Leaf Comin

Lubricating Oils Based on Chemically Modified

Vegetable Oils

A. Birova, A. Pavlovi4ova, and J. Cvengro5

Faculty of Chemical Technology STU, Bratislava, Slovakia

Abstract

Vegetable oils are a type of easily biodegradable ester-type lubricant derilped

ji-om renewable resources. Their importance, ji-om the environmental view-
point, is evident, especially in loss lubrication, hydraulic systems with
increased risk of damuge, etc. They ure characterised by good lubricity and
good anticorrosion and temperature-viscosity properties. Some disadvant-
ages, particularly low thermal oxidation stability and poor cold flow behav-
iour, can be mitiguted by structural modijications. In this study, possible
substitutions of the alcohol part of triacylglycerols as well as changes in acyl
unsaturated chains are discussed. Attention is paid particularly to the
epoxidising of double bonds in acyls resulting in thejormation of oxirane
rings. By opening these in the presence oj hydrogen donors, it is possible to
obtain new derivatives and polyjunctional compounds that are acceptable as
en~,ironmentallvfr-iendly lubricants.

Keywords

lubricants. vegetable oils, ester oils, oleochemistry

INTRODUCTION

One of the problems of the modem world concerns the present state of the en-
vironment, which is nearing the limit of sustainability, and which is also the
cause of serious damage to living things, including man. This critical state of
the environment is the result of a whole set of development processes that
have had, simultaneously, through deliberate and unconscious actions, a neg-
ative effect on man and his surroundings. The environmental impact of petrol-
eum and petroleum products is one element of this set. Classic lubricants -
mineral oils - belong to the group of petroleum products. Their negative
effects are particularly linked to their inappropriate use, which results in sur-
face water and groundwater contamination, air pollution, soil contamination,

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J . S~intheticLiibr.icatio,i
and, consequently, agricultural product and food contamination. There are
also certain current technologies that are a sour e of permanent environmental
pollution (e.g., loss lubrication), and which need to be replaced by non-
hazardous technologies.
Environmental problems in tribology technology have been addressed for
several years, especially in the following areas:

improvement of machinery systems and their integrity

increasing lubricant life
decreasing lubricant consumption
introducing new environmentally friendly lubricants
collection, recycling, or elimination of used lubricants.

Products based on vegetable oils best meet the criteria for non-hazardous and
environmentally friendly lubricants. It would be acceptable if more than 90%
of all lubricants could be manufactured from renewable raw materials.’ The
main advantages of these lubricants are that:

they are non-hazardous when in contact with skin, mucous membranes,

and respiratory and digestive systems;
their biodegradability results in self-decomposition into non-toxic
products:
they do not contribute to the greenhouse effect caused by increasing
amounts of carbon dioxide in the atmosphere.

VEGETABLE-OIL BASED LUBRICANTS

The safety of vegetable-oil based lubricants in terms of human health is evi-

dent since these oils are also used in foods. However, the use of additives can
detract from their biodegradability. Products with a degradability higher than
80%within 2 1 days, according to the CEC L-33-A-93 test, are considered eas-
ily biodegradable. While the biodegradability of vegetable oils is about 99%,
after additivation it usually drops to 9&98%. On the other hand, the biode-
gradability of mineral oils is around 20%.
Vegetable oils are the products of photosynthesis. When the oils undergo
oxidation, there is no more CO, created than is consumed in their synthesis.
Therefore, the CO, balance is zero and the ‘production’ of vegetable oils does
not add to the greenhouse effect. When considering lubricants based on

.I.
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Luhricatilig oils based oti chemically modified vegrtuble oils 293

vegetable oils, it is necessary to take into account their technical and economic
parameters as well as environmental criteria.
Vegetable oils belong to the category of renewable raw materials. Their
production is limited by the area of free arable land; in many areas priority is
given to using arable land to produce human food. In developed countries, the
potential for food production exceeds that for food consumption, and land can
thus be used for products other than food. For the time being, price consider-
ations are not favourable to the wide use of lubricants based on vegetable oils.
However, differences between the prices of mineral and vegetable oils are de-
creasing with the higher taxes imposed on petroleum products.
The best applicationsof lubricants based on vegetable oils are those where
their environmental advantages can be exploited. Firstly, they can be used for
loss lubrication of machinery, such as saw chains and blades, railway points,
conveyors, and two-stroke engines. Further, they can be used for lubrication
where the risk of oil leakage due to worn seals or other damage is involved,
such as in hydraulic and transmission systems of agricultural and forestry
equipment. Finally, they can be used as corrosion prevention agents and
where petroleum products may contaminate the environment’-’ (for example,
for separation oil in the construction industry or for preservation oil).
Lubricants based on vegetable oils must meet the required tribological
parameters. Compared to mineral oils, vegetable oils have different structures
and properties. While mineral oils consist mostly of saturated linear,
branched, and cyclic hydrocarbons, vegetable oils consist of triacylglycerols
with carboxylic groups on hydrocarbon chains with saturated bonds. These
structural differences manifest themselves in positive and negative ways.
Lubricity, as a basic criterion, is generally better for vegetable oils than
for mineral oils. Also the viscosity-temperature dependence is more favour-
able, with the viscosity index reaching values of about 200. However, the pro-
duction of lubricants over a wide range of viscosity classes is not possible. The
products fall into the following viscosity classes: I S 0 22, 32, 68, and 100.
Higher viscosity classes can be reached only after modifying the oil’s struc-
ture. The anticorrosion properties of vegetable oils are better than those of
mineral oils, and they have a higher affinity to metal surfaces. Since they have
high flash points - above 300°C - vegetable oils are classified as non-
flammable liquids.
However, vegetable oils have a lower thermal oxidative stability than
mineral oils. This can be attributed to the glycerol P-carbon and to the double
bonds of the acyl groups. This stability can only be partially improved by

