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International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

Synthesis Cocamide DEA as Green Surfactant from Virgin


Coconut Oil

N Aryanti* , L Khoiriyah, D R Heny, A Nafiunisa, D H Wardhani


Department of Chemical Engineering, Diponegoro University, Semarang, Central
Java, 50275, Indonesia

Email: nita.aryanti@che.undip.ac.id

Abstract. Petroleum-based surfactants are not biodegradable. In this study, a surfactant mad e
from natural ingredients, namely cocamide DEA. Di-ethanolamine (DEA) is one of the
surfactants from non-ionic natural ingredients which has the ad vantage o f b ein g n o nt oxic,
biodegradable, and environmentally friendly. Cocamide DEA is used fo r t h e s yn thesis o f a
wide variety of heterocyclic compounds and has a wide application in the pha rmaceutical,
surfactant, polisher and cosmetic industries. Cocamide DEA is obtained from Virgin Co co n u t
Oil (VCO) which contains fatty acids. Manufacture of Cocamide DEA surfactants by the
Transesterification-amidase process. Transesterification is the process of chemical
transformation of fatty acids reacted with methanol and a catalyst that produces methyl esters.
Amidation is the reaction of the formation of amide compounds between di-ethanolamin e an d
methyl esters (ME). Preparation of surfactant Cocamide DEA from VCO by esterification-
amidase process with a ratio of ME:DEA (1:1, 1:1,25, 1:1,5, 1:1,75 1:2) w/w, variations NaOH
catalyst (0.25%, 0.5%, 0.75%, 1%, 2% and 3%) and operating temperatures (150°C, 160°C,
170°C, 180°C). The study was conducted on the optimization of Transesterification-Amidation
proses, and to analyze the cocamide DEA functional groups with FTIR. The o p t imizat io n o f
Transesterification-Amidation proses about ME:DEA ratio, catalyt concentration, and
temperature of conversion. The result show that the transesterificat io n-amid ase p ro cess o f
cocamide DEA obtained optimum conditions at the ratio ME:DEA = 1:2 w/w, 3% NaOH
catalyst concentration on 180oC.

1. Introduction
Surfactants (surface active agents) are substances added to liquids to increase their dispersion
properties by reducing the surface tension of the liquid. The ability of surfactants to reduce stress is
because the surfactants have an amphipathic molecular structure, which is a molecular structure
consisting of a hydrophilic group and a hydrophobic group [1]. These surfactants are widely applied in
terms of washing and cleaning (clean and washing products).
Surfactants from petroleum which are commonly used so far have the disadvantages of being
non-renewable, non-biodegradable so they are not environmentally friendly [2] [3] [4] [5]. Meanwhile,
surfactants from vegetable oils such as virgin coconut oil (VCO) have the advantage of being
renewable, cleaner and purer [6]. Surfactants are divided into 4 groups based on hydrophilic groups
including anionic, cationic, amphoteric and nonionic [7] [8]. Anionic and nonionic surfactants are the
most widely used [9]. One of the nonionic surfactants that can be synthesized from vegetable oil is di-
ethanolamine (DEA).

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution
of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.
Published under licence by IOP Publishing Ltd 1
International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

Availability of coconut oil in Indonesia is abundant. Indonesia virgin coconut oil are cooperating
with many coconut farmers from Sumatra, Sulawesi and Java. Cocamide DEA is produced from virgin
coconut oil (VCO) which contains fatty acids and is present in large quantities in nature, reac hing 44
million tons [10]. Cocamide DEA surfactant can be obtained from VCO by transesterification-
amidation process. The transesterification process is the chemical transformation process of fatty acids
which are reacted with alcohol (methanol) with the help of a catalyst (base) which produces s maller
molecules and a straight chain, namely (methyl ester) [11] [12]. While Amidase is a reaction betw een
alkanolamine and vegetable fatty acids (methyl esters) to form amide compounds [13].
The study was conducted on the optimization of Transesterification-Amidation proses, and to
analyze the cocamide DEA functional groups with FTIR. The optimization of Transesterification-
Amidation proses about ME:DEA ratio, catalyt concentration, and temperature of conversion. In
addition, this study to synthesis green surfactant with low prices and sustainable raw material can be a
novelty in the field of surfactants, especially the use of concept of eco-friendly chemistry in producing
sustainable surfactant [14].

