Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
  • C10M135/34—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
  • C10M129/88—Hydroxy compounds
  • C10M129/91—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/14—Side-groups
  • C08G2261/141—Side-chains having aliphatic units
  • C08G2261/1412—Saturated aliphatic units
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
  • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
  • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions

Definitions

• the present invention relates to control of sludge formation in lubes.
• Oxides of nitrogen are by-products of the operation of internal combustion engines. These oxides are emitted, for example, as exhaust gas from the combustion of hydrocarbon fuels. They react even at relatively low temperatures (e.g., 70° - 120°C) with components of motor oils, such as additives, to form sludge and contribute to lube oil degradation. It would be advantageous to develop additives, lube oil formulations, and methods that can address lube oil degradation and minimize sludge formation particularly in the presence of NO x . Applicants' invention addresses these needs.
• the present invention provides for a method for mitigating sludge formation in engine oils by adding to an engine oil of lubricating viscosity an effective, minor amount of a molecule having at least one head portion enriched in NO * reactive carbon-carbon unsaturation and at least one oil soluble aliphatic and aromatic hydrocarbyl tail portion having an absence of carbon-carbon unsaturation of suitable chain length in an optimum ratio of head to tail sufficient to reduce NO x -induced sludge formation in the engine oil.
• Preferred examples of such molecules include polyethylene propylene copolymer- and polyisobutylene-grafted hydroquinone polyalkylthiophenes, fullerene-grafted lube oil basestock, ethylene propylene polymer-grafted phenol and ethylene butylene polymer-grafted phenol.
• the present invention also provides for lube oil compositions and additive concentrates for mitigating sludge formation containing the foregoing molecules.
• the present invention may suitably comprise, consist or consist essentially ofthe elements or steps disclosed herein and may be practiced in the absence of an element or step not specifically disclosed.
• the present invention provides for methods for controlling sludge (i.e., insolubles) formation, particularly that induced by NO x , in lube oils and the lube degradation resulting from the combustion of hydrocarbonaceous fuels using NO x -reactive sludge control additives (also referred to herein as "antinoxidant additives"), and provides for formulated lube oil compositions and additive concentrates containing these additives.
• NO x -reactive sludge control additives also referred to herein as "antinoxidant additives”
• examples of such fuels include those typically used for internal combustion engines such as crankcase lubricating fuels for spark-ignited and compression-ignited internal combustion engines, such as automobile, truck, marine diesel and railroad diesel engines and such as, for example, in U.S. Patent 5,558,802.
• Nitrous oxides and reactive intermediates of their reactions are produced in internal combustion engines from a variety of sources such as blowby gases and thermal degradation of organonitrates.
• NO x -reactive includes reactivity to nitrous oxides and to the products of reactive organonitrate species such as sludge precursors.
• the most typical oxide of nitrogen is NO 2 , however, other reactive nitrogen oxides may also be present and the present invention also may be effectively carried out in the presence of such oxides.
• Lube oils and additives typically present therein degrade in the engine in the presence of NO x , oxygen and heat to form sludge precursors and sludge. Applicants have discovered novel additives and methods for reducing the occurrence of such degradation chemistry.
• Applicants' invention provides a method for mitigating sludge formation associated with certain currently available additives by rendering them resistant to degradation into insolubles, i.e., sludge.
• the invention is also useful in the design of new additives suitable for use to minimize sludge formation.
• Applicants' method of controlling sludge formation in lube oils is based on the discovery of the existence of a class of molecules that have in an optimum relationship of both carbon-carbon unsaturated NO x -reactive portions and oil soluble aromatic, preferably aliphatic, hydrocarbyl portions having a chain length sufficient to maintain solubility of the NO x -reactive and NO x -reacted molecule in a lube oil.
• the method also may be employed, for example, to render current additives resistant to sludge formation.
• One embodiment is a method of retarding or controlling sludge formation and lube oil degradation which comprises combining with an engine oil of lubricating viscosity an effective amount of at least one sludge mitigation compound having at least one first moiety or portion enriched in NO x -reactive carbon-carbon unsaturation and at least one second moiety or portion deficient in NO x -reactive carbon-carbon unsaturation and enriched in aliphatic and/or aromatic hydrocarbyl groups.
• the relative proportion of first and second moieties must be effective to render the molecule NO x -reactive and lube oil soluble.
• Aliphatic hydrocarbyl groups are preferably essentially free of carbon- carbon unsaturation.
• moieties also are, respectively, referred to herein as "head” or " NO x "-reactive head,” and “tail” or “aliphatic hydrocarbyl tail” portions or “centers” or moieties for convenience. These terms are meant to indicate a localization or concentration of the particular structure or feature identified.
• a molecule useful in the present invention will have, in combination, at least one head and tail portions, provided that the number, structure and combination are sufficient to impart NOx-reactivity to the head portion and to impart oil solubility to the tail portion and to the molecule as a whole both in its NO x -reactive and NO x -reacted forms.
• the dual character of the molecule as being NO x -reactive and oil soluble are essential to the invention.
• compositions that contain a major portion or amount of a basestock boiling in the lube oil range and a minor portion of the sludge mitigation/control (antinoxidant) additive.
• the effect of using the compound is to reduce propensity of NOour in the base oil to react form insolubles, i.e., sludge.
• the minor portion or amount of the additive is an amount effective to mitigate or control sludge formation and lube oil degradation. Typically, this may be achieved in amounts from about 0.1 to about 10 wt%, preferably from about 0.2 to about 5 wt% of the additive compound.
• the formulation may optionally contain other additives such as viscosity modifiers, antioxidants, dispersants, detergents, antiwear agents, friction modifiers, corrosion inhibitors, demulsifiers, pour point depressants and antifoam agents.
• the additive can chemically immobilize NO x by reaction of the NO x -reactive carbon-carbon unsaturated portion(s) of the molecule with NO x while remaining soluble in the lube oil. This result is unexpected because other additives used in lube oils typically react with NO x to form sludge precursors and sludge rather than oil soluble species. Applicants' invention mitigates this result.
• Fullerene grafted hydrocarbons may be prepared as known in the art.
• Fullerene adducts of base oils may be prepared similarly.
• NO ⁇ -reactive moieties suitable for use as head portions include reactive carbon-carbon unsaturated bonds that react with NO x and reaction products thereof to form oxidatively stable reaction products.
• Other reactive carbon-carbon unsaturation includes reactive acetylenic, olefinic, conjugated dienes, aryl and heteroaromatic groups (aromatic ring containing sulfur, oxygen, nