Optimal Preparation Conditions for Some Diester-
Based Synthetic Lubricants
LA. El-Magly, E.S. Nasr Egyptian Petroleum Research Institute, Nasr
City, Cairo, Egypt; and M.S. El-Samanoudy Armed Forces Technical
Research Centre, Cairo, Egypt
In this paper, work is reported on the esterification of various materials,
where di-2-ethylhexyl esters of succinic, adipic, azelaic and sebacic acid
were prepared. Waterproduced by the reaction was separated continuously
and the reaction progress was followed up by measurement of the acid
content. Factors afSecting the esterification were studied and the optimal
conditionsfor conversion of about 92% to 95% (by weight) were found to
be: temperature - I79 "C; molar ratio of acid to alcohol - I :2.4; catalyst
concentration -3% (by weight) based on acid; agitation rate -350 rlmin.
KEYWORDS: esters, esterification, diesters, acid, alcohol, water, catalyst
INTRODUCTION
Dibasic acid esters have found increased use in industrial applications.
This is attributed to their good lubricity, thermal and oxidation-corrosion
stability, low pour point and relatively high viscosity index.
In 1947, the US Bureau of Aeronautics followed US Naval Research
Laboratory (NRL) recommendations that sebacate and azelate diester oils
be tested in turboprop and turbojet engines.2The resulting USAF MIL-L-
7808 specification for gas turbine engine oils was for a 3 cSt diester oil.
Today, oils with a viscosity of 7.5 cSt in the DERD 2487 spccification
are based on dibasic acid esters and a thickener. Wide temperature range
greases satisfying MIL-G-3278A and MIL-G-7118 employ dibasic acid
ester base s t o ~ k Some
. ~ &basic acid esters are also useful as plasticizers
for polymers. The first high-temperature hydraulic fluid meeting the MIL-
H-8446 specification was formulated by blending a dibasic acid ester with
silicates. A general purpose oil based on diester base stock is described in
the MIL-L-6085-A specification (equivalent to British DTD 822).
Numerous methods have been mentioned in the literature for the
preparation of these esters in the presence of various catalysts."-' In the
present work some factors affecting the esterification' are reported. These
JSL (7) 89 0265-6582 $5.00 + $2.00
90 El-Magly and El-Samanoudy JSL 7-2
were studied with the aim of finding the optimal preparation conditions for
various diesters.
EXPERIMENTAL
Succinic, adipic, azelaic, and scbacic acid were reacted with 2-ethylhexmol
to give the corresponding esters. Temperature, molar ratio of rcactants,
agitation rate and catalyst conccntration were studied as factors affecting
the esterification.
Apparatus
A four-necked, 500 ml purex double jacketed reactor was used. This was
fitted with a thermometer, a stirrer and an efficient cooling condenser with
a graduated trap ending with a tap. The fourth neck was used for charging
the starting materials and catalyst. Heating of the reactor was by circulation
of silicon oil from a well-controlled heating thermostat. The heating
temperature was controlled at the desired value 60.1"C.
Preparation of diesters
The dibasic acid (0.5 mol), the alcohol (one mole) and the catalyst were
charged in the reactor and then heated to the required temperature with
continuous stirring. Samples from the reaction mixture were withdrawn
periodically and the acid content was determined by titration against 0.1
N NaOH solution. The reaction progrcss was followed by measurements
of both the acid content and the amount of water continuously separated
as one of the reaction products. At the end, the reaction mixture was
neutralized with 5% aqueous sodium carbonatc solution followed by
repeated washing with distilled water, and aspirated in a rotary evaporator,
then dried over anhydrous sodium sulphate and decolorized by active
charcoal if needed. The acid number of the product was measured.
RESULTS AND DISCUSSION
Esterification conditions
The technique of continuous removal of water as one of the reaction
products ensures the irreversibility of the reaction. The novel application
JSL 7-2 Diester lubricant preparation conditions 91
of alkoxytitanate and alkoxyzirconate as catalysts, and use of agitation,
lead to higher conversion within a shorter time.
Followingthe esterification reaction programme by the water measurements
and the acid determination was a good way of tracing the reaction’s
progress.
Study of the factors affecting the esterification revealed the following
effects.
