Journal of the Science of Food and Agriculture

J Sci Food Agric 86:17691780 (2006)

Review Plant-oil-based lubricants and hydraulic uids

Manfred P Schneider
Wuppertal, D-42097 Wuppertal, Germany FB C Bergische Universitat

Abstract: It is estimated that, at present, approximately 50% of all lubricants sold worldwide end up in the environment via total loss applications, volatility, spills or accidents. More than 95% of these materials are currently mineral oil based. In view of their high ecotoxicity and low biodegradability, mineral oil-based lubricants constitute a considerable threat to the environment. In contrast, most lubricants and hydraulic uids based on plant oils are rapidly and completely biodegradable and are of low ecotoxicity; moreover, lubricants based on plant oils display excellent tribological properties and generally have very high viscosity indices and ashpoints. However, in order to compete with mineral-oil-based products, some of their inherent disadvantages must be corrected, such as their sensitivity to hydrolysis and oxidative attack, and their behaviour at low temperatures. Various methods to improve the undesirable properties of native plant oils will be discussed. In parallel, government regulations that encourage or enforce the use of bio-based uids, at least in ecologically sensitive areas, will help to increase their market share. Using the numerous possibilities for selective breeding and/or chemical improvement of the double bond systems of natural fatty acids by increased R&D, the major obstacles regarding the use of plant-based raw materials for the production of lubricant base uids can be overcome and bio-based uids should expect a future with increasing market shares. 2006 Society of Chemical Industry

Keywords: plant oils; high oleic sunower oil; rapeseed (canola); oxidative attack; biodegradability; ecotoxicity; chemical modications; additives; eco-labels; lubricants; hydraulic uids

INTRODUCTION: LUBRICANTS AND THE ENVIRONMENT The environment must be protected against pollution by lubricants and hydraulic uids based on mineral oils. This is, of course, best done by preventing undesirable losses and by reclaiming and reusing lubricants. Alternatively, environmentally acceptable lubricants and hydraulic uids should be used whenever and wherever possible. According to literature reports, varying amounts of lubricants at present end up in the environment they disappear. It is claimed that in the EU alone in 1990 13% (661 106 L of a total of 4959 106 L) were lost in the environment.1,2 In the USA 32% (432 106 gallons of 1351 106 gallons) of lubricating oils ended up in landlls or were dumped. It is claimed that 50% of all lubricants sold worldwide end up in the environment via total loss application (chainsaw oils, two-stroke engines, concrete mould release oils, exhaust fumes in engines and metal cutting and forming processes) spillage and volatility.3 Estimates for the loss of hydraulic uids are as high as 7080%.4,5 Most problematic are uncontrolled losses via broken hydraulic hoses or accidents whereby large quantities of uids escape into the environment.6 They

contaminate soil, surface-, ground- and drinking water and also the air. In Table 1 the estimated amounts of lubricants used in Germany,7 the EU8 and worldwide9 are listed, together with the (estimated) losses. In contrast to mineral oils, lubricants and hydraulic uids based on plant oils are generally rapidly and completely biodegradable and are also of low ecotoxicity. At present the use of pure native plant oils is limited to total loss applications (lubricants for chainsaws, concrete mould release oils) and those with very low thermal stress. Hydraulic uids are of increasing importance for applications in environmentally sensitive areas where a potential total loss could be encountered, such as excavators, earthmoving equipment and tractors, in agricultural and forestry applications and in fresh water (groundwater) sensitive areas.10,11 Mineral oils are toxic for mammals, sh and bacteria. Considering the sump capacities of such machinery (up to 1000 L) the ecological impact is obvious as are the economics of the resulting cleanup operations. Although it seems obvious that the increased use of rapidly biodegradable lubricants would be of considerable ecological and economical advantage, the present market share of these materials is relatively

Wuppertal, D-42097 Wuppertal, Germany Correspondence to: Manfred P Schneider, FB C Bergische Universitat E-mail: schneid@uni-wuppertal.de Contract/grant sponsor: German Ministry of Agriculture (BVMEL) (Received 18 November 2005; accepted 31 March 2006) Published online 3 August 2006; DOI: 10.1002/jsfa.2559 2006 Society of Chemical Industry. J Sci Food Agric 00225142/2006/$30.00

MP Schneider
Table 1. Consumed lubricants and (estimated) losses (in tons per annum)

Germany Amount consumed Losses Losses in % 1 000 000 400 000 40

EU

World

higher viscosity index (multi-range oils); excellent biodegradability; high ashpoints; low water pollution classication.

