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WO1999036387A1 - Matieres de base d'esters synthetiques a nombre de groupes hydroxyles eleve biodegradables et lubrifiants formes a partir de ces matieres - Google Patents

Matieres de base d'esters synthetiques a nombre de groupes hydroxyles eleve biodegradables et lubrifiants formes a partir de ces matieres Download PDF

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Publication number
WO1999036387A1
WO1999036387A1 PCT/US1999/000581 US9900581W WO9936387A1 WO 1999036387 A1 WO1999036387 A1 WO 1999036387A1 US 9900581 W US9900581 W US 9900581W WO 9936387 A1 WO9936387 A1 WO 9936387A1
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Prior art keywords
acid
branched
synthetic ester
biodegradable
ester composition
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PCT/US1999/000581
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English (en)
Inventor
Thomas H. Henry
Richard H. Schlosberg
Carolyn B. Duncan
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Exxon Chemical Patents Inc.
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Priority to AU23157/99A priority Critical patent/AU2315799A/en
Publication of WO1999036387A1 publication Critical patent/WO1999036387A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/30—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with trihydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups

Definitions

  • the present invention relates generally to the use of high hydroxyl synthetic esters to improve the biodegradable properties of an otherwise unacceptably poor biodegradable fully esterified synthetic ester of the same reactants. Furthermore, these unique high hydroxyl esters exhibit a unique and wholly unexpected synergistic biodegradable affect when they are blended with otherwise poor biodegradable base stocks.
  • biodegradable high hydroxyl synthetic esters or blends of esters are particularly useful in the formation of biodegradable lubricants in two-cycle engine oils, catapult oils, hydraulic fluids, drilling fluids, water turbine oils, greases, compressor oils, gear oils, and other industrial and engine applications where biodegradability is needed or desired.
  • Base stocks for biodegradable lubricant applications should typically meet five criteria: (1) solubility with dispersants and other additives such as polyamides; (2) good cold flow properties (such as, less than -40°C pour point; less than 7500 cps at -25°C); (3) sufficient biodegradability to off-set the low biodegradability of any dispersants and/or other additives to the formulated lubricant; (4) good lubricity without the aid of wear additives; and (5) high flash point (greater than 260°C, flash and fire points by COC (Cleveland Open Cup) as measured by ASTM test number D-92).
  • solubility with dispersants and other additives such as polyamides
  • good cold flow properties such as, less than -40°C pour point; less than 7500 cps at -25°C
  • sufficient biodegradability to off-set the low biodegradability of any dispersants and/or other additives to the formulated lubricant
  • OECD The Organization for Economic Cooperation and Development (OECD) issued draft test guidelines for degradation and accumulation testing in December 1979.
  • the Expert Group recommended that the following tests should be used to determine the "ready biodegradability" of organic chemicals: Modified OECD Screening Test, Modified MITI Test (I), Closed Bottle Test, Modified Sturm Test and the Modified AFNOR Test.
  • the Group also recommended that the following "pass levels" of biodegradation, obtained within 28 days, may be regarded as good evidence of "ready biodegradability”: (Dissolved Organic Carbon (DOC)) 70%; (Biological Oxygen Demand (BOD)) 60%; (Total Organic Carbon (TOD)) 60%; (C0 2 ) 60%; and (DOC) 70%, respectively, for the tests listed above. Therefore, the "pass level" of biodegradation, obtained within 28 days, using the Modified Sturm Test is at least (CO 2 ) 60%.
  • DOC Dissolved Organic Carbon
  • the OECD guideline for testing the "ready biodegradability" of chemicals under the Modified Sturm test involves the measurement of the amount of CO 2 produced by the test compound which is measured and expressed as a percent of the theoretical CO 2 (TC0 2 ) it should have produced calculated from the carbon content of the test compound. Biodegradability is therefore expressed as a percentage of TCO 2 .
  • the Modified Sturm test is run by spiking a chemically defined liquid medium, essentially free of other organic carbon sources, with the test material and inoculated with sewage micro-organisms. The CO 2 released is trapped as BaCO 3 .
  • the total amount of CO 2 produced by the test compound is determined for the test period and calculated as the percentage of total CO 2 that the test material could have theoretically produced based on carbon composition. See G. van der Waal and D. Kenbeek, “Testing, Application, and Future Development of Environmentally Friendly Ester Based Fluids", Journal of Synthetic Lubrication, Vol. 10, Issue No. 1, April 1993, pp. 67-83, which is incorporated herein by reference.
