EP1853684B1 - Zusammensetzung und verfahren zur erhöhung der oxidationsstabilität industrieller flüssigkeiten - Google Patents
Zusammensetzung und verfahren zur erhöhung der oxidationsstabilität industrieller flüssigkeiten Download PDFInfo
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- EP1853684B1 EP1853684B1 EP06736719A EP06736719A EP1853684B1 EP 1853684 B1 EP1853684 B1 EP 1853684B1 EP 06736719 A EP06736719 A EP 06736719A EP 06736719 A EP06736719 A EP 06736719A EP 1853684 B1 EP1853684 B1 EP 1853684B1
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- oil
- fluid
- additives
- antioxidant
- industrial fluid
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- the present invention relates to industrial fluids. More particularly, the present invention relates to improved hydraulic fluids that exhibit oxidative stability, ready biodegradability, low volatility, and a high viscosity index.
- TLV threshold limit value
- HEAR high erucic acid rapeseed
- U. S. Patent No. 6,531,429 discloses compositions comprising thiophosphoric acid esters and dithiophosphoric acid esters or phosphoric acid thioesters and oil additives from the group of the polyol partial esters, amines and epoxides, and also to the use of those lubricant compositions in improving the performance properties of lubricants, such as greases, metal-working fluids, gear fluids or hydraulic fluids.
- Thiophosphoric acid esters and dithiophosphoric acid esters or phosphoric acid thioesters are present in the compositions preferably in a concentration of less than 400 ppm.
- U. S. Patent No. 6,583,302 discloses the modification of triglyceride oils having unsaturated fatty acid substituents to convert sites of unsaturation to C 2 to C 10 diesters.
- the resulting derivatives are said to be characterized by thermal and oxidative stability, have low temperature performance properties, are environmentally-friendly, and have utility as hydraulic fluids, lubricants, metal working fluids and other industrial fluids.
- the triglyceride oils are most easily prepared via epoxidized vegetable oils which are converted to the diesters in either a one- or two-step reaction.
- ECO epoxidized canola oil
- the present invention is directed to using an epoxidized vegetable oil or synthetic ester to make an oxidatively stable biodegradable industrial fluid wherein said fluid is used in combination with at least one antioxidant.
- an industrial fluid is defined as any of a class of biodegradable oils used for automotive engine oils, two-stroke engine oils, aviation turbine oils, automotive gear oils, industrial gear oils, hydraulic fluids, compressor oils, metalworking fluid, textile oils, chain saw oils, and greases.
- the present invention is directed to a biodegradable industrial fluid comprising
- present invention is directed to a method for improving the oxidation stability of industrial fluids comprising employing as the base oil of said industrial fluid an epoxidized tall oil octyl ester, wherein said ester is used in combination with at least one antioxidant selected from the group consisting of alkylated diphenylamines, N-alkylated phenylenediamines, secondary diarylamines and hindered phenolic compounds.
- the industrial fluid is a hydraulic fluid.
- the tall oil employed in the practice of the present invention can be esterified either before or after it is epoxidized.
- the alkyl moiety of the ester portion comprises eight carbon atoms, e.g., octyl, isomers of the foregoing, and the like.
- the alkyl moiety is 2-ethylhexyl, i.e., an isomer of octyl.
- Esterification and epoxidation of the tall oil can be carried out by methods well known to those skilled in the art.
- Antioxidants that can be used in the practice of the present invention include alkylated diphenylamines and N-alkylated phenylenediamines.
- Secondary diarylamines are well known antioxidants and there is no particular restriction on the type of secondary diarylamine that can be used in the practice of the present intervention.
- the secondary diarylamine antioxidant is of the general formula R 11 -NH-R 12 , where R 11 and R 12 each independently represent a substituted or unsubstituted aryl group having 6 to 46 carbon atoms.
- substituents for the aryl group are aliphatic hydrocarbon groups such as alkyl having 1 to 40 carbon atoms, hydroxyl, carboxyl, amino, N-alkylated amino, N',N-dialkylated amino, nitro, or cyano.
- the aryl is preferably substituted or unsubstituted phenyl or naphthyl, particularly where one or both of the aryl groups are substituted with alkyl, such as one having 4 to 24 carbon atoms.
- Preferred alkylated diphenylamines that can be employed in the practice of the present invention include nonylated diphenylamine, octylated diphenylamine (e.g., di(octylphenyl)amine), styrenated diphenylamine, octylated styrenated diphenylamine, and butylated octylated diphenylamine.
- the alkyl moiety of 1 to 40 carbon atoms can have either a straight or a branched chain, which can be either a fully saturated or a partially unsaturated hydrocarbon chain, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethyl hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, oleyl, nonadecyl, eicosyl, heneirosyl, docosyl, tricosyl, tetracosyl, pentacosyl, tricontyl, pentatriacontyl, tetracontyl, and the like, and isomers and
- Secondary diarylamines that can be employed in the practice of the present invention include: diphenylamine, dialkylated diphenylamine, trialkylated diphenylamine, or mixtures thereof, 3-hydroxydiphenylamine, 4-hydroxydiphenylamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, mono- and/or di-butyldiphenylamine, mono- and/or di-octyldiphenylamine, mono- and/or di-nonyldiphenylamine, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, di-heptyldiphenylamine, mono- and/or di-( ⁇ -methylstyryl)diphenylamine, mono- and/or di-styryldiphenylamine, N,N'-diisopropyl-p-phenylenediamine, N,
- oil soluble hindered phenolic compounds may be listed alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebis phenols, benzyl compounds, acylaminophenols, and esters and amides of hindered phenol-substituted alkanoic acids.
- 3,5-di- t -butyl-4-hydroxy-hydrocinnamic acid, a C 7 -C 9 branched alkylester of 2,6-di- t -butyl- p -cresol, and mixtures thereof are included in the hydraulic fluid compositions.
- antioxidant type that can be used in combination with the additives of the present invention are oil soluble copper compounds, and the like.
- the base oil and antioxidants of the hydraulic fluids of this invention can be used in combination with other additives typically found in hydraulic and other industrial fluids, and such combinations may, in fact, provide synergistic effects toward improving the desired properties, such as improved deposit control, anti-wear, frictional, antioxidant, low temperature, and like properties, of the fluid.
- Typical additives found in hydraulic fluids include dispersants, detergents, rust inhibitors, antiwear agents, antifoamants, friction modifiers, seal swell agents, demulsifiers, VI improvers, and pour point depressants.
- dispersants examples include polyisobutylene succinimides, polyisobutylene succinate esters, Mannich Base ashless dispersants, and the like.
- detergents include metallic alkyl phenates, sulfurized metallic alkyl phenates, metallic alkyl sulfonates, metallic alkyl salicylates, and the like.
- anti-wear additives examples include organo borates, organo phosphites, organic sulfur-containing compounds, zinc dialkyl dithiophosphates, zinc diaryl dithiophosphates, phosphosulfurized hydrocarbons, and the like.
- friction modifiers include fatty acid esters and amides, organo molybdenum compounds, molybdenum dialkylthiocarbamates, molybdenum dialkyl dithiophosphates, and the like.
- An example of an antifoamant is polysiloxane, and the like.
- An example of a rust inhibitor is polyoxyalkylene polyols, and the like.
- Examples of VI improvers include olefin copolymers and dispersant olefin copolymers, and the like.
- An example of a pour point depressant is polymethacrylate, and the like.
- Compositions when containing these additives, typically are blended into the base oil in amounts that are effective to provide their normal attendant function. Representative effective amounts of such additives are illustrated as follows: Broad Preferred Compositions Wt % Wt % V.I. Improver 1-12 1-4 Corrosion Inhibitor 0.01-3 0.01-1.5 Oxidation Inhibitor 0.01-5 0.01-1.5 Dispersant 0.1-10 0.1-5 Lube Oil Flow Improver 0.01-2 0.01-1.5 Detergents and Rust Inhibitors 0.01-6 0.01-3 Pour Point Depressant 0.01-1.5 0.01-0.5 Anti-Foaming Agents 0.001-0.1 0.001-0.01 Antiwear Agents 0.001-5 0.001-1.5 Seal Swellant 0.1-8 0.1-4 Friction Modifiers 0.01-3 0.01-1.5 Base Oil Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance
- additive concentrates comprising concentrated solutions or dispersions of the subject additives whereby several additives can be added simultaneously to the base oil to form the hydraulic fluid composition. Dissolution of the additive concentrate into the tall oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
- the concentrate or additive-package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant.
