickly added to the flask. After components ECD/Methenol = 1/10. Catalyst is p-
reaction was complete, the product is neutralized, toluenesulfonic acid with content 6% w/w. The
washed with excess distilled water till neutral to stiring rates of 1500 rpm and time of reaction is
litmus and dried over anhydrous sodium sulfate. from 0.5h to 3.5h.The conversion efficiency of the
Finally, toluene was removed by distillation under oxirane ring opening reaction of ECD is calculated
vacuum at 800C for 2h to yield the product. The based on the amount of hydroxyl group formed in
scheme of the idealized synthesis route of the reaction. The results are shown in Figure 2.
polyolcardanol based on epoxidizedcardanol are
shown in Figure 1.

Fig.2: Effect of temperature on the oxirane

ring opening reaction of ECD

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The results in Fig.2 show that the conversion
efficiency (CE) of the oxirane ring opening reaction
of ECD is lowest at 400C and highest at 500C. The
CE of the reaction increases when raising the
temperature, but temperature increases to high the
CE decreases. This can happen because when
temperature high, methanol easy volatile and polyol
group formed is unstable and easy to decompose.
Thatwhy, 500C is the temperature chosen for the
oxirane ring opening reaction of ECD.
The effect of catalyst content on the oxirane ring
opening reaction of ECD
Catalyst is p-toluenesulfonic acid with content Fig.4: Effect of the initial component ratio on
change from 2%, 4%, 6% and 8% w/w. The oxirane ring opening reaction of ECD
reaction was carried out at 500C. Other conditions The results in Fig.4 show that the CE of oxirane
of oxirane ring opening reaction are kept the same ring opening reaction of ECD is lowest at molar
as in the above. The analysis results are shown in ratio ECD/methanol = 1/6 and highest at
Figure 3. ECD/methanol = 1/10. When increasing methanol,
the reaction efficiency increases. However, if it
continues to increase, the efficiency will clearly
decrease. This may be because the amount of
methanol has reached saturation or side reactions
may have occurred. Thus, the molar ratio
ECD/methanol = 1/10 is optimal for the oxirane
ring opening reaction of ECD under the
investigated conditions.
The effect of the stirring rate on the oxirane ring
opening reaction of ECD
The stirring rate in the oxirane ring opening
Fig.3: The effect of catalyst content on the reaction of ECD is changed as follows: 1200 rpm;
oxirane ring opening reaction of ECD 1500 rpm; 1800 rpm and 2100 rpm. The
The results in Figure 3 show that the CE of the temperature of the oxirane ring opening reaction of
reaction is lowest with catalyst was 2%, the highest ECD is 500C and catalyst of 6% p-toluenesunfonic
with catalyst was 6%. When the catalyst increases, acid. The molar ratio of ECD/methanol = 1/10. The
the CE of the reaction increases. However, when analysis results are shown in Figure 5.
the catalyst is too high, the CE decreases. Because
p-toluenesulfonic acid is a strong acid, it easily
causes side reactions to create esters. Therefore, 6%
p-toluenesunfonic acid is optimal content for the
oxirane ring opening reaction of ECD
The effect of the initial component ratio on
oxirane ring opening reaction of ECD
The molar ratio of the initial components to the
oxirane ring opening reaction of ECD is changed as
follows: ECD/methanol = 1/6; 1/8; 1/10; and 1/12
at 500C and catalyst content 6% p-toluenesunfonic
acid. The results are shown in Figure 4.
Fig.5: The effect of the stirring rate on the
oxirane ring opening reaction of ECD
The results in Fig.5 show that the CE of the oxirane
ring opening reaction is lowest when the stirring
speed is 2100 rpm, the highest when the stirring
speed is 1500 rpm. When the stirring speed is
increased, the reaction efficiency increases.