5 000 000 3040 000 000 2 500 000 20 000 000 50 55

Table 2. Market share of bio-lubesa in Europe by geography for 2000 and expected for 2006

Year 2000 2006

a

ScandGermany France UK Benelux inavia Italy 4.0 15.1 0.1 0.3 0.2 0.4 2.9 4.9 9.0 10.8 1.3 2.0

Switzerland Austria 5.7 8.4

Their technical properties are thus largely comparable with mineral-oil-based uids. However, they are thermally less stable than mineral oils, sensitive to hydrolysis and oxidative attack, and their low-temperature behaviour is frequently unsatisfactory properties which can be corrected by a number of measures: exchange of glycerol by other polyols, in particular trimethylolpropane (TMP); avoiding or modifying multiply unsaturated fatty acids; suitable additivation. For the development of lubricants and hydraulic uids on the basis of renewable resources such as native plant oils one will always have to make a compromise between the performance based on the chemical structure and the desired biodegradability and ecotoxicity. All lubricants and hydraulic uids are composed of so-called base uids and additives.

Biodegradable lubricants derived from renewable resources including plants and animals.

small12 (2% in the EU and worldwide, with an estimated growth rate of 510%), as shown in Table 2 for a selection of European countries.13 (It should be noted that the Frost and Sullivan market survey and prediction is probably overoptimistic and that a 10% increase per annum would be considered already a success by oil manufacturers. Increases of 510% are in fact observed in reality; see also Whitby.14 ) For hydraulic uids this amount is increasing more rapidly, with estimates ranging from 25% to 75%.5,15 In order to increase this market share, the acceptability must be improved. Technical performance, acceptable price and ecological compatibility will constitute the basis for future developments along these lines. From an EU-sponsored study it seems that biolubricants are already available for the majority of applications and that the technical performance is comparable and sometimes even better than for conventional lubricants. Furthermore, the price of mineral oil will continue to increase over the years to come and the present-day advantage of low cost for mineral oil products may be completely lost in a decade from now.16,17

PLANT-OIL-BASED LUBRICANTS AND HYDRAULIC FLUIDS: PROPERTIES In practical applications lubricants and hydraulic uids have multiple functions. They are needed for lubrication, transmission of energy, protection against corrosion, wear (attrition) and heat removal. Plant-based uids meet these requirements ideally. They display: excellent tribological properties (ester functions stick well to metal surfaces); lower friction coefcients than mineral-oil-based uids; lower evaporation (Noack) up to 20% less than mineral-oil-based uids;
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BASE FLUIDS Native oils These are triglycerides, esters composed of various natural fatty acids and glycerol. The most important fatty acids contained in plant oils are unsaturated molecules such as oleic acid (C18:1), linoleic acid (C18:2) and linolenic acid (C18:3), as well as (saturated) palmitic acid (C16:0) and stearic acid (C18:0). At present, the most important sources for native oils are rapeseed (canola), sunower (various qualities) and soybean. The fatty acid compositions of potential plant oils are summarized in Fig. 1.18 The structures of fatty acids both chain length and degree of unsaturation are directly related to their operational stabilities and lubricant properties such as viscosity, viscosity index and low-temperature behaviour (e.g. pour point). Thus the oxidative stability of native oils increases with decreasing amounts of polyunsaturated acids (compare oxidative attack below). Since at least one cis- (Z ) double bond is essential for the required low-temperature behaviour, a high content of oleic acid is optimal. The best compromise at present among the above factors is high oleic sunower oil (HOSO) with 90% oleic acid <2% C18:0, <3.5% C18:2, no C18:3 (HOSO has now become commercially available in sufcient quantities:www.tutoc.de). Clearly, both rapeseed and soybean oil of standard quality do not meet these criteria and would thus require extensive chemical modication of the polyunsaturated fatty acids, including selective hydrogenation or epoxidation (see chemical modications below) in order to become suitable or would need additivation. Thus at the
J Sci Food Agric 86:17691780 (2006) DOI: 10.1002/jsfa

Plant-oil-based lubricants and hydraulic uids

100 90 80 70 60 [%] 50 40 30 20 10 0 C16:0 C18:0 C18:1 Fatty Acids C18:2 C18:3 rapeseed oil soybean oil high-oleic soybean oil corn oil cottonseed oil sunflower oil (80%) sunflower oil (90%)

safflower oil high-oleic safflower oil high-linoleic safflower oil sunlower oil

Figure 1. Fatty acid composition of various vegetable oils (worldwide).

present time we have two options: (a) to provide sufcient quantities of native oils with a high content of oleic acid by breeding or GMOs; or (b) to modify rapeseed oil (canola) or soybean oil by a variety of chemical measures (see below). Synthetic esters Native oils, i.e. triglycerides, contain glycerol as the alcohol component. They are inherently sensitive towards hydrolysis and thermal degradation. Much improved performance is achieved in products where the glycerol has been replaced by other polyols such as trimethylolpropane (TMP),19 neopentyl glycol (NPG) or pentaerythritol (PE)20,21 (Fig. 2). Some of these esters display extraordinary thermal stabilities. NPG esters are used as lubricants in jet engines. Several of such derivatives are used under arctic conditions. PE derivatives of carboxylic acids C5 C9 are employed in modern gas turbine engines. TMP esters of oleic acid are among the most widely applied materials for hydraulic uids at present. These bio-based esters show very good biodegradability, moderate oxidative stability and have a moderate price level. They are generally of high viscosity and display good shear stability. With some additivation they are the optimal choice for medium to heavy applications. A subgroup of these materials is called complex or oligo esters, resulting from the above polyols and mixtures of mono-, di- and tricarboxylic acids (for an example see Bondioli et al .22 ) (Fig. 3).

