Patent Application
20110269655
The present invention relates to gear oil formulations comprising a gear oil and a film forming agent. When used as an automotive gear oil formulation the specifications for API GL-4 gear oils are at least satisfied. Use of the gear oil formulation in manual transmissions, transfer cases and differentials and use of the gear oil formulation in an industrial gear suitable for lubricating spur, helical, bevel, worm and hypoid gears are disclosed. Methods of lubrication are also disclosed.
Economic and environmental demands on gear oils mean that such compositions are being constantly pushed to their performance limits. Therefore choice of the combination of base fluid and additive package is crucial.
In automotive gear oils one such trend is towards extending oil drain intervals therefore it is necessary to develop gear oil formulations that have greater resistance to oxidation. It is recognised that antioxidant technology can carry some of the burden of resisting oxidation but choice and design of base fluid and other additives can also provide beneficial oxidative stability. Extension of oil drain intervals also means that the gear oils must have low volatility to prevent premature fluid loss.
Automotive lubricants must also maintain their proper viscosity and resist shear-down. Gear oils, in particular long lived gear oils and manual transmission lubricants experience tremendous shearing forces.
These property requirements have already led to the increased use of synthetic base fluids, specifically polyalphaolefin (PAO) base fluids. These base fluids have been shown to give added wear protection, better thermal and oxidative stability and much reduced volatility when compared to mineral oil formulated base fluids. Examples include PAO2, PAO4, PAO6 and PAO8 themselves (typically having kinematic viscosities at 100° C. of 2, 4, 6 and 8 mm s−1 respectively) or as mixtures and also with small amounts of higher PAOs, for example PAO4O and PAO100.
Higher molecular weight PAOs, for example PAO 40, PAO100, PAO1000, PAO3000 and combinations of such PAO are used as lubricity agents, in combination with the above PAO base fluids, where they form a thin film coating on the moving parts of the gears. However these higher molecular weight PAO are expensive to manufacture and currently there are limited commercial sources of these materials.
For many gears, both automotive and industrial, a cause of concern is micropitting of gear teeth. Micropitting is surface fatigue occurring in Hertzian contacts caused by cyclic contact stresses and plastic flow on the asperity scale. It results in microcracking, formation of micropits and loss of material. It occurs under elastohydrodynamic lubrication (EHL) oil films where the film thickness is of the same order as composite surface roughness, and the load is borne by surface asperities and lubricant. When a significant portion of load is carried by asperities, collisions between asperities on opposing surfaces cause elastic or plastic deformation depending on local loads. Micropitting is recognised as damaging to gear tooth accuracy and in some cases can be a mode of primary gear failure. It is particularly seen as an issue for windmill gear boxes.
Investigations undertaken by the inventors have led to the identification of a polymeric ester (also known as a complex ester) which is suitable to be used as a film forming agent in both automotive and industrial gear oil formulations. The film forming agent of the invention has been found to provide good film thickness coverage at low speeds, has superior lubricity and has enhanced shear stability as compared to the known PAO additives. Furthermore it provides an enhanced boast to the viscosity index of the gear oil formulation as compared to some of the known PAO additives. The film forming agent also provides beneficial oxidative stability to the gear oil formulation.
The gear oil formulation has improved low temperature properties when compared to use of the known PAO additives.
According to the present invention, a gear oil formulation comprising a gear oil and a film forming agent comprising a polymeric ester which is the reaction product of
The Gear Oil
The gear oils may be either automotive or industrial gear oils. Automotive gear oils include those suitable for use in manual transmissions, transfer cases and differentials which all typically use a hypoid gear. By transfer case we mean a part of a four wheel drive system found in four wheel drive and all wheel drive systems. It is connected to the transmission and also to the front and rear axles by means of driveshafts. It is also referred to in the literature as a transfer gearcase, transfer gearbox, transfer box or jockey box. Industrial gear oils include those suitable for use with spur, helical, bevel, hypoid and worm gears. Specifically included are those suitable for use in windmill gear boxes which typically have helical gears.
Automotive gear oils will normally have a viscosity in the range of SAE 50 to SAE 250, and more usually will range from SAE 70W to SAE 140. Suitable automotive base oils also include cross-grades such as 75W-140, 80W-90, 85W-140, 85W-90, and the like. Automotive gear oils are classified by the American Petroleum Institute (API) using GL ratings. API classification subdivides all transmission oils into 6 classes as follows
Most modern gearboxes require a GL-4 oil, and separate differentials (where fitted) require a GL-5 oil.
Industrial gear oil specifications are governed primarily by American Gear Manufacturers Association (AGMA) in North America or by individual manufacturers themselves. A typical specification for American industrial gear oils is shown below in Table One.