  • rapeseed oil i.e., a triglyceride of fatty acids, e.g., 7 % saturated C 12 to C 18 acids, 50% oleic acid, 36% linoleic acid and 7% linolenic acid, having the following properties: a viscosity at 40°C of 47.8 cSt, a pour point of 0°C, a flash point of 162°C and a biodegradability of 85% by the Modified Sturm test. Although it has very good biodegradability, its use in biodegradable lubricant applications is limited due to its poor low temperature properties and poor stability.
  • esters synthesized from both linear acids and linear alcohols tend to have poor low temperature properties. Even when synthesized from linear acids and highly branched alcohols, such as polyol esters of linear acids, high viscosity esters with good low temperature properties can be difficult to achieve.
  • pentaerythritol esters of linear acids exhibit poor solubility with dispersants such as polyamides, and trimethylolpropane esters of low molecular weight (i.e., having a carbon number less than 14) linear acids do not provide sufficient lubricity. This lower quality of lubricity is also seen with adipate esters of branched alcohols.
  • Branched synthetic polyol esters have been used extensively in non- biodegradable applications, such as refrigeration lubricant applications, and have proven to be quite effective if 3,5,5-trimethylhexanoic acid is incorporated into the molecule at 25 molar percent or greater.
  • trimethylhexanoic acid is not biodegradable as determined by the Modified Sturm test (OECD 30 IB), and the incorporation of 3,5,5-trimethylhexanoic acid, even at 25 molar percent, would drastically lower the biodegradation of the polyol ester due to the quaternary carbons contained therein.
  • trialkyl acetic acids i.e., neo acids
  • OECD 30 IB Modified Sturm test
  • Polyol esters of all branched acids can be used as refrigeration oils as well. However, they do not rapidly biodegrade as determined by the Modified Sturm Test (OECD 301B) and, therefore, are not desirable for use in biodegradable applications.
  • polyol esters made from purely linear C 5 and C 10 acids for refrigeration applications would be biodegradable under the Modified Sturm test, they would not work as a lubricant in hydraulic or two-cycle engine applications because the viscosities would be too low and wear additives would be needed. It is extremely difficult to develop a lubricant base stock which is capable of exhibiting all of the various properties required for biodegradable lubricant applications, i.e., high viscosity, low pour point, oxidative stability and biodegradability as measured by the Modified Sturm test.
  • U.S. Patent No. 4,826,633 (Carr et al.), which issued on May 2, 1989, discloses a synthetic ester lubricant base stock formed by reacting at least one of trimethylolpropane and monopentaerythritol with a mixture of aliphatic mono- carboxylic acids.
  • the mixture of acids includes straight-chain acids having from 5 to 10 carbon atoms and an iso-acid having from 6 to 10 carbon atoms, preferably iso-nonanoic acid (i.e., 3,5,5-trimethylhexanoic acid).
  • This base stock is mixed with a conventional ester lubricant additive package to form a lubricant having a viscosity at 99°C (210°F) of at least 5.0 centistokes and a pour point of at least as low as -54°C (-65°F).
  • This lubricant is particularly useful in gas turbine engines.
  • the Carr et al. patent differs from the present invention for two reasons. Firstly, it preferably uses as its branched acid 3,5,5-trimethylhexanoic acid which contains a quaternary carbon in every acid molecule. The incorporation of quaternary carbons within the 3,5,5-trimethylhexanoic acid inhibits biodegradation of the polyol ester product.
  • the lubricant according to Carr et al. exhibits high stability, as measured by a high pressure differential scanning calorimeter (HPDSC), i.e., about 35 to 65 minutes, the micro-organisms cannot pull them apart.
  • HPDSC high pressure differential scanning calorimeter
  • the lubricant according to the present invention is low in stability, i.e., it has a HPDSC reading of about 12-17 minutes.
  • the lower stability allows the micro-organisms to attack the carbon-to-carbon bonds about the polyol structure and effectively cause the ester to biodegrade.
