Bioresource Technology 87 (2003) 35–39

Preparation of polyol esters based on vegetable and animal fats

S. Gryglewicz *, W. Piechocki, G. Gryglewicz
Department of Chemistry, Wrocław University of Technology, ul. Gda

nska 7/9, 50-344 Wrocław, Poland

Abstract
The possibility of using some natural fats: rapeseed oil, olive oil and lard, as starting material for the preparation of neopentyl
glycol (NPG) and trimethylol propane (TMP) esters is reported. The syntheses of final products were performed by alcoholysis of
fatty acid methyl esters, obtained from natural fats studied, with the appropriate polyhydric alcohol using calcium methoxide as a
catalyst. The basic physicochemical properties of the NPG and TMP esters synthesized were the following: viscosity at 40 °C in the
range of 13.5–37.6 cSt, pour point between )10.5 and )17.5 °C and very high viscosity indices, higher than 200. Generally, the esters
of neopentyl alcohols were characterized by higher stability in thermo-oxidative conditions in comparison to native triglycerides.
Due to the low content of polyunsaturated acids, the olive oil based esters showed the highest thermo-oxidative resistance. Also,
methyl esters of fatty acids of lard would constitute a good raw material for the synthesis of lubricating oils, provided that their
saturated acids content was lowered. This permits synthesis of NPG and TMP esters with a lower pour point (below )10 °C) than
natural lard (þ33 °C).
Ó 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Animal fat; Fatty acid methyl ester; Polyol ester; Transesterification; Vegetable oil

1. Introduction In recent years, increasing attention has again been

paid to natural triglycerides, fatty acids derived from
Vegetable oils and animal fats were the first lubri- them, and their potential applications (Vizintin et al.,
cants used by humans. However, some properties of 2000; Arnsek and Vizintin, 2000). This raw material
natural triglycerides limit their direct application in lu- is cheap and renewable. Moreover, natural fats and
brication technology (Lal and Carrick, 1994). Natural products derived from them are generally environmen-
triglycerides have a low resistance to both oxidation and tally friendly.
high temperature treatment and they readily undergo However, glycerol, a component of the triglyceride
hydrolysis, particularly under the influence of natural molecule is readily destructible at high temperatures.
hydrolases. Fats, especially animal fats, have a high This disadvantageous property stems from the presence
pour point and generally, exhibit a narrow viscosity of hydrogen atoms in position b relative to the hydroxyl
range. group in the glycerol molecule. This structural feature is
Since the 19th century, vegetable oils and animal fats conducive to the partial defragmentation of the mole-
commonly used in lubrication technology have been cule and the formation of unsaturated compounds
gradually replaced by hydrocarbon-based lubricants (B€unemann et al., 2000), Fig. 1. The compounds formed
derived from petroleum. But the latter products did not undergo polymerisation, increasing the liquidÕs viscosity
always meet the increasingly stringent technical re- and resulting in the formation of precipitate particles.
quirements. This spurred the development of synthetic The problem can be solved by replacing glycerol with
lubricants which have become substitutes for conven- another polyhydric alcohol which does not contain b-
tional mineral oils and greases (Rudnick and Schubkin, hydrogen atoms, i.e., neopentyl glycol (NPG), trime-
1999). thylol propane (TMP) or pentaerythritol. Although such
alcohols also decompose at high temperatures, their
thermal decomposition has a radical character and
proceeds slowly.
*
Corresponding author. Fax: +48-71-322-1580. Synthetic esters produced from natural acids can-
E-mail address: [email protected] (S. Gryglewicz). not be used at extremely high temperatures, but they

0960-8524/03/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 0 - 8 5 2 4 ( 0 2 ) 0 0 2 0 3 - 1
36 S. Gryglewicz et al. / Bioresource Technology 87 (2003) 35–39

Fig. 1. Thermal destruction of esters.