O O R1 O O O O R3 n

O OR2

Figure 3. An oligo- or complex ester (schematic).

Diesters Only partly or to a lesser degree derived from renewable resources are synthetic diesters prepared from dicarboxylic acids and monovalent alcohols. The employed dicarboxylic acids can be derived either from natural sources such as azelaic acid (ozonolysis of oleic acid), sebacic acid or dimeric fatty acid, isostearic acid or from purely petrochemical sources such as adipic acid or maleic acid. The alcohols are generally branched for better low-temperature performance such as 2-ethylhexanol (isooctanol), isodecanol or guerbet alcohols (Fig. 4). Also branched fatty acids, e.g. 12-hydroxystearic acid (derived from rhizinoleic acid), can be employed.

O HO O OH +2 HO

O O O R O O O O R R R O O O R O O

O R R R O Ester of neopentylglycol

O O
O O O O R

O O O O O H H

Ester of trimethylolpropane

Ester of pentaerythritol

Figure 2. Esters of trimethylolpropane (TMP), pentaerythritol (PE) and neopentylglycol (NPG).

Figure 4. Diesters from adipic and maleic acids and 2-ethylhexanol.

J Sci Food Agric 86:17691780 (2006) DOI: 10.1002/jsfa

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Base uids: structure and properties There is a denite relationship between the structure of the molecules and their properties such as viscosity, viscosity index (VI), low-temperature performance such as pour point and the oxidative stability. Viscosity of the base uid generally increases with the chain length of the carboxylic acid and the alcohol. However, if polyols are employed the viscosity also depends on the number of hydroxy functions present, and base uids with identical fatty acid residues would show the following series of viscosities depending on the employed polyol: PE (40) > TMP (27) > Glycerol (20) > NPG (12) Viscosity index describes the dependence of viscosity on the temperature. A high viscosity index means that there is little change over a wide temperature range. It increases with increasing chain length of carboxylic acid and alcohol, while branching in either the carboxylic acid or the alcohol results in a lowering of the viscosity index. Base oils based on natural fatty acids in general are known for their high viscosity indices and can be considered multi-range oils. Good low-temperature properties require a low content in saturated fatty acids (C16:0 and C18:0) and/or shortening of the chain length. In contrast, unsaturated fatty acids display excellent low-temperature properties. Thus, the pour points of simple esters derived from saturated and unsaturated fatty acids of identical carbon atom number are dramatically different (Fig. 5).
100 80 Pourpoint [C] 60 40 20 0 -20 -40 6:0 8:0 10:0 12:0 14:0 16:0 18:0 18:1 18:2 18:3 Fatty acid

Also, the pour point is lowered (improved) with increasing branching and shortening of the chain length. Oxidative stability requires a low content in polyunsaturated fatty acids (C18:2 and C18:3), while one double bond such as in oleic acid (C18:1) is essential for good low-temperature properties and does not negatively inuence the oxidative stability (see below). Fully saturated esters exhibit excellent oxidative stability,23,24 while partially unsaturated systems need improvement for applications in automotive (engine, transmission uids), diesel and industrial (hydraulic, compressor) lubricants. Fully saturated diesters in general show good lowtemperature performance (branched alcohol) and a high viscositytemperature index. By adjusting the chain length of the dicarboxylic acid the viscosity can be modied. These oils are highly stable towards oxidation (saturated compounds). Hydrolytic stability is strongly dependent on the ester structure. In general, saturated esters with straightchain components are more stable than unsaturated or branched equivalents. The most stable derivatives are saturated dicarboxylic esters. This is usually attributed to steric effects although there is some debate over this. Base uids: chemical structure and performance As already pointed out above, native plant oils (triglycerides) are sensitive towards hydrolysis, thermal degradation by elimination and oxidation (caused by the multiply unsaturated fatty acids). In order to turn them into lubricants or hydraulic uids with improved performance and stability, chemical modications, special additives or even de novo syntheses may be required. Thus native oils, straight out of the barrel, can only be employed for low-performance applications, at least without suitable additivation. Bio-based synthetic esters in which the glycerol moiety has been replaced by polyols such as trimethylolpropane (TMP), neopentylglycol (NPG) or pentaerythritol (PE) are suitable for higher performance requirements. While some mineral-oilbased materials, including poly- -olens (PAOs), clearly show even better performance and stability, fully synthetic esters in which the acid or alcohol component can be derived either from petrochemicals

Figure 5. Dependence of pour point on fatty acid structure. Table 3. Various base uids for lubricants and hydraulic uids: properties

Base uid rape seed oil (canola) high oleic sunower soybean TMP trioleate TMP trioleate, high oleic PAO-8 Mineral oil (150N)
a

Viscosity, 40 C (cSt) 33 39 31 50 47 47 ISO 32

Pour point ( C) 21 21 9 50 45 50 12

oxidative stability Moderate Good Poor Moderate Good Good Excellent

Biodegrad. (CEC)a 100 100 99 90 90 <50 15

Biodegrad. (OECD)a >70 >70 >70 >60 >60 30 5

For denitions see biodegradability section.

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Plant-oil-based lubricants and hydraulic uids

(directly or indirectly) or from native oils frequently outperform mineral-oil-based uids. However, the degree of biodegradability in general terms decreases with increasing stability and performance as increasingly non-natural components are employed (Table 3). From Table 3 it becomes clear that biodegradability decreases as oxidative stability increases. Consequently, a compromise between performance and biodegradability will always be necessary. Regardless of the employed base oil, additives against corrosion, wear and tear (attrition) and oxidation are usually needed, with the exception of total loss applications. Also the low-temperature performance (viscosity and pour point) is usually improved by additivation. A good selection of currently available base uids and their properties has been summarized by LR Rudnick.25

Table 4. Commonly used additives

Additive Antioxidants

Compound BHT and other phenols Alkylsubstituted diphenylamines Benzotriazoles Ester sulfonates Succinic acid esters Zn dithiophosphate Malan styrene copolymers Polymethacrylates Carbodiimides

Water pollution classa 1 1 2 1 1 2(3) Not identied Not identied Not identied

Deactivators for Cu, Zn etc. Corrosion inhibitors Anti-wear additives Pour point depressants Hydrolysis protection
a

0, no danger; 1, little danger; 2, danger; 3, strongly endangering.

ADDITIVES As outlined above, lubricants and hydraulic uids are materials which are composed of a base uid and so-called additives. These again are usually mixtures of compounds. Their composition is usually a trade secret and the mixtures are developed largely on a trial and error basis. Their effects can be agonistic or antagonistic and the interplay between the molecules is little understood in scientic terms. In hydraulic uids the amount of additives is usually small (12%). However, in motor oils usually 10% of additives are present. For special applications (e.g. transmission oils) these can reach up to 30%. Commonly used additives are antioxidants, rust (corrosion) inhibitors, demulsiers, anti-wear additives, additives for pour point depression and, more recently, carbodiimides, which largely inhibit the hydrolysis of ester bonds by trapping the produced water and fatty acids. In most cases, although claimed to be safe, the toxicological properties of many additives are still somewhat obscure. In summary, at the moment only very few additives are available which could pass the requirements for low toxicity. In Table 4 some widely used additives are summarized. Natural additives Unfortunately, to the best of our best knowledge, there are at present no bio-based additives being used in practice. Tocopherols (vitamin E) are natural antioxidants well known for their ability to scavenge radicals. Their presence in plant oils is usually greater than in mammalian fats. They therefore constitute a natural protection system within the plant against oxidative attack. Another natural antioxidant is L-ascorbic acid (vitamin C; E300), which can be added to plant oils in lipid modied form, e.g. as palmitate (E304) and will generally amplify the antioxidant properties of tocopherols. Esters of gallic acid (e.g. of lauric alcohol, dodecanol; E312) would be interesting and acceptable alternatives (E311, E312) to the more toxic phenolic antioxidants mentioned
J Sci Food Agric 86:17691780 (2006) DOI: 10.1002/jsfa

above. One could also envisage the application of citric acid derivatives or lipid-modied EDTA derivatives as synthetic metal scavengers. Natural antioxidants are typically unstable under the harsh conditions in which machinery, including hydraulic systems, operate. In view of the doubtful ecotoxicity of currently used additives, research regarding the development and use of bio-based additives is denitely recommended.

