Applied Catalysis A: General 221 (2001) 429442

Lubricant base uids based on renewable raw materials Their catalytic manufacture and modication
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 uids. Compared to conventional mineral oil based uids 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 modication. 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 uids are mentioned too, e.g. breeding successes with high oleic sunower oil. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Renewable resources; Renewable raw material; Lubricants; Chemical modication; Vegetable oils; Oleochemicals; Biodegradable; Environmentally friendly; Base uids; Sustainable materials

1. Introduction About 1.15 million tonnes of lubricants are used every 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 specic reasons where they can cause pollution of the environment [1]. The use of rapidly biodegradable lubricants could signicantly reduce this environmental pollution. In Germany, ecologically friendly lubricants currently account for about 45% 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).

so far. To increase this market share, the acceptance 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 modied vegetable oil esters can be used as a base stock for preparation of environmentally friendly, rapidly biodegradable lubricants. This review will cover the use of vegetable oils and their derivatives as base uids 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

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the manufacture of oleochemicals with the appropriate characteristics for the lubricants sector. The production of environmentally friendly, rapidly biodegradable uids for lubricants based on petrochemicals such as polyalfaolens, polyglycols, polyalkylene glycols and synthetic esters has been disclosed in the literature and various patents [2,47]. Some of the rapidly biodegradable lubricants are based on pure, unmodied vegetable oils. In Europe predominantly rapeseed oil and sunower 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-specic and therefore variable. The fatty acids found in natural vegetable 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 applications with low thermal stress. These include total loss applications like mold release and chain saw oils. The reason for the thermal and oxidative instability 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 especially 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 olen. A further weakness of natural esters is their tendency to hydrolyse in the presence of water [810]. An improvement of the thermal, oxidative and hydrolytic stability of vegetable oils can be primarily

achieved by a chemical modication. Vegetable oils are mostly split into their oleochemical components such as fatty acids or fatty acid methylesters and glycerine before they are modied. Fatty alcohols can be formed out of fatty acid methylesters. However, the vegetable oil can be directly modied, for example, by direct transesterication or selective hydrogenation. The most important modications 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 modications which are of signicance to manufacture lubricant base uids. The improvement of natural oils by plant cultivation or genetic modication will be mentioned briey.

2. Modications of the carboxyl group 2.1. Esterication/transesterication One of the most important modications of the carboxyl group of the fatty acid chain is the transesterication of the glycerine esters or the esterication of the fatty acids obtained by cleavage of such esters. Those processes are performed on large scale. Transesterication or esterication reactions are normally catalysed with acidic or basic catalysts. Typical homogeneous catalysts are p-toluene sulphonic acid, phosphoric acid, sulphuric acid, sodium hydroxide, sodium ethoxide and sodium methoxide. In some cases, heterogeneous catalysts such as Sn-oxalate or cation exchange resins are used. Enzyme catalysed reactions are also known [1116]. Fig. 2 shows a general esterication reaction.

Fig. 1. Plant oilglycerine ester of different fatty acids; critical points: -CH-group and unsaturated fatty acid residues.

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Fig. 2. General esterication reaction.

The features of the substrates selected inuence the properties of the ester manufactured. The most important properties for the use as lubricants are viscosity, viscositytemperature behaviour and oxidation stability. At the same time, low-temperature behaviour and evaporation tendencies are of signicance 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-, polycarboxylic acids as well as aliphatic and aromatic carboxylic acids) and alcohols (diols, polyols as well as linear and branched alcohols). The above-mentioned properties can be inuenced by the choice of the divers alcohols and acids. Some examples of esterication and transesterication 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 esteried 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 esteried with alcohols such as 2-ethylhexanol, isodecanol and Guerbet alcohols. Based on renewables, 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 manufactured in commercial processes using oleic acid a principal 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 petrochemical way. 2.1.3. Polyolesters Polyolesters are formed from polyols with a quaternary carbon atom (neopentylalcohols) as for example neopentylglycol, trimethylolpropane and pentaerythritol. This class of products offer extraordinary stability 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 esterication of polyols with mixtures of mono-, di-, and tricarboxylic acid esters. Such processes result dependent on reaction conditions in diverse oligomerig