Effect of temperature
The esterification was carried out at 150’C, 160C and 170’C, while
keeping the other conditions as follows:
Acid/alcohol molar ratio 1:2
Catalyst concentration 0.00 wt% (based on acid)
Agitation rate 350 r/min
Table 1 Variation of conversion X with time at different temperatures
for the esterification of sebacic acid with 2-ethyl hexanol
Time Conversion X
(min) 150°C 160°C 7 70°C
00 0.0000 0.0000 0.0000
20 0.1353 0.2050 0.2835
40 0.2432 0.3400 0.4500
60 0.3270 0.4330 0.5451
80 0.3950 0.551 0 0.6152
100 0.4502 0.5620 0.6671
120 0.5001 0.6060 0.7092
140 0.5352 0.6501 0.7361
160 0.5650 0.6732 0.7581
180 0.5948 0.6933 0.7750
200 0.6150 0.7000 0.7750
220 0.6252 0.7000 0.7820
240 0.6300 0.7055 0.7850
Acid/alcohol molar ratio 1:2
Catalyst concentration (wt% based on acid) 0.00
Agitation rate (r/min) 350
92 El-Magly and El-Samanoudy JSL 7-2
Table 2 Variation of conversion X with time at different temperatures
for the esterification of azelaic acid with 2-ethyl hexanol
Time Conversion X
(min) 150°C 160'C 170'C
00 0.0000 0.0000 0.0000
20 0.1 662 0.2352 0.3000
40 0.2851 0.3763 0.4632
60 0.3772 0.4625 0.5602
80 0.4437 0.5422 0.6352
100 0.5061 0.6000 0.6922
120 0.5470 0.6423 0.7275
140 0.5838 0.6721 0.7577
160 0.61 23 0.6914 0.7832
180 0.6214 0.7021 0.7983
200 0.6252 0.7045 0.8048
220 0.6253 0.7050 0.8050
240 0.6250 0.7050 0.8040
260 0.6251 0.7050 0.8070
Acid/alcohol molar ratio: 1 :2. Catalyst concentration (wt% based on
acid): 0.00. Agitation rate (r/min): 350.
Figure 1 Conversion ( X ) versus time ( t ) for esterification of sebacic acid
with 2-ethyl hexanol, at different temperatures. Acid-alcohol molar ratio:
1 : 2; catalyst concentration: 0.0 wt %; and agitation rate: 350 r/min
JSL 7-2 Diester lubricant preparation conditions 93
Figure 2 Conversion (X)versus time (t) for esterification of azelaic acid
with 2-ethyl hexanol, at different temperatures. Acid-alcohol molar ratio:
1 :2; catalyst concentration: 0.0 wt %; and agitation rate: 350 r/min
Table 3 Variation of conversion X with time at different temperatures
for the esterification of adipic acid with 2-ethyl hexanol
Time Conversion X
(min) 150 'C 160'C 170°C
00 0.0000 0.0000 0.0000
20 0 2525 0.3100 0.3749
40 0.4000 0.4750 0.5450
60 0.5073 0.5856 0.6427
80 0.5802 0.6485 0.7080
100 0.6240 0.6954 0.7465
120 0.6635 0.7262 0.7780
140 0.7000 0.7505 0.7981
160 0.7203 0.7735 0.8080
180 0.7352 0.7877 0.8276
200 0.7500 0.8000 0.8352
220 0.7502 0.8030 0.8400
240 0.7500 0.8050 0.8400
260 0.7500 0.8050 0.8400
Acid/alcohol molar ratio: 1:2. Catalyst concentration (wt o/o based on
acid): 0.00. Agitation rate (r/min): 350
94 El-Magly and El-Samanoudy JSL 7-2
Figure 3 Conversion ( X ) versus time ( t ) for esterification of adipic acid
with 2-ethyl hexanol, at different temperatures. Acid-alcohol molar ratio:
1 : 2; catalyst concentration: 0.0 wt %; and agitation rate: 350 r/min
&-A-+-A--.
