Eur. J. Lipid Sci. Technol.

2010, 112, 519–530 519

Review Article
Biolubricants: Raw materials, chemical modifications and
environmental benefits

Jumat Salimon1, Nadia Salih1 and Emad Yousif2

1
School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, Bangi, Selangor, Malaysia
2
Department of Chemistry, College of Science, Al-Nahrain University, Baghdad, Iraq

The depletion of the world’s crude oil reserve, increasing crude oil prices, and issues related to
conservation have brought about renewed interest in the use of bio-based materials. Emphasis on the
development of renewable, biodegradable, and environmentally friendly industrial fluids, such as
lubricants, has resulted in the widespread use of natural oils and fats for non-edible purposes. In this
study, we have reviewed the available literature and recently published data related to bio-based raw
materials and the chemical modifications of raw materials. Additionally, we have analyzed the impacts
and benefits of the use of bio-based raw materials as functional fluids or biolubricants. The term
biolubricants applies to all lubricants, which are both rapidly biodegradable and non-toxic to
humans and other living organisms, especially in aquatic environments. Biodegradability provides an
indication of the persistence of the substance in the environment and is the yardstick for assessing the eco-
friendliness of substances. Scientists are discovering economical and safe ways to improve the properties
of biolubricants, such as increasing their poor oxidative stability and decreasing high pour points.
‘‘Green’’ biolubricants must be used for all applications where there is an environmental risk.

Keywords: Biolubricants / Eco friendly / Environmentally acceptable lubricants / Plant oil / Renewable

Received: September 17, 2009; Revised: January 22, 2010; accepted: February 2, 2010
DOI: 10.1002/ejlt.200900205

1 Introduction
The use of natural fats and oils by man dates back to antiq-
uity. The chemical composition of fats and oils and their
specific properties have allowed them to be used as foods,
fuels and lubricants. The sources of natural fats and oils are
numerous and encompass vegetable, animal and marine
sources. The usefulness of fats and oils are determined by
their chemical nature, and these compounds have common
characteristics. Fats and oils are naturally occurring substan-
ces that consist – predominantly – of mixtures of fatty acid
esters derived glycerol [1].
The present emphasis on conservation has brought about
renewed interest in the use of these ‘‘natural oils’’ for non-
Correspondence: Professor Dr. Jumat Salimon, School of Chemical
Sciences & Food Technology, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
E-mail: jumat@ukm.my
Fax: þ60 3 8921 5410
Abbreviations: PE, pentaerythritol; PP, pour point; PTSA, p-
toluenesulfonic acid; TMP, trimethylolpropan
edible purposes. The sources of natural oils and fats come
from various plants and animals-based raw materials (e.g., soy
bean, palm, tallow, lard) [2]. Plant oils are superior in terms
of biodegradability, especially when compared to mineral
oils. Attention has been focused on technologies that incorp-
orate plant oils as biofuels and industrial lubricants [3], due to
the fact that they are renewable and non-toxic.
The application of plant oils and animal fats for industrial
purposes, specifically as lubricats, has been in practice for
many years. Environmental and economic reasons lead to the
utilization of plant oils and animal fats, or used oils and fats
after their appropriate chemical modification. Plant oil-based
lubricants and derivatives have excellent lubricity and bio-
degradability, for which they are being investigated as a base
stock for lubricants and functional fluids [4].
Biodegradation is the process by which organic substan-
ces are broken down by the enzymes produced by living
organisms. The term is often used in relation to ecology,
waste management, and environmental remediation (biore-
mediation). Organic material can be degraded aerobically,
with oxygen or anaerobically, without oxygen. A term related
to biodegradation is biomineralization, in which organic mat-
ter is converted into minerals. By definition, biodegradation is

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520 J. Salimon et al. Eur. J. Lipid Sci. Technol. 2010, 112, 519–530

Table 1. Oleochemicals for selected applications

Product/use Source

Polymer materials
Polymerized soybean oil, castor oil Drying oils Soybean oil, castor oil
Polymerized linseed oil Linoleum Linseed oil
Additives
Epoxides Stabilizers, plasicizers Soybean oil
Soaps (Ba/Cd, Ca/Zn) Stabilizers stearic acid
Fatty acid esters,- amides Lubricants Rapeseed oil
Building blocks
Dicarboxylic acids Polyamides, polyesters, alkyl resins, lubricants Tall oil, soybean oil, castor oil
Ether-/ester polyols Polyurethanes, lubricants Sunflower oil, linseed oil, oleic acid

