Applied Catalysis A: General 221 (2001) 429–442

Lubricant base fluids based on renewable raw materials

Their catalytic manufacture and modification
Helena Wagner∗ , Rolf Luther, Theo Mang
Fuchs Petrolub AG, Friesenheimer Strasse 17, 68169 Mannheim, Germany

Abstract
Lubricants based on renewable raw materials and their derivatives are drawing increased attraction in various applications.
Here, the environmental awareness is the key factor of success. The use of such rapidly biodegradable materials is especially
favourable in loss-lubrication and hydraulic systems with increased risk of damage. Environmentally friendly, biodegradable
alternatives are available for a large variety of mineral oil based lubricants. The substitution of mineral oil with biodegradable
base oils is a primary objective. Vegetable oils are the major source of these base fluids. Compared to conventional mineral oil
based fluids most of such substances exhibit lower thermal and oxidation stability and even worse low-temperature behaviour.
These physical and chemical properties can be improved by chemical modification. This review covers chemical reactions
performed on fatty compounds on both laboratory and industrial scale. Economic processes are presented as well as new
reactions with potential market value. Alternative routes to improved rapidly biodegradable base fluids are mentioned too,
e.g. breeding successes with high oleic sunflower oil. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Renewable resources; Renewable raw material; Lubricants; Chemical modification; Vegetable oils; Oleochemicals; Biodegradable;
Environmentally friendly; Base fluids; Sustainable materials

1. Introduction so far. To increase this market share, the acceptance

About 1.15 million tonnes of lubricants are used ev-
ery year in Germany [1]. The 53% of this amount are
collected as waste oils. These are then recycled or
used as a source of heating energy. The rest, about
540,000 tonnes, is lost to the environment as a result
of leakages, total loss applications or system spe-
cific reasons where they can cause pollution of the
environment [1].
The use of rapidly biodegradable lubricants could
significantly reduce this environmental pollution. In
Germany, ecologically friendly lubricants currently
account for about 4–5% of all lubricants consumed
∗ Corresponding author. Tel.: +49-621-3802-226;
fax: +49-621-3802-159.
E-mail address: helena.wagner@fuchs-oil.de (H. Wagner).
and reliability of rapidly biodegradable lubricants
must be increased and their price must be reduced.
This is the objective of development work on new
high-performance lubricants. Ecological compatibility
as well as technical performance are major objectives
of all research and development projects.
From a technical point of view, it is accepted that
more than 90% of all present-day lubricants could be
formulated to be rapidly biodegradable. On the other
hand, a great deal of development work still needs to
be done and present costs are high [2,3].
Vegetable products as well as modified vegetable oil
esters can be used as a base stock for preparation of
environmentally friendly, rapidly biodegradable lubri-
cants. This review will cover the use of vegetable oils
and their derivatives as base fluids for such lubricants.
Special attention will be paid to new syntheses for