are very suitable in less extreme applications such 2. Methods

as two-stroke engine oils, chain bar oils, cutting oils,
concrete mould release agents and cosmetics ingredi- 2.1. Reagents
ents.
The properties of esters also depend on the structure NPG, TMP and isooctane were obtained from Ald-
of the constituent fatty acids and alcohols, i.e., on the rich, Steinheim, Germany. Sodium hydroxide and
length of their aliphatic chain and the number and rel- methanol were purchased from POCH Gliwice, Poland.
ative position of unsaturated bonds. Saturated acids are Olive oil was obtained from F.ll.i Ruata, Italy and low
highly resistant to oxidation and high temperature, but erucic acid rapeseed oil from Fat Processing Plant in
their estersÕ pour point is high due to the linear structure Warsaw, Poland. All fats and oils were edible grade.
of the acids. The high pour point of saturated fatty acids Calcium methoxide was synthesized by the direct reac-
makes it possible to separate the latter from unsaturated tion of calcium with methanol.
acids by physical methods, e.g., through freezing out.
Polyunsaturated fatty acids, especially those which 2.2. FAME preparation
contain conjugated bonds, are the most susceptible to
oxidation and thermal degradation. As a rule, these Four hundred and fifty grams of the desired trigly-
acids, particularly their cis-isomers, are characterized by ceride and 0.5 g of NaOH dissolved in 35 g of methanol
very low pour points. The degree of unsaturation can be were placed in a 1000 ml glass bath reactor equipment
reduced via electrophilic substitution with, for example, with a magnetic stirrer and capped with a reflux con-
naphthalene (Herdan, 1999). Modifying the structure of denser. The reactor temperature was maintained be-
fatty acids through the Diels–Alder cyclo addition re- tween 65 and 70 °C, slightly below the boiling point of
sults in a removal of conjugated double bonds (Patil methanol. The reaction was carried out for 30 min. The
et al., 1998). One solution is to use monounsaturated reaction mixture was cooled down to ambient temper-
oleic acid, which is a major component of many animal ature and the resulting two layers were separated. The
and vegetable fats, for the manufacture of synthetic oils upper layer contained a solution of methyl esters.
(EP 95/04767, 1996).
Two basic methods of synthesizing fatty acid esters of 2.3. Chromatographic analysis
neopentyl alcohols can be distinguished. One consists of
direct esterification of fatty acids with polyhydric alco- Analysis of FAME was performed on a HP 5890II
hols in the presence of acidic catalysts (EP 0712 834 B1, gas chromatograph fitted with a capillary inlet system
1996). and flame ionization detector. The capillary column, HP
The other method consists of a two-stage transeste- INNOWAX, was 30 m long, with 0.32 mm i.d. and 0.25
rification. Triglycerides are subjected to alcoholysis with lm film thickness. A split injection system 20:1 was used
methanol to obtain fatty acid methyl esters (FAME) with nitrogen carrier gas at head pressure of 0.6 atm.
and subsequently transesterified with a polyhydric al- The column temperature was held at 50 °C throughout
cohol (Schuchardt et al., 1998). the entire 6 min run. Temperature programming was
The objective of this research was to explore the initiated at 50 °C at the rate of 10 °C min1 to reach a
possibilities of producing fatty acid esters of NPG and temperature of 250 °C. The inlet temperature was 250
TMP. Rapeseed oil, olive oil and lard were used as the °C and the detector temperature was 280 °C. The oil
sources of fatty acids. The esters evaluated in this study reference standard, AOCS for Low Erucic Rapeseed Oil
were synthesized through transesterification. from Sigma––Aldrich, Steinheim, Germany was used as
 S. Gryglewicz et al. / Bioresource Technology 87 (2003) 35–39 37