the chemical transformation of a substance by organisms or
their enzymes [5].
Plant oils have different unique properties compared to
mineral oils, due to their unique chemical structure. Plant oils
have a greater ability to lubricate and higher viscosity indices.
Superior anticorrosion properties are observed in vegetable
oils and are induced by a greater affinity for metal surfaces.
High flash points over 3008C classify vegetable oils as non-
flammable liquids. However, the applicability of vegetable
oils in lubrication is partly limited, as these oils tend to show
low oxidative stability and higher melting points. Chemical
modification of vegetable oils is an attractive way of solving
these problems [6]. Biolubricants formulated from plant oils
should have the following advantages derived from the chem-
istry of the base stock:
(i) Higher lubricity leading to lower friction losses, yield-
ing more power, and better fuel economy.
(ii) Lower volatility resulting in decreased exhaust
emissions.
(iii) Higher viscosity indices.
(iv) Higher shear stability.
(v) Higher detergency eliminating the need for detergent
additives.
(vi) Higher dispersancy.
(vii) Rapid biodegradation and hence decreased environ-
mental/toxicological hazards.
This paper gives a short overview of biolubricants and
provides specific examples of the chemical modifications of
plant oil-based materials for biolubricants. Additionally, a
discussion on the contribution of biolubricants to the
reduction of environmental hazards is included.
2 Oleochemicals as raw materials
Oleochemicals have been used in polymers for a long period
of time. One can differentiate between the use of oleochem-
icals as polymer materials and lubricants. Traditionally, oleo-
chemicals such as linseed oil and soybean oil have been used
as drying oils in the polymer industry. Oleochemicals have
also been used as polymer additives, such as epoxidized
soybean oil, which is used as a plasticizer. Oleochemicals
are used as monomers for polymer, such as dicarboxylic
acids, which are used in polyesters or polyamides
(Table 1) [7]. Naturally derived materials continue to find
use in polymer-related and lubricant-based applications,
especially in niche markets [8, 9].
Oleochemical-based monomers, such as epoxidized oils,
maleinated oils, and amidated fats are under investigation
[10]. Oleochemical-based dicarboxylic acids, such as azelaic,
sebacic, and dimer acid (Fig. 1) amount to
100 000 tones /
year are used as base materials for polymers and lubricants.
Oleochemical dicarboxylic acids approximate is about 0.5%

Figure 1. Building blocks for oleochemicals

based on natural oils.

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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530 Biolubricants: Raw materials, chemical modifications and environmental benefits
of the total dicarboxylic acid market for monomers, where
phthalic and terephthalic acids represent 87% [11, 12].
The chemical nature of these oleochemical-derived dicar-
boxylic acids tends to alter or modify condensation polymers,
and will therefore remain in a special niche market. Some
desirable properties related to oleochemical derived dicar-
boxylic acids are elasticity, flexibility, high impact strength,
hydrolytic stability, hydrophobicity, lower glass transition
temperatures, and flexibility [13]. The critical reaction in
the development of oleochemicals as building blocks in poly-
meric materials, coating, and lubricants, is conducted on the
double bond of unsaturated triacylglycerol or fatty acids.
These reactions such as caustic oxidation, ozonolysis, dime-
rization, autooxidation, epoxidation, and epoxide ring open-
ing are important processes (Fig. 2) [14]. In the following
sections recent developments in the field of biolubricants will
be presented in greater detail.
3 Biolubricants and the environment
Strong environmental concerns and growing regulations over
contamination and pollution in the environment have
increased the need for renewable and biodegradable lubri-
cants. Accelerating research and development in this area has
also been driven by public demand, industrial concern, and
government agencies. Better ways to protect the ecosystem or
reduce, or reduce the negative impact of spills or leakage of
lubricants must be outlined [15]. Many terms are used for the
classification of lubricants and include products that are
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521
Figure 2. Dimerization of unsaturated fatty
acids.
environmentally friendly, environmentally acceptable, biode-
gradable, non-toxic, etc. Approximately 1% of the total
mineral oil consumption is used to formulate lubricants.
Figure 3 reveals the volume of the worldwide lubricant
market, showing that about one third of all lubricants are
consumed in Europe, America, and Asia. Between 13% (EC
countries) and 32% (USA) of all used lubricants return to the
environment with altered physical properties and appearan-
ces [16]. These lubricants included those used in frictional
loss lubrication and total
40 000 tons annually in Germany.
Lubricants that remain in the environment also include those
used in circulation systems, which are not collected and
disposed. In addition, leaked lubricants and those remaining
in filters or containers have to be taken into account.
Altogether, the environment in Germany is exposed to about
150 000 tons annually. This value is based on the on the static
mentioned above and represent the lubricant volume that
returns to the environment [17]. A calculation based on the
actual lubricants consumption in Germany and the disposal
Figure 3. Worldwide consumption of lubricants.
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522 J. Salimon et al.
rates for different types of lubricants results in about
250 000 tons annually. Once the volume representing lost
lubricants and undefined lubricants is accounted for the total
volume of lubricants in Germany returning to the environ-
ment may be on the order at least 300 000 t/a [18].
The production, application, and disposal of lubricants
have to meet the requirements for the best possible protection
of the environment and of living beings in particular. Most
often, health hazards to humans are derived from indirect
routes through the environment. For all cases of direct con-
tact between lubricants and human beings, compatibility has
to be verified. All measures have to be taken to keep the
impairment of the environment at the lowest possible level. In
evaluating acceptable detrimental effects upon the environ-
ment, the benefit of lubricants, such as their performance or
economic properties, must be considered and weighed
against the risks associated with these lubricants [19].
4 Environmental definition aspects of
biolubricants
A lubricant is a substance (often a liquid) introduced between
two moving surfaces to reduce the friction between them,
improving efficiency and reducing wear. Lubricants dissolve
or transport foreign particles and distribute heat. Some bio-
lubricants also contain small amounts of additives. Plant oils
or synthetic liquids such as hydrogenated polyolefins, esters,
silicone, and fluorocarbons are used as base oils. Additives
deliver reduced friction and wear, increased viscosity,
improved viscosity index, resistance to corrosion and oxi-
dation, aging or contamination, etc. [24]. In addition to
industrial applications, lubricants are used for many other
purposes. Other uses of lubricants include bio-medical appli-
cations (e.g., lubricants for artificial joints) and the use of
personal lubricant for sexual purposes. In an attempt to
classify lubricants according environmental risk, many differ-
ent terms have been established (Table 2).
It is useful to rank the terms related to environment risk,
as in Table 3. According to this catergorization, no lubricant
can be regarded as environmentally friendly, because this
term implies an improvement to the environmental con-
ditions. One has to be content with the fact that the lubricant
is environmentally acceptable and that it affects the environ-
ment to a less pronounced degree [21].
5 The role, functions, and requirements of a
lubricant
A lubricant is a material used to facilitate the relative motion
of solid bodies by minimizing friction and wear between
interacting surfaces. In addition to the primary purposes of
reducing friction and wear, lubricating oils are also required
to carry out a range of other functions, including the removal
of heat, corrosion prevention, and the transfer of power.
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530
Table 2. Terms regarding lubricants and the environment
Environmentally positive – non-injurious
Environmentally friendly – eco-friendly
Environmentally sociable – socially friendly
Environmentally justified – environmentally favorable
Environmentally careful – environmentally conservative
Environmentally neutral – harmless to the environment
Environmentally protective – preserves the environment