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

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mixtures with higher viscosity. They are highly viscous and generally shear-stable. In addition, intramolecular transesterication 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 modications 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 modication processes of fatty acid chains which are of interest for the lubricants sector are discussed. 3.1. Selective hydrogenation The hydrogenation of double bonds in unsaturated fatty compounds is performed on large scale. This process primarily serves to improve the stability as well as to increase the melting point of unsaturated fatty derivatives [12,13,19]. In industrial processes heterogeneous 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 sometimes resulting from selective hydrogenation is the

3. Modications of the fatty acid chain Due to their high reactivity, the double bonds of unsaturated fatty acids and their derivatives form excellent starting points for further modication. Some modications such as hydrogenation (foodstuff chemistry), epoxidation (PVC plasticisers and stabilisers, paints and dyes) or dimerisation (bonders, hardeners) became commercialised a long time ago. In the eld of lubricant base uids, reactions at the double bonds are used to increase the product stability. At the same time, the introduction of functional groups and branches change the physical properties of those newly-created uids considerably. For example, 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 inuence the physical properties as follows: High degree of branching High linearity Low saturation High saturation

Outstanding low-temperature characteristics, high hydrolytic stability, low viscosity index High viscosity index, relatively poor low-temperature characteristics Outstanding low-temperature characteristics, limited oxidation stability Outstanding oxidation stability, poor low-temperature characteristics formation of congurational- and cis/trans-isomers of the remaining double bonds. By selective hydrogenation the easily oxidisable compounds are transformed into more stable components. This signicantly improves the ageing behaviour of the oils.

At present, less than 10% of the known reactions of fatty acid chains are industrially applied. These possibilities represent a great potential for expanding the oleochemical product line in the future and the greater economic exploitation of vegetable oils and fats. These reactions are also of considerable

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Fig. 4. Selective hydrogenation of linolenic acid methyl ester.

Up to now, the problem of the selective hydrogenation of multiple unsaturated fatty acids was only solved partially. This is a hot topic in industrial and university research institutes that are testing various heterogeneous and homogeneous catalytic systems [2027]. One example is the selective hydrogenation with ZieglerSloanLapporte 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 [2527]. Fig. 4 illustrates selective hydrogenation with the example of linolenic acid methyl ester [26]. 3.2. Dimerization/oligomerisation Another technologically feasible modication 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

residual alkyls. C18 fatty acids with one or more double bonds react with each other at temperatures of about 210250 C in the presence of layered aluminosilicate 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 lubricants [29]. It is assumed that the reaction to the dimeric fatty acids (C36 ) takes place via a DielsAlder-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

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acids and their derivatives is signicantly 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 ashpoint make saturated, branched fatty acids highly desirable base uids in the lubricants industry and to the cosmetic, plastier, plastics, defoamer industry. Branching of the fatty acids residues is initiated by CC and CO linkages. In the following are listed some reactions that lead to the branching of chains.
Fig. 5. Dimerization of C18 -fatty acids via DielsAlder 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 double bonds in those compounds results in a solid (straight-chain fatty acids) and a liquid phase (technical 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 esterication and subsequent hydrogenation of dimeric fatty acids [29]. 3.3. Formation of CC and CO bonds Branched fatty acids are interesting base uids for lubricants because of their extraordinary physical features. For example, the pour point of fatty

3.3.1. Cooligomerization One possibility of manufacturing alkyl-branched fatty acid derivatives is cooligomerisation. For example 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 simplied reaction scheme for the reaction of ethene with methyl linoleate [32]. After conjugation of the methyl linoleate (initial substance: sunower methylester) to 10,12- or 9,11-octadecadienoic acid methyl ester, ethene addition 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 created 1:1 products can be conjugated and ultimately attract ethene. Multiple addition only occurs on the side chain.

Fig. 6. Other products in the dimerization of C18 -fatty acids.

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

The cooligomerisation of propene with conjugated 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].

3.3.2. Hydroformylation The introduction of an aldehyde group by hydroformylation opens up further opportunities of modifying fatty acid chains (Fig. 9). Hydroformylation or oxo-synthesis is used on a large-scale process for the production of aldehydes from olens. Catalysts are Co- or Rh-complexes which have various ligands, such as amines and phosphines as activity or selectivity modiers [3739]. Hydroformylation also allows the branching of unsaturated fatty acid chains [3739]. The reaction with methyl oleate, for example, results

Fig. 8. Structure of propene addition products.

