Petroleum and Coal

Article Open Access

SYNTHESIS AND CHARACTERIZATION OF MIXED ESTERS AS SYNTHETIC LUBRICANTS

Rasha S. Kamal, Nehal S. Ahmed and Amal M. Nassar

Department of Petroleum Applications, Egyptian Petroleum Research Institute, Nasr City, P.O. Box
11727, Cairo, Egypt

Received August 2, 2017; Accepted October 4, 2017

Abstract
Esters have been used successfully in lubrication for more than 60 years and are the preferred stock
in many severe applications where their benefits solve problems. In many ways esters are very similar
to the more commonly known and used synthetic hydrocarbons. In the present work, the different
mixed esters were prepared by reaction of pentaerythritol with different ratio of butyric acid and
octanoic acid. Structure of the prepared compounds was confirmed by study the physico -chemical pro-
perties as (Infra-Red Spectroscopy, Nuclear Magnetic Resonance, Thermo Gravimetric Analysis TGA,
Total Acid Number, density, reflective index, specific gravity, flash point and the Determination of the
Molecular Weights) for all the prepared compounds. The efficiency of the prepared compounds were
investigated as synthetic refrigeration lubricating oil. It was found that the prepared compounds have
low temperature properties (pour point), high viscosity index (VI) and the rheological behavior is simple
Newtonian fluid.
Keywords: Synthetic lubricant; mixed ester; viscosity index; pour point and rheology.

1. Introduction
Lubricants are necessary for the efficient use of machinery. Because of this, the variety of
lubricating fluids has grown to satisfy the demands of new machines having more stringent
requirements due to their operation under more severe conditions or in challenging environ-
ments [1]. Thus, while natural mineral oil-based fluids represent the majority of the market
demand, many technological advances in equipment and machinery would not be possible
without the benefits offered by the synthetic lubricants [2-3]. Organic esters represent one of
the largest groups of synthetic lubricants in use today [4]. Synthetic esters have demonstrated
during the last years to be a good ecological alternative to mineral based lubricants. This means
that synthetic oils can combine a high biodegradability and low ecotoxicity with high technical
features (although price can be four times higher) [5]. In addition to esters, mixtures of fatty
alcohols with carboxylic acid esters have been proposed as lubricating additives [6]. Esters
Just as categorizing a lubricant as synthetic is too broad, the same is true with categorizing a
synthetic lubricant as an ester. Various types of esters are used as synthetic lubricants,
including diesters, monoesters, phthalates, trimellitates/pyromellitates and polyol esters. While
all contain a similar chemical structure, there are chemical variances in the entire molecule
that provide differences in the performance. Ester-based synthetic lubricant may not be the
same as another company’s, and for that reason, it is a good idea to ask compatibility and
performance questions of the lubricant marketer prior to just immediately making the lubricant
change to or from an ester-based synthetic lubricant [7-9]. Synthetic ester lubricants, on the
other hand are prepared from manmade base stocks having uniform molecular structures, and
therefore well-defined properties that can be tailored to specific applications. Lubricants based
on synthetic polyol esters are growing in popularity in cold rolling oil applications. Environ-
mentally friendly synthetic polyol esters constitute alternatives to mineral and vegetable oil
based cold rolling lubricants. Various types of synthetic-based oils used to formulate synthetic

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lubricants have certain advantages over conventional mineral-oil based products. These
advantages are low pour point, low volatility, low toxicity, high viscosity index, high oxidation
stability and high flash and fire points [10-14]. In the present work we prepared some synthetic
lubricant based on mixed esters by esterification of pentaerythritol with butyric acid and
octanoic acid, then study the physico-chemical properties and rheological properties of the
prepared compounds.
2. Experimental
2.1. Preparation of mixed ester
Reaction of pentaerythritol with different ratio of butyric acid C4 and octanoic acid C8. The reac-
tions were carried out in a resin kettle flask in presence of 1wt % a catalyst and xylene as a
solvent. The esterification reactions were carried out under a slow stream of deoxygenated
nitrogen; the reactions were agitated using mechanical stirrer at 500 rpm. The reactants which
were mixed with an equal weight of xylene then heated gradually from room temperature to
170°C ± 0.5°C using a well controlled thermostat. The extent of reaction was followed by
monitoring the amount of liberated water to give products A, B, C, D and E as given in Table (1)
Table 1. The designation of the prepared ester