2. Material and methods


This study was designed to obtain the surfactant cocamide DEA from VCO with amidase process and
saponin extract from lerak (Sapindus rarak) with high purity.

2.1. Materials
The tools used are a three-neck flask, reverse cooler, thermometer, magnetic stirrer
(scilogex), magnetic stirrer bar, water bath, stative clamp and Fourier-transform Infrared
Spectroscopy (FTIR), burette. the ingredients used include analytical grade of diethanolamine
(C4H11 NO), coconut oil used as commercial oil that is Braco®, Methanol (CH3 2OH), sulfuric acid
(H2 SO4 ) 4% w solution, sodium hydroxide (NaOH) 1% w solution, Aquadest, Na2 SO4 anhydrous. All
chemicals were analytical grade and from Merck (Darmstadt, Germany).

2.2. Methods
Virgin Coconut oil (VCO Brand Barco) as much as 200 ml, reacted with 100 ml methanol which
has been mixed with H2 SO4 catalyst (4% by weight of solution) inside reactor (three neck flask)
equipped with a waterbath. The mixture is stirred with a magnetic stirrer at 60ºC for 2 hours to form
methyl ester. Separate the methyl esters from glycerol using separating funnel. Methyl ester which has
separated from glycerol with a separating funnel, neutralized the pH with NaOH. Warm aquadest is
added to the methyl ester to make the remaining methanol, glycerol and other impurities apart from
methyl esters. Add anhydrous Na2 SO4 to the inside separate methyl esters from Na2 SO4 anhydrous and
analysis of initial esters. The research was conducted in duplicate.
Conversion of the cocamide DEA obtained in the amidation process. First, the methyl ester is
reacted with DEA with a weight ratio reacting ME: DEA varied (1: 1, 1: 12,5, 1: 1,5, 1: 1,75 1:20)
w/w) and the addition of NaOH catalyst with varied NaOH catalyst concentrations (0.25%, 0.5%,
0.75%, 1%, 2% and 3%). Then, the reaction was carried out at 160° C for 3 hours, the catalyst used is
NaOH, the reaction takes place in a three-neck flask equipped with a waterbath, the mixture is s tirred
with a magnetic stirrer with a stirring scale on the magnetic stirrer. Diethanolamide formed is analyzed
remaining ester number and analyzed for functional groups by FTIR.

3. Result and discussion

3.1. Analysis of Transesterification Results of Cocamide DEA


Based on figures 1 - 3, it is known that the conversion value of cocamide DEA the highest obtained
through experiment was 82.37%, namely at a ratio of 1:2 methyl esters: di-ethanolamine, 3% NaOH
concentration and 180° C operating temperature.

2
International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

3.1.1. Effect of ME:DEA ratio to cocamide DEA conversion. Observation of the effect of the methyl
ester is reacted with DEA with a weight ratio reacting ME:DEA is shown in Figure 1. In the subs trate
weight ratio varied (1: 1, 1: 1,25, 1: 1,5, 1: 1,75, 1: 2) v/v) with NaOH 3% and 180° C it appears that
the conversion of methyl esters to cocamide DEA tends to increase along with the increase in the
substrate mole ratio to certain limits. The conversion in the mole ratio of methyl ester and
dietanolamine 1: 1 is 78.64% then the conversion increases at a mole ratio of 1: 1.25 by 80.33%. For a
mole ratio of 1: 1.5 the conversion is 81.01% whereas the mole ratio of 1: 1.75 the conversion is
82.37%. The best cocamide DEA conversion was obtained at 1:2 weight ratio reacting ME:DEA w ith
NaOH 3% and 180° C of 82,37%. This is due to the mole ratio of the reagent will affect the shift of the
reaction yield on balance. If the mole of one of the reactants is made excess, it reacts the balanc e w ill
shift to the right so that dietanolamine is produced increase. The reaction mechanism of methyl es ter
and DEA with NaOH catalyst can be describe as follows:

RCOOCH3 + NaOH Æ RCOONa + CH3OH …. (1)


RCOONa + NH(C2 H4 OH)2 Æ RCON(C2 H4 OH)2 + NaOH .…. (2)
RCOOCH3 + NaOH + NH(C2 H4 OH)2 Æ RCON(C2 H4 OH)2 + CH3 OH + NaOH

The second reaction is the reaction between RCOONa and di-ethanolamine (NH(C2 H4 OH)2 ) which
forms di-ethanolamine. Ionized di-ethanolamine react with RCOONa. The reaction mechanism:

RCOONa Æ RCO+ + NaO-


NH(C2 H4 OH)2 Æ N(C2 H4 OH)2 - + H+
RCO+ + N(C2 H4 OH)2 - Æ RCON(C2 H4 OH)2
NaO+ + H+ Æ NaOH
RCOONa + NH(C2 H4 OH)2 Æ RCON(C2 H4 OH)2 + NaOH

In the second reaction, excess DEA will be used di-ethanolamine. The reaction that plays a role in the
formation of di-ethanolamine is
RCO+ + N(C2 H4 OH)2 - Æ RCON(C2 H4 OH)2

Ion N(C2 H4 OH)2 - is the ionization of di-ethanolamine releasing H+. On in this reaction the presenc e of
the N(C2 H4 OH)2 - influential in formation di-ethanolamine.

83
82
Conversion (%)

81
80
79
78
77
76
1 1/1,25 1/1,5 1/1,75 1/2
ME/DEA Ratio (w/w)

Figure 1. The effect of ME:DEA ratio to cocamide DEA conversion at NaOH 3% and 180° C

3.1.2. Effect of NaOH Concentration on Transesterification-Amidation Conversion. In Figure 2. the


greater the percent by weight of the catalyst, so the greater the conversion. The conversion reac hes a
maximum at 3% catalyst weight by conversion amounted to 82.37%. However, at 0.5% catalyst

3
International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

weight the conversion decreased by about 1% due to the ability of the catalyst to break the bonds on
the forming methyl esters reduced diethanolamine. The function of the NaOH catalyst is to break the
bond on methyl ester in order to facilitate the reaction and the formation of more diethanolamide than
without a catalyst. Mechanism of methyl ester amidase reaction with DEA and the help of NaOH
catalyst:

RCOOCH3 + NaOH Æ RCOONa + CH3 OH .…. (3)


RCOONa + NH(C2 H4 OH)2 Æ RCON(C2 H4 OH)2 + NaOH ….. (4)
RCOOCH3 + NaOH + NH(C2 H4 OH)2 Æ RCON(C2 H4 OH)2 + CH3 OH + NaOH

The NaOH catalyst breaks the methyl ester bonds in the first stage of the reaction, the catalyst Ionized
NaOH breaks methyl ester bonds. Ion Na+ binds to the ester group being the OH ion- with a methyl
group to form methanol. First reaction mechanism:

RCOOCH3 Æ RCOO- + CH3


NaOH Æ Na+ + OH-
RCOO- + Na+ Æ RCOONa
+
CH3 + OH - Æ CH3 OH
RCOOCH3 + NaOHÆ RCOONa + CH3 OH

NaOH catalyst is strong alkaline and easy to ionize, Na ion will bind ester ions to RCOONa which
reacts to form dietanolamine. The reaction to form dietanolamide occurs in the second reaction in
which the RCO ion reacts with N ions (C2 H4 OH)2 - form dietanolamide. The greater it is the
concentration of the methyl ester catalyst bond is more easily broken so RCO the easier it is formed
and the greater the resulting dietanolamide. Ion OH- forming methanol, while NaOH is formed again
at the end of the reaction.