Environmentally conformable – respectful of the environment
Table 3. Common terms related to the environment
Friendly – improves the environment
Neutral – unimportant, harmless
Threshold of Perception
Sociable – low, unsuitable
Start of Legal Regulations
Annoying – disagreeable, unpleasant, impairing
Irksome – troublesome, inconvenient
Limit of Burdening
Endangering – excessive, unimputable
Harmful – dangerous, irreversible effects
Additionally, lubricants must provide a liquid seal at moving
contacts and remove of wear particles. In order to perform
these roles, lubricating oils must have specific physical and
chemical characteristics. Perhaps the fundamental require-
ment of lubricants is that the oil should remain a liquid over a
broad range of temperatures. In practice, the usable liquid
range is limited by the pour point (PP) at low temperatures
and the flash point at high temperatures. The PP should be
low to ensure that the lubricant is pump-able when the
equipment is started from extremely low temperatures
[22]. The flash point should be high to allow the safe oper-
ation and minimum volatilization at the maximum operating
temperature. For the most demanding applications, such as
aviation jet engine lubricants, an effective liquid range over
3008C may be required. The efficiency of the lubricant in
reducing friction and wear is greatly influenced by its
viscosity. The relationship between speed, viscosity, load,
oil film thickness, and friction is illustrated by the Stribeck
diagram (Fig. 4) [24].
Furthermore, biodegradability is the most important
aspect with regard to the environmental fate of a substance.
Primary degradation is the first step in the breakdown of a
substance and involves the disappearance of the original
molecule. However, the determination of the ultimate
degradability or the mineralization of substances to
CO2, H2O, and the formation of biomass is important.
Ultimate biodegradability guarantees the safe reintegration
of the organic material in the natural carbon cycle
and is important for its environmental classification.
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530 Biolubricants: Raw materials, chemical modifications and environmental benefits
Figure 4. Stribeck diagram. The coefficient of friction for bearing is
plotted against the dimensionless duty parameter mN/s, where m is
the dynamic viscosity of the lubricant, N the rotational speed of the
shaft, and s is the loading force per unit area [24].
Biodegradability depends more on the chemical structure of
the lubricant than on its water solubility.
5.1 Basic properties and benefits of biolubricant
The term biolubricants applies to all lubricants that are both
rapidly biodegradable and non-toxic to humans and aquatic
environments. A biolubricant may be plant oil-based (e.g.,
rapeseed oil) or derived from synthetic esters manufactured
from modified renewable oils or from mineral oil-based prod-
ucts [18, 20]. Table 4 summarizes some of the benefits of
biolubricants.
Table 4. Benefits of biodegradable lubricants
Less emission – due to the higher boiling temperatures of esters. Native
triacylglycerol leads to partly gummy structures at high temperature
and can accumulate acroleins, which are irritating.
Totally free of aromatics – over 90% biodegradable oils, non-water
polluting.
Oil mist and oil vapor reduction-leads to less inhalation of oil mist into
the lungs.
Better skin compatibility – less dermatological effects.
High cleanliness at the work place.
Equal and often higher tool life – due to a higher wetting tendency of
polar esters, which leads to a reduction in friction.
Higher viscosity index – viscosity does not vary with temperature as
much as mineral oil. This can be an advantage when designing lubri-
cants for use over a wide temperature range. This can also result in
lower viscosity classes for the same applications combined with easier
heat transfer.
Higher safety on shop floor – higher flashpoints at the same viscosity.
Cost savings on account of less maintenance, man power, storage, and
disposal costs.
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6 Biolubricants laws and regulations
In several European countries regulations and policies exist in
favor of biolubricants [25]:
(i) In Germany, Austria, and Switzerland regulations are
in place that forbid the use of mineral oil-based lubri-
cants around inland waterways and in forest areas.
In addition, the German federal government has
introduced a program called ‘‘Market Introduction
Program (MIP) Biolubricants and Biofuels’’ for the
reimbursement of costs associated with substituting
mineral oil-based lubricants for lubricants based on
renewable resources with a mass content greater than
50%. This program, which is managed by the German
Agency of Renewable Resources, is a success especially
for hydraulic fluids.
(ii) The Swedish City of Gothenburg has set up an advice
and technology program for lubricant products, which
has encouraged the manufacturing industry to switch
to biolubricants. This so-called ‘‘Ren Smörja’’ (Clean
Lubricants) project was a co-operation between
municipal authorities, consultants, and industries
and has resulted in environmental criteria for lubricat-
ing greases and hydraulic fluids. These criteria have
been identified and are now a part of Swedish
Standards. In addition, in the Scandinavian countries
a tax exemption on biolubricants is in place.
(iii) In Italy, there is a tax on mineral oils and products that
contain them.
(iv) In 1991, Portugal introduced a regulation mandating
the use of biolubricant two-stroke engine oils in out-
board boat engines.
(v) Belgium has enacted legislation that requires biolubri-
cants to be used in all operations that take place near
non-navigable waters.
(vi) In the Netherlands, the Dutch Ministry of Spatial
Planning, Housing and the Environment issued a
policy and action program in favor of biolubricants
in 1996. Tax incentives affecting biolubricants are
operated under the Dutch VAMIL, which allows for
the accelerated depreciation of environmental
investments.
(vii) Within the USA, the Department of Agriculture is
proposing the establishment of guidelines for the
designation of items made from bio-based products
(including plant-based lubricants) that would be given
federal procurement preference, as required under the
Farm Security and Rural Investment Act of 2002.
7 Chemical structure of plant, mineral, and
synthetic oils
Plant oils are composed mostly of triacylglycerol (98%) and
contain of different fatty acids attached to a single molecule of
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524 J. Salimon et al.
glycerol. They also contain minor amounts of mono- and di-
glycerols (0.5%), free fatty acids (0.1%), sterols (0.3%), and
tocopherols (0.1%) [25]. Fatty acids are mainly long chain
(C18–C24) unbranched aliphatic acids, with hydrogen atoms
attached to carbons and other groups, and a carboxylic acid
terminating the chain. The shortest non-branched fatty acid
chains (C6) is water-soluble due to the presence of the polar
–COOH group. By increasing the length of the chain, the
fatty acid takes on oily or fatty characteristics and becomes
increasingly less water-soluble. The carbon chain of a fully
saturated fatty acid is straight. When hydrogen atoms are
missing from adjacent carbon atoms, the carbons share a
double bond instead of a single bond. This type of fatty acid
is called an unsaturated fatty acids. These acids have lower
melting points than saturated fatty acids. The fatty acid is
polyunsaturated if double bonds occur at multiple sites.
Therefore fatty acids can be classified as being saturated,
mono-, di-, tri-unsaturated, etc. [26].
Mineral oils, on the other hand, are extremely complex
mixtures of C20–C50 hydrocarbons containing a range of
linear alkanes (waxes), branched alkanes (paraffinics), alicy-
clic (naphthenic), olefinic, and aromatic species. They also
contain significant amounts of heteroatoms, mainly sulfur.
Mineral oils are more stable, cheaper, and more readily
available than natural oils, and are also available in a wider
range of viscosities. One issue regarding mineral oils is that
oils derived from different fields have different characteristics.
Another issue regarding mineral oils is the volatilization of
low molecular weight components, which leads to a tendency
to thicken during use. The presence of low molecular weight
components also reduce the flash point of mineral oils com-
pared to natural oils of the same viscosity [27].
There are some applications where performance require-
ments cannot be met by mineral oils, and it is necessary to
chemically synthesize base lubricants with superior proper-
ties. There are a range of synthetic lubricants such as poly(a-
olefins) (PAOs). These lubricants have characteristics similar
to highly refined paraffinic mineral oils, but with a
more narrowly defined molecular weight distribution.
Alkylbenzenes are a class of synthetic hydrocarbons, although
the lubricant industry now almost exclusively uses branched
alkylbenzenes, as they have better low temperature fluidity
[28]. Synthetic organic esters are another class of widely used
lubricants. Examples include esters derived from C8–C13
mono-alcohols and diacids such as adipic acid (diesters)
and esters of C5–C18 monoacids with neopentyl polyols, such
as pentaerythritol (PE, polyol esters). The presence of the
ester group confers low temperature fluidity and reduces
volatility at high temperatures. It also provides an affinity
for metal surfaces. Esters were originally developed for the
lubrication of aircraft jet engines but have subsequently found
wide-spread use, particularly in applications where biode-
gradability is required [29]. For applications where chemical
stability is an overriding requirement, non-hydrocarbon-
based fluids such as poly(dimethyl siloxanes) and
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530
perfluoroalkyl ethers may be used. However, the use of these
non-hydrocarbon-based lubricants is restricted by their rela-
tively high cost and their incompatibility with other lubricants
and standard additives. All synthetic lubricants are normally
used as formulations containing the same types of functional
additives as are used in mineral oils [30]. Table 5 shows
further informations regarding synthetic lubricants available
on the market.
8 Modification of plant oils for biolubricants
Direct applications of plant oils as lubricants are less favor-
able due to a variety of factors. Plant oils have poor oxidative
and thermal stability, which is due to the presence of acyl
groups. The presence of the glycerol backbone in oil gives
tertiary b-hydrogen, which is thermally unstable. The chemi-
cal modification of plant oils by addition reactions to the
double bonds constitutes a promising manner of obtaining
valuable commercial products from renewable raw materials.
In order to use plant oil-based lubricants with special addi-
tives, chemical modifications, de novo synthesis, breeding,
and/or biotechnology play an important role. These methods
improve the performance and stability of base oils in lubricat-
ing formulations. They also provide a sufficient capacity of
plant-based oil substrates for green engineering.
8.1 Antioxidants and other additives
As outlined above, lubricants and hydraulic fluids are
materials that are composed of a base fluid and additives.
In hydraulic fluids additives account for only 1–2% of the
formulation and
10% of the total volume in motor lubri-
cants. In transmission oils, additives constitute about 30% of
the formulation. Typically, additives are used as antioxidants,
rust (corrosion) inhibitors, de-emulsifiers, wear reducers, PP
depressors, and hydrolysis inhibitors. Most additives are
common in mineral and plant oils, but the toxicity of cur-
rently used additives require research on the development
and use of alternatives bio-based additives.
Naturally occurring antioxidants such as tocopherol (vita-
min E), L-ascorbic acid (vitamin C), esters of gallic acid, citric
acid derivatives, or lipid-modified EDTA derivatives serve as
synthetic metal scavengers and may be investigated as altern-
atives to the currently used toxic antioxidants [31].
8.2 Chemical modifications
Chemical modifications such as epoxidation, estolides for-
mation, and tranesterification of plant oils with polyols have
been shown to improve the oxidative stability of plant oil-
based lubricants and to achieve optimal characteristics for
extreme applications [13].
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530 Biolubricants: Raw materials, chemical modifications and environmental benefits 525

Table 5. Type and application of synthetic lubricants

Class Type Operating Applications Advantages Limiting

temp. (8C) vs. mineral oil properties

Synthesized fluids Polyalphaolefins, 155 to 45 Machine tool High temperature Solvency/detergency,
hydrocarbons (SFHs) alkylated aromatics, spindles, stability, long life, seal compatibility
polybutenes, freezer Low temperature
cycloaliphatic plants-motors, fluidity, high
conveyors, viscosity index,
bearings Improved wear
protection,
Low volatility,
oil economy
Organic esters Dibasic acid ester, 204 to 35 Commercial No wax, high Seal compatibility,
polyol ester manual temperature mineral oil compatibility,
transmission stability, antiwear and extreme
long life, pressure, hydrolytic
low temperature stability, paint
fluidity, compatibility
solvency/detergency
Phosphate esters Triaryl phosphate ester, 180 to -18 Hydraulic Fiber resistance, Seal compatibility, low
(phosphoric trialkyl phosphate ester, systems lubricating ability viscosity index,
acid esters) mixed alkylaryl paint compatibility,
phosphate esters metal corrosion,
hydrolytic stability
Polyglycols Polyalkylene, 245 to 20 Gas turbines Water versatility, Mineral oil compatibility,
polyoxyalklylene, high viscosity index, paint compatibility,
polyethers, glycols low temperature fluidity, oxidation stability
antirust, no wax

8.2.1 Epoxidation of the carbon–carbon double bond
Plant oils and animal fats are increasingly used as green raw
materials in various areas of industry. In the field of lubri-
cants, environmental, and economic reasons lead to the util-
ization of plant oils and animal fats, or used oils and fats after
appropriate chemical modifications. The temperature flow
property of pant oils is extremely poor, and this limits their
use at low operating temperatures, especially in automotive
and industrial fluids. Plant oils have a tendency to form
macrocrystalline structures at low temperatures through
uniform stacking of the ‘‘bend’’ in the triacylglycerol back-
bone. Such macrocrystals restrict flow due to the loss of
kinetic energy of individual molecules during self-stacking.
Several diester compounds have been synthesized from com-
mercially available oleic acid and common fatty acids
[32–35]. The key steps in the three step synthesis of oleo-
chemical diesters includes epoxidation and ring opening of
epoxidized oleic acid with different fatty acids (octanoic, non-
anoic, lauric, myristic, palmitic, stearic, and behenic acids)
using p-toluenesulfonic acid (PTSA) as a catalyst to yield
mono-ester compounds. The esterification reaction of these
compounds with butanol, isobutanol, octanol, and 2-ethyl-
hexanol was further carried out in the presence of 10 mol%
H2SO4, producing the desired diester compounds (Fig. 5)
[32–35].
Not surprisingly, as the length of the mid-chain increase, a
corresponding improvement in low temperature behavior is
observed. This phenomenon is due to the increased ability of
the long chain esters to disrupt macrocrystalline formation at
low temperatures. Another observation is the positive effect
of branching at the chain end on the low temperature per-
formance of the resultant products, which leads to the
formation of microcrystalline structures rather than macro-
crystalline structures.
8.2.2 Estolides of oleic acid and saturated fatty acids
Estolides are a class of esters-based on plant oils and are
synthesized by the formation of a carbocation at the site of
unsaturation. This carbocation can undergo nucleophilic
attack by other fatty acids, with or without carbocation
migration along the length of the chain, to form an ester
linkage. Estolides were developed to overcome some of the
short-falls associated with plant oils, such as poor thermal
oxidative stability [36] and poor low temperature properties
[29]. Some deficiencies can be improved with the use of
additives but usually at the expence of biodegradability,