In Europe, as well as most of the Rest of the World, industrial gear oil specifications are typically written by Deutches Institut fur Normung (DIN).
The gear oils in which the compositions of this invention are employed can be based on natural or synthetic oils, or blends thereof, provided the lubricant has a suitable viscosity for use in gear oil applications. The gear oils for such use can be mineral oil base stocks such as for example conventional and solvent-refined paraffinic neutrals and bright stocks, hydrotreated paraffinic neutrals and bright stocks, naphthenic oils, cylinder oils, etc., including straight run and blended oils. Synthetic base stocks can also be used in the practice of this invention, such as for example PAO, alkylated aromatics, polybutenes, diesters, polyol esters, polyglycols, polyphenyl ethers, etc., and blends thereof. It is also known for PAOs and esters to be blended with mineral oils to form semi synthetics. Synthetic base stocks are preferred, especially base stocks having PAO or mixtures of PAOs as a major component.
At Least One Polyfunctional Alcohol
The at least one polyfunctional alcohol is preferably a polyol. The polyol preferably is of formula R(OH)n where n is an integer, which ranges from 2-10 and R is a hydrocarbon chain, either branched or linear, more preferably branched, of 2 to 15 carbon atoms. The polyol is suitably of low molecular weight, preferably in the range from 50 to 650, more preferably 60 to 150, and particularly 60 to 100. Examples of suitable polyols include ethylene glycol, propylene glycol, trimethylene glycol, diols of butane, neopentyl glycol, trimethyol propane and its dimer, pentaerythritol and its dimer, glycerol, inositol and sorbitol. Preferably the polyol is a neopentyl polyol. Preferred examples of neopentyl polyols are neopentyl glycol, trimethylol propane and pentaerythritol. Preferably the neopentyl polyol comprises at least 50% by weight of neopentyl glycol, more preferably at least 70%, even more preferably at least 90%.
Dimer Fatty Acid
The term dimer fatty acid is well known in the art and refers to the dimerisation product of mono- or polyunsaturated fatty acids and/or esters thereof. Preferred dimer fatty acids are dimers of C10 to C30, more preferably C12 to C24, particularly C14 to C22, and especially C18 alkyl chains. Suitable dimer fatty acids include the dimerisation products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid with oleic acid being particularly preferred. The dimerisation products of the unsaturated fatty acid mixtures obtained in the hydrolysis of natural fats and oils, e.g. sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil and tall oil, may also be used. These dimer fatty acids have iodine values typically of at least 100, measured according to a test method equivalent to ASTM D1959-85. Hydrogenated, for example by using a nickel, platinum or palladium catalyst, dimer fatty acids may also be employed. These hydrogenated dimer fatty acids have iodine values less than 25, preferably less than 20, more preferably less than 15, especially less than 10.
Hydrogenated dimer acids are especially preferred for use in the present invention.
In addition to the dimer fatty acids, dimerisation usually results in varying amounts of oligomeric fatty acids (so-called “trimer”) and residues of monomeric fatty acids (so-called “monomer”), or esters thereof, being present. The amount of monomer and trimer can, for example, be reduced by distillation. Particularly preferred dimer fatty acids used in the present invention, have a dimer content of greater than 50%, more preferably greater than 70%, particularly greater than 85%, and especially greater than 90% by weight. The trimer content is preferably less than 50%, more preferably in the range from 1 to 20%, particularly 2 to 10%, and especially 3 to 6% by weight. The monomer content is preferably less than 5%, more preferably in the range from 0.1 to 3%, particularly 0.3 to 2%, and especially 0.5 to 1% by weight.
Whilst it is desirable for the polymeric ester to have some polarity, it is recognised that too high a polarity can lead to undesirable effects such as seal swell and/or too high surface affinity which could cause antagonistic interactions with inorganic antiwear additives also present in the gear oil formulation. Non-polarity index, NPI is one method of assessing polarity and is defined as
total number of carbon atoms * molecular weight
The NPI of the film forming agent is between 1000 and 4000, preferably between 1500 and 3000.
Optionally an Aliphatic Dicarboxylic Acid
An aliphatic dicarboxylic acid may be used to optimise the polarity of the polymeric ester. Examples of suitable aliphatic dicarboxylic acids include glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, dodecanedioic, tridecanedioic, tetradecanedioic, pentadecanedioic, hexadecanedioic acids and mixtures thereof. The aliphatic dicarboxylic acid preferably has from 7 to 16 carbon atoms, more preferably from 8 to 14 carbon atoms. The aliphatic dicarboxylic acid is preferably linear. Azelaic acid, sebacic acid and dodecanedioic acid are particularly preferred. Azelaic acid is especially preferred.