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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 9099%. A rhodium-triphenylphosphine system is used as catalyst. Subsequent hydrogenation such aldehydes forms the corresponding alcohols. 3.3.3. FriedelCrafts alkylation The FriedelCrafts alkylation is another possibility for synthesis of branched fatty acids and their derivatives. The reaction of oleic acids with isopropyl 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) [4043]. Isopropylation can also be performed with natural oils such as sunower oil. Highly alkylated products 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 feasible because about two aluminium alkyl molecules have to be used per one molecule of fatty components. High-performance catalysts could transform alkylation into a technologically interesting reaction. 3.3.4. FriedelCrafts acylation The FriedelCrafts acylation is a reliable method for the functionalisation of unsaturated fatty substances. 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 [4446]. The EtAlCl2 -induced acylation of oleic acid with acetyl chloride produces a mixture with approximately 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.

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Fig. 11. EtAlCl2 induced FriedelCrafts 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 because of the high catalyst consumption. 3.3.5. Ene-reaction The ene-reaction is dened as the reaction of an alkene having an allylic hydrogen (the ene compound) with a substance containing a double or triple bond (the enophile) to form a new CC-bond with migration of the ene double bond and with a 1,5-hydrogen shift (Fig. 12) [4749]. This reaction type represents a further modication 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-decient aldehydes as formaldehyde or glyoxylic ethylester can

react as an enophile. Thereby, dimethylaluminium chloride acts as an ene-reaction catalyst. The reaction 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 diand 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 ethylaluminium chloride are used. Other catalysts such as SnCl4 , noble metal halides and boron triuoride are under investigation [52]. 3.3.6. Radical addition Short branches can be introduced by addition of electrophilic radicals to the double bond thus forming 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

Fig. 13. Ene-reaction products of formaldehyde with oleic acid double bonds.

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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 petrochemical industry on large scale to vary the olen chain lengths. A fundamental differentiation exists between self metathesis (between the same olens) and co-metathesis (between two different olens). Olen 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 using a tungsten(VI) chloride tetramethyltin catalyst 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 olens such as ethene (ethenolysis) or 2-butene, produces unsaturated fatty acid methyl esters of chain lengths C10 C15 and the corresponding olens. 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 /

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 acyloxylation. This is yet another method for modifying the double bonds of vegetable oils. This modication and the use of sterically hindered acids, improves the hydrolytic and oxidation stability of the fatty substances which is the reason why neo acids are often used [5557]. An example is the addition of pivalic acid to methyl oleate using a heterogeneous naon/silica composite

Fig. 15. Addition of pivalic acid to methyl oleate over solid acid catalysts.

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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 avours and fragrances [59]. This metathesis reaction with fatty substances generates often an unselective mixture of products. The poor performance of the expensive catalytic system is another disadvantage for the use of this reaction in commercial scale; at present 1 mol of tungsten compound is required to produce 150 mol ester. The selective catalytic system Re2 O7 B2 O3 /AL2 O3 SiO2 SnBu4 is also too expensive due to the required high amount [12,17,59]. The research for new, more effective and less expensive catalysts involves homogeneous as well as heterogeneous catalysts, e.g. rhenium oxide on aluminium and silica carriers [25,60,61].

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. Because of their good lubricity and high oxidation stability in comparison to rapeseed oil, pure epoxidised rapeseed oil can also be used as a lubricant base uid [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 uids, additives, etc.

Fig. 17. Metathesis of oleic acid methyl ester and ethene.

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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 production of azelaic acid which is used for the manufacture 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].