Alcohol Acids ratio

Prepared esters
(Butyric C 4+Octanoic C 8)
1 mole of pentaerythritol 2 mole C 4 +2 mole C 8 A
1 mole of pentaerythritol 3 mole C 4 +1 mole C 8 B
1 mole of pentaerythritol 1 mole C 4 +3 mole C 8 C
1 mole of pentaerythritol 4 mole C 4 D
1 mole of pentaerythritol 4 mole C 8 E

2.2. Purification of prepared esters

The prepared esters were purified according to the following procedures:
 Filtrate it from the catalyst which washed with methanol and used it again
 Take the filtrate and washed it by 10% sodium carbonate solution in separating funnel and
shaked well.
 The entire process was repeated several times to ensure complete removal of unreacted acid.
 The purified ester was then washed several times with distilled water to remove any traces
of sodium carbonate then the ester was left overnight on calcium chloride anhydrous for drying.
 The anhydrous CaCl2 was then removed by filtration and the xylene was removed by rotary.
2.3. IR spectroscopic analysis
IR spectra of the prepared compounds were determined by using FTIR spectrometer Model
Type Mattson Infinity Series Top 961.
2.4. 1HNMR spectroscopic analysis
The 1HNMR spectra of prepared compounds were measured by Magnet: 400 Megahertz,
console (Spectrometer): Varian model mercury plus, probe: Varian 5 millimeter.
2.5. Determination of the molecular weights
The molecular weights of the prepared ester were determined by using gas chromatography
(GC- mass). Agilent technologies Model Type 5977A MSD, 7890B GC system, column DB- 5MS
(0.25nm x 30cm, 0.1µm film) and flame ionization detector. Pure nitrogen was used as a carrier
gas. The oven temperature program was varied from 40-320oC at a fixed rate of 20oC/min.
The temperature of the injector detector was 300 oC.

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2.6. Thermal analyses

Thermogravimetric analyses (TGA) were performed to study the structural changes of the
prepared samples with thermal treatment. A 10 mg of sample was heated up to 700 oC, with
a heating rate of 10ᵒC min-1 in an (air or N2) flow at a rate of 100 ml min-1 on SDTQ-600 (TA-
USA) thermo balance instrument.
2.7. Total acid number (TAN)
The total acid number (TAN) of prepared compounds were determined according to ASTM
D664 by using Model Type Mehrshom CLO-05.
2.8. Density
Density at 15 ᵒC (g/ml) of the prepared compounds were determined by using Standard
Test Method for Density according to ASTM D1298
2.9. Reflective Index
The reflective index of prepared compounds was determined according to ASTM D1747
2.10. Specific Gravity
Specific Gravity at 15 ᵒC of the prepared compounds were determined by using Standard Test
Method for Specific Gravity according to ASTM D4052 by using Model Type Metler Toledo DUO.
2.11. Flash Point
The flash point of prepared compounds was determined according to ASTM D 92 by using
Cleveland open cup tester
2.12. Measure viscosity index
The kinematic viscosity of the prepared esters was determined at 40°C and 100°C. Then
viscosity index was calculated according to ASTMD 22-70
2.13. Measure pour point
The pour point of the prepared compounds was determined according to the ASTM-97-93.
The instrument used for measuring the pour point was the Cold Filter Plugging Point Automatic
Tester (CFPPA-T), model 1st CPP97-2.
2.14. Study rheological properties
The rheological properties of prepared compounds were studied by using Model Type the
Modular Compact Rheometer 502 (Anton Paar).
3. Results and discussions
3.1. Preparation of mixed ester
Reaction of 1 mole of pentaerythritol with 2 mole of butyric acid C 4 and 2 mole octanoic acid
C8. The esterification reactions were carried out and the extent of reaction was followed by
monitoring the amount of liberated water to give product A, as showing in the reaction scheme A.
Reaction of 1 mole of pentaerythritol with 3 mole of butyric acid C4 and 1 mole octanoic
acid C8. The esterification reactions were carried out and the extent of reaction was followed
by monitoring the amount of liberated water to give product B, as showing in the reaction
scheme B.
Reaction of 1 mole of pentaerythritol with 1 mole of butyric acid C 4 and 3 mole octanoic
acid C8. The esterification reactions were carried out and the extent of reaction was followed
by monitoring the amount of liberated water to give product C, as showing in the reaction
scheme C