0926-860X/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 8 9 1 - 2
430 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
the manufacture of oleochemicals with the appropriate
characteristics for the lubricants sector. The produc-
tion of environmentally friendly, rapidly biodegrad-
able fluids for lubricants based on petrochemicals such
as polyalfaolefins, polyglycols, polyalkylene glycols
and synthetic esters has been disclosed in the literature
and various patents [2,4–7].
Some of the rapidly biodegradable lubricants are
based on pure, unmodified vegetable oils. In Europe
predominantly rapeseed oil and sunflower oil are
used. Chemically, these are esters of glycerine and
long-chain fatty acids (triglycerides). The alcohol
component (glycerine) is the same in all vegetable
oils. The fatty acid components are plant-specific and
therefore variable. The fatty acids found in natural veg-
etable oils differ in chain length and number of double
bonds. Besides functional groups may be present.
Natural triglycerides are very rapidly biodegradable
and are highly effective lubricants. However, their
thermal, oxidation and hydrolytic stability is limited.
Therefore, pure vegetable oils are only used in appli-
cations with low thermal stress. These include total
loss applications like mold release and chain saw oils.
The reason for the thermal and oxidative instabil-
ity of vegetable oils are the structural “double bond”
elements in the fatty acid part and the “␤-CH group”
of the alcoholic components (Fig. 1). In particular,
multiple double bonds are a hindrance for technical
application. Double bonds in alkenyl chains are espe-
cially reactive and already react with the oxygen in the
air. The ␤-hydrogen atom is easily eliminated from
the molecular structure. This leads to the cleavage of
the esters into acid and olefin. A further weakness
of natural esters is their tendency to hydrolyse in the
presence of water [8–10].
An improvement of the thermal, oxidative and hy-
drolytic stability of vegetable oils can be primarily
Fig. 1. Plant oil–glycerine ester of different fatty acids; critical points: ␤-CH-group and unsaturated fatty acid residues.
achieved by a chemical modification. Vegetable oils
are mostly split into their oleochemical components
such as fatty acids or fatty acid methylesters and glyc-
erine before they are modified. Fatty alcohols can be
formed out of fatty acid methylesters. However, the
vegetable oil can be directly modified, for example,
by direct transesterification or selective hydrogena-
tion. The most important modifications concern the
carboxyl group of the fatty acids. They accounts for
about 90% of the oleochemical reactions, whereas
reactions of the fatty acid chain only account for less
than 10% [11,12].
The present review will focus on modifications
which are of significance to manufacture lubricant
base fluids. The improvement of natural oils by plant
cultivation or genetic modification will be mentioned
briefly.
2. Modifications of the carboxyl group
2.1. Esterification/transesterification
One of the most important modifications of the car-
boxyl group of the fatty acid chain is the transesteri-
fication of the glycerine esters or the esterification of
the fatty acids obtained by cleavage of such esters.
Those processes are performed on large scale. Trans-
esterification or esterification reactions are normally
catalysed with acidic or basic catalysts. Typical homo-
geneous catalysts are p-toluene sulphonic acid, phos-
phoric acid, sulphuric acid, sodium hydroxide, sodium
ethoxide and sodium methoxide. In some cases, het-
erogeneous catalysts such as Sn-oxalate or cation ex-
change resins are used. Enzyme catalysed reactions
are also known [11–16]. Fig. 2 shows a general ester-
ification reaction.
 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442 431

Fig. 2. General esterification reaction.

The features of the substrates selected influence the
properties of the ester manufactured. The most impor-
tant properties for the use as lubricants are viscosity,
viscosity–temperature behaviour and oxidation stabil-
ity. At the same time, low-temperature behaviour and
evaporation tendencies are of significance as well as
their compatibility with technical materials such as
elastomers.
A broad variety of esters can be synthesised from
the available carboxylic acids (mono-, di-, polycar-
boxylic acids as well as aliphatic and aromatic car-
boxylic acids) and alcohols (diols, polyols as well as
linear and branched alcohols). The above-mentioned
properties can be influenced by the choice of the
divers alcohols and acids.
Some examples of esterification and transesterifica-
tion products are (see Fig. 3) as follows.
2.1.1. Mono-esters
Monocarboxylic acid esters are usually derivatives
of linear fatty acids with a C8 –C22 alkyl chain length
esterified with branched and/or linear mono-alcohols.
2.1.2. Dicarboxylic acid esters (diesters)
Typical dicarboxylic acid esters are synthesised, for
example, out of adipic acid, sebacic acid, azelaic acid
or dimeric fatty acid (see Section 3.2). These acids
can be esterified with alcohols such as 2-ethylhexanol,
isodecanol and Guerbet alcohols. Based on renew-
ables, sebacic acid is obtained from the oxidation of
castor oil in the presence of a Pb(II) oxide as catalyst
[12,17]. Azelaic and dimeric fatty acids are manufac-
tured in commercial processes using oleic acid a prin-
cipal components of vegetable oils (see Sections 3.2
and 3.5.2). Adipic acid, however is produced via the
oxidation of cyclohexane in the conventional petro-
chemical way.
2.1.3. Polyolesters
Polyolesters are formed from polyols with a quater-
nary carbon atom (neopentylalcohols) as for example
neopentylglycol, trimethylolpropane and pentaerythri-
tol. This class of products offer extraordinary stabil-
ity due to the absence of a secondary hydrogen in the
␤-position and the presence of a quaternary C-atom in
the centre.
2.1.4. Complex esters
Complex or oligomer esters can be prepared by the
esterification of polyols with mixtures of mono-, di-,
and tricarboxylic acid esters. Such processes result de-
pendent on reaction conditions in diverse oligomerig

Fig. 3. Structure of the different types of esters.

432 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442

mixtures with higher viscosity. They are highly vis-
cous and generally shear-stable.
In addition, intramolecular transesterification that
keeps the glycerine structure is possible. An example
for this reaction is the exchange of the long-chain
acidic residues of rapeseed oil (C18 ) being exchanged
for medium chain-length residues from palm oil
(C8 /C10 /C12 ). Such reactions are catalysed with acids
as well as alkalines. Here again, enzyme catalysed
reactions are known [18].
interest for other oleochemical applications such as
washing powders and detergents, cosmetics, paints
and additives. Many of these modifications are highly
promising, but at present, are still in the development
stage. Industrial and academic research institutes
are currently actively engaged in researching these
areas.
In the following captures, selected modification pro-
cesses of fatty acid chains which are of interest for the
lubricants sector are discussed.

3.1. Selective hydrogenation

3. Modifications of the fatty acid chain
Due to their high reactivity, the double bonds of
unsaturated fatty acids and their derivatives form ex-
cellent starting points for further modification. Some
modifications such as hydrogenation (foodstuff chem-
istry), epoxidation (PVC plasticisers and stabilisers,
paints and dyes) or dimerisation (bonders, hardeners)
became commercialised a long time ago.
In the field of lubricant base fluids, reactions at the
double bonds are used to increase the product stabil-
ity. At the same time, the introduction of functional
groups and branches change the physical properties
of those newly-created fluids considerably. For exam-
ple, ageing resistance can be improved by selectively
increasing the degree of saturation. The introduction
of branches improves the low-temperature behaviour
and hydrolytic stability. Furthermore, the polarity can
be altered by the introduction of hetero-atoms such as
oxygen or nitrogen.
Generally speaking the chemical structure of
the substances influence the physical properties as
follows:
The hydrogenation of double bonds in unsaturated
fatty compounds is performed on large scale. This pro-
cess primarily serves to improve the stability as well
as to increase the melting point of unsaturated fatty
derivatives [12,13,19]. In industrial processes hetero-
geneous catalysts such as carrier catalysts (palladium
on active carbon), skeletal catalysts (Raney-Nickel)
or metal oxide catalysts (copper-chrome oxide) are
mostly used.
Selective hydrogenation, in which the fatty acid
residue is not fully saturated, is of greatest interest in
the area of lubricant chemistry. Natural fats and oils
often contain multiple unsaturated fatty acids such as
linoleic- and linolenic acid, which seriously impair
the ageing stability of the oil even if they are present
in very small quantities. Selective hydrogenation can
transform the multiple unsaturated fatty acids into
single unsaturated fatty acids without increasing the
saturated part of the substance. This is necessary to
avoid a deterioration in low-temperature behaviour
such as on the pour point. Not wanted but some-
times resulting from selective hydrogenation is the

High degree of branching Outstanding low-temperature characteristics, high hy-

drolytic stability, low viscosity index
High linearity High viscosity index, relatively poor low-temperature characteristics
Low saturation Outstanding low-temperature characteristics, limited oxidation stability
High saturation Outstanding oxidation stability, poor low-temperature characteristics