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 sunower oil (HOSO). The development of high oleic types of sunower was rst 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 content of 1.01.5% [67,68]. In 1999, about 5 tonnes of such an oil was obtained from an HOSO Pilot Cultivation in Germany. This oil is extremely oxidationand ageing-stable when compared to rapeseed oil and trimethylolpropane (TMP) oleate which is synthesised using rapeseed oil. The achieved low stearic acid content inuences positively the products 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 unmodied, it is suitable as base uid for various biodegradable lubricants. Furthermore, it is a highly popular starting material for chemical modications in other sectors of the chemical industry because of its outstanding purity. However, it remains to be seen how successful these ennoblements are, what the yields from the various 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 rapeseed oil, rapeseed oil with a high C12 /C14 -fatty acid content, etc. genetic modication is also being investigated [66,69].

4. Modied cultivations of natural vegetable oils Apart from a chemical modication, it is also possible to ennoble the plants that supply the fatty acids. The oil industry is working together with plant cultivators to develop new oils whose fatty acid make-up is better suited for the demands of industrial applications. However, oleic acid or oleic acid esters still are the starting point of the chemical modications 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 materials resulting in more efcient reaction and purer end-products. This is why the industry is highly 5. Conclusion Vegetable oils have particularly good tribological properties. Due to their specic structure, they combine good boundary friction lubricity and general wear protection with stable viscositytemperature behaviour and very low evaporation. In addition, they are easily biodegradable. All-in-all, they are excellent 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 ageing resistance of these products. As a result they are

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either not, or only sometimes suitable for circulation lubricant systems. Vegetable oil-based products are perfect for total loss applications in which the lubricant 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 specic technical properties such as: hydrolytic stability; foaming; viscosity; evaporation; oxidation stability, etc.

improve selective catalyst recycling methods, particularly 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 eld of lubricants will be to improve certain characteristics of vegetable oils without impairing their excellent tribological and environmentally-relevant properties. This implies the utilisation and sustainment of the natural chemistry of vegetable oils to a high extend. References
[1] N.N., in: Bundesministerium f ur Ern ahrung, Landwirtschaft ber biologisch schnell abbaubare und Forsten, Bericht u Schmierstoffe und Hydraulik ussigkeiten, Bonn, 1999. [2] T. Mang, in: F.D. Gunstone (Ed.), Lubricants, Lipid Technologies and Applications, New York, 1997, p. 737. [3] T. Mang, Fett/Lipid 100 (1998) 524. [4] R. van Voorst, F. Alam, JSL 16 (4) (2000) 313. [5] M. Rees, EP 0468109 A1 (1992), Ethyl Petroleum Additives. [6] C.B. Duncan, EP 0904338 A (1999), Exxon Chemical Patents INC. [7] R.J. Wittenbrink, D.F. Ryan, R.F. Bauman, EP 0876446 A (1998), Exxon Research and Engineering Company. [8] R.L. Goyan, R.E. Melley, P.A. Wissner, W.C. Ong, Lubrication Eng. (1998) 10. [9] W. Bauman, K. Bauman, P. Kotal, in: Technische Akademie Esslingen (Ed.), Lehrgang Biologisch abbaubare Schmierstoffe und Arbeits ussigkeiten, speziell auf panzlicher Basis, 1997. [10] D. Klamann, Schmierstoffe und verwandte Produkte: Herstellung, Eigenschaften, Anwendung, Verlag Chemie, Weinheim, 1982. [11] U. Onken, A. Behr, Lehrbuch der Technischen Chemie, Vol. 3, Thieme, Stuttgart, 1996. [12] H. Baumann, M. B uhler, H. Fochem, F. Hirsinger, H. Zoebelein, J. Falbe, Angew. Chem. 100 (1988) 41. [13] Ullmanns Encyklop adie der technischen Chemie, Vol. 11, Verlag Chemie, Weinheim, 1976. [14] S. Gryglewicz, JLS 17 (3) (2000) 191. [15] M. Mittelbach, M. Koncar, US Patent 5 849 939 (1996), Vogel & Noot Industrieanlagenbau GmbH. [16] A. Westfechtel, W. Giede, WO 99/57092 (1999), Cognis Deutschland GmbH. [17] H. Zoebelein, Chemie in unserer Zeit 26 (1) (1992) 27. [18] S. Nagaoka, M. Ibuki, US Patent 6 117 827 (1997), Fuji Oil Co., Ltd. [19] M.W. Balakos, E.E. Hernandez, Catal. Today 35 (1997) 415. [20] A. Behr, H. Schmidke, Chem.-Ing.-Tech. 65 (5) (1993) 568. [21] A. Behr, N. D oring, S. Durowicz-Heil, C. Kozik, C. Lohr, H. Schmidtke, Fat. Sci. Technol. 95 (1) (1993) 2. [22] A. Behr, C. Lohr, B. Ellenberg, DE 4109246 A1 (1992), Henkel K.-G.a.A.