- the additives can be added to small amounts of base oil or other compatible solvents to form additive-packages containing active ingredients in collective amounts of typically from 2.5 to 90%, and preferably from 15 to 75%, and most preferably from 25 to 60% by weight additives in the appropriate proportions with the reminder being base oil.
- the final formulations may employ typically 1-20 wt. % of the additive-package with the remainder being base oil.
- weight percents expressed herein are based on active ingredient (AI) content of the additive, and/or upon the total weight of any additive-package or formulation, which will be the sum of the (AI) weight of each additive plus the weight of total oil or diluent.
- the preferred hydraulic fluid compositions of the invention contain the additives in a concentration ranging from 0.01 to 30 weight percent.
- a concentration range for the additives ranging from 0.01 to 10 weight percent based on the total weight of the composition is preferred.
- a more preferred concentration range is from 0.2 to 5 weight percent.
- fatty acid distributions of the vegetable oils employed herein are given in Table 1.
- Descriptions of the epoxidized vegetables and their iodine values (degree of unsaturation) are listed in Table 2.
- the detergents used were 400 TBN amorphous overbased calcium sulfonate (Calcinate C400CLR), 300 TBN amorphous overbased calcium sulfonate (Calcinate C300R), 400 TBN crystalline overbased calcium sulfonate (Calcinate C400W), and overbased calcium carboxylate (OBC)
- the antioxidants used were nonylated diphenyl amine (Naugalube 438L), 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid C 7 -C 9 branched alkyl ester (Naugalube 531), alkylated phenyl-alpha-naphthylamine (Naugalube APAN) and a tolutriazole derivative (Metal Passi
- C18-3 is linolenic acid.
- C22-1 is erucic acid.
- Table 2 Description of Epoxidized Vegetable Oils Name Description Oxirane Oxygen (%) Iodine Value ESO epoxidized soybean oil 7.0 1.6 ELO epoxidized linseed oil - - ECO epoxidized canoloa oil 5.6 4.5 EOTE epoxidized 2-ethylhexyl tallate 4.7 2.5
- test methods were used in the following examples. These test methods included: Pressurized Differential Scanning Calorimetry (PDSC), ASTM D6186; Demulsibility, ASTM D1401; Four-Ball Wear, ASTM D2266; Four-Ball EP, ASTM D4172); Hydrolytic Stability, ASTM D2619; Rotating Bomb Oxidation (RBOT) or Rotating Pressure Vessel Oxidation Test (RPVOT), ASTM D2272; and Turbine Oil Stability Test (TOST), ASTM D943.
- PDSC Pressurized Differential Scanning Calorimetry
- ASTM D6186 Demulsibility
- ASTM D1401 Four-Ball Wear
- ASTM D4172 Four-Ball EP
- Hydrolytic Stability ASTM D2619
- Rotating Bomb Oxidation RBOT
- Rotating Pressure Vessel Oxidation Test RVOT
- ASTM D2272 Rotating Pressure Vessel Oxidation Test
- TOST Turbine Oil Stability Test
- Examples 1-3 demonstrate the poor oxidative stability of the typical vegetable oils (high erucic acid rapeseed oil, canola oil, and high oleic acid canola oil) in PDSC, RPVOT and TOST testing
- Examples 4-6 demonstrate the excellent oxidative stability of the typical epoxidized vegetable oils (canola oil, soybean oil, and linseed oil) in PDSC, RPVOT, and TOST testing.
- Example 7 demonstrates the synthetic ester OTE, based on octyl tallate, is significantly less oxidatively stable in PDSC, RPVOT, and TOST testing than its epoxidized octyl tallate ester analog in Example 9.
- Example 8 demonstrates another synthetic ester, based on trimethylol propane caprate, is significantly less oxidatively stable in PDSC, RPVOT, and TOST testing than the epoxidized octyl tallate ester in Example 9. (*) does not fall within the scope of protection being claimed
- Example 9 demonstrates the octyl tallate ester is stable in typical industrial lubricant testing (emulsion characteristics, four-ball wear, foaming tendency, PDSC, RPVOT, and TOST).
- Examples 10-11 demonstrate the baseline oxidative stability of canola oil (CO1) using aminic antioxidant
- Examples 12-13 demonstrate the baseline oxidative stability of high oleic acid canola oil (CO2) using aminic antioxidant
- Examples 14-15 demonstrate the improved oxidative stability and demulsibility of epoxidized soybean oil (ESO) using aminic antioxidant
- Examples 16-17 demonstrate the improved oxidative stability of epoxidized octyl tallate ester (EOTE) using aminic antioxidant.
- EOTE epoxidized octyl tallate ester
- Examples 18-19 demonstrate the improved oxidative stability of epoxidized canola oil (ECO) using aminic antioxidant
- Example 20 demonstrates the baseline performance of ethoxylated octyl tallate ester (EOTE) in industrial fluid testing.
- EOTE ethoxylated octyl tallate ester
- Examples 21-24 demonstrate the performance of ethoxylated octyl tallate ester (EOTE) with various aminic antioxidants.
- EOTE ethoxylated octyl tallate ester
- Examples 25-26 demonstrate the poor oxidation performance of octyl tallate ester (OTE) compared to the epoxidized analogs (Example 20), but improved PDSC, hydrolytic stability, and RPVOT with the addition of antioxidant.
- OTE octyl tallate ester
- Examples 27-28 demonstrate the performance of ethoxylated octyl tallate ester (BOTE) with metal passivator in typical industrial fluid tests.
- BOTE ethoxylated octyl tallate ester
- Examples 29-30 demonstrate the performance of ethoxylated octyl tallate ester (EOTE) with overbased sulfonate and ZDDP for EP/AW in typical industrial fluid tests.
- EOTE ethoxylated octyl tallate ester
- ZDDP ZDDP
- PDSC and RPVOT oxidative stability tests
- Examples 31-32 demonstrate the performance of octyl tallate ester (OTE) and ethoxylated octyl tallate ester (EOTE) with ZDDP for EP/AW in typical industrial fluid tests.
- OTE octyl tallate ester
- EOTE ethoxylated octyl tallate ester
- the four-ball wear, PDSC, and RPVOT are all synergistically improved with the addition of the ZDDP. (*) does not fall within the scope of protection being claimed
- Examples 33-36 demonstrate the performance of ethoxylated octyl tallate ester (EOTE) with various overbased detergents and ZDDP for EP/AW in typical hydraulic fluid tests.
- EOTE ethoxylated octyl tallate ester
- Examples 37-38 demonstrate the performance of ethoxylated octyl tallate ester (EOTE) with overbased sulfonate and ZDDP for EP/AW in typical hydraulic fluid tests in optimized concentrations.
- EOTE ethoxylated octyl tallate ester
- ZDDP ZDDP
- Example 39 demonstrates the performance of ethoxylated octyl tallate ester (EOTE) with overbased sulfonate and ZDDP for EP/AW and GMO for lubricity in typical hydraulic fluid tests in optimized concentrations.
- EOTE ethoxylated octyl tallate ester
- ZDDP ethoxylated octyl tallate ester
- the emulsion, four-ball wear, hydrolytic stability, PDSC, and RPVOT performance was acceptable for a hydraulic fluid.
- Example 40 demonstrates the performance of ethoxylated octyl tallate ester (EOTE) with overbased sulfonate and sulfurized olefin for EP/AW in typical hydraulic fluid tests in optimized concentrations.