At present, less than 10% of the known reactions
of fatty acid chains are industrially applied. These
possibilities represent a great potential for expand-
ing the oleochemical product line in the future and
the greater economic exploitation of vegetable oils
and fats. These reactions are also of considerable
formation of configurational- and cis/trans-isomers
of the remaining double bonds. By selective hy-
drogenation the easily oxidisable compounds are
transformed into more stable components. This sig-
nificantly improves the ageing behaviour of the
oils.
 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
Fig. 4. Selective hydrogenation of linolenic acid methyl ester.
Up to now, the problem of the selective hydrogena-
tion of multiple unsaturated fatty acids was only solved
partially. This is a hot topic in industrial and univer-
sity research institutes that are testing various hetero-
geneous and homogeneous catalytic systems [20–27].
One example is the selective hydrogenation with
Ziegler–Sloan–Lapporte catalysts. In the presence of
a system based on palladium-bis-(acetylacetonate)
and triethyl aluminium, linoleic acid methylester
(C18:2) can be transformed into the C18:1 ester with
a selectivity of 92% at a conversion of 100%. The
disadvantages, however, are the large quantities of
triethyl aluminium required and the present inability
to recycle the catalyst [25–27]. Fig. 4 illustrates se-
lective hydrogenation with the example of linolenic
acid methyl ester [26].
3.2. Dimerization/oligomerisation
Another technologically feasible modification of
the double bonds of unsaturated fatty acids is their
dimerisation and oligomerisation. That involves two
or more fatty acid molecules being attached to the
433
residual alkyls. C18 fatty acids with one or more dou-
ble bonds react with each other at temperatures of
about 210–250 ◦ C in the presence of layered alumi-
nosilicate catalysts (e.g. montmorillonite) forming a
complex mixture of C36 dicarboxylic acids (dimeric
fatty acids), C54 trimer fatty acids and C18 monomer
fatty acids [12,17,28].
Industrially manufactured di- and trimeric acids are
primarily used in hot glues, printing colours and epoxy
hardeners. However, they may also be used in lubri-
cants [29].
It is assumed that the reaction to the dimeric fatty
acids (C36 ) takes place via a Diels–Alder-addition,
whereby one fatty acid molecule (after double bond
shifting) seems to have the function of the diene and
the other the function of the dienophil (Fig. 5) [12].
Parallel to this reaction other mechanisms can occur
such as ene-reactions (see Section 3.3.5) and reactions
of carbo-cations, whereas other dimer products are
formed (Fig. 6) [17].
Additional by-products of the dimerization are
C18 -monomeric fatty acids which consist out of a
mixture of straight-chain, branched, saturated and
434 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
Fig. 5. Dimerization of C18 -fatty acids via Diels–Alder reaction.
(A) Head/head reaction; (B) head/tail reaction. In the products:
y = x, R = RCH2 or y = x + 1, R = R.
unsaturated fatty acids. Hydrogenation of the dou-
ble bonds in those compounds results in a solid
(straight-chain fatty acids) and a liquid phase (tech-
nical isostearic acid). The main components of the
isostearic acid are mono- and poly-branched C18 fatty
acids whose branching points are mainly concentrated
in the centre of the molecule [30,31].
With a low pourpoint similar to oleic acids and good
thermal and oxidation resistance, isostearinic acid and
its derivatives are ideal raw materials for lubricants,
cosmetics and plastic additives.
The dimerization reaction also opens the door to
higher-molecular aliphatic dioles. These are obtained
by esterification and subsequent hydrogenation of
dimeric fatty acids [29].
3.3. Formation of C–C and C–O bonds
Branched fatty acids are interesting base fluids
for lubricants because of their extraordinary phys-
ical features. For example, the pour point of fatty
Fig. 6. Other products in the dimerization of C18 -fatty acids.
acids and their derivatives is significantly lowered by
branching. By adding sterically hindered branches,
hydrolytic stability can also be increased. Their low
pour point, low viscosity, high chemical stability and
high flashpoint make saturated, branched fatty acids
highly desirable base fluids in the lubricants indus-
try and to the cosmetic, plastifier, plastics, defoamer
industry.
Branching of the fatty acids residues is initiated by
C–C and C–O linkages. In the following are listed
some reactions that lead to the branching of chains.
3.3.1. Cooligomerization
One possibility of manufacturing alkyl-branched
fatty acid derivatives is cooligomerisation. For exam-
ple the cooligomerisation of ethene with C18:2-fatty
acid derivatives produce yields of branched fatty
acids of up to 95%. This reaction is homogeneously
catalysed over RhCl3 ·3H2 O [32,33].
Fig. 7 shows a simplified reaction scheme for the
reaction of ethene with methyl linoleate [32]. Af-
ter conjugation of the methyl linoleate (initial
substance: sunflower methylester) to 10,12- or
9,11-octadecadienoic acid methyl ester, ethene ad-
dition takes place on one of the two double bonds,
thus forming the corresponding vinyloctadecenoic
acid methylester. Branching takes place at the C9
and C10 atoms in the fatty acid chain. For clarity,
Fig. 7 only shows products that are branched at
position C10 .
Besides simple addition, also multiple addition
takes place. If methyl esters are used, consecutive
reactions permits higher addition. The initially cre-
ated 1:1 products can be conjugated and ultimately
attract ethene. Multiple addition only occurs on the
side chain.
 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442 435