BIODEGRADABILITY AND ECOTOXICITY Major arguments for environmentally acceptable plant-oil-based lubricants and hydraulic uids are (a) high biodegradability and (b) low ecotoxicity. Biodegradability One has to distinguish between primary and ultimate biodegradation. Primary degradation describes the disappearance of the parent organic compound and may or may not indicate that the substance will biodegrade completely. By this method the disappearance of IR bands of CH bonds (CH3 : 2958 cm1 ; CH2 : 2928 cm1 ) is measured. The method is known as test method CECL-33-A-93 (CEC, Coordinating European Council; www.cec.org).26 Since the exact fate of the products remains obscure, this test may not be acceptable for the certication of environmentally acceptable uids under future, more stringent European regulations.27 Ultimate or total degradation means conversion of the tested material into CO2 and H2 O by microbial action within 28 days. The test method OECD 301 B (OECD, Organisation of Economic Cooperation and Development) has found worldwide acceptance. Numerous standardized test methods are available and have been reviewed.28,29 The biodegradability of plant-oil-based lubricants has been tested under operating conditions.24,30,31 It seems that biodegradability is not affected by usage and that antioxidant additives have a positive effect.
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Ecotoxicity Aquatic toxicity tests measure the extent to which a uid will poison selected environmental species such as algae (OECD 201), Daphnia magna (OECD 202-12), sh (athead minnows Oncorhynchus mykiss or Brachydanio rerio (OECD 203-13) and bacteria (Pseudomonas putida) (OECD 209). Mammalian toxicities are determined using rats (Sprague-Dawley) according to OECD 401. Typical criteria for environmentally friendly base uids are: biodegradability (CECL-33-A-93) >80% after 28d, (OECD 301B) >60% after 28d; aquatic toxicity LD50 >1000 ppm. Yet in spite of these criteria the term environmentally acceptable lubricants must be properly dened, especially for formulated oils. A formulated oil consisting of a highly biodegradable base uid in combination with toxic additives environmentally is not acceptable: while the bulk of uid is indeed biodegradable, the overall lubricant is not. It should be noted that the criteria for biodegradable oils according to the ISO 15 380 classication are much less stringent. Also, regarding the disposal of oils there is no dened regulation. It is left to the corresponding country to regulate the relevant procedure. It seems, however, that there is a European initiative under way based on the ISO 15 830 document. Several European countries are providing eco-labels for lubricants, which can be termed environmentally acceptable,5,10,32 such as the Blue Angel (Germany) and Nordic Swan (Nordic countries); recently introduced was a European eco-label called Euromargerite.

radical intermediate which reacts with molecular oxygen in a so-called radical chain reaction. The resulting hydroperoxides are further degraded with the production of water, aldehydes, ketones, carboxylic acids and further condensation, resulting in increasing viscosity of such oils and even formation of sediments by polycondensation. The most sensitive positions for such processes are bis-allylic CH groups, which are present in multiply unsaturated fatty acids such as linoleic (C18:2) and linolenic acid (C18:3). Yet oxidative attack also occurs with CH bonds in normal hydrocarbons as present in mineral oils and related compounds. The relative reactivities of selected CH bonds are qualitatively shown in Fig. 6(a). The differences in reactivity between these positions are quite large. Thus, while oleic acid with only one double bond is quite stable towards oxidation, linoleic and linolenic acids with two and three double bonds, respectively, are much more sensitive in this respect (Fig. 6b);33 for mechanistic studies see Porter et al .34 The differences are even more dramatic if saturated systems are included (Fig. 6c). From this it becomes clear that polyunsaturated fatty acids are deadly regarding oxidative stability, which increases as the number of double bonds decreases. Thus HOSO and polyol esters derived therefrom have considerably higher stabilities (lifetime) as compared to materials that contain multiply unsaturated fatty acids. Test methods The oxidative stability of native vegetable oils and biobased uids can be tested in a number of standardized ways, such as: Baader test (DIN 51554 part 3); TOST test (DIN 51587); rotary bomb test (ASTM D 211293); ASTM D-943. The hydrolytic stability beverage (coke) bottle test is described in ASTM D 2619 and the TOST test is described in ASTM D-943. Further tests can be carried out using special test rigs.24,35,36 A detailed description of all these methods, unfortunately, is beyond the scope of this article. Structure and performance: summary In summary, the performance of lubricants and hydraulic uids in terms of stability/lifetime is strongly related to the chemical structures of these materials and the relative stabilities are as follows:
H H << < H H

AGEING PROCESSES: LOSS OF PERFORMANCE The ageing of plant-based oils or bio-based uids in general is related to the chemical structures described above whereby three processes dominate: (a) oxidative attack at the allylic positions, mainly of polyunsaturated fatty acids modulated also by heavy metals such as Cu, Pb or Sn; (b) hydrolytic degradation of the ester bonds caused by water; (c) thermal elimination. Oxidative attack: chemistry Oxidative attack on unsaturated fatty acids is initiated by a one-electron transfer process leading to a

(a)

RCH2 - H < R2C-H < R3C-H < <<

(b)

rel = 1 <<<

rel = 12 << rel.100 rel. 1200 <

rel = 25

(c)

rel = 1

rel 2500

Figure 6. (a) Relative reactivities of selected CH bonds towards oxidative attack. (b) Relative reactivities of unsaturated systems towards oxidative attack. (c) Relative reactivities of hydrocarbon moieties towards oxidative attack.