  • the high hydroxyl ester of the present invention will be higher in oxygen content and lower in molecular weight, both of which typically result in greater solubility in water and, thus, result in an ester base stock which exhibits a greater degree of biodegradability than fully esterified esters. Due to enhanced biodegradability, such high hydroxyl esters are capable of utilizing 3,5,5-trimethyl hexanoic acid to enhance thermal and oxidative stability, while still maintaining a high degree of biodegradation versus fully esterified ester using 3,5,5-trimethyl hexanoic acid.
  • biodegradable lubricants using biodegradable base stocks with good cold flow properties, good solubility with dispersants, and good lubricity can be achieved using base stocks of high hydroxyl esters or blends thereof with other base stocks.
  • Lubricants formed using biodegradable high hydroxyl ester provide the following cumulative advantages over lubricants formed from fully esterified base stocks: (1) increased water solubility; (2) leaving some free hydroxyl groups reduced steric hindrance around the quaternary carbon of polyols, thus increasing the molecules' biodegradability; and (3) increased thermal and oxidative stability.
  • lubricant formulators who use esters with high hydroxyl numbers should see increased biodegradability for those ester with free hydroxyl groups over those that are completely esterified.
  • a biodegradable high hydroxyl base stock which preferably comprises the reaction product of: a branched or linear alcohol having the general formula R(OH) n , wherein R is an aliphatic or cyclo-aliphatic group having from about 2 to 20 carbon atoms and n is at least 2; and at least one branched or linear mono- carboxylic acid which has a carbon number in the range between about C 5 to C 20 ; wherein the synthetic ester composition has between about 2-50%, preferably between about 5-35% unconverted hydroxyl groups, based on the total amount of hydroxyl groups in the branched or linear alcohol; wherein the ester exhibits the following properties: at least 25% biodegradation in 28 days as measured by the Modified Sturm test; and a pour point of less than -25°C.
  • the branched or linear alcohol of the high hydroxyl ester is present in an excess of about 10 to 35 equivalent percent for the amount of the branched acid or branched/linear mixed acids used. Between about 60 to 90% of the hydroxyl groups from the branched or linear alcohol are converted upon the esterification of the branched or linear alcohol with the acid.
  • the resultant synthetic polyol ester composition according to the present invention exhibits a thermal/oxidative stability measured by HPDSC at 220°C, 3.445 MPa air and 0.5 wt. % Vanlube® 81 antioxidant (i.e., dioctyl diphenyl amine) of greater than 10 minutes, preferably greater than 100 minutes.
  • Linear acids may be present in an amount of between about 0 to 100 wt. % based on the total amount of the branched mono-carboxylic acid.
  • the linear acid is any linear saturated alkyl carboxylic acid having a carbon number in the range between about C 2 to C 12 , preferable a commercially available C810 linear acid.
  • This novel synthetic polyol ester composition exhibits between about 20 to
  • the fully esterified synthetic polyol ester composition of the present invention typically has a hydroxyl number which is greater than 5, preferably in the range between about 5 to 150, more preferably between about 5 to 100, and most preferably between about 10 to 80.
  • the present invention also includes a lubricant which is prepared from at least one synthetic polyol ester composition having unconverted hydroxyl groups as set forth immediately above and a lubricant additive package. Additionally, a solvent may also be added to the lubricant, wherein the lubricant comprises about 60-99% by weight of the synthetic polyol ester composition, about 1 to 20% by weight the additive package, and about 0 to 20% by weight of the solvent.
  • Still other lubricants can be formed according to the present invention by blending this unique biodegradable high hydroxyl ester base stock with at least one additional base stock selected from the group consisting of: mineral oils, highly refined mineral oils, poly alpha olefins, polyalkylene glycols, phosphate esters, silicone oils, diesters and polyol esters.
  • the high hydroxyl ester base stock is blended with the additional base stocks in an amount between about 1 to 50 wt. %, based on the total blended base stock, preferably 1 to 25 wt. %, and most preferably 1 to 15 wt. %.
  • the biodegradable polyol ester composition of the present invention is preferably formed by reacting a polyhydroxyl compound with at least one branched or linear acid.
  • the polyol is preferably present in an excess of about 10 to 35 equivalent percent or more for the amount of acid used.
  • the composition of the feed polyol is adjusted so as to provide the desired composition of the product ester.