Fig. 7. Reaction of methyl linoleate with ethene over RhCl3 ·3H2 O.

The cooligomerisation of propene with conjugated 3.3.2. Hydroformylation

C18 fatty acid methylesters results in up to 92% yield
of 1:1- and 2:1 products [32,34]. Fig. 8 illustrates the
structure of these propene adducts, with the branching
at position C10 [32]. Similarly to ethene addition, a
second addition takes place at the existing branch. 3:1
propene products were not observed.
A further hydrogenation of these cooligomerates
over Pd/carbon catalysts generates the corresponding
saturated derivatives which are also of interest to the
lubricants industry [35,36].
The introduction of an aldehyde group by hydro-
formylation opens up further opportunities of mod-
ifying fatty acid chains (Fig. 9). Hydroformylation
or oxo-synthesis is used on a large-scale process for
the production of aldehydes from olefins. Catalysts
are Co- or Rh-complexes which have various ligands,
such as amines and phosphines as activity or selectiv-
ity modifiers [37–39]. Hydroformylation also allows
the branching of unsaturated fatty acid chains [37–39].
The reaction with methyl oleate, for example, results

Fig. 8. Structure of propene addition products.

436 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442

Fig. 9. Hydroformylation of methyl oleate over rhodium-triphenyl phosphine catalyst.

in an equimolar mixture of methyl-9-formylstearate
and methyl-10-formylstearate with a yield of 90–99%.
A rhodium-triphenylphosphine system is used as cata-
lyst. Subsequent hydrogenation such aldehydes forms
the corresponding alcohols.
3.3.3. Friedel–Crafts alkylation
The Friedel–Crafts alkylation is another possibil-
ity for synthesis of branched fatty acids and their
derivatives. The reaction of oleic acids with iso-
propyl chloroformate in the presence of Et3 Al2 Cl3
forms a 1:1 mixture of the two regioisomers, 9- and
10-isopropyloctadecanoic acid with a yield of 72%
(Fig. 10) [40–43].
Isopropylation can also be performed with natural
oils such as sunflower oil. Highly alkylated prod-
ucts are formed with properties such as low pour
point, good oxidation resistance and good hydrolytic
stability. They are of interest for the lubricants and
cosmetics industries.
However, such a process is not economically fea-
sible because about two aluminium alkyl molecules
have to be used per one molecule of fatty components.
High-performance catalysts could transform alkyla-
tion into a technologically interesting reaction.
3.3.4. Friedel–Crafts acylation
The Friedel–Crafts acylation is a reliable method
for the functionalisation of unsaturated fatty sub-
stances. It allows the induction of a keto group in the
side chain. Over Lewis acids such as AlCl3 , SnCl4
or ZnCl2 , a mixture of ␤,␥-unsaturated ketones is
obtained [44–46].
The EtAlCl2 -induced acylation of oleic acid with
acetyl chloride produces a mixture with approxi-
mately similar quantities of 9- and 10-regioisomers