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Plant-oil-based lubricants and hydraulic uids

Bio-based esters (native vegetable oils) < Bio-based synthetic esters (e.g. TMPs) < Mineral-oil-based saturated synthetic esters Mineral oils PAOs The lower the degree of unsaturation, the longer is the lifetime. Native oils in which the glycerol moiety has been replaced by polyols such as TMP, NPG or PE show improved lifetime. Saturated synthetic esters are clearly the most stable ester materials at present. However, in many cases the biodegradability is less than satisfactory. At present it seems that the best compromise between performance, price and biodegradability are high oleic oils.36 These can be obtained either by cultivation (selective breeding), with high oleic sunower oil (90%+ oleic acid) being the most prominent example, followed in the future possibly by high oleic rapeseed and soybean (selective breeding or GMO). Alternatively, chemical modications of commodities such as rapeseed oil or biodiesel would be an interesting alternative. Base uids with high contents of oleic acid also display excellent low-temperature properties with pour points of 35 C (HOSO) and 50 C (TMP, trioleate high oleic). As outlined above, the products resulting from such materials in combination with polyols such as TMP display excellent properties as hydraulic base uids.37 In fact, TMP esters of oleic acid are among the most widely applied materials for hydraulic uids at present. They are largely bio-based (i.e., they contain natural fatty acids), and show very good biodegradability, moderate oxidative stability and moderate price level. With some additivation they are an optimal choice for medium to heavy applications. The properties of such a material are summarized in Table 5.38 At present, HOSO is available only in limited quantities and for a comparatively high price. However, this may change rapidly as the development of environmentally friendly uids increases. Moreover, new species (GMO) of high oleic rapeseed and soybean are at the brink of development, while high oleic safower may not make it to the market place owing to low productivity of the plant. In order to nd a compromise between availability, price and performance one could consider the following possibilities:

1. With low-priced rapeseed oil or biodiesel as starting material one could (a) remove the polyunsaturated fatty acids by selective hydrogenation and (b) exchange the glycerol moiety with polyols such as TMP. 2. With high-priced high oleic sunower oil one would just have to replace the glycerol moiety by TMP. The cost of chemical transformations in rapeseed oil is estimated to be approximately 0.5 euro per step and per kilogram and could therefore compete with the high price of high oleic sunower. It would be a question of economy to choose the best route. If the cost of native high oleic sunower oil comes down, this would clearly be the better and faster route to high-performance base uids.

IMPROVEMENT OF NATIVE OILS BY CHEMICAL MODIFICATIONS As pointed out above, native oils (triglycerides) are, depending on their chemical structures, of only limited stability and prone to oxidative attack, hydrolysis and thermal decomposition. Based on their general structure there are basically only two positions in native plant oils (triglycerides) where a chemical modication can be effected39 41 (Fig. 7): (a) the ester moieties, especially the critical -hydrogen in native triglycerides; and (b) the double bonds along the fatty acid chains. Modications of the ester moieties Triglycerides contain glycerol as the alcohol component and have the critical -H position, which renders the molecules sensitive to thermal degradation by elimination. As already pointed out above, much improved performance is achieved in products where the glycerol is replaced by other polyols such as TMP, NPG or PE. Recent research results seem to indicate, however, that both the hydrolytic and oxidative stability of native oils is considerably increased if the fatty acid portion consists entirely of oleic acid. Thus native HOSO displays a similarly high stability as the combination of standard oleic acid (6872%) with TMP. This has to be studied in greater detail, since it would bring the use of neat vegetable oils without any modication a giant step forward.

Table 5. Properties of high oleic (90% +) TMP trioleate

Property viscosity, 40 C (cSt) Viscosity, 100 C (cSt) Viscosity index (VI) Pour point ( C) Flame point ( C) Evaporation rate (%) Oxidation stability (Baader) Biodegradation CEC (%) Biodegradation OECD (%)

Data 47 9.5 190 45 300 1.3 Middle to good 95 90

O O R O O H O O R

Figure 7. Critical positions in triglycerides susceptible to chemical modications.

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Modications of the double bond system As outlined above, multiple double bonds are extremely sensitive towards oxidative attack. In contrast, fatty acids with only one isolated cis double bond such as oleic acid (C18:1) are stable towards oxidation by an order of magnitude or more. Selective hydrogenation Ideally all unsaturation should be removed, e.g. by catalytic hydrogenation. Yet, this hardening leads to saturated fatty acids such as stearic acid and would turn the (liquid) oil into (solid) fat useless for applications as lubricants and hydraulic uids. Thus at least one isolated cis double bond is required in order to obtain oils with good (low-temperature) performance (viscosity, pour point). Therefore selective hydrogenation of multiply unsaturated fatty acids to materials in which all but one unsaturation is removed would provide the ultimate solution to this problem and linolenic acid would lead to oleic acid and its positional isomers, each of which carries only one isolated cis double bond (Fig. 8). Catalysts achieving such transformations already exist42 45 yet have not been applied on a technical scale. Previous attempts along these lines by industry were largely unsuccessful. While the amount of C18:2 and C18:3 acids was indeed reduced, a large proportion of the cis C18:1 had isomerized to the undesirable trans C18:1 (elaidic acid), which has similar undesirable properties to stearic acid (C18:0), thus rendering this process obsolete. Clearly the industrial development of this process would allow improvement of readily available base uids such as rapeseed oil and rapeseed oil methylester (RME), i.e. biodiesel.
O HO