an external standard for quantitative analysis. For one methods, i.e., acid number to ASTM D 974, viscosity to
sample, the GC analysis was performed in duplicate. ASTM D 445, viscosity index to ASTM D 2270 and
Relative standard deviations of duplicate measurements pour point to ASTM D 97.
of fatty acids composition was below 5%. Thermo-oxidative stability, evaluated by viscosity
increase and acid number increase, was determined after
treatment under the following conditions: a temperature
2.4. Modification of fatty acids composition of 100 °C, bubbling of 12 l h1 air in 45 g sample and a
treatment time of 24 h. At the end of the test, the relative
A two-stage process of low temperature crystalliza- increase of viscosity at 40 °C (Dm, %) and the acid
tion was used to fractionate lard methyl esters. A 1000 g number increase (DAc) were determined. Two mea-
sample of FAME was cooled down to a temperature of surements were done for each sample.
0 °C. The semi-fluid mixture of FAME was filtered using
a Schott G-4 funnel. The filtrate obtained (Filtrate I)
was cooled to )10 °C and again subjected to filtration,
3. Results and discussion
resulting in a mixture of lard-based FAME (Filtrate II)
enriched with unsaturated methyl esters with a yield of
The GC analysis of the FAME obtained from rape-
46%.
seed oil, olive oil and lard is given in Table 1. Olive
oil, whose major constituent is oleic acid, contains a
2.5. Syntheses of esters of polyhydric alcohols relatively small amount of linoleic acid (7.2%), and
about 14% saturated fatty acids. In comparison to olive
Fatty acid esters of neopentyl alcohols were synthe- oil, rapeseed oil has a lower saturated acid content
sized by transesterifying FAME with NPG and TMP. (8.3%), which is advantageous, and a higher polyun-
Fifty grams of FAME, 8.0 g of NPG or 6.7 g of TMP, saturated fatty acids content (28%). The presence of
0.3 g of calcium methoxide used as catalyst, and 50 ml of large amounts of polyunsaturated acids results in low-
isooctane were placed in a 500 ml flask. The flask mouth ering the resistance to oxidative-thermal treatment.
was fitted with a Dean-Stark cap in order to carry out Lard-based FAMEs have the lowest polyunsaturated
the azeotropic distillation of methanol–isooctane. The acids content, but the saturate content is as high as 50%.
temperature was raised to the boiling point of the re- Hence, even at room temperature FAMEs derived from
action mixture. The methanol formed by the reaction lard contain large amounts of solids. By freezing out, the
was continuously removed. The quantity of the metha- saturated fatty acids content was lowered to nearly
nol removed was used to measure the conversion of the 17.4% (Filtrate II). FAMEs obtained in this way from
reaction. The reaction was carried out for 20 h. When lard are similar to FAMEs from olive oil in terms of
the reaction was complete, the synthesized ester was fatty acids composition.
separated from the catalyst by filtration. The isooctane The syntheses of fatty acid esters of NPG and TMP
was removed using a rotary evaporator under reduced proceeded according to the reactions presented in Fig. 2.
pressure at 95 °C. Each synthesis was performed four The rather slow rate of the reactions is noticeable. A
to five times to obtain sufficient quantities of the final yield of 85–90% was reached after 20 h of reaction time.
products for determining their properties. The yield This happened despite the removal of the methanol re-
calculated was an average of all syntheses done. action product. In comparison, the methanolysis of tri-
glycerides conducted under optimum conditions lasted
only a few minutes and its yield was high. In the
2.6. Physicochemical properties determination methanolysis reaction, the principal reacting substance
is a small, mobile methoxide anion stabilized by solva-
The physical properties of the prepared esters were tion with methanol molecules. As a result, a high reac-
determined according to the following standard test tion rate can be achieved. The transesterification of

Table 1
Fatty acids composition
Methyl ester (wt.%)
14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 22:1
Olive oil – 11.7 0.8 3.0 77.9 7.2 – – –
Rapeseed oil – 4.8 – 1.8 62.7 19.5 8.6 1.7 1.0
Lard 1.8 29.0 2.6 17.9 41.9 6.8 – – –
Lard––Filtrate I 1.2 17.2 3.6 7.8 62.8 7.4 – – –
Lard––Filtrate II 1.0 13.5 3.9 4.9 69.1 7.6 – – –
38 S. Gryglewicz et al. / Bioresource Technology 87 (2003) 35–39

Fig. 2. The syntheses of fatty acid esters of NPG and TMP.