Fig. 10. Ethylaluminium sesquichloride induced reaction of oleic acid and isopropyl chloroformate to the alkylated product. Molar ratio
of oleic acid:isopropyl chloroformate:Et3 Al2 Cl3 = 1:1.2:1.8.
 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
Fig. 11. EtAlCl2 induced Friedel–Crafts acylation of oleic acid with acyl chloride to unsaturated oxo-carboxylic acids. Molar ratio of oleic
acid:acyl chloride:EtAlCl2 = 1:1:2.
Fig. 12. Ene-reaction.
as (E)-adducts. Yield is about 55% (Fig. 11)
[44].
Again, this process is not economically viable be-
cause of the high catalyst consumption.
3.3.5. Ene-reaction
The ene-reaction is defined as the reaction of an
alkene having an allylic hydrogen (the “ene” com-
pound) with a substance containing a double or triple
bond (the “enophile”) to form a new C–C-bond
with migration of the ene double bond and with a
1,5-hydrogen shift (Fig. 12) [47–49]. This reaction
type represents a further modification possibility of
the double bond and is suitable for the introduction
of side chains with hetero functions such as –COOR,
–OH, –CN in unsaturated fatty substances. Apart
from a shift in position, the fatty substance double
bond remains intact.
A special case of ene-reactions are the carbonyl
ene-reactions in which electron-deficient aldehy-
des as formaldehyde or glyoxylic ethylester can
Fig. 13. Ene-reaction products of formaldehyde with oleic acid double bonds.
437
react as an enophile. Thereby, dimethylaluminium
chloride acts as an ene-reaction catalyst. The reac-
tion of formaldehyde with oleic acid results to a
1:1 mixture of isomeric pairs of the branched fatty
acids 9(10)-hydroxymethyloctadec-10(8)-enoic acid
(Fig. 13) [43,45,50].
Ene-additions of formaldehyde to vegetable oils
take place by the formation of the corresponding di-
and tri-functionalised triglyceride [45].
The use of further substances in the ene-reaction,
such as maleic acid, glyoxylic acid ethyl ester and
mesoxalic acid diethyl ester offer a further series of
interesting products [12,51].
Unfortunately in these reactions stoichiometric
quantities of dimethyl aluminium chloride or ethyla-
luminium chloride are used. Other catalysts such as
SnCl4 , noble metal halides and boron trifluoride are
under investigation [52].
3.3.6. Radical addition
Short branches can be introduced by addition of
electrophilic radicals to the double bond thus form-
ing functionalised and branched fatty acids and their
derivatives. An example of this type of reaction is the
radical addition of acetone to oleic acid methyl ester.
This reaction is catalysed by manganese(III)-acetate.
First, an acetonyl radical is formed which afterwards
adds to the regioisomers 9-(10)-acetonylstearic acid
438 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
Fig. 14. Radical addition of acetone to oleic acid methyl ester.
methylester (Fig. 14). The product mixture yield is up
to 72% [43,53,54].
Following manganese(III)-acetate initiation further
enolisable compounds such as acetic acid and malonic
acid were added to fatty substances [45].
3.3.7. Acyloxylation
The addition of carboxylic acids to the double bonds
of unsaturated fatty substances is known as acyloxy-
lation. This is yet another method for modifying the
double bonds of vegetable oils. This modification and
the use of sterically hindered acids, improves the hy-
drolytic and oxidation stability of the fatty substances
which is the reason why neo acids are often used
[55–57].
An example is the addition of pivalic acid to methyl
oleate using a heterogeneous nafion/silica composite
Fig. 15. Addition of pivalic acid to methyl oleate over solid acid catalysts.
catalyst. The yield of this reaction is 44% at a product
selectivity of 93% (Fig. 15).
This type of reaction has yielded a number of new
raw materials which represent a largely unexplored
potential.
3.4. Metathesis
Metathesis reactions are applied in the petro-
chemical industry on large scale to vary the olefin
chain lengths. A fundamental differentiation exists
between self metathesis (between the same olefins)
and co-metathesis (between two different olefins).
Olefin metathesis is catalysed by transition metal
compounds (molybdenum, tungsten and rhenium)
[12,17,45,58,59]. This reaction type can also be
transformed to vegetable oil chemistry. A mixture of
corresponding diesters and alkenes is formed from
two carboxylic acid ester molecules.
Self metathesis of oleic acid methyl ester us-
ing a tungsten(VI) chloride tetramethyltin cata-
lyst system produces 9-octadecene and dimethyl
9-octadecenedioate-1,18 in an equlibrium mixture