The double bonds in unsaturated fatty acids offer numerous other possibilities for chemical modications. One must always be aware, however, that a compromise between the following criteria must be found: Performance (tribological properties) Stability towards oxidation Low-temperature performance Biodegradability

Branched fatty acids Clearly the best way to improve the stability against oxidation would be the complete removal of all double bonds. Yet in order to maintain the lowtemperature properties branched substituents must be introduced. These, however, typically cause a lowering of the biodegradability. Base uids synthesized from branched fatty acids (e.g. isostearic acid) display excellent low-temperature behaviour such as low pour point, low viscosity, high chemical stability and high ashpoint. Commercial isostearic acid is a mixture resulting from the thermal isomerisation of polyunsaturated C-18 fatty acids, followed by hydrogenation. Branching points are concentrated in the centre part of the molecule.46,47 Alternatively, 12hydroxystearic acid, derived from rhizonoleic acid by hydrogenation, can be employed. Chemical modications A number of examples for the modication of double bonds are summarized in Fig. 9.21,48 These include alkylation,49 radical addition,49 52 acylation,53 enereaction,54 hydroformylationoxo-synthesis,55 57 cooligomerisation,58,59 hydroaminomethylation60 and acyloxylation (addition of carboxylic acids).61,62 Epoxidation and derivatives derived therefrom Epoxidation of native plant oils transforms multiply unsaturated functions into oxiranes (epoxides), which are susceptible to ring opening reactions. Epoxidations can be achieved via classical, chemical methods using peracids63 (for industrial applications see also Westfechtel and Giede64 ) and also enzymatically.65,66 This allows the production of fully saturated esters with improved stability against oxidative attack and thus an innovative approach for the conversion of native oils,67 including epoxidized soybean oil into useful base uids for lubricants (Fig. 10).68 The alcohols used were so-called Guerbet alcohols (Jarcol I-18T), a mixture of 2-octyldecanol, 2hexyldodecanol (C16 1520%; C18 4654%, C20 2733%). Employed fatty acids were C2 C6 . The resulting uids, developed in the US Department of Agriculture (USDA), are currently being tested by a number of companies regarding their practical properties. In summary, one can state that many of the products resulting from the above transformations show interesting properties for practical applications,
J Sci Food Agric 86:17691780 (2006) DOI: 10.1002/jsfa

H2 / selective catalyst O HO + O HO O HO +

O HO
Figure 8. Selective hydrogenation of multiply unsaturated fatty acids (schematic).

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Plant-oil-based lubricants and hydraulic uids

10 O + 9-regioisomer O Et3Al2Cl3 O Cl O Mn(OAc)3 O OR Oleic acid ester 1. Isomerization H2 / CO Rh-catalyst, Ph3P 10 O H O + 9-regioisomer CH2 CH2 O OR 1:2 adduct OR 1:1 adduct CH2 CH2 2. RhCl3 x 3H2O O OR [Rh(COD)Cl]2 p(CO/H2) 70bar 10 N H + 9-regioisomer O NH2 OH + 10,11 - regiosiomer EtAlCl2 O 10 O + 9-regioisomer O Cl 9 8 O O

OR

OR

OR

+ 10,11 - regiosiomer

10 O O O

OR

Pivalic acid catalyst

10 9

CH2O

9 8 O

OR

+ 9-regioisomer

OR

Figure 9. Chemical modications of oleic acid derivatives (clockwise from upper left): (a) alkylation; (b) radical addition; (c) acylation; (d) enereaction; (e) aminoalkylation; (f) co-oligomerization; (g) hydroformylation; (h) acyloxylation.

O O O O O O O O

epoxidized soybean oil (schematic) R-OH H+ OH(R) 3 (R)HO OH(R) O R= C1 - C5 O O (R)HO R O O

Figure 10. Base uids from epoxidized soybean oil.

(Guerbet alcohols) Jarcol I-18T

OH(R) CO2R

O O R

OH(R) CO2R R

yet frequently biodegradability has not yet been properly addressed. In any case, the eld is wide open for innovative research.

GOVERNMENT REGULATIONS AND LEGISLATURE It seems that Portugal was the rst country to make use of biodegradable outboard two-stroke engine oils obligatory in 1991. Yet the source of the base uid was not further specied and only a 66%
J Sci Food Agric 86:17691780 (2006) DOI: 10.1002/jsfa

minimum requirement of biodegradability according to CEC-L-33-T-82 was imposed. In Austria the use of plant-oil-based lubricants for chain bar saws is mandatory (Federal Regulation). In all other countries there are no compulsory legislative measures regarding the use of lubricants for special applications. Recommendations exist in the UK69,70 and Canada.71 Numerous state (county) or community regulations are in (voluntary) force requiring contractors and subcontractors to use environmentally acceptable lubricants and hydraulic uids. This obligation
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MP Schneider