One or More Ingredients to Reduce the Acid Value of the Polymeric Ester to Below 5 mgKOH/q
Examples of such an ingredient include an aliphatic monocarboxylic acid having 5 to 24 carbon atoms or an aliphatic monofunctional alcohol having 5 to 24 carbon atoms. The monoacid or monoalcohol reacts with any OH or COOH groups respectively which remain unreacted after reaction between the polyfunctional alcohol and the dimer fatty acid. Examples of the aliphatic monocarboxylic acid include the saturated straight chained acids of pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, tridecanoic, tetradecanoic, pentadecanoic, hexadecanoic, heptadecanoic, octadecanoic, arachidic, behenic and lignoceric acids and mixtures thereof. Examples also include unsaturated and/or branched variants of the disclosed saturated, straight-chained acids. The aliphatic monocarboxylic acid preferably has 7 to 20 carbon atoms, more preferably 8 to 18 carbon atoms. It may be branched or straight chained and preferably is saturated. Particularly preferred monoacids are a mixture of octanoic and decanoic acids, and isostearic acid.
Examples of the aliphatic monofunctional alcohol include pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and mixtures thereof. Examples also include unsaturated and/or branched variants of the disclosed saturated, straight chained acids The aliphatic monofunctional alcohol preferably has 7 to 16 carbon atoms, more preferably 8 to 14 carbon atoms. It may be branched or straight chained and preferably is saturated. 2-Ethylhexanol is particularly preferred.
A further example of such an ingredient is an acid catcher, for example a glycidyl ester.
The one or more further ingredient may be added to the reaction mixture at the same time as a), b) and optionally c) or after reaction of a), b) and optionally c) has completed.
Preferably the acid value is reduced to below 1 mgKOH/g, more preferably below 0.5 mgKOH/g and especially below 0.2 mgKOH/g
The resulting polymeric ester has a kinematic viscosity at 100° C. of 400 to 5000, preferably 500 to 3000, more preferably 500 to 2500, especially 500-2200 mm2/s.
The polymeric ester has a weight average molecular weight between 5000 and 20000. A weight average molecular weight of below 5000 is deemed unsuitable with respect to the ability of the film forming agent to reliably form a film. A polymeric ester with a weight average molecular weight above 20000 is deemed unsuitable to meet the needs of the present invention because it is believed that such a high molecular weight will not have the required shear stability. The polymeric ester preferably has a weight average molecular weight range of 5000 to 18000, more preferably 5000 to 17000 and especially 5000 to 15000. In cases where the polymeric ester has a high molecular weight (typically above 13000) a lower molecular weight ester, for example a diester or a polyol ester, may need to be added to the gear oil formulation to ensure that the polymeric ester is fully soluble in the gear oil. A suitable example of such a cosolvent is Priolube™ 3970 available ex Croda Europe Ltd. The dose rate of the lower molecular weight ester is chosen such that the polymeric ester is fully soluble but also that the overall polarity of the esters is suitable so as to not lead to undesirable effects as detailed above.
The polymeric ester suitably has an iodine value less than 50, more preferably less than 35, even more preferably less than 25, especially less than 15 and more especially less than 10. Iodine value analysis was carried out following a test method equivalent to ASTM D1959-85.
Preferred film forming agents include a polymeric ester which is the reaction product of a polyol, preferably a neopentyl polyol, more preferably neopentylglycol with dimer acid, preferably hydrogenated dimer acid, and then end capped with a monoalcohol, preferably 2-ethyl hexanol.
The film forming agent may further comprise a second ester which is the reaction product of at least one polyfunctional alcohol and a dimer fatty acid with the resultant ester having a kinematic viscosity at 100° C. ranging from 20 to 100mm2/s. Preferably the polyfunctional alcohol for this second ester is a diol, specifically ethylene glycol. The dimer fatty acid for this second ester may be unhydrogenated or hydrogenated. Preferably it is hydrogenated.
Preferably the ratio of the polymeric ester to the second ester is in the range of 5:1 to 1:5, more preferably 3:2 to 2:3.
The Gear Oil Formulation
For automotive gear oils the gear oil formulation at least satisfies the requirements of GL-4 rating classification of the American Petroleum Institute.
Gear oil formulations of the invention preferably exhibit a percentage viscosity loss, measured using a modified version of CEC L-40-A-93, over a 20 hour period of less than 20%, more preferably less than 10% and especially less than 5%. Gear oil formulations of the invention preferably exhibit a percentage viscosity loss, measured using a modified version of CEC L-40-A-93, over a 100 hour period of less than 25%, more preferably less than 20% and especially less than 15%.