(Fig. 16).
The co-metathesis of erucic acid or oleic acid
methyl ester with short-chain olefins such as ethene
(ethenolysis) or 2-butene, produces unsaturated fatty
acid methyl esters of chain lengths C10 –C15 and the
corresponding olefins. From the co-metathesis of
oleic acid methyl ester and ethene methyl-9-decenoate
is formed with a yield of >80% over Re2 O7 ·B2 O3 /
 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
Fig. 16. Self metathesis of oleic acid methyl ester.
AL2 O3 ·SiO2 ·SnBu4 as catalyst (see Fig. 17) [59].
The resulting fatty acid methylesters such as
methyl-9-decenoate and methyl-13-tetradecenoate
are of interest for the manufacture of polyamides,
polyesters, lubricants and for flavours and fragrances
[59].
This metathesis reaction with fatty substances
generates often an unselective mixture of prod-
ucts. The poor performance of the expensive cat-
alytic system is another disadvantage for the use
of this reaction in commercial scale; at present
1 mol of tungsten compound is required to pro-
duce 150 mol ester. The selective catalytic system
Re2 O7 ·B2 O3 /AL2 O3 ·SiO2 ·SnBu4 is also too expen-
sive due to the required high amount [12,17,59].
The research for new, more effective and less expen-
sive catalysts involves homogeneous as well as hetero-
geneous catalysts, e.g. rhenium oxide on aluminium
and silica carriers [25,60,61].
Fig. 17. Metathesis of oleic acid methyl ester and ethene.
439
Fig. 18. Epoxidation reaction of vegetable oils.
3.5. Oxidation
3.5.1. Epoxidation
Epoxidation is one of the most important double
bond addition reactions. In the case of unsaturated
fatty acid esters, it is often performed in situ using
the performic acid method (Fig. 18). This process is
industrially performed on a large scale [12,17].
At present the vegetable oil epoxides are used in
PVC and stabilisers [12,17,29]. Furthermore, they are
also used to improve the lubricity in lubricants. Be-
cause of their good lubricity and high oxidation sta-
bility in comparison to rapeseed oil, pure epoxidised
rapeseed oil can also be used as a lubricant base fluid
[62].
Epoxidised fatty components are reactive substrates
for a number of interesting products. Ring opening of
such epoxidised oils with organic acids or alcohols
produce epoxy polyol esters and epoxy polyethers.
These are widely used in polymer chemistry, e.g. in
the areas of paints and dyes. The cleavage of the epoxy
ring allows also the introduction of hetero-atoms and a
whole series of functional groups [12,17,45,63]. Thus,
a whole new series of oleochemical products can be
manufactured which can be used as lubricant base flu-
ids, additives, etc.
440 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
Fig. 19. Ozonolysis of oleic acid.
3.5.2. Oxidative cleavage
Ozonolysis leads to oxidative cleavage of the
C=C double bonds. The highly selective ozonolysis
of unsaturated fatty acids initially creates ozonides
which are transformed to mono- and dicarboxylic
acids. Oleic acid is used for the commercial produc-
tion of azelaic acid which is used for the manufac-
ture of high-performance lubricants, polyesters and
polyamides (Fig. 19) [12,17,64].
Others oxidation agents are presently investigated
because the economics of this process are presently
unsatisfactory. One possible solution is the use of
metal complex catalysts, for example ruthenium or
rhenium [25,45,65].
4. Modified cultivations of natural vegetable oils
Apart from a chemical modification, it is also pos-
sible to ennoble the plants that supply the fatty acids.
The oil industry is working together with plant culti-
vators to develop new oils whose fatty acid make-up
is better suited for the demands of industrial appli-
cations. However, oleic acid or oleic acid esters still
are the starting point of the chemical modifications
already mentioned. The oleic acid part in common
rapeseed oil is between 60 and 70%. It is clear that
a >90% technical oleic acid content would produce
much fewer by-products than with present raw ma-
terials resulting in more efficient reaction and purer
end-products. This is why the industry is highly
interested in tailor-made raw materials. Such natural
structural uniformity of vegetable raw materials is a
utilisable input in the chemical processing.
One cultivation success is high oleic sunflower oil
(HOSO). The development of high oleic types of sun-
flower was first reported by Soldatov in 1976 and was
further developed [66].
At present HOSO is available with an oleic acid
content of >90% and a very small stearic acid con-