  • the acid is preferably a highly branched acid such that the unconverted hydroxyl groups which are bonded to the resultant ester composition act similarly to an antioxidant such that it transfers a hydrogen atom to the unstable carbon radical which is produced when the ester molecule is under thermal stress, thereby effecting a "healing" of the radical (i.e., convert the carbon radical to a stable alcohol and oxygen).
  • These unconverted hydroxyl groups which act as internal antioxidants can substantially reduce or, in some instances, eliminate the need for the addition of costly antioxidants to the polyol ester composition.
  • esters having unconverted hydroxyl groups bonded thereto demonstrate substantially enhanced thermal/oxidative stability versus esters having similar amounts of antioxidants admixed therewith.
  • linear acids can be used either alone or in an mixture with the branched acids.
  • linear and branched acids are used in a mixture it is preferable that they be mixed in a ratio of between about 1 :99 to 80:20 and thereafter reacted with the branched or linear alcohol as set forth immediately above.
  • the same molar excess of alcohol used in the all branched or all linear case is also required in the mixed acids case such that the synthetic ester composition formed by reacting the alcohol and the mixed acids still has between about 2-50%, preferably about 5-35%, unconverted hydroxyl groups, based on the total amount of hydroxyl groups in the alcohol.
  • the esterification reaction is preferably conducted, with or without a catalyst, at a temperature in the range between about 140 to 250°C and a pressure in the range between about 30 mm Hg to 760 mm Hg (3.999 to 101.308 kPa) for about 0.1 to 12 hours, preferably 2 to 8 hours.
  • the stoichiometry in the reactor is variable, with the capability of vacuum stripping excess acid to generate the preferred final composition.
  • the preferred esterification catalysts are titanium, zirconium and tin catalysts such as titanium, zirconium and tin alcoholates, carboxylates and chelates. Selected acid catalysts may also be used in this esterification process. See U.S. Patent Nos. 5,324,853 (Jones et al.), which issued on June 28, 1994, and 3,056,818 (Werber), which issued on October 2, 1962, both of which are incorporated herein by reference. ALCOHOLS
  • polyols i.e., polyhydroxyl compounds
  • R is any aliphatic or cyclo-aliphatic hydrocarbyl group (preferably an alkyl) and n is at least 2.
  • the hydrocarbyl group may contain from about 2 to about 20 or more carbon atoms, and the hydrocarbyl group may also contain substituents such as chlorine, nitrogen and/or oxygen atoms.
  • the polyhydroxyl compounds generally may contain one or more oxyalkylene groups and, thus, the polyhydroxyl compounds include compounds such as polyetherpolyols.
  • the number of carbon atoms i.e., carbon number, wherein the term carbon number as used throughout this application refers to the total number of carbon atoms in either the acid or alcohol as the case may be
  • number of hydroxy groups i.e., hydroxyl number
  • the following alcohols are particularly useful as polyols: neopentyl glycol, 2,2-dimethylol butane, trimethylol ethane, trimethylol propane, trimethylol butane, mono-pentaerythritol, technical grade pentaerythritol, di-pentaerythritol, tri-pentaerythritol, ethylene glycol, propylene glycol and polyalkylene glycols (e.g., polyethylene glycols, polypropylene glycols, 1 ,4-butanediol, sorbitol, glycerol and the like, 2-methylpropanediol, polybutylene glycols, etc., and blends thereof such as a polymerized mixture of ethylene glycol and propylene glycol).
  • polyalkylene glycols e.g., polyethylene glycols, polypropylene glycols, 1 ,4-butaned
  • the most preferred alcohols are technical grade (e.g., approximately 88% mono-, 10% di- and 1-2% tri-pentaerythritol) pentaerythritol, monopentaerythritol, di- pentaerythritol, neopentyl glycol and trimethylol propane.
  • the branched acid is preferably a mono-carboxylic acid which has a carbon number in the range between about C 5 to C 13 , more preferably about C 7 to C 10 wherein methyl or ethyl branches are preferred.
  • the mono-carboxylic acid is preferably at least one acid selected from the group consisting of: 2,2- dimethyl propionic acid (neopentanoic acid), neoheptanoic acid, neooctanoic acid, neononanoic acid, neodecanoic acid, 2-ethyl hexanoic acid (2EH), 3,5,5-trimethyl hexanoic acid (TMH), isoheptanoic acid, isooctanoic acid, isononanoic acid, oleic acid and isodecanoic acid.
