Efficient greener methodology for the preparation of bio-based phase change materials from lipids

Article abstract of DOI:10.1080/10426507.2020.1845681

In the present work, a new, highly efficient and simple strategy has been developed for the synthesis of long chain esters from fatty acids and fatty alcohols as phase change materials. Equivalent amounts of the selected starting compounds were taken to the esterification reaction at 110 °C in a solventless medium. In order to catalyze the esterification reaction, non-hygroscopic triphenylphosphine-sulfur trioxide adduct was used (0.83 mmol%) which is an easily accessible compound. The relevant reaction was completed in a very short time (2 h) and under optimized esterification conditions, excellent conversion were reached. The targeted mono ester compounds (15 examples) were obtained in good to excellent yields even after a simple crystallization step (72-99%). Additionally, a catalyst reuse investigation and study covering the scale-up production of stearyl stearate was also carried out. The triphenylphosphine-sulfur trioxide catalyzed solvent free process can compete with existing processes and proved to be a cheaper, practical and environmentally-friendly method for the esterification of fatty acids and alcohols.

Full text of DOI:10.1080/10426507.2020.1845681

Phosphorus, Sulfur, and Silicon and the Related Elements
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Efficient greener methodology for the preparation
of bio-based phase change materials from lipids
Ayhan Yıldırım & Kaan Kıraylar
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preparation of bio-based phase change materials from lipids, Phosphorus, Sulfur, and Silicon and
the Related Elements, DOI: 10.1080/10426507.2020.1845681
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2020.1845681
Efficient greener methodology for the preparation of bio-based phase change
materials from lipids
Ayhan Yıldırım and Kaan Kıraylar
ꢀ
Faculty of Arts and Sciences, Department of Chemistry, Bursa Uludag University, Bursa, Turkey
ABSTRACT
ARTICLE HISTORY
Received 28 July 2020
Accepted 30 October 2020
In the present work, a new, highly efficient and simple strategy has been developed for the syn-
thesis of long chain esters from fatty acids and fatty alcohols as phase change materials.
Equivalent amounts of the selected starting compounds were taken to the esterification reaction
at 110ꢀC in a solventless medium. In order to catalyze the esterification reaction, non-hygroscopic
triphenylphosphine-sulfur trioxide adduct was used (0.83 mmol%) which is an easily accessible
compound. The relevant reaction was completed in a very short time (2 h) and under optimized
esterification conditions, excellent conversion were reached. The targeted mono ester compounds
(15 examples) were obtained in good to excellent yields even after a simple crystallization step
(72-99%). Additionally, a catalyst reuse investigation and study covering the scale-up production
of stearyl stearate was also carried out. The triphenylphosphine-sulfur trioxide catalyzed solvent
free process can compete with existing processes and proved to be a cheaper, practical and envir-
onmentally-friendly method for the esterification of fatty acids and alcohols.
KEYWORDS
Esterification; renewable
resources; green chemistry;
triphenylphosphine-sulfur
trioxide complex; wax ester;
phase change materials
GRAPHICAL ABSTRACT
Introduction
esterification reactions between long chain fatty acids and
long chain fatty alcohols, several catalytic methods have
Due to the rapid depletion of fossil resources (which are
known as biomass that has undergone transformations over
periods of millions of years), as well as increased environ-
mental concerns, an inevitable trend has begun toward bio-
mass-based raw materials with renewable and biodegradable
properties.[1,2] Animal and vegetable originated fats and oils,
one of the most important components of these materials,
have been considered as important renewable feedstock for
the synthesis of versatile oleochemicals.[3–5] Moreover, cata-
lytic chemical esterification or transesterification reactions of
fats and vegetable oils with long chain alcohols to produce
ester compounds as bio-based phase change materials
(PCM) has become popular both for scientific and industrial
[7,8]
been employed which have also some drawbacks.