40 00 120 I60 200 240 2 0
Table 4 Variation of conversion X with time at different temperatures
for the esterification of succinic acid with 2-ethyl hexanol
Time Conversion X
(min) 150'C 76U'C 17U'C
00 0.0000 0.0000 0.0000
20 0.3050 0.3500 0.4047
40 0.4690 0.51 83 0.5765
60 0.5682 0.6200 0.6700
80 0.6300 0.6835 0.7313
100 0.6745 0.7300 0.7728
120 0.7148 0.7653 0.8000
140 0.7360 0.7805 0.8160
160 0.7584 0.7983 0.8251
180 0.7761 0.8150 0.8430
200 0.7853 0.81 74 0.8490
220 0.7920 0.81 80 0.8500
240 0.8000 0.8200 0.8505
260 0.8000 0.8200 0.8501
Acid/alcohol molar ratio: 1 :2. Catalyst concentration (wt % based on
acid): 0.00. Agitation rate (r/min): 350
JSL 7-2 Diester lubricant preparation conditions 95
Figure 4 Conversion ( X ) versus time (t) for esterification of succinic acid
with 2-ethyl hexanol, a t different temperatures. Acid-alcohol molar ratio:
1: 2; catalyst concentration: 0.0 wt 5%; and agitation rate: 350 r/min
40 00 120 160 200 240 280
Figure 5 Conversion ( X ) versus time (t) for esterification of sebacic,
azelaic, adipic and succinic acids with 2-ethyl hexanol. Temperature:
170°C; acid-alcohol molar ratio: 1:2; catalyst concentration: 0.0 wt %;
and agitation rate: 350 rlmin
0.n
0.1
0.6
0.5
0.4
0.3
D. 2
0. I
40 00 izn 160 ZOO zto ZBQ
96 El-Magly and El-Samanoudy JSL 7-2
Effect of varying the catalyst concentration
Alkoxytitanate or alkoxyzirconate catalysts were used in different
concentrations (wt %, based on acid) for the preparation of the scbacate
diester, (0.5, 2,3, 4,wt%) with respect to TiMor to Z P . while the other
parameters were kept as follows:
Acid/alcohol molar ratio 1:2
Agitation rate 350 r/min
Temperature 170°C
Tables 5 and 6 and Figures 6 and 7 (overleaf) show that increasing the
catalyst concentration to 3.0% increases the rate of the reaction. Any
further increase in catalyst concentration does not appreciably affect the
conversion. The catalytic activity of Z P is higher than that of TiM.
Increasing the catalyst conccntration from 0.0% to 3% increases the
Table 5 Variation of conversion X with time at different Ti "catalyst
concentrations for the esterification of sebacic acid with 2-ethyl hexanol
X: conversion at different catalyst concentrations as (wt %)
Time
(min) 0 0.5 2 3 4
00 0.0000 0.0000 0.0000 0.0000 0.0000
20 0.2835 0.4000 0.4500 0.4921 0.4923
40 0.4500 0.5498 0.6245 0.6515 0.651 7
60 0.5451 0.6500 0.7208 0.7362 0.7363
80 0.6152 0.71 28 0.7625 0.7870 0.7880
100 0.6671 0.7499 0.791 0 0.8125 0.8130
120 0.7092 0.7770 0.81 11 0.8300 0.8300
140 0.7361 0.7982 0.8300 0.8420 0.8421
160 0.7581 0.8073 0.8395 0.8533 0.8533
180 0.7760 0.8200 0.8501 0.8587 0.8588
200 0.7750 0.8230 0.8550 0.8602 0.861 0
220 0.7820 0.8261 0.8600 0.8650 0.8651
240 0.7850 0.8300 0.8630 0.8670 0.8670
260 0.7900 0.8330 0.8650 0.8670 0.8671
Acid/alcohol molar ratio: 1 : 2. Temp.: 170°C. Agitation rate (r/min): 350
JSL 7-2 Diester lubricant preparation conditions 97
Table 6 Variation of conversion X with time at different Zr”cata1yst
concentrations for the esterification of sebacic acid with 2-ethyl hexanol
X: conversion at different catalyst concentrations as (wt %)
Time
(min) 0 0.5 2 3 4
00 0.0000 0.0000 0.0000 0.0000 0.0000
20 0.2835 0.4382 0.5351 0.5650 0.5660
40 0.4500 0.6023 0.6900 0.7148 0.7150
60 0.5451 0.7000 0.7666 0.7862 0.7868
80 0.6152 0.7505 0.8000 0.8221 0.8225
100 0.6671 0.7845 0.8251 0.8450 0.8461
120 0.7092 0.8076 0.841 1 0.861 6 0.8650
140 0.7361 0.8203 0.8600 0.8750 0.8760
160 0.7581 0.8400 0.8652 0.8850 0.8860
180 0.7750 0.8500 0.8750 0.8942 0.8993
200 0.7750 0.8500 0.8831 0.9000 0.9000
220 0.7820 0.8505 0.8850 0.9050 0.9055
240 0.7850 0.8509 0.8873 0.91 10 0.91 15
260 0.7900 0.8513 0.8900 0.9120 0.91 23
Acid/alcohol molar ratio: 1 : 2. Temp.: 170’C. Agitation rate (rfmin): 350
Figure 6 Conversion (X)versus time ( t ) for esterification of sebacic acid
with 2-ethyl hexanol, at different Ti “catalyst concentrations. Acid-alcohol
molar ratio: 1 : 2; temperature: 170°C; and agitation rate: 350 r/min
98 El-Magly and El-Samanoudy J S L 7-2
Figure 7 Conversion (X)versus time ( t ) for esterification of sebacic acid
with 2-ethyl hexanol, at different Zr catalyst concentrations. Acid-alcohol
molar ratio: 1 : 2; temperature: 170°C; and agitation rate: 350 r/min
0.7
0.8
0.1
0.6
0.5
0.4
0.3
0.2
0. I
conversion from 0.79 to 0.867 in the case of TiM,while it changes the
conversion up to 0.9 12 in case of ZP.
Effect of varying the molar ratio of the reactants
Esterificationof sebacic acid was carried out using the following different
(acid/alcohol) molar ratios: 1 :2, 1:2.2., 1 :2.4. The other parameters
remained fixed as follows:
Temperature 170°C
Catalyst concentration 3% wt (based on acid)
Agitation rate 350 r/min.
As can be observed from Table 7 and Figure 8, increasing the acid/
alcohol molar ratio from 1:2 to 1:2.2 and then to 1:2.4 does not greatly
JSL 7-2 Diester lubricant preparation conditions 99
Table 7 Variation of conversion X with time at different acidalcohol molar
ratios for the esterification of sebacic acid with 2-ethyl hexanol
X: conversion at different acid /alcohol molar ratios
Time
(min) 1 :2 1 :2.2 1 :2.4
00 0.0000 0.0000 0.0000
20 0.5650 0.6000 0.6495
40 0.7148 0.7582 0.7887
60 0.7862 0.8250 0.8474
80 0.8221 0.8560 0.8751
100 0.8450 0.8743 0.8900
120 0.8616 0.8800 0.9043
140 0.8250 0.9000 0.91 11
160 0.8850 0.9050 0.9150
180 0.8942 0.9100 0.9158
200 0.9000 0.9150
220 0.9050
240 0.91 10
260 0.9120
Zr+4 catalyst concentration (wt O h ) 3.0
Temperature 170°C
Agitation rate (r/min) 350
affect the conversion, but reduces the time of esterification from 240 min
to 180, then to 140 min respectively.
Effect of varying the agitation rate
In this study, the agitation rate was increased from 350 r/min to 400, and
thcn to 450 r/min, for the preparation of di-2-ethylhexyl sebacate, while
kecping the other parameters fixed as follows:
Temperature 170°C
Acid/alcohol molar ratio 1:2.4
Catalyst concentration 3% wt (based on acid).
100 El-Magly and El-Samanoudy JSL 7-2
It is clear from Table 8 and Figure 9 that increasing the agitation rate
within the mentioned range does not affect the reaction conversion.