  • 2,2- dimethyl propionic acid neopentanoic acid
  • neoheptanoic acid neoocta
  • branched acid is 3,5,5- trimethyl hexanoic acid.
  • the term "neo" as used herein refers to a trialkyl acetic acid, i.e., an acid which is triply substituted at the alpha carbon with alkyl groups. These alkyl groups are equal to or greater than CH 3 as shown in the general structure set forth herebelow:
  • R ]5 R 2 , and R 3 are greater than or equal to CH 3 and not equal to hydrogen.
  • 3,5,5-trimethyl hexanoic acid has the structure set forth herebelow:
  • the preferred mono- and /or di-carboxylic linear acids are any linear saturated alkyl carboxylic acid having a carbon number in the range between about C 2 to C 18 , preferably C 2 to C 12 .
  • linear acids include acetic, propionic, pentanoic, heptanoic, octanoic, nonanoic, and decanoic acids.
  • Selected diacids include any C 2 to C 12 diacids, e.g., adipic, azelaic, sebacic and dodecanedioic acids.
  • n is an integer having a value of at least 2
  • R is any aliphatic or cyclo- aliphatic hydrocarbyl group containing from about 2 to about 20 or more carbon atoms and, optionally, substituents such as chlorine, nitrogen and/or oxygen atoms
  • R' is any branched aliphatic hydrocarbyl group having a carbon number in the range between about C 4 to C 12 , more preferably about C 6 to C 9 , wherein methyl or ethyl branches are preferred
  • (i) is an integer having a value of between about 0 to n.
  • the biodegradable high hydroxyl reaction product from Equation 1 above can either be used by itself as a lubricant base stock or in admixture with other base stocks, such as mineral oils, highly refined mineral oils, poly alpha olefins (PAO), polyalkylene glycols (PAG), phosphate esters, silicone oils, diesters and polyol esters.
  • base stocks such as mineral oils, highly refined mineral oils, poly alpha olefins (PAO), polyalkylene glycols (PAG), phosphate esters, silicone oils, diesters and polyol esters.
  • the partial ester composition according to the present invention is preferably present in an amount of from about 1 to 50 wt. %, based on the total blended base stock, more preferably between about 1 to 25 wt. %, and most preferably between about 1 to 15 wt. %.
  • One preferred additional base stock is selected from the group consisting of: biodegradable synthetic ester base stocks which comprise the reaction product of: a branched or linear alcohol having the general formula R(OH) n , wherein R is an aliphatic or cyclo-aliphatic group having from about 2 to 20 carbon atoms and n is at least 2; and mixed acids comprising about 30 to 80 molar % of a linear acid having a carbon number in the range between about C 5 to C 12 , and about 20 to 70 molar % of at least one branched acid having a carbon number in the range between about C 5 to C 13 ; wherein the ester base stock exhibits the following properties: at least 60% biodegradation in 28 days as measured by the Modified Sturm test; a pour point of less than -25°C; and a viscosity of less than 7500 cps at -25°C.
  • biodegradable synthetic ester base stocks which comprise the reaction product of: a branched or linear alcohol having the general formula
  • the polyol ester composition according to the present invention can be used in the formulation of various lubricants, such as, crankcase engine oils (i.e., passenger car motor oils, heavy duty diesel motor oils, and passenger car diesel oils), two-cycle engine oils, catapult oil, hydraulic fluids, drilling fluids, aircraft and other turbine oils, greases, compressor oils, gear oils, functional fluids and other industrial and engine lubrication applications.
  • crankcase engine oils i.e., passenger car motor oils, heavy duty diesel motor oils, and passenger car diesel oils
  • catapult oil catapult oil
  • hydraulic fluids drilling fluids
  • aircraft and other turbine oils i.e., lubricating oils
  • greases i.e., compressor oils, gear oils, functional fluids and other industrial and engine lubrication applications.
  • lubricating oils contemplated for use with the polyol ester compositions of the present invention include both mineral and synthetic hydrocarbon oils of lubricating viscosity and mixtures thereof with other synthetic oils.
  • the synthetic hydrocarbon oils include long chain alkanes such as cetanes and olefin polymers such as oligomers of hexene, octene, decene, and dodecene, etc.