Some
of these drawbacks are the excessive use of one of the
reagents to achieve high ester yields, the preference of
metal-based expensive catalysts, the use of toxic organic sol-
vents and the isolation of the product can be rather trouble-
some.[6,8] In our recent study, we have developed a highly
environmentally friendly method suitable for the synthesis
of wax esters using an ionic liquid as a catalyst.[9]
Due to the high cost of energy production and the rapid
increase in energy demand, it is very important to use
energy resources efficiently and to store the produced energy
properly for later use.[10] Therefore, in order to store ther-
community in recent years.[6–9] In order to accelerate the mal energy effectively and environmentally, advanced
ꢀ
Faculty of Arts and Sciences, Department of Chemistry, Bursa Uludag University, Bursa, Turkey.
CONTACT Ayhan Yıldırım
yildirim@uludag.edu.tr
Supplemental data for this article can be accessed here.
ß 2020 Taylor & Francis Group, LLC

2
A. YILDIRIM AND K. KIRAYLAR
technological studies must be continued.[11] Substances used solvent-free method, the targeted long chain fatty acid esters
were obtained with good to excellent yields.
for latent heat storage known as phase change materials can
be classified mainly as organic, inorganic and eutectics. In
order for a substance to be suitable as a phase change
material, it must meet various physical and chemical criteria
in addition to its economic and environmental characteris-
tics.[12–14] There are different physical and chemical proc-
esses for thermal energy storage, which have been discussed
extensively by Jouhara et al.[14] Recently, Wang et al.
reported that, a composite material assembled from a regen-
erated porous cellulose membrane is a suitable candidate as
a thermal energy storage material.[15] On the other hand,
relatively cheaper bio-based phase change materials with
desirable biocompatibility and high enthalpy properties were
Results and discussion
In the esterification reactions carried out in the present
work, triphenylphosphine-sulfur trioxide adduct was used as
an efficient catalyst. This non-hygroscopic solid which is sta-
ble in air was prepared readily according to original proced-
ure given in literature (Scheme 1).[34] The molecular
structure of this complex adduct has been well established
by X-ray crystallography.[35] Moreover, this adduct is an
effective coupling reagent in peptide synthesis[34] but to the
best of our knowledge, it has not used previously for esteri-
developed by Liu et al.[16] and Landi et al.[17] An attractive fication or transesterification reactions. Therefore, in this
study we investigated the catalytic activity of this compound
in esterification reaction of long chain fatty acids and alco-
hols. As shown in Table 1, in order to optimize the condi-
tions of the performed esterification reaction, stearic acid
and stearyl alcohol were chosen as the starting compounds.
The conducted studies have shown that the targeted product
could not be obtained when the esterification reaction is car-
ried out in a catalyst free medium. In the present solventless
process, in order to keep the reaction medium in a molten
state and allow it to proceeds more safely and smoothly, the
minimum reaction temperature value was set to 80 ꢀC. This
temperature is slightly above the melting points of stearic
acid and stearyl alcohol. As can be seen from Table 1, after
several trials, it was determined that increasing the reaction
temperature by 10 ꢀC causes slight increases in prod-
uct yield.
The Table 1 shows the average yields of stearyl stearate
(based on two runs) obtained depending on the amount of
the catalyst and the reaction time and to the highest product
yields was reached under the conditions given in entries 9
and 12. The yield of the ester decreases slightly when the
reaction time is kept constant and the catalyst is taken as
10 mg (entry 10). As can be seen from Table 1 the condi-
tions given in entry 12 are the optimal reaction conditions
for the general esterification procedure. Therefore, the esteri-
fication reactions were carried out with equivalent amounts
of fatty acid and fatty alcohol in the presence of 5 mg of the
triphenylphosphine-sulfur trioxide adduct in solventless
medium for 2 h at 110 ꢀC. The temperature given here
belongs to the oil bath and during this 2 h period the TLC
(Thin layer chromatography) analysis showed depletion of
the starting compounds. According to the conducted pro-
cedure the obtained crude esters are pure enough to be used
class of organic phase change materials used for this purpose
is fatty acids and their different derivatives such as fatty acid
esters and amides.[18–24] Recently, these organic phase mate-
rials have gained great interest in the textile industry.[25]
Fatty acids and their derivatives have a wide range of appli-
cations in consumer and industrial markets and some com-
mon commercial uses of these valuable renewable materials
are schematized in Figure 1.