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526 J. Salimon et al.
toxicity, and cost. Cermak and Isbell [37] synthesized satu-
rated mono-estolide esters and enriched saturated mono-
estolide 2-ethyl hexyl esters from oleic and saturated fatty
acids using three different synthetic routes (Fig. 6). The
estolide numbers (ENs), the average number of fatty acid
units added to a base fatty acid, varied and was dependent on
synthetic conditions. The physical property data indicated
that both chain length and EN affect low temperature
properties.
Tallow is a fat that is derived primarily from cattle, but can
also be obtained from sheep and goats. Some researchers
have used tallow as source of animal fats because the demand
for tallow in the global food market has gradually decreased
due to health concerns and competition from other fats and
oils. Value-added products, such as nutraceuticals, cleaning
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530
Figure 5. Epoxidation of oleic acid, followed
by ring opening acylation of EOA using PTSA
as a catalyst. RCOOH is octanoic, non-anoic,
lauric, myristic, palmatic, stearic, and behenic
acid. The esterification reaction was carried out
using alcohol (butanol, isobutanol, 2-ethylhex-
anol, octanol) and H2SO4 as a catalyst.
solvents, and biofuels are developed from tallow to improve
its commercial value [38]. Tallow is currently in use as an
edible oil but is slowly being replaced with healthier oils. With
the slow trend away from edible applications to industrial
applications, tallow is found in a wide range of products from
plastics [39] to lotions and softeners [40], soaps and deter-
gents [41], tires [42], candles [43], paints and varnishes [44],
lubricants and fuels [45], and even pharmaceuticals [46].
Foglia et al. [47] determined the low-temperature proper-
ties of alkyl esters derived from tallow and recycled greases in
neat esters and 20% ester blends in No. 2 low-sulfur diesel
fuel. The properties studied included cloud point (CP), PP,
cold filter plugging point (CEPP), low-temperature flow test
(LTFT), crystallization onset temperature (Tc), and kin-
ematic viscosity. The compositional properties of the alkyl
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530 Biolubricants: Raw materials, chemical modifications and environmental benefits
Figure 6. Schematics of the synthesis of oleic estolide esters.
esters determined included water, residual free fatty acids,
and free glycerol content. In general, secondary alkyl esters of
tallow showed significantly improved cold-temperature prop-
erties over normal tallow alkyl ester derivatives. Wu et al. [48]
prepared three monoalkyl fatty acid esters derived from tal-
low and grease by lipase-catalyzed transesterification and
evaluated the esters as prospective diesel engine fuels. The
low temperature properties of the esters, both neat and as
20% blends in No. 2 diesel fuels were evaluated. The proper-
ties investigated included CP, PP, CEPP, LTFT and crys-
tallization onset temperature. Other properties of the esters,
such as kinematic viscosity, heating value, and calculated
cetane number, were also determined. All three esters had
acceptable physical and low-temperature properties as well as
acceptable fuel properties, when used as a 20% blend in
diesel. Tallow-oleic estolide 2-ethylhexyl (2-EH) esters were
synthesized in a one-pot perchloric acid-catalyzed process
from 90% industrial oleic and tallow fatty acids with varying
ratios. Varying the ratio of tallow and oleic fatty acids, along
with the esterification process, provided a functional fluid
that may be used as a lubricant [49] (Fig. 7):
8.3 Organic polyesters synthesis
Biodegradable organic polyesters derived from the transes-
terification/esterification of plant oils and branched neopo-
lyols such as trimethylolpropan (TMP) and PE have been
developed for various applications (Fig. 8). Uosukainen et al.
[50] described the synthesis of biodegradable TMP [2-ethyl-
ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
527
2-(hydroxymethyl)-1,3-propanediol esters of rapeseed oil
fatty acids via enzymetic and chemical methods. Sodium
methylate (0.5% w/w) was employed as catalyst, and the
reaction mixture was refluxed under a reduced pressure of
3.3 kPa. Approximately 99% conversion was achieved at
110–1208C in 10 h. Using 40% w/w Candida rugosa lipase,
only 64% of the TMP was converted to triesters in 24 h at
5.3 kPa at 478C. With immobilized Rhizomucor miehei (50%
w/w), the highest conversion to the TMP triester was 90%
and was achieved in 66 h.
Yunus et al. [51] demonstrated that palm oil TMP esters
containing 98% w/w triester can be successfully synthesized
in less than an hour. The chemical transesterification of TMP
with palm oil methyl esters was attainable under a reduced
pressure of at least 20 mbar at T ¼ 1208C with a 3.9:1 molar
ratio and the use of sodium methoxide as a catalyst. The
optimum molar ratio was established as 3.9:1, and the cata-
lyst was required at less than 1.0% w/w, a quantity far less
than the lipase required for enzymatic transesterification