When the film thickness of the gear oil formulation falls below the level of the highest asperity on the gear surface then wear occurs. Such poor film thickness is known to occur under low speed and/or high load conditions. Therefore formation of a good film thickness at a low speed is advantageous in preventing wear. The film forming agent is of the invention preferably forms a film thickness of 5 nm at speeds of less than 0.04 m s−1, more preferably less than 0.025 m s−1
High frequency friction reciprocating testing (HFRR) is a recognised screening tool for wear evaluation. A wear scar of less than 600 μm, preferably less than 550 μm, more preferably less than 500 μm and especially less than 450 μm measured using HFRR according to CEC F-06-A-96 is obtained when the gear oil formulation is used.
The film forming additive also acts as a viscosity index improver. The film forming additive provides a viscosity index boost to the gear oil formulation of at least 40%, preferably at least 55%, more preferably at least 65%, especially at least 70%.
Gear oil formulations according to the invention have good low temperature properties. The viscosity of such formulations at −35 ° C. is less than 120,000 centapoise (cP), more preferably less than 100,000 cP, especially less than 90,000 cP.
To obtain surface effects only, for example film thickness enhancement, the film forming agent is preferably present at levels between 0.3 to 2% by weight, preferably 0.4 to 1% by weight, especially 0.5% by weight.
To also obtain bulk effects, for example oxidative stability, shear stability and boost of viscosity index the film forming agent is preferably present at levels between 3 and 50% by weight, more preferably between 5 and 35% and especially between 5 and 25% in the gear oil formulation.
The gear oil formulation may further comprise an antioxidant preferably in the range 0.2 to 2%, more preferably 0.4 to 1% by weight. Antioxidants include hindered phenols, alkyl diphenylamines and derivatives and phenyl alpha naphthylamines and derivatives of. Especially preferred antioxidants are Irganox™ L57 and Irganox™ L06 available ex Ciba. Gear oil formulations with the presence of the antioxidant preferably exhibit a percentage viscosity loss, measured using a modified version of CEC L-40-A-93, over a 100 hour period of less than 20%, more preferably less than 15% and especially less than 10%.
Other additives may be present in the gear oil formulation of known functionality at levels between 0.01 to 30%, more preferably between 0.01 to 20% more especially between 0.01 to 10% of the total weight of the gear oil formulation. These can include detergents, extreme pressure/antiwear additives, dispersants, corrosion inhibitors, rust inhibitors, friction modifiers, foam depressants, pour point depressants, and mixtures thereof. Extreme pressure/antiwear additives include ZDDP, tricresyl phosphate, amine phosphates. Corrosion inhibitors include sarcosine derivatives, for example Crodasinic O available from Croda Europe Ltd. Foam depressants include silicones and organic polymers. Pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, terpolymers of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. Ashless detergents include carboxylic dispersants, amine dispersants, Mannich dispersants and polymeric dispersants. Friction modifiers include amides, amines and partial fatty acid esters of polyhydric alcohols. Ash-containing dispersants include neutral and basic alkaline earth metal salts of an acidic organic compound . Additives may include more than one functionality in a single additive.
According to a further embodiment of the present invention use of the above mentioned gear oil formulation in a machine such as a manual transmission, a transfer case and/or a differential.
According to a further embodiment of the present invention use of the gear oil formulation in an industrial gear.
According to a further embodiment of the present invention use of the gear oil formulation in a windmill gear box.
According to a further embodiment a method of lubricating a machine such as a manual transmission, a transfer case and/or a differential.
According to a further embodiment a method of lubricating an industrial gear.
According to a further embodiment use of the film forming agent to increase shear stability, lubricity and/or viscosity index of the gear oil formulation.
The invention will now be described further by way of example only with reference to the following Examples.
Shear stability testing was carried out according to CEC L-40-A-93 modified in that a smaller pot was used. The test conditions were:
Start temperature 60° C.
1450 revolutions per minute
50 Kg load
20 or 100 hours run time
20 g sample
Table Two illustrates percentage viscosity loss after both 20 and 100 hours for 75W-140 gear oil formulations with PAO6 gear oil and Priolube™ 3970 as solubilising agent for film forming agent in gear oil formulation containing esters of the current invention and comparative esters.
Ester A according to the invention is the reaction product of neopentylglycol (167 kg) with dimer acid with at least 95% dimer present (833 kg) and C9 dicarboxylic acid (12.5 kg). 5% w/w Cardura™ E10 was then added to reduce acid value. The ester has a viscosity at 100° C. of about 1800 mm2/s. The ester has an NPI of 2624 and an iodine value of 33 g/100 g.