On the other hand, it is very well known that esters of
long chain fatty acids and fatty alcohols, also known as wax
esters, have a wide range of industrial uses.[26–30] Therefore,
it is important to synthesize these compounds with high
yields through simple and environmentally friendly methods.
Herein, triphenylphosphine which is widely used both as a
reagent and a catalyst in many organic transformations was
chosen as a catalyst component with sulfur trioxide for the
esterification reactions.[31–33] With the present developed
Figure 1. Some common uses of renewable fatty acids and derivatives.
Scheme 1. Preparation of Ph3PꢁSO3 adduct.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Table 1. Optimization of the reaction conditions for esterification of stearic acid.
Entry
Catalyst loading (mg)
Catalyst loading (mmol%)
Time (h)
Temperature ( ꢀC)
Yield (%)a
1
2
3
4
5
6
7
8
Without catalyst
–
2
0.5
0.5
0.5
0.5
1
4
1
4
4
110
80
90
No conversion
2.5
2.5
3
2.5
2.5
2.5
5
5
10
5
0.42
0.42
0.50
0.42
0.42
0.42
0.83
0.83
1.66
0.83
0.83
70
71
72
78
88
97
92
98
95
96
98
90
110
110
110
110
110
110
90
9
10
11
12
2
2
5
110
aYields obtained after crystallization from MeOH/Acetone/THF.
weight (g) of the analyze sample and 56.1 is the molecular
weight of KOH. The stearic acid conversion rate is calcu-
lated by using the following equation:
Table 2. Wax esters obtained by the esterification procedures.
Entry
Wax ester
Name
Mp (ꢀC) (Lit. Mp [9])
Yield (%)a
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
1o
Lauryl laurate
Myristyl laurate
Stearyl laurate
30-31 (29-30)
41-42 (41-42)
47-48 (46-47)
72
82
89
76
85
99
79
93
91
85
96
98
89
96
97
AV0 ꢂ AV1
ð Þ
SA conversion % ¼
ꢃ 100
AV0
Lauryl myristate
Myristyl myristate
Stearyl myristate
Lauryl palmitate
Myristyl palmitate
Stearyl palmitate
Lauryl stearate
Myristyl stearate
Stearyl stearate
Lauryl behenate
Myristyl behenate
Stearyl behenate
39-40 (38-39)
44.5-45 (44-45)
53.6-54.2 (53-54)
44.5-45.4 (44-45)
53-54 (52-53)
61.3-62 (61-62)
47-48.2 (46-48)
56-56.8 (54-55)
62-63 (63-64)
Where, AV0 is the initial acid value and AV1 is the acid
value after a specific time (the final acid value). The graphs
containing these calculated values are given in Figures 2a
and 2b respectively. As seen from the both figures, the ester-
ification reaction proceeds very quickly within the first
20 minutes. In this case, the acid value was 30.86 mg KOH
9
10
11
12
13
14
15
54.4-55.1 (54-55)
59-60 (58-59)
68.2-69.3 (68-69)
g
ꢂ1, and the degree of esterification was 78%. After
120 minutes, the calculated acid value of the reaction mix-
ture remains constant, which indicating that the esterifica-
tion process has terminated.
To reveal the synthetic utility of the esterification method
developed in the present work, a large scale synthesis of
stearyl stearate was carried out. Therefore, for a gram scale
preparation of stearyl stearate, 20 g of stearic acid was
reacted with 19 g of stearyl alcohol in the presence of
200 mg of the catalyst and as a result of heating at 110 ꢀC
for 2 h, the corresponding ester 1l was obtained with a yield
of 97%.