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Reaction scheme A

Reaction scheme B

Reaction scheme C

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Reaction of 1 mole of pentaerythritol with 4 mole of butyric acid C4. The esterification
reactions were carried out and the extent of reaction was followed by monitoring the amount
of liberated water to give product D, as showing in the following reaction

Reaction scheme D

Reaction of 1 mole of pentaerythritol with 4 mole of octanoic acid C 8. The esterification

reactions were carried out and the extent of reaction was followed by monitoring the amount
of liberated water to give product E, as showing in the following reaction

Reaction scheme E

IR spectroscopy was used to elucidate the completion of the esterification reactions. All
esters afford similar IR spectrum, IR spectrum given for example in Figure (1) which indicate
the following: absence of strong absorption band at 3200cm-1 of aliphatic (–OH) group, the
characteristic absorption bands of the carboxylic acids. These bands are broad peak extending
from 3300 cm-1 to 2500cm-1 due to hydrogen bonded (– OH) and the (C-H) stretching
vibrations. Appearance of the ester group bands at 1740 cm-1 ± 10 cm-1 and 1280 cm-1 ±
100 cm-1 due to (C=O) and (C-O-C) stretching respectively. The band for (C–H) aliphatic
appear near 2850cm-1 & 2950cm-1. This is indicates that the esterification process is carried
out successfully.

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Figure 1. IR spectrum of the prepared compound (A)

The chemical structures of the prepared compounds can be proved from 1HNMR analysis,
which is represented for example in Figure (2). In this respect, the signal at 3.9 ppm (which
is assigned to O-CH2 groups), the signal at 2-2.5 ppm (which is assigned to O=C-CH2 groups)
and the signal at 1.5–2 ppm (which is assigned to aliphatic protons) were selected to
determine the esterification of the prepared compounds.

Figure 2. 1HNMR spectrum of the prepared compound (B)

The mean molecular weights of prepared compounds by using gas chromatography are
given in Table 2, as shown the theoretical and experimental mean molecular weight are equal
for all prepared compounds. Finally compound E is the largest molecular weight while compound
D is the smallest one.
Table 2. The mean molecular weights of prepared compounds

Designation of the Mean molecular weight(gm/ mole )

Molecular formula
prepared esters Theoretical Experimental
A C 29 H52 O8 528.71838 528.1
B C 25 H44 O8 472.61206 472.8
C C 33 H60 O8 584.8247 584.8
D C 21 H36 O8 416.50574 417.1
E C 37 H68 O8 640.93102 640.8

Mass spectra for some prepared compound as example are given for example in Figures
(3 and 4).

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Figure 3. Mass spectra of the prepared compound (A)

Figure 4. Mass spectra of the prepared compound (D)

Thermal analyses
Thermal stability of the prepared compounds was studied using thermal gravimetric
analysis “TGA”. TGA is a technique which the thermal properties of a material are determined
as a function of temperature [19]. The thermal tests measure the change of weight and
enthalpy as the sample is heated. TGA has been extensively used for measurement of
degradation as we see in Table 3. (T 1) is the temperature when primary degradation step
occurs with weight loss % (W 1) and (T 2) is the temperature when major degradation step
occurs with weight loss % (W 2).

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Table 3. The thermal stability of prepared compounds

Synthetic lube T1 W1 T2 W2
oil designation (℃) (%) (℃) (%)
A 292 7.88 374 97.757
B 260 13.99 335 97.799
C 311 13.6 379 99
D 247 13.9 303 99.04
E 341 14.71 399 98.3

TGA analysis, the thermo gravimetric study has shown a good thermal stability for the
prepared compounds, and this confirms the suitability of using the prepared compounds as
synthetic lubricating oil as it can be used at high temperature without degradation, which is
represented for example in Figures (5 and 6).