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2 94 Birova, Puvlovi?ov6,and Cvetigroi

Figure 1 Examples of polyols used for manufacturing esters

CH, - OH CH, - OH
I I
CH,- C - CH, CH,- CH,- C - CH,- OH
I I
CH, - OH CH, - OH

Neopentyl glycol Trimethylol propane

CH, - OH
I
OH - CH,- C - CH,- OH
I
CH, - OH
Pentaerythritol

CH, - OH CH, - OH
I I
OH -CH,-C-CH,-0-CH,-C -CH,-OH
I I
CH, - OH CH, - OH

Dipentaerythritol

additives. Therefore, the temperature limit for these oils is 6OoC, exception-
ally 100°C. Despite this, a vegetable oil has been used successfully as a motor
oil with a new lubrication concept.xAlso, the freezing points of vegetable oils
are higher then those of mineral oils, this being linked to non-branched acyl
groups. Even if suitable freezing-point depressants are added, the lower tem-
perature limit for their use is about -3OOC. In common with other esters,
vegetable oils have a low resistance to hydrolysis.

CHEMICALLY MODIFIED VEGETABLE OILS

In order to improve, or eliminate, the negative properties of lubricants based

on vegetable oils, synthetic lubricants - oleochemical products, the compon-
ents of which are of vegetable or animal fat origins - have begun to be used.
It was forecast that by the end of 2002, about 10%of all lubricating oils used
in Germany would be easily degradable.'

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Lubricating oils based on chentically modified vegetable oils 295

Figure 2 Chemical modifications of acyl groups

Oils -
-
Epoxidation Epoxy triglycerides

-
Hardening

Sulphation
1
I
Saturatedfats

Sulphated oil
I
I

r-acids
-
Dimerisation

-
Ozonation
Dimer fatty acids

Mono/dicarboxylicacids

-
Conjugation

Sulphonation

-
Conjugation fatty acids

Sulphonated acids

acid
methyl
esters
-Epoxidation

Sulphonation

____,
Carbonisation
Epoxy esters

Sulphonated esters

Dicarboxylic acid esters

The low stability of the glycerol P-carbon may be eliminated by trans-

esterification. In this reaction, the glycerol is replaced with a more suitable
polyhydric alcohol with a neopentyl structure without P-carbons, such as tri-
methylol propane or pentaerythritol (Figure 1).'-13 Polyol esters possess good
lubricity and thermal stability.
Figure 2 shows possible reactions involving the alkyl chains of the acyl
groups in triacylglycerols, fatty acids, and fatty acid methyl esters." The most
reactive double bonds can be eliminated by oxidation, polymerisation, or oli-
gomerisation. This also enables the production of lubricants with different vis-
cosities, because lubricant viscosity always increases during oxidation and
oligomerisation reactions. Depending on the conditions of these reactions, it
is possible to prepare oils in the viscosity range 10-104mmzs-' at 40°C.How-
ever, this procedure will not substantially improve the thermal oxidative sta-
bility. Excessive lengthening and branching of chains may decrease the

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2 96 Birova, Pavlovi&wa, arid Cvetigro~

Figure 3 Splitting of epoxy rings

-I t H,O

I
- CH-
8H 8H
Diols
CH -

1
I

I t ROH
______,
-CH- CH -

1
-
8H k R
I Ether alcohols
~
I
+ RCOOH - CH- CH -
I 1

-
OH OCOR
Ester alcohols

+ RCONH, - CH- CH -

FI-
I I
CH NHCOR
- CH - CH - Hydroxy alkylamides

+ H,S -CH- CH -
I I
OH SH
Hydroxy mercaptans

I -CH-CH- 1

- + HCI

+ HCN
II
Hydroxy amines

-CH-CH-

Chlorohvdrins II

- + NaHSO,
I Hydroxy nitriles

Hydroxy sulphonates
1

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Lubricating oils based on chemically modified vegetable oils 297