Lubricants based on these synthetic esters based on vegetable oil are subject to performance and cost constraints. At the moment, many oleochemical synthetic esters are too expensive to take over any worthwhile market share. The European market 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 factors for this development are environmental protection and, to a lesser extent, technical requirements. In this paper various catalytic processes for the modication of vegetable oils and other raw materials are covered. The most important modication relates to the carboxyl group of fatty acids, e.g. esterication. In each case, the overriding objective is to realise application-relevant properties (see Section 3). Apart from the well-established processes, a number 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 selective and cheaper catalyst systems. Work is ongoing to

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H. Wagner et al. / Applied Catalysis A: General 221 (2001) 429442 [51] A. Behr, M. Fiene, Eur. J. Lipid Sci. Technol. (2000) 212. [52] A. Behr, H.P. Handwerk, Fat. Sci. Technol. 94 (12) (1992) 443. [53] J.O. Metzger, U. Riedner, Fat. Sci. Technol. 91 (1989) 18. [54] J.O. Metzger, U. Linker, Fat. Sci. Technol. 93 (1991) 244. [55] U. Keller, J. Fischer, W.F. H olderich, H. Murrenhoff, M. Schmidt, W. Dott, A. Eisentr ager, S. Hahn, G. Maxam, Olhydraulik und Pneumatik 44 (4) (2000) 240. [56] J. Fischer, W.F. H olderich, J. Catal. 194 (2000) 294. [57] U. Keller, W.F. H olderich, P. Weckes, L.A. Rios, M. Schmidt, in: Proceedings of the 7th Symposium on Nachwachsende Rohstoffe f ur die Chemie, Dresden, Germany, 2022 March 2001. [58] S. Warwel, P. Bavaj, B. Ercklentz, M. Harperscheid, M. R usch gen. Klaas, S. Thomas, in: M. Eggersdorf, S. Warwel, G. Wulff (Eds.), Nachwachsende Rohstoffe-Perspektiven f ur die Chemie, VCH, Weinheim, 1993, p. 69. [59] S. Warwel, P. Bavaj, M. R usch gen. Klaas, B. Wolff, in: H. Eierdanz (Ed.), Perspektiven nachwachsender Rohstoffe in der Chemie, VCH, Weinheim, 1996, p. 119. [60] D. Mandelli, M.J.D.M. Jannini, R. Buffon, U. Schuchardt, JAOCS 73 (2) (1996) 229. [61] S. Warwel, C. Demes, M. Kunz, J. Tillack, in: Fachagentur Nachwachsende Rohstoffe e.V. (Ed.), Proceedings of the Final Conference on CTVO-NET-Chemical-Technical Utilisation of Vegetable Oils, Bonn, 2021 June 2000, p. 303. [62] X. Wu, X. Zhang, S. Yang, H. Chen, D. Wang, JAOCS 77 (5) (2000) 561. [63] A. Pavlovicov a, J. Cvengro s, Petroleum and Coal 41 (2) (1999) 99. [64] R.G. Fayter, in: H. Eierdanz (Ed.), Perspektiven nachwachsender Rohstoffe in der Chemie, VCH, Weinheim, 1996, p. 107. [65] S. Warwel, M. R usch gen. Klaas, Lipid Technol. (1997) 10. [66] W. L uhls, K.J. Dehmer, R. Bergmann, W. Friedt, in: H. Eierdanz (Ed.), Perspektiven nachwachsender Rohstoffe in der Chemie, VCH, Weinheim, 1996, p. 232. [67] H. K ab, in: Fachagentur Nachwachsende Rohstoffe e.V. (Ed.), Proceedings of the Final Conference on CTVO-NETChemical-Technical Utilisation of Vegetable Oils, Bonn, 2021 June 2000, p. 269. [68] J. Seemann, B. Olbrich-Deuner, R. Gro-Lannert, SOFW J. 126 (10) (2000) 50. [69] D. Brauer, G. R obbelen, R. T opfer (Eds.), BioEngineering f ur Rapssorten nach Ma-Ergebnisse eines BMBF-Forschungsverbunds, G ottingen, 1999. [70] Frost & Sullivan, European Biolubricant Markets, 3799-39, 2000.