becomes part of the contract and must also be included in the nancial offer by the contractor. Increasing legislative pressure would promote the use of plant-based lubricants.14 For this, however, politicians would have to decide whether they consider the release of large quantities of lubricants into the environment tolerable or a danger in the sense of pollution. Unless there is a political decision of some sort there is little or no pressure on the consumer, industrial companies, contractors etc. to use plant-based lubricants or hydraulic uids. At present they will base their decision on price and performance (lifetime) rst, followed by environmental considerations. Partly it is a question of cost versus environment. Another major obstacle for the introduction of plant-based oils is the fact that manufacturers of machinery, including hydraulic equipment, are not easily convinced to clear their machines for the use of plant-based oils. Yet this is denitely required by the customer, who needs to know that the manufacturer gives full warranty for his machinery under these conditions. Although the required changes in most cases are relatively minor, there is still considerable reluctance both with manufacturers and customers. The reasons are relatively simple: 1. With a market share of presently 25% none of the manufacturers sees the need for acting towards the use of plant based oils. If the market share reaches 10-15% this problem would be solved automatically. 2. An oil change requires the following activities: (a) Change of elastomers, gaskets etc. for very little cost (penny articles). This is generally only for older equipment (before 1995), while modern machines already have high-quality elastomers built in, such as viton, which will withstand all kinds of lubricants. (b) Flushing of the system with two loads of plantbased oil in order to reduce the amount of residual, conventional oil to <2%. These two llings have to be discarded. (c) Introduction of one new lling with plantbased oil. In summary, the change of elastomers (with older equipment) is required and three llings of oil are needed. In view of the considerable sump volumes in some equipment, the cost for three llings for one oil change is quite expensive for the user, who is unlikely to do that unless some form of government incentive is provided. Although the elastomers to be changed are of very low cost, the machine has to be dismantled and reassembled, which is a labour-intensive process. In this sense it would certainly help if the government were to pay for the rst lling with environmentally acceptable uids. However, in view of the small market share manufacturers are unlikely to stock such uids separately at the end of their assembly line.
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The German Market Introduction Programme (MIP) In order to promote the increased use of plant-based lubricants and especially hydraulic uids the German government has introduced a programme in which a large part of the initial cost for the switch is covered by the taxpayer. The programme covers, in particular, (a) expenses for the oil and (b) labour cost required for the change. The MIP has been well accepted and in the rst year 4000 machines (equivalent to ca 1000 tons of consumed oil) have been changed over to plantbased (environmentally acceptable) oils. 90% of these were hydraulic uids and here mostly (90%) biobased synthetic esters (e.g. TMP oleates), with only ca 1% of native oils (a positive list of accepted uids can be found in www.panzenoel-initiative.de; www.fnr.de; www.rwth-aachen.de). Very few damages and/or problems were encountered, and only ve machine malfunctions have been reported. It looks as if the programme will turn out to be successful, mainly in the sense that the public and many customers are becoming increasingly aware of the environmental aspects of such changes. Also the programme allows the accumulation of experiences regarding the performance of such uids over a 5-year period.

ECONOMIC SITUATION AND FUTURE DEVELOPMENT It can be stated in general terms that the cost for biodegradable lubricants and hydraulic uids is depending on the product quality frequently higher than that of comparable mineral-oil-based products. Since the price level is also dependent on the corresponding additivation and the amounts purchased it is difcult to dene the exact differences. Generally, the price of rapeseed oil is much lower than that of synthetic esters, with differences of up to 200%. However, the price differences have to be seen also in relation to differences in quality and extended lifetime (i.e., extended periods between oil changes). The current differences in prices between bio-based and mineral-oil-based uids may, however, become irrelevant if one looks into the very near future. It can be predicted that mineral oil production will reach its peak (Hubberts peak) in ca 20032006 (right now!)16 and decline after that.17,72 74 This will as demonstrated presently at your own lling station cause a tremendous increase in the price level for all mineral-oil-based products, including lubricants and hydraulic uids. A price advantage for mineral oils may therefore no longer exist in the foreseeable future. Moreover, with increasing bidding for the dwindling reserves there may be a supply shortage. Since biolubricants are already available for numerous applications, with performance being well comparable and sometimes even better than those of mineral oil products combined with the methods for chemical
J Sci Food Agric 86:17691780 (2006) DOI: 10.1002/jsfa

Plant-oil-based lubricants and hydraulic uids

derivatizations increasingly being developed plant oils are an attractive alternative as raw materials for lubricants.

ACKNOWLEDGEMENTS We thank the German Ministry of Agriculture (BVMEL), administered by the Fachagentur Nachwachsende Rohstoffe (FNR), for the generous and continuous support of our work. We also acknowledge numerous and fruitful discussions with our scientic partners of many years, the IFAS Institute in Aachen (Prof. Dr H Murrenhoff and Dr H Theissen) and Fuchs Petrolub AG, Mannheim (Angela Kesseler, Rolf Luther and Prof. Dr. Theo Mang).

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