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However, when the stirring speed increases too  The temperature of the reaction: 500C.
high, the efficiency decreases. This may happen  The catalyst content of the reaction: 6% p-
because the reaction system here is heterogeneous
toluenesunfonic acid.
with ECD and toluene being the hydrophobic
phases, and p-toluenesulfonic acid and methanol  The stirring speed of the reaction: 1500 rpm.
being the hydrophilic phases, thus uniform  The time of the reaction: 3h.
dispersion of the substances in the reaction system.
is essential because the reaction will take place on The conversion efficiency of the oxirane ring
the phase interface. With different stirring speeds, opening reaction of ECD with above is 76.18%.
different contact capabilities and phase contact The characterization of the polyolcardanol
times lead to different reaction efficiencies. Thus, (PCD)
the stirring rate of 1500 rpm is the optimal stirring The physico-chemical properties of the PCD
speed for the oxirane ring opening reaction of ECD synthesized according to the above conditions are
with the investigated conditions. shown in Table 2
The effect of the time on the oxirane ring Table 2: Physico-chemical properties of the
opening reaction of ECD. polyolcardanol (PCD)
The time in the oxirane ring opening reaction of Parameters Value
ECD is changed as follows: 0.5h; 1h; 1.5h; 2h; Viscosity (250C), Cps 22.18
2.5h; 3h and 3.5h. the temperature of the reaction is Density (250C) 0.938
500C and catalyst of 6% p-toluenesunfonic acid. Hydroxyl value, mgKOH/g 334.9
The stirring rate of the reaction is 1500 rpm. The Epoxy group content, % 2.15
molar ratio of the initial components as follows: Oxirane index, % 0.8
ECD/methanol = 1/10. The results are shown in Iot index, mg/g 10.15
Figure 6.
Humidity, % 1.3
The results in Fig.6 show that the CE of oxirane Ash, % 0.85
ring opening reaction of CE increases gradually
over time. The highest CE when reaction time is 3h. .FT-IR technique was imployed first to study the
The CE of the reaction decreases when continuing structure of the epoxidizedcardanol (ECD) and
the reaction. This may happen because as the polyolcardanol (PCD). The spectra of ECD and
reaction continues to prolong, a side reaction occurs PCD are depicted in Figure 7.
that hinders the process of opening the ring of the
epoxy group to create a hydroxyl group. Therefore,
the reaction time of 3h is the optimal time for the
oxirane ring opening reaction of ECD.

Fig.7: The spectra of ECD and PCD

Observing the infrared spectra of ECD and PCD, it
Fig.6: Effect of the time on oxirane ring was found that both peaks of the OH group
opening reaction of ECD appeared at 3356 cm-1, showing the presence of the
Thus, the optimal conditions for the oxirane ring phenol hydroxyl group of cardanol, however, at
opening reaction of ECD (synthesis polyolcardanol PCD, the peak area expanded due to resonance. of
(PCD)) as follows: the OH group in the PCD chain. The typical peak of
 The initial component molar ratio of the oxirane the epoxy group at 848 cm-1 and 918 cm-1 of ECD
ring opening reaction of ECD: ECD/methanol = have almost disappeared in the spectrum of PCD. In
1/10. addition, on the spectrum of PCD, peak 1352 cm-1

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 International Journal of Trend in Scientific Research and Development @ www.ijtsrd.com eISSN: 2456-6470
appears, representing the OH group attached to the Observing on the graph of Figure 9, we see that the
hydrocarbon branch chain. peaks in region 55.5 – 54.7 ppm present in the ECD
1 spectrum have almost disappeared from the PCD
H-NMR spectrs of ECD and PCD are displayed in
spectrum. Thus, it can be seen that the epoxy
Figure 8.
groups present at ECD have transformed into OH
groups of PCD.
Conclusion
In this study, the polyolcardanol (PCD) was
synthesized by oxirane ring opening reaction of the
epoxydizedcardanol (ECD) with methanol as a
switching component. The reaction occurs under the
following conditions: initial component molar ratio
ECD/methanol = 1/10; temperature 500C; 6%
catalyst p-toluenesunfonic acid; stirring speed 1500
rpm and time of reaction 3h. The conversion
efficiency of the oxirane ring opening reaction of
ECD is 76.18%. The analysis of FT-IR, 1H-NMR
and 13C-NMR spectra of ECD and PCD showed
that the epoxy groups in ECD have almost
disappeared in the spectrum of PCD and the
spectrum of PCD, peak 1352 cm-1 appears,
representing the OH group attached to the
hydrocarbon branch chain.
Fig.8: 1H-NMR pectra of ECD and PCD
Acknowledgment
In both ECD and PCD spectra in Fig.8, a peak at
The authors would like to thank the National Key
5.2 ppm representing the phenolic hydroxyl group
Laboratory for Polymer and Composite Materials -
is still observed. The peaks at 2.9 - 3.2 ppm are
Hanoi University of Science and Technology for
clearly shown in the ECD spectrum, but in the PCD
helping during this study.
spectrum these peaks have decreased a lot, meaning
that there is a ring opening of the epoxy group to References
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