[23] A. Behr, N. D oring, C. Kozik, H. Schmidtke, S. Durowicz, DE 4012873 A1 (1991), Henkel K.-G.a.A. [24] L.E. Johansson, S.T. Lundin, JAOCS 56 (1979) 974. [25] A. Behr, Fat. Sci. Technol. 92 (10) (1990) 375. [26] B. Fell, W. Sch afer, Fat. Sci. Technol. 92 (7) (1990) 264. [27] B. Fell, W. Sch afer, A. Kotoko, J. Sojka, in: Forschungszentrum J ulich GmbH (Ed.), Statusseminar des BMFT-Forschungsverbundvorhabens Neue Einsatzm oglichkeiten nativer Ole und Fette als Chemierohstoffe, Oldenburg, 1415 February 1991, J ulich, 1992, p. 113. [28] R.M. Koster, M. Bogert, B. de Leeuw, E.K. Poels, A. Bliek, J. Mol. Catal. A: Chem. 134 (1998) 159. [29] R. H ofer, in: H. Eierdanz (Ed.), Perspektiven nachwachsender Rohstoffe in der Chemie, VCH, Weinheim, 1996, p. 91. [30] K.D. Haase, A.J. Heynen, N.L.M. Laane, Fat. Sci. Technol. 91 (9) (1989) 350. [31] W. Link, G. Spiteller, Fat. Sci. Technol. 92 (1) (1990) 19. [32] A. Behr, A. Laufenberg, Fat. Sci. Technol. 93 (1) (1991) 20. [33] A. Behr, A. Laufenberg, DE 4002012 A1 (1991), Henkel K.-G.a.A. [34] A. Behr, A. Laufenberg, DE 4002008 A1 (1991), Henkel K.-G.a.A. [35] A. Behr, A. Laufenberg, DE 4002009 A1 (1991), Henkel K.-G.a.A. [36] A. Behr, A. Laufenberg, DE 4002011 A1 (1991), Henkel K.-G.a.A. [37] E.H. Pryde, JAOCS 61 (1984) 419. [38] E.N. Frankel, E.H. Pryde, JAOCS 54 (1977) 873A. [39] Z. Xia, U. Kloeckner, B. Fell, Fett/Lipid 98 (9) (1996) 313. [40] U. Biermann, J.O. Metzger, Angew. Chem. 111 (1999) 3874. [41] U. Biermann, J.O. Metzger, in: Fachagentur Nachwachsende Rohstoffe e.V. (Ed.), Proceedings of the Final Conference on CTVO-NET-Chemical-Technical Utilisation of Vegetable Oils, Bonn, 2021 June 2000, p. 265. [42] U. Biermann, J.O. Metzger, Angew. Chem. Int. Engl. 38 (1999) 3675. [43] J.O. Metzger, U. Biermann, R. Mahler, in: H. Eierdanz (Ed.), Perspektiven nachwachsender Rohstoffe in der Chemie, VCH, Weinheim, 1996, p. 255. [44] J.O. Metzger, U. Biermann, Liebigs Ann. Chem. (1993) 645. [45] U. Biermann, W. Friedt, S. Lang, W. L uhls, G. Machm uller, J.O. Metzger, M.H.J. Sch afer, M.P. Schneider, M. R usch gen. Klaas, Angew. Chem. 112 (2000) 2292. [46] J.O. Metzger, U. Biermann, Fat. Sci. Technol. 94 (1992) 329. [47] H.M.R. Hoffmann, Angew. Chem. 81 (16) (1969) 597. [48] B.B. Snider, Acc. Chem. Res. 13 (1980) 426. [49] W. Oppolzer, V. Snieckus, Angew. Chem. 90 (1978) 506. [50] U. Bierman, J.O. Metzger, Fat. Sci. Technol. 93 (8) (1991) 282.