Some studies related to triphenylphosphine based catalyst
reusability have also been carried out. In order to investigate
the reusability of the catalyst, stearic acid and stearyl alcohol
were reacted under the optimized esterification conditions
depicted in Table 1, entry 12. The crude product stearyl
stearate obtained as a result of the reaction was purified by
crystallization from acetone/THF/MeOH solvent mixture to
give pure wax ester 1l nearly in quantitative yield (98%).
The obtained filtrate was concentrated under reduced pres-
sure and the residue containing the catalyst was used for the
next esterification reactions. This residue was used in the
next similar runs and the results obtained are given in
in industrial applications, but if desired these esters can be
crystallized from the appropriate solvent or solvent mixtures
which one of them is given in Table 1. The esters synthe-
sized in this study are given with both of their found and
literature melting points respectively in Table 2 and as seen
in the table, all the esters were obtained in excellent yields.
The progress of the esterification reaction was followed
by the depletion of stearic acid. At certain time intervals,
the sample of the reaction mixture was analyzed for the
remaining stearic acid in the mixture by titrimetric
method. In other words, the extent of the esterification
reaction can be determined by the acid value and the ste-
aric acid conversion rate. The acid number is directly
related to the amount of stearic acid remained in the reac-
tion mixture and the high stearic acid amount corresponds
to the high acid number. The acid value is calculated by
using the following equation:
MKOH x VKOH x 56:1
AV ¼
m
Where, MKOH is the molarity of the KOH solution (mol/ Figure S1 (Supplemental Material). According to the yields
L), VKOH is the volume of the KOH solution (mL), m is the obtained (yields of esterification obtained after crystallization

4
A. YILDIRIM AND K. KIRAYLAR
a weak nucleophile such as fatty alcohol to attack the acti-
vated carbonyl functional group of stearic acid molecule
(Figure 3). Actually, in the catalytic esterification reaction
carried out in this study, triphenylphosphine act as a solid
support that contains the sulfur trioxide molecule which has
a Lewis acid character. In addition, the sulfuric acid released
in the continuation of the reaction may also play a role in
catalyzing the esterification reactions by acting as a Brønsted
acid catalyst. Thus, under these catalytic conditions, the two
voluminous compounds easily interact and forming the cor-
responding ester in a short reaction time (2 h).
160
140
120
100
80
140.25
60
40
30.86
20.2
16.83
14.03
10.66
120
6.73
20
6.73
140
0
0
20
40
60
80
100
Time (min)
On the other hand, some interpretations can be made
through Lewis acid–base interactions supported by some the-
oretical calculations. The calculated highest occupied molecu-
lar orbital (HOMO) and lowest unoccupied molecular orbital
(LUMO) energetics of the stearic acid and the catalyst
involved in the esterification with their optimized geometries
are given in Figure 5. The geometry optimization was per-
formed using the MM2 force field option through the
Chem3D software, PerkinElmer Informatics. As seen from the
Figure 5, the HOMOstearic acid – LUMOsulfur trioxide energy gap
(a)
100
90
80
70
60
50
40
30
20
10
0
95.2
95.2
92.4
90
88.2
85.6
78
is lower than the HOMOstearic acid – LUMO
triphenylphosphine
(10.158 eV and 11.462 eV respectively). This
sulfur trioxide adduct
reveals that in esterification reactions, initially the released
SO3 activates the stearic acid against the nucleophilic attack of
the stearyl alcohol molecule. Moreover, the HOMOstearyl alcohol
– LUMOsulfur trioxide energy gap is higher (10.809 eV) than the
HOMOstearic acid – LUMOsulfur trioxide energy gap (10.158 eV)
which indicated the more favorable interaction between ste-
aric acid and SO3.
0
20
40
60
80
100
120
140
Time (min)
(b)
Figure 2. (a) Graph of calculated acid values versus reaction time; (b) graph of
calculated stearic acid conversion (%) values versus reaction time.
from acetone/THF/MeOH), it is seen that this catalyst is
convenient to use two times without a significant loss in
its activity.