Ester B according to the invention is the reaction product of neopentylglycol (167 kg) with hydrogenated dimer acid with at least 95% dimer present (833 kg). 5% w/w Cardura™ E 10 was then added to reduce acid value. The ester has a viscosity at 100° C. of about 1600 mm2/s. The ester has an iodine value of 4.3 g/100 g.
Ester C according to the invention is the reaction product of monoethylene glycol (>2 mol) with dimer acid with at least 65% dimer present (1 mol). The ester has a viscosity at 100° C. of about 60 mm2/s.
Ester D according to the invention is the reaction product of monoethylene glycol (>2 mol) with hydrogenated dimer acid with at least 65% dimer present (1 mol). The ester has a viscosity at 100° C. of about 60 mm2/s.
The results in the Table clearly show that gear oil formulations comprising a film forming agent according to the present invention have a much lower viscosity loss after 20 hours and are therefore more shear stable than gear oil formulations having PAO1000 or PAO3000 additives. Therefore they are more suitable for use in gear oil formulation which are known to be subject to extensive shear forces. Furthermore the results after 100 hours show that the gear oil formulations of the invention still maintain a low viscosity loss.
Table Three illustrates percentage viscosity loss after 100 hours for the 75W-140 gear oil formulations containing polymeric esters of the current invention as per Example One with further addition of 0.5% by weight of Irganox™ L57 antioxidant available ex Ciba.
It can be seen that the presence of the antioxidant further reduces the percentage viscosity loss.
Table four illustrates size of wear test scar measured for 150 ppm (wt/wt) solutions of polymeric esters of the current invention and comparative esters in ultra low sulphur diesel (ULSD). The wear scar size in μm was measured using a high frequency reciprocating rig (HFRR) under test conditions according to EN590, CEC-0-A-96.
The results show that a ULSD formulation comprising a film forming agent according to the invention has a wear test scar less than that comprising comparative materials.
Film thickness was measured, using principle of optical interferometry, on a PCS Instruments ultra thin film rig with a silica coated glass disc positioned above a loaded ball in the gear oil formulation for a variety of speeds.
Temperature 40° C.
Load 50N
Speeds 4 m/s to 0.004 m/s
Gear oil—PAO 2 with viscosity of˜2.6 mms−1 at 100° C.
Table Five illustrates speed at which two specific film thicknesses were formed for these gear oil formulations including film forming agents of the invention and for comparators.
Table Six shows film thickness obtained at a specific low speed, 0.057 ms−1 for a film forming agent according to the invention and a comparator.
The data in Tables Five and Six shows that use of a film forming agent according to the invention in a gear oil formulation leads to quicker formation of film thickness, i.e. there is good film thickness at low speeds which helps reduce wear. It is postulated that such film thickness will reduce surface fatigue in the gears therefore helping to reduce micropitting.
Table Seven shows the viscosity index boost for 75W-140 gear oil formulations as according to the invention and comparators. Kinematic viscosity measurements were undertaken using Anton Paar Viscometer SVM 3000. For Ester A the viscosity at 40° C. was too high to take a measurement. Therefore the viscosity was measured at 80° C. and 100° C. and both 40° C. viscosity and VI were then calculated from these measurements using ASTM D2270. The gear oil used was PAO2 with a VI of 124.
The data in Table Seven illustrates the VI boost provided by a film forming agent of the invention. It is to be noted that PAO1000 itself provides a larger VI boost BUT it does not have all the other properties as according to the invention.
Table Eight shows the viscosity at −35° C. for 75W-140 gear oil formulations as according to the invention, measured using a Brookfield cold crank simulator
The data in Table Eight illustrates that a gear oil formulation according to the invention has a low viscosity at a low temperature, −35° C. This is important for cold start.
Oxidative stability of film forming agents according to the invention and comparators was measured using a modified version of hot tube test, IP 280/85.
The duration of the test was 168 hours in which air was blown through a first tube, containing a steel coupon and gear oil formulation at 140° C., followed by a second tube containing water at room temperature.
Coupon loss in g, volatile acid in the water (mg KOH/g) and net acid increase of the gear oil formulation were measured.
Table Nine shows the oxidative stability for film forming agents according to the invention in PAO 6 gear oil.
As can be seen film forming agents according to the invention provide oxidative stability. PAO1000 itself provides enhanced oxidative stability BUT does not have the other properties as required according to the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0822256.4 | Dec 2008 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/GB2009/002765 | 11/27/2009 | WO | 00 | 7/12/2011 |