THE OPTIMUM CONDITIONS FOR ESTERIFICATION OF
DIBASIC ACIDS WITH 2-ETHYL HEXANOL
Thc data obtained from the aforementioned studies indicate that di-2-
ethylhexyl sebacate can be successfully prepared under the following
optimum conditions:
Temperature 170°C
Acid/alcohol molar ratio 1:2.4
Catalyst concentration 3% wt (based on acid)
Agitation rate 350 r/min
The other homologous series of esters were prepared under the above
specified conditions. The results are presented in Table 9 and Figure 10,
Table 8 Variation of conversion X with time at different agitation rates
for the esterification of sebacic acid with 2-ethyl hexanol
X: conversion at different agitation rates (r/mjn)
Time
(min) 350 400 450
00 0.0000 0.0000 0.0000
20 0.6495 0.6500 0.6500
40 0.7887 0.7888 0.7900
60 0.8474 0.8480 0.8500
80 0.8251 0.8777 0.8781
100 0.9800 0.8933 0.8950
120 0.9043 0.9081 0.9100
140 0.91 11 0.9150 0.9150
160 0.9150 0.9157 0.9158
180 0.9158 0.9160 0.91 61
Zr+4 catalyst concentration (wt O h ) 3.0
Temperature 170°C
Agitation rate (r/min) 350
JSL 7-2 Diester lubricant preparation conditions 101
Figure 8 Conversion ( X ) versus time ( t ) for esterification of sebacic acid
with 2-ethyl hexanol, at different acid-alcohol molar ratios. Zr catalyst
concentration: 3.0 wt %; temperature: 170°C; and agitation rate: 350 r/min
40 80 120 160 200 240 280
Figure 9 Conversion ( X ) versus time ( t ) for esterification of sebacic acid
with 2-ethyl hexanol, at different agitation rates. Temperature: 170°C;
acid-alcohol molar ratio: 1 :2.4; Zr “catalyst concentration: 3.0 wt %.
l , l , l , l , l , l a ~ , l
102 El-Magly and El-Samanoudy JSL 7-2
Figure 10 Conversion ( X ) versus time (t) for esterification of the dibasic
acids with 2-ethyl hexanol under optimum conditions. Temperature:
170°C; acid-alcohol molar ratio: 1 : 2.4; Zr Jcatalyst concentration: 3.0
wt %; agitation rate: 350 r/min.
which show % conversions of approximately 91.6, 93, 94, 95 forscbacic,
azelaic, adipic and succinic acids respectively.
References
1.Ranney, M.W., Synthetic Oils and Greasesfor Lubricants:Recent Developments,
Noyes Data Corporation, Park Ridge, New Jcrsey, USA, 1976.
2. Szydywar, J., ‘Ester-basedLubricant for Aviation and Industry’,International
Seminar on the Performance, Testing and Development of Lubricating Oils,
Fuels and Chemicals, Research Centre, Gharnra, Cairo, 2-5 April 1979.
3. Goddard, D.R., ‘Synthetic Lubricants’, in Lubrication andlubricants, edited
by Braithwaite, E., Elsevier Publishing Co. Amsterdam, London, New York,
1967.
4.Hussain, S.Z., and Kamath, N.R., Indian Techn., 5 June 1967.
5.Tandara, M., Kem, Ind., 19,578 (1970).
JSL 7-2 Diester lubricant preparation conditions 103
Table 9 Variation of conversion X with time for the esterification
of the dibasic acids with 2-ethyl hexanol under optimum conditions
Conversion X
Time
(min) Sebacic Azelaic Adipic Succinic
00 0.0000 0.0000 0.0000 0.0000
20 0.6495 0.6885 0.7150 0.7423
40 0.7887 0.8052 0.8250 0.8487
80 0.8751 0.8850 0.9000 0.9173
120 0.9013 0.9134 0.9246 0.9403
160 0.91 50 0.9274 0.9372 0.9500
200 0.9160 0.9300 0.9400 0.9507
Temperature 170°C
Acid/alcohol molar ratio 1 : 2.4
Zr+4 catalyst concentration (wt %) based on acid 3.0
Agitation rate (r/min) 350
6.Finar, G.K., Organic Chemistry, Longman, London (1968), pp. 2,178,181,
250.
7.El-Samanoudy, M.S. ‘Studies on Some Synthetic Lubricants of the Dibasic
Acid Ester Type’, Ph.D. Thesis, Faculty of Engineering, Cairo Univ., 1988.
S.Mokhtar, W.M., El-Magly, I.A., and Gharieb, H.K. ‘Optimal Conditions for
the Preparation of TrimethylolpropanoctanoateS ynlube Base’, 5th International
Seminar on New Developments in Engine Oils, Industrial Oils, Fuelsand
Additives, Research Centre, Ghamra, Cairo, 14-17 Oct. 1985, Ref: C.A. 104 :
71363 (1986).
Paper presented at ‘Synthetic Lubricants’ meeting of the Hungarian Chemical
Society in Sopron, Hungary.