  • the other synthetic oils include (1) fully esterified ester oils, with no free hydroxyls, such as pentaerythritol esters of monocarboxylic acids having 2 to 20 carbon atoms, trimethylol propane esters of monocarboxylic acids having 2 to 20 carbon atoms, (2) polyacetals and (3) siloxane fluids.
  • Especially useful among the synthetic esters are those made from polycarboxylic acids and monohydric alcohols.
  • ester fluids made by fully esterifying pentaerythritol, or mixtures thereof with di- and tri- pentaerythritol, with an aliphatic monocarboxylic acid containing from 1 to 20 carbon atoms, or mixtures of such acids.
  • a solvent be employed depending upon the specific application.
  • Solvents that can be used include the hydrocarbon solvents, such as toluene, benzene, xylene, and the like.
  • the formulated lubricant according to the present invention preferably comprises about 60-99% by weight of at least one polyol ester composition of the present invention, about 1 to 20% by weight lubricant additive package, and about 0 to 20% by weight of a solvent.
  • the high hydroxyl ester base stock of the present invention can be used in the formulation of biodegradable lubricants together with selected lubricant additives.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions. Typical amounts for individual components are also set forth below.
  • the preferred biodegradable lubricant contains approximately 80% or greater by weight of the base stock and 20% by weight of any combination of the following additives:
  • Antifoaming Agents 0.001-0.1 0.001-0.01
  • Antiwear Agents 0.001-5 0.001-1.5
  • the biodegradable high hydroxyl ester base stock can be used in the formulation of biodegradable two-cycle engine oils together with selected lubricant additives.
  • the preferred biodegradable two-cycle engine oil is typically formulated using the biodegradable high hydroxyl esterbase stock formed according to the present invention together with any conventional two-cycle engine oil additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, coupling agents, dispersants, extreme pressure agents, color stabilizers, surfactants, diluents, detergents and rust inhibitors, pour point depressants, antifoaming agents, and antiwear agents.
  • the biodegradable two-cycle engine oil according to the present invention can employ typically about 75 to 85% base stock, about 1 to 5% solvent, with the remainder comprising an additive package.
  • Patent No. 5,663,063 (Davis), which issued on May 5, 1987; U.S. Patent No.
  • Catapults are instruments used on aircraft carriers at sea to eject the aircraft off of the carrier.
  • the biodegradably high hydroxyl ester base stock can be used in the formulation of biodegradable catapult oils together with selected lubricant additives.
  • the preferred biodegradable catapult oil is typically formulated using the biodegradable high hydroxyl ester base stock formed according to the present invention together with any conventional catapult oil additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, extreme pressure agents, color stabilizers, detergents and rust inhibitors, antifoaming agents, antiwear agents, and friction modifiers.
  • the biodegradable catapult oil according to the present invention can employ typically about 90 to 99% base stock, with the remainder comprising an additive package.
  • Biodegradable catapult oils preferably include conventional corrosion inhibitors and rust inhibitors. If desired, the catapult oils may contain other conventional additives such as antifoam agents, antiwear agents, other antioxidants, extreme pressure agents, friction modifiers and other hydrolytic stabilizers. These additives are disclosed in Klamann, "Lubricants and Related Products", Verlag Chemie, Deerfield Beach, FL, 1984, which is incorporated herein by reference.
  • the branched synthetic ester base stock can be used in the formulation of biodegradable hydraulic fluids together with selected lubricant additives.
  • the preferred biodegradable hydraulic fluids are typically formulated using the biodegradable high hydroxyl ester base stock formed according to the present invention together with any conventional hydraulic fluid additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, viscosity index improvers, corrosion inhibitors, boundary lubrication agents, demulsif ⁇ ers, pour point depressants, and antifoaming agents.
  • the biodegradable hydraulic fluid according to the present invention can employ typically about 90 to 99% base stock, with the remainder comprising an additive package.
  • the branched synthetic ester base stock can be used in the formulation of biodegradable drilling fluids together with selected lubricant additives.
  • the preferred biodegradable drilling fluids are typically formulated using the biodegradable high hydroxyl ester base stock formed according to the present invention together with any conventional drilling fluid additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, viscosity index improvers, corrosion inhibitors, wettinging agents, water loss improving agents, bactericides, and drill bit lubricants.
  • the biodegradable drilling fluid according to the present invention can employ typically about 60 to 90% base stock and about 5 to 25% solvent, with the remainder comprising an additive package. See U.S. Patent No. 4,382,002
  • Suitable hydrocarbon solvents include: mineral oils, particularly those paraffin base oils of good oxidation stability with a boiling range of from 200- 400°C such as Mentor 28®, sold by Exxon Chemical Americas, Houston, Texas; diesel and gas oils; and heavy aromatic naphtha.
  • the branched synthetic ester base stock can be used in the formulation of biodegradable water turbine oils together with selected lubricant additives.
  • the preferred biodegradable water turbine oil is typically formulated using the biodegradable high hydroxyl ester base stock formed according to the present invention together with any conventional water turbine oil additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, thickeners, dispersants, anti-emulsifying agents, color stabilizers, detergents and rust inhibitors, and pour point depressants.
  • the biodegradable water turbine oil according to the present invention can employ typically about 65 to 75% base stock and about 5 to 30% solvent, with the remainder comprising an additive package, typically in the range between about
  • the branched synthetic ester base stock can be used in the formulation of biodegradable greases together with selected lubricant additives.
  • the main ingredient found in greases is the thickening agent or gellant and differences in grease formulations have often involved this ingredient.
  • the thickener or gellants, other properties and characteristics of greases can be influenced by the particular lubricating base stock and the various additives that can be used.
  • the preferred biodegradable greases are typically formulated using the biodegradable high hydroxyl ester base stock formed according to the present invention together with any conventional grease additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, viscosity index improvers, oxidation inhibitors, extreme pressure agents, detergents and rust inhibitors, pour point depressants, metal deactivators, antiwear agents, and thickeners or gellants.
  • the biodegradable grease according to the present invention can employ typically about 80 to 95% base stock and about 5 to 20% thickening agent or gellant, with the remainder comprising an additive package.
  • thickening agents used in grease formulations include the alkali metal soaps, clays, polymers, asbestos, carbon black, silica gels, polyureas and aluminum complexes.
  • Soap thickened greases are the most popular with lithium and calcium soaps being most common.
  • Simple soap greases are formed from the alkali metal salts of long chain fatty acids with lithium 12-hydroxystearate, the predominant one formed from 12-hydroxystearic acid, lithium hydroxide monohydrate and mineral oil.
  • Complex soap greases are also in common use and comprise metal salts of a mixture of organic acids.
  • One typical complex soap grease found in use today is a complex lithium soap grease prepared from 12- hydroxystearic acid, lithium hydroxide monohydrate, azelaic acid and mineral oil.
  • the branched synthetic ester base stock can be used in the formulation of biodegradable compressor oils together with selected lubricant additives.
  • the preferred biodegradable compressor oil is typically formulated using the biodegradable high hydroxyl ester base stock formed according to the present invention together with any conventional compressor oil additive package.
  • the additives listed below are typically used in such amounts so as to provide their normal attendant functions.
  • the additive package may include, but is not limited to, oxidation inhibitors, additive solubilizers, rust inhibitors/metal passivators, demulsifying agents, and antiwear agents.
  • the biodegradable compressor oil according to the present invention can employ typically about 80 to 99% base stock and about 1 to 15% solvent, with the remainder comprising an additive package.
  • EXAMPLE 1 The following comparative data in Table 1 shows that the biodegradable high hydroxyl ester according to the present invention has a higher oxygen content and lower molecular weight than their full ester counterparts, both of which typically result in greater solubility in water and enhanced biodegradability.
  • Blend of Samples 1 and 3 (ratio of20:80) 65.36
  • V-81 is dioctyl diphenyl amine.
  • TechPE is technical grade pentaerythritol (i.e., 88% mono-, 10% di- and 1-2% tri- pentaerythritol).
  • TMH is 3,5,5-trimethyl hexanoic acid.
  • L9 is blend of 62-70 mole % linear C 9 acid and 30-38 mole % branched C 9 acid.