- EOTE ethoxylated octyl tallate ester
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Claims (11)
- Biologisch abbaubare industrielle Flüssigkeit, umfassend(a) als Basisöl einen epoxidierten Tallöloctylester und(b) mindestens ein Antioxidationsmittel, das aus der Gruppe ausgewählt ist, die aus alkylierten Diphenylaminen, N-alkylierten Phenylendiaminen, sekundären Diarylaminen und gehinderten phenolischen Verbindungen besteht.
- Biologisch abbaubare industrielle Flüssigkeit nach Anspruch 1, wobei das genannte Antioxidationsmittel des Weiteren öllösliche Kupferverbindungen umfasst.
- Biologisch abbaubare industrielle Flüssigkeit nach Anspruch 1, wobei die genannte industrielle Flüssigkeit des Weiteren Additive zur Verbesserung der Ablagerungssteuerung, Anti-Abnutzungs-, Reibungs-, Antioxidations-, Niedrigtemperatur- und weiterer Eigenschaften der genannten Flüssigkeit umfasst.
- Biologisch abbaubare industrielle Flüssigkeit nach Anspruch 3, wobei die genannten Additive aus der Gruppe ausgewählt sind, die aus Dispergiermitteln, Detergenzien, Rosthemmern, Antiverschleißmitteln, Antischaummitteln, die Reibung modifizierenden Mitteln, Dichtungsquellmitteln, Demulgatoren, Viskositätsindexverbesserern und Stockpunkterniedrigern besteht.
- Biologisch abbaubare industrielle Flüssigkeit nach Anspruch 3, wobei die genannten Additive in einer Konzentration von 0,1 bis 30 Gew.-% vorhanden sind.
- Biologisch abbaubare industrielle Flüssigkeit nach Anspruch 1, wobei die genannte industrielle Flüssigkeit eine hydraulische Flüssigkeit ist.
- Verfahren zum Verbessern der Oxidationsstabilität von industriellen Flüssigkeiten, wobei das Verfahren das Verwenden eines epoxidierten Tallöloctylesters als das Basisöl der industriellen Flüssigkeit umfasst, wobei der genannte Ester in Kombination mit mindestens einem Antioxidationsmittel verwendet wird, das aus der Gruppe ausgewählt ist, die aus alkylierten Diphenylaminen, N-alkylierten Phenylendiaminen, sekundären Diarylaminen und gehinderten phenolischen Verbindungen besteht.
- Verfahren nach Anspruch 7, wobei das genannte Antioxidationsmittel des Weiteren öllösliche Kupferverbindungen umfasst.
- Verfahren nach Anspruch 7, wobei Additive zu dem Basisöl zur Verbesserung der Ablagerungssteuerung, Antiverschleiß-, Reibungs-, Antioxidations-, Niedrigtemperatur- und weiterer Eigenschaften der genannten Flüssigkeit zugegeben werden.
- Verfahren nach Anspruch 9, wobei die genannten Additive aus der Gruppe ausgewählt sind, die aus Dispergiermitteln, Detergenzien, Rosthemmern, Antiverschleißmitteln, Antischaummitteln, die Reibung modifizierenden Mitteln, Dichtungsquellmitteln, Demulgatoren, Viskositätsindexverbesserern und Stockpunkterniedrigern besteht.
- Verfahren nach Anspruch 7, wobei die industrielle Flüssigkeit eine hydraulische Flüssigkeit ist.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US65739505P | 2005-03-02 | 2005-03-02 | |
PCT/US2006/007447 WO2006094138A2 (en) | 2005-03-02 | 2006-03-01 | Method for improving the oxidative stability of industrial fluids |
Publications (2)
Publication Number | Publication Date |
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EP1853684A2 EP1853684A2 (de) | 2007-11-14 |
EP1853684B1 true EP1853684B1 (de) | 2012-11-14 |
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Application Number | Title | Priority Date | Filing Date |
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EP06736719A Not-in-force EP1853684B1 (de) | 2005-03-02 | 2006-03-01 | Zusammensetzung und verfahren zur erhöhung der oxidationsstabilität industrieller flüssigkeiten |
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