(40–50% w/w [50, 52]).
Esters of neopentylpolyols were prepared by an esterifi-
cation reaction between PE and erucic acid catalyzed by 4-
toluenesulfonic acid ( p-PTSA) in xylenes [53]. The reaction
mixture was heated to 2008C under a nitrogen atmosphere.
Since PE becomes the backbone of the new esters, four types
of esters were obtained and included: – tetra, tri, di, and
monoesters. These esters provided improved low tempera-
ture behavior. Animal fats were also used to synthesize polyol
esters using calcium methoxide, but the rate of the reaction
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528 J. Salimon et al.
Figure 7. Reaction scheme for the formation of tallow-oleic estolide 2-ethylhexyl ester.
Figure 8. TMP transesterification.
was slow. The yield of the reaction was 85–90% after 20 h
[54]. A two-stage low temperature crystallization process was
used to improve the PPs.
9 Biolubricants and triboreactive materials for
automotive applications
Replacing hydrocarbon-based oils with biodegradable prod-
ucts is one of the ways to reduce adverse effects on the
ecosystem caused by the use of lubricants. The use of low
or no sulfur, low ash and phosphorous (low SAP) esters- or
polyglycol-based oils (intended for passenger car engine
lubricants as substitutes for hydrocarbon-based oils) requires
the preparation of a composition of lubricants with
ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Lipid Sci. Technol. 2010, 112, 519–530
comparable tribological and functional properties. Igartua
et al. [55] summarized the results obtained when developing
biodegradable passenger car lubricants in combination with
triboreactive materials. The study was focused on passenger
car motor oils (PCMO) with reduced metal–organic addi-
tives. This was necessary in order to reduce the ash build-up
in the treatment system and to improve its efficiency and
lifetime. High fuel efficiency and long drain intervals are also
necessary. Additionally, these oils have to be biodegradable
and non-toxic to aqueous environments, according to the
directive EC/1999/45, which is in agreement with other
international standards. In a modern diesel or gasoline
engine, the engine oils has to fulfill a number of functions,
such as lubricating and cooling the system, protecting against
wear, the handling of soot and particles with low deposit
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Eur. J. Lipid Sci. Technol. 2010, 112, 519–530 Biolubricants: Raw materials, chemical modifications and environmental benefits
tendency, etc. The study of the biodegradability, toxicity, and
tribological properties has been carried out for newly devel-
oped prototype engine bio-oils. Furthermore, plasma-
sprayed triboreactive coatings have been deposited on cast
iron piston rings and studied for their tribological properties.
Finally, the behaviors of bio-oils and plasma-sprayed tribor-
eactive coatings on piston rings have been screened in a real
engine.
10 Conclusions
A tremendous demand for plant oils in the lubricant industry
is expected over the next few years because plant oils are
natural, renewable, non-toxic, non-polluting, and cheaper
than synthetic oils. They will become an important class of
base stocks for lubricant formulations due to their positive
qualities. Due to growing environmental concerns, plant oils
are finding their way into lubricants for industrial and trans-
portation purposes. Plant oils, in comparison to mineral oils
have different properties due to their unique chemical struc-
tures. Plant oils have better lubrication ability, viscosity
indices, and superior anticorrosion properties, which are
due to the higher affinity of plant oils to metal surfaces. In
addition, flash points greater than 3008C classify plant oils as
non-flammable liquids. To improvement characteristics such
as sensitivity to hydrolysis and oxidative attacks, poor low
temperature behavior, and low viscosity index coefficients,
plant oils may be chemically modified. Plant oils may be used
in almost all automotive and industrial applications. It will
become more difficult to find a balance between the
economic possibilities of biolubricants and their ecological
requirements. Products with toxicological and ecological
issues must be excluded from further use in lubricants, if
they pose a significant health risk. However, it must be taken
into account that the technological level of lubricants will
decrease if unnecessary restrictions are put into place. In
conclusion, plant bio-based oils are an important part of
new strategies, policies, and subsidies, which aid in the
reduction of the dependence on mineral oil and other non-
renewable sources.
The authors acknowledge the Universiti Kebangsaan Malaysia for
funding (‘‘Code UKM-GUP-NBT-08-27-113’’ and ‘‘UKM-
OUP-NBT-28-145/2009’’), and the direct contributions of the
support staff from the School of Chemical Sciences and Food
Technology, the faculty of Science and Technology, Universiti
Kebangsaan Malaysia.
The authors have declared no conflict of interest.
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