Figure 4 Estolides

0
2x

Fatty acid

0 0

Monoestolide

biodegradability and increase the acidity. The substitution of unsaturated

acyls with saturated ones leads to solid products, and is not a solution. Liquid
products with lower viscosity are obtained by substituting saturated acyls with
lower carbon numbers (8-10). The viscosity can be increased by incorporat-
ingdicarboxylic acids into the oil's structure, i.e., by the formation of complex
esters. These complex esters are formed by esterification of polyols with mix-
tures of mono-, di-, and tricarboxylic acids and are complex oligomer mix-
tures, which are characterised by their high shear stability.".'"
During ozonolysis of unsaturated fatty acids, cleavage of the molecules at
the double bond occurs, resulting in the formation of shorter, saturated mono-
and dicarboxylic acids. For instance, monocarboxylic pelargonic acid (C9)
and dicarboxylic azelaic acid (diC9) are formed from oleic acid (C 18: 1). Sim-
ilarly, pelargonic acid and brassidic acid (diC 13) are formed from erucic acid
(C22:I). Various possible combinations of fatty acids and alcohols lead to
diverse categories of ester
Epoxidising the double bonds of unsaturated acyls results in the formation
of oxirane rings that can be easily opened. Possible reactions during the open-
ing of these rings in the presence of water or other hydrogen donors are shown
in Figure 3. It is possible to prepare different hydroxy compounds with cor-
responding substituted groups, which are interesting from the point of view of
biodegradable lubricant preparation.
Low hydrolytic stability is related to the ester bases of these lubricants.
Their resistance to hydrolysis is governed by the type of alcohol in the ester
and by the extent of acyl branching. Linear acyls are more susceptible to
hydrolysis than are branched ones.

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298 Birova, Pavlovizova, arid Cvengro~

Figure 5 Dimerisation

(CH,),COOH

CH3(CH2)5 =Q/ CH=CH(CH,),COOH

(CH,),COOH CH,(CH,),CH=CH

CH3(CH2)5 CH3(CH2)3

Monocyclic DiFa Bicyclic DiFa

CH,(CH,),CH(CH,),COOH
I
CH3(CH,),CH=C(CH,),COOH

Acyclic DiFa

Besides the oxidation and oligomerisation mentioned above, an increase

in viscosity can also be achieved by changing the chain length of the acyls and
by branching them. The viscosity increases with the acyl length. In isolated
acyls, branching results in a viscosity decrease; however, in branched acyls,
the viscosity increases if cross-linking occurs. Cross-linking does not
necessarily occur via carbons, but can occur via ether or sulphide bonds.
An interesting group of compounds are the estolides. Estolides are the
products of the inner esterification of unsaturated fatty acids when the
carboxylic acid group of one acid is attached to the unsaturated carbon of
another fatty acid, as shown in Figure 4. Even a saturated fatty acid can form
an ester link with the unsaturated chain of another fatty acid. Polyestolides are
formed by adding more fatty acids to an existing estolide unit. Estolides have
high viscosity indices, good oxidative stability, and good biodegradability.
They are quite stable at temperatures up to 250°C even when exposed to air.“
They have the potential for use in a variety of applications, such as in
lubricants, greases, plastics, inks, cosmetics, and surfactants.”
High fatty acid-based materials with larger molar mass and increased vis-
cosity can also be prepared from dimeric fatty acids after esterification of the
acid groups with monobasic alcohols. Dimeric fatty acids are commercially
available and are prepared by high-temperature clay-catalysed polymerisation
of unsaturated fatty acids. The source unsaturated fatty acids are usually mix-
tures of oleic, linoleic, and linolenic acids. Dimerisation by the Diels-Alder
reaction leads to the formation of cyclic structures; dimerisation by radical

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Lubricatittg oils based oti cheniically modified vegetable oils 299

polymerisation accompanied by the transfer of hydrogen yields acyclic

structures (Figure 5).
The biodegradability of ester lubricants decreases with the length of the
acyl and alcohol chains and also with the degree of chain branching.

CONCLUSION

Natural oils, which have some disadvantageous properties, can be structurally

modified to increase their usefulness. The issue of lubricants based on
vegetable oils thus becomes one concerned with the areas of oleochemistry
and synthetic lubricant formulation and production with all their economic
implications. In lubricant applications where environmental safety plays a
major role, this aspect can be decisive in the selection of an oil despite the
higher costs involved.

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A revised version of a paper presented at Intertribo, The High Tatras, Slovakia.

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