tent of 1.0–1.5% [67,68]. In 1999, about 5 tonnes of
such an oil was obtained from an HOSO Pilot Cul-
tivation in Germany. This oil is extremely oxidation-
and ageing-stable when compared to rapeseed oil and
trimethylolpropane (TMP) oleate which is synthesised
using rapeseed oil.
The achieved low stearic acid content influences
positively the product’s low-temperature behaviour.
The extremely good physical and chemical properties
of HOSO may lead to this vegetable oil being used in
the non-food sector on a large scale. Even unmodified,
it is suitable as base fluid for various biodegradable
lubricants. Furthermore, it is a highly popular starting
material for chemical modifications in other sectors of
the chemical industry because of its outstanding pu-
rity. However, it remains to be seen how successful
these ennoblements are, what the yields from the var-
ious regions are and how economical their industrial
application turns out to be.
Apart from using ennoblement to obtain tailor-made
vegetable oils such as HOSO, high oleic acid rape-
seed oil, rapeseed oil with a high C12 /C14 -fatty acid
content, etc. genetic modification is also being inves-
tigated [66,69].
5. Conclusion
Vegetable oils have particularly good tribological
properties. Due to their specific structure, they com-
bine good boundary friction lubricity and general
wear protection with stable viscosity–temperature be-
haviour and very low evaporation. In addition, they
are easily biodegradable. All-in-all, they are excel-
lent raw materials for the formulation of ecologically
friendly lubricants. All their highly positive physical
features are countered by a few major limitations,
the most important of which is the inadequate age-
ing resistance of these products. As a result they are
 H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429–442
either not, or only sometimes suitable for circulation
lubricant systems. Vegetable oil-based products are
perfect for total loss applications in which the lubri-
cant inevitably enters the environmental cycle (e.g.
chain saw oils).
The scope of oleochemistry allows almost any
synthetic ester to be tailor-made. The resulting
high-performance lubricants are technologically at
least as good, if not, in some cases, much better than
mineral oils.
The optimisation of natural oils refers to specific
technical properties such as:
• hydrolytic stability;
• foaming;
• viscosity;
• evaporation;
• oxidation stability, etc.
Lubricants based on these synthetic esters based
on vegetable oil are subject to performance and
cost constraints. At the moment, many oleochemi-
cal synthetic esters are too expensive to take over
any worthwhile market share. The European mar-
ket share of biodegradable lubricants is currently
only 2%.
Nevertheless, the opportunities for expanding the
market share of lubricants based on renewable raw
materials are promising. This development has been
forecast in at least one market survey [70]. According
to this study, the biodegradable lubricants market will
almost triple in the next 6 years. In 1999 biodegradable
lubricants accounted for 1.9% or 101,950 tonnes of the
European market with a value of US$ 231 millions.
The market potential for 2006 totalled 242,950 tonnes
with a value of US$ 664.5 millions. The decisive fac-
tors for this development are environmental protection
and, to a lesser extent, technical requirements.
In this paper various catalytic processes for the mod-
ification of vegetable oils and other raw materials are
covered. The most important modification relates to
the carboxyl group of fatty acids, e.g. esterification.
In each case, the overriding objective is to realise
application-relevant properties (see Section 3).
Apart from the well-established processes, a num-
ber of fatty acid and fatty acid derivative reactions
have been described which are still in the investigation
stage. The search is continuing for new, more selec-
tive and cheaper catalyst systems. Work is ongoing to
441
improve selective catalyst recycling methods, particu-
larly for expensive noble metal catalysts.
Successes in this area reduce the dependence on
petrochemical raw materials and create new synthesis
processes. The challenge for research in the field of
lubricants will be to improve certain characteristics of
vegetable oils without impairing their excellent tribo-
logical and environmentally-relevant properties. This
implies the utilisation and sustainment of the natural
chemistry of vegetable oils to a high extend.
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