Table 2
Comparison of physicochemical properties for native triglycerides and fatty acids neopentyl estersa
Synthetic esters, starting Yield (%) Acid value Viscosity (m cSt) Viscosity Pour point Thermo-oxidative
material (mg KOH/g) index (°C) stability
FAME Alcohol 40 °C 100 °C Dm (%) DAc
Olive oil NPG 94.0 0.40 15.32 4.31 209.8 )15.5 þ70.8 þ2.55
Rapeseed oil NPG 93.1 0.57 15.62 4.36 208.7 )17.5 þ142.6 þ6.25
Lard––Filtrate II NPG 91.9 0.93 13.51 4.05 226.2 )13.5 þ71.7 þ3.37
Olive oil TMP 85.1 0.55 36.00 8.32 218.3 )13.0 þ72.1 þ2.15
Rapeseed oil TMP 87.2 0.24 35.34 7.99 209.2 )15.5 þ100.7 þ3.29
Lard––Filtrate II TMP 84.0 0.68 37.65 9.06 234.7 )10.5 þ65.1 þ2.06
Native triglycerides
Olive oil – 1.17 39.44 8.39 196.6 )15.1 þ97.5 þ4.14
Rapeseed oil – 0.23 36.36 7.96 200.1 )21.0 þ153.2 þ8.06
Lard – 0.55 – – – þ32.3 – þ4.32
a
NPG: neopentyl glycol; TMP: trimethylol propane; Dm: percentage of viscosity change; DAc: acid number change.

FAME with NPG and TMP, being actually an oppo- The pour points of NPG esters are much lower than
site reaction, proceeds at a much lower rate. Calcium those of TMP esters. It was observed that the pour point
methoxide, which is sparingly soluble and can be easily of both NPG and TMP esters is clearly dependent on
separated from the reaction products by filtration, was the kind of triglycerides from which they were synthe-
used as the catalyst. Table 2 compares the basic prop- sized and decreases as follows:
erties for the synthesized NPG and TMP esters with
rapeseed oil > olive oil > lard—Filtrate II
those for native triglycerides.
Generally, TMP esters of fatty acids have higher This increase agrees with the increase in the unsatu-
viscosity than that of analogous NPG esters. This is rated fatty acids content. For lard––Filtrate II NPG and
probably due to the fact that there are three acid groups TMP esters, a significantly lower pour point ()13.5 and
in the structure of TMP esters and only two such groups )10.5 °C, respectively) in comparison to natural lard
in the molecules of NPG esters. Both the synthesized (þ32.3 °C) was observed.
esters and native triglycerides studied have a high vis- The resistance to oxidation and thermal treatment,
cosity index, around 200 and higher. Moreover, the expressed by an increase in the acid number (DAc) and
viscosity index is slightly higher for the synthesized viscosity (Dm), follows this pattern:
esters than that of native triglycerides. This is a highly
lard—Filtrate II  olive oil > rapeseed oil
desirable property in view of their use as lubricants.
The viscosity of liquid with high viscosity indices This trend is connected with the presence of poly-
changes very little with temperature. High viscosity in- unsaturated fatty acids which play a crucial role. Since
dex is characteristic of compounds which have long, rapeseed oil has the highest content of such acids, the
unbranched hydrocarbon chains, e.g. fatty acids of most products derived from it are less resistant to the action
natural triglycerides. of oxygen and high temperature. Moreover, the kind of
 S. Gryglewicz et al. / Bioresource Technology 87 (2003) 35–39 39

alcohol used has a great influence on the thermo-oxi- References

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