Figure 5. TGA analysis of the prepared compound (C )

Figure 6. TGA analysis of the prepared compound (E)

Measuring the viscosity index

The VI increases with increasing the mean molecular weight of the prepared compounds
compared with the mineral oil as shown in Table 4. [15].
Table 4. Measuring the viscosity at 40℃ and at 100℃and calculate the viscosity index

Designation of the
Viscosity at 40℃ Viscosity at 100℃ Viscosity index
prepared compounds
A 23.49876 4.626468 116
B 21.65572 4.259288 101
C 25.3418 4.993648 125
D 14.51394 3.194466 72
E 27.6456 5.360828 131
Mineral Oil 86.16212 9.766988 90

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Measuring the pour point

The pour point is defined as the lowest temperature at which the oil will pour or flow when
it is chilled without disturbance under prescribed conditions [16]. A pour point in synthetic
lubricating oil is lower than the mineral oil due to absence of crystal formed interlocking growth
restricts the pour of oil, and pour point decrease according to decrease in the molecular weight
of the prepared synthetic lubricating oil as shown in Figure 7.

Figure 7. Dependence of PP on the mean molecular weight of synthetic lubricating oils (A, B, C , D and E)

Study rheological properties

The rheological behavior of oils and their products is generally simple Newtonian fluid
(viscosity is independent of shear rate). Shear rate is a measure of the rate of shear
deformation [17-8]. Shear Stress is an applied force per unit area needed to produce defor-
mation in a fluid. A Newtonian liquid is one that flows immediately on application of even the
smallest force, and for which the rate of flow is directly proportional to t he force applied. All
the prepared synthetic lubricating oil is Newtonian fluid behavior as shown for example in
Figures (8 and 9).

Figure 8. The rheological behavior of synthetic lubricating oil (C )

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Figure 9. The rheological behavior of synthetic lubricating oil (E)

Comparison of the physical properties between the prepared esters and the comer-
cial refrigeration oil specifications
The comparative study indicates that the prepared esters could be considered as synthetic
refrigeration lubricating oil [20].
Table 5. The physico-chemical properties of prepared compounds

Properties A B C D E
Total Acid Number (TAN) (mg KOH/g) Nil Nil Nil Nil Nil
Density (g/ml) at 20ᵒC 1.024 1.035 0.997 1.048 0.989
Reflective Index at 28ᵒC 1.4565 1.4565 1.4566 1.4565 1.4566
Specific Gravity at 15ᵒC 1.0516 1.0210 1.0580 1.0006 1.0616
Flash point (C OC ) ᵒC 310 267 318 253 346

Table 6. Properties of the commercial refrigeration oil

Properties C ommercial refrigeration oil

Viscosity at 40℃ 18.9
Viscosity at100℃ 4.2
Viscosity index 120
Pour point 52-
Total Acid Number (TAN) (mg KOH/g) 0.01
Density (g/ml) at 20ᵒC 0.995
Reflective Index at 28ᵒC 1.4519

4. Conclusion
 The mixed ester obtained by reaction of pentaerythritol with different ratio of butyric acid and
octanoic acid.
 Study the physicochemical properties (FTIR, 1HNMR, determination of the molecular
weights, TGA, total acid number TAN, density, reflective index, specific gravity and flash
point) of the prepared compounds.
 Evaluation of the prepared esters as synthetic lubricating oil by measuring viscosity index,
pour point and study rheological properties. It was found that the prepared compounds
have low temperature properties (pour point), high viscosity index (VI) and the rheological
behavior is simple Newtonian fluid.

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 Comparative study between the commercial refrigeration oil and the prepared ester
indicates that the prepared esters can be used as synthetic refrigeration lubricating oil
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T o whom correspondence should be addressed: Dr. Rasha S. Kamal, Department of Petroleum Applications,
Egyptian Petroleum Research Institute, Nasr City, P.O. Box 11727, Cairo, Egypt, [email protected]

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