Figure 2. Effect of NaOH Concentration on Transesterification-Amidation conversion


at 180° C and 1:2 ratio

3.1.3. Effect of Temperature on the Transesterification-Amidation conversion. In Figure 3. the


influence of temperature on the conversion of reactions, almost all the reaction becomes fas ter w hen
the temperature is raised, because of the heat that is given off increase the kinetic energy of the
reacting particles. Consequently, amount and energy the impact got bigger.

4
International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

Figure 3. Ratio Effect of Temperature on the Transesterification-Amidation conversion


on NaOH concentration 3% and a ratio of 1:2

3.2. Identification of Cocamide DEA


In Cocamide DEA the main absorbance peak seen in the FTIR results Figure 4. in the range 1400-
1800 cm-1 where the peaks show bonding C-H which forms the CH3 (methyl) group. This methyl
group will increase during the transesterification process takes place. Meanwhile, the C = O bond is in
the 1600-1800 range cm-1 there was a change in absorbance before and after the reaction, w hic h w as
during the transesterification process takes place a change in the functional group.
In the FTIR spectrum results in the range 1000-1190 cm-1 show bond O-CH3 on the diethanolamide
ion. Meanwhile, the peak of 2800-3000 cm-1 has occurred the change in the decrease in absorbanc e in
the C = C bond, indicated by the formation of a fairly high C = C group. Can be seen in the image
below.
According to Silverstein et al., (2005) stated that at the peak absorption in the asymmetric and
symmetrical wave area of 2925 cm-1 and 2855 cm-1 indicates the presence of a methylene c ompound
group [15]. From the FTIR spectrum test results sample in Figure 4., this shows the peak of absorption
in the area of 2922.60 cm-1 and 2851.15 cm-1 indicates the presence of a methylene group. Vibration C
= O for unsaturated esters at wave number 1800-1700cm-1 , vibration -CH3 on wave number 1446 cm -1
and O-CH3 vibrations which denotes a cluster biodiesel in the wave figure 1196 cm -1 . The C-O
vibration for the saturated ester is on wave number 1030.98 cm -1 - 1240.08 cm-1 . From the res ults of
the FTIR sample spectrum test, showing the absorption peak in the 1740.97cm wave area indicates the
presence of groups C = O and 1113.49 cm -1, 1167.76 cm-1, 1196.23 cm-1 indicates the presence of the
CO group in this wave number region which indicates the sample contains both saturated and
unsaturated ester groups, absorption peak 1436 cm -1 for the -CH3 group, and 1196.23 cm-1 for Groups
O-CH3 . Next, the ester group will be converted to the inner amide. More research on the manufac ture
of cocamide diethanolamine.

Figure 4. FTIR spectrum for cocamide DEA

5
International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

4. Conclusions
Based optimization of amidification of ME from virgin coconut oil with DEA using NaOH catalyst
were succeessfuly performed. The result show thtat the transesterification process-amidase c ocamide
DEA obtained optimum conditions at the ratio Methyl Ester:Diethanolamine = 1:2 w/w, 3% NaOH
catalyst concentration and 180o C.
In Cocamide DEA the main absorbance peak seen in the FTIR results in the range 1400-1800 c m - 1
where the peaks show bonding C-H which forms the CH3 (methyl) group. This methyl group will
increase during the transesterification process takes place. Meanwhile, the C = O bond is in the 1600 -
1800 range cm-1 there was a change in absorbance before and after the reaction, which was during the
transesterification process takes place a change in the functional group.
In the FTIR spectrum results in the range 1000-1190 cm-1 show bond O-CH3 on the diethanolamide
ion. Meanwhile, the peak of 2800-3000 cm-1 has occurred the change in the decrease in absorbanc e in
the C = C bond, indicated by the formation of a fairly high C = C group. Can be seen in the image
below.

5. Acknowledgments
The author would like to thank Allah SWT, my parents, chemical engineering department at
Diponegoro University for their guidance and all members of the DEA cocamide surfactant
manufacturing practicum for their cooperation so that this paper is well resolved.

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International Conference on Chemical and Material Engineering (ICCME 2020) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1053 (2021) 012066 doi:10.1088/1757-899X/1053/1/012066

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