Experimental
Reagents and chemicals
The decrease activity of the catalyst might be attributed
possibly to the loss of gaseous sulfur trioxide catalyst in the
course of esterification. On the other hand, the other pos-
sible reason for the catalyst to lose its effectiveness after its
use twice is probably due to its degradation in the form of
sulfuric acid, as shown in the proposed esterification mech-
anism given in the subsequent section (Figure 3). Thus, the
sulfuric acid molecule released during the progress of the
reaction most likely interacts with the fatty alcohol molecule,
causing some changes in its structure that reduces the yield
of the desired ester (Figure 4). As depicted in this figure, the
fatty alcohol may form the relevant decomposition products
via these well-known reactions.[36] However, a comprehen-
sive analysis of the reaction mixture can be carried out in
further studies to prove the formation of these products
which studies are not performed in the present study yet.
The triphenylphosphine-sulfur trioxide adduct used in
this study most likely catalyzes the performed esterification
reactions as follows: Under the thermal reaction conditions,
sulfur trioxide first released from this adduct, transferred to
the molten reaction mixture and forming an intermediate
All reagents and solvents were purchased from either Merck
or Sigma–Aldrich (St. Louis, MO) and used without further
purification. Thin-layer chromatography was performed
using silica gel (60 F254, Merck, Darmstadt,
Germany) plates.
Instrumentation
€
Melting points were recorded by BUCHI melting point B-
€
540 apparatus (BUCHI Labortechnik AG in Flawil,
Switzerland). The IR spectra were measured by Nicolet FTIR
6700 spectrometer (ThermoFisher Scientific, Massachusetts,
USA). The NMR spectra were measured using A600a
Agilent DD2 600 MHz NMR spectrometer (Santa Clara, Ca,
USA), chloroform-d (CDCl3) using tetramethylsilane (TMS)
as an internal standard. Chemical shifts (d) are reported in
ppm and J values in Hertz. The elemental analyses were per-
formed using an LECO CHNS-932 elemental analyzer (Saint
Joseph, MI, USA). The Supplemental Materials contains
1
complex with stearic acid molecule by acting as a Lewis acid sample IR, H and 13C NMR spectra of the products 1a-o
catalyst.[34] This action of sulfur trioxide makes it easier for (Figures S2–S46).

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Figure 3. Proposed mechanistic pathway for the Ph3PꢁSO3 catalyzed esterification.
Figure 4. Proposed mechanistic pathways for the formation of decomposition products from fatty alcohol.
Esterification
the obtained solid was crystallized from methanol/acetone/
tetrahydrofuran to afford pure crystalline product.
In order to perform the esterification reaction, into a single-
necked reaction flask, at equivalent quantities stearic acid
(0.50 g, 1.76 mmol) and myristyl alcohol (0.48 g, 1.77 mmol)
were added. After addition of the catalyst (5 mg), the mixture
was heated with stirring in an oil bath at 110 ꢀC (bath tem-
Method for determination of the acid value
The acid value is determined by titration of the sample
perature) for 2 h. Finally the reaction mixture was cooled and (withdrawn with a Pasteur pipette from the reaction flask)

6
A. YILDIRIM AND K. KIRAYLAR
Figure 5. FMO orbitals of stearic acid, stearyl alcohol and catalyst as in the form of Ph3Pþ SO3- and SO3.
̶
which is dissolved in 3 mL of EtOH-toluene (1:1 v/v) mix-
ture. The titration process was performed with standard
0.1 M alcoholic KOH solution. In order to estimate the
unreacted stearic acid in terms of its acid value one droplet
of 1% alcoholic phenolphthalein solution was used as an
indicator. 0.2 mL aliquot of samples was withdrawn from
the reaction flask for titration at 0, 20, 40, 60, 80, 100, 120
and 140 minute intervals after the onset of the reaction. This
sample taken from the reaction flask solidifies immediately
and 0.1 gram from this solid is weighed and titrated with
the alcoholic base solution. In order to dissolve the solid
sample completely, the obtained mixture was heated each
time to 40 ꢀC in a water bath and then titrated until the
faint pink color persists for at least 30 s.
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