  • Samples 4 and 5 demonstrate that decomposition of the polyol ester compositions having a hydroxyl number less than 5 occurs much more rapidly compared to polyol ester compositions of the same acid and polyol having a hydroxyl number greater than 50 (e.g., Samples 1 and 2) regardless of whether or not an antioxidant is admixed with the respective polyol ester composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un lubrifiant biodégradable préparé à partir de: au moins une matière de base d'ester synthétique biodégradable comprenant un alcool ramifié ou linéaire de la formule générale R(OH)n, dans laquelle R représente un groupe aliphatique ou cycloaliphatique possédant entre 2 et 20 atomes de carbone environ et n représente au moins 2; et au moins un acide monocarboxylique ramifié ou linéaire possédant un nombre d'atomes de carbone compris entre C5 et C20 environ; la composition d'ester synthétique comprenant 2 à 50 % de groupes hydroxyles non convertis sur la base de la quantité totale de groupes hydroxyles compris dans l'alcool ramifié ou linéaire. La matière de base d'ester présente les propriétés suivantes: une biodégradation d'au moins 25 % en 28 jours telle que mesurée par le test de Sturm modifié et un point d'écoulement inférieur à -25 °C. L'invention concerne également un emballage d'additif.
PCT/US1999/000581 1998-01-13 1999-01-11 Matieres de base d'esters synthetiques a nombre de groupes hydroxyles eleve biodegradables et lubrifiants formes a partir de ces matieres WO1999036387A1 (fr)

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AU23157/99A AU2315799A (en) 1998-01-13 1999-01-11 Biodegradable high hydroxyl synthetic ester base stocks and lubricants formed therefrom

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US7101398P 1998-01-13 1998-01-13
US60/071,013 1998-01-13

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9115303B2 (en) 2012-11-20 2015-08-25 Chevron U.S.A. Inc. Biologically-derived monoesters as drilling fluids
US9115556B2 (en) 2012-11-20 2015-08-25 Chevron U.S.A. Inc. Method of using biologically-derived monoesters as drilling fluids
US9115326B2 (en) 2012-11-20 2015-08-25 Chevron U.S.A. Inc. Monoester-based lubricants and methods of making same
US9238783B2 (en) 2012-11-20 2016-01-19 Chevron U.S.A. Inc. Monoester-based lubricants and methods of making same
EP3042945A4 (fr) * 2013-09-02 2017-04-26 Nippon Steel & Sumitomo Metal Corporation Composition pour former un film de revêtement lubrifiant, et jonction filetée pour tuyau en acier
WO2019147515A1 (fr) * 2018-01-29 2019-08-01 Exxonmobil Chemical Patents Inc. Fluides biodégradables par voie anaérobie pour des applications de forage
EP4520805A1 (fr) * 2023-09-08 2025-03-12 Infineum International Limited Ameliorations apportees a des compositions d'additifs et a des huiles combustibles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5698502A (en) * 1996-09-11 1997-12-16 Exxon Chemical Patents Inc Polyol ester compositions with unconverted hydroxyl groups for use as lubricant base stocks

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5698502A (en) * 1996-09-11 1997-12-16 Exxon Chemical Patents Inc Polyol ester compositions with unconverted hydroxyl groups for use as lubricant base stocks

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9115303B2 (en) 2012-11-20 2015-08-25 Chevron U.S.A. Inc. Biologically-derived monoesters as drilling fluids
US9115556B2 (en) 2012-11-20 2015-08-25 Chevron U.S.A. Inc. Method of using biologically-derived monoesters as drilling fluids
US9115326B2 (en) 2012-11-20 2015-08-25 Chevron U.S.A. Inc. Monoester-based lubricants and methods of making same
US9238783B2 (en) 2012-11-20 2016-01-19 Chevron U.S.A. Inc. Monoester-based lubricants and methods of making same
US9309452B2 (en) 2012-11-20 2016-04-12 Chevron U.S.A. Inc. Methods of making monoester-based drilling fluids
EP3042945A4 (fr) * 2013-09-02 2017-04-26 Nippon Steel & Sumitomo Metal Corporation Composition pour former un film de revêtement lubrifiant, et jonction filetée pour tuyau en acier
US9725671B2 (en) 2013-09-02 2017-08-08 Nippon Steel & Sumitomo Metal Corporation Lubricant film-forming composition and screw joint for steel pipe
WO2019147515A1 (fr) * 2018-01-29 2019-08-01 Exxonmobil Chemical Patents Inc. Fluides biodégradables par voie anaérobie pour des applications de forage
EP4520805A1 (fr) * 2023-09-08 2025-03-12 Infineum International Limited Ameliorations apportees a des compositions d'additifs et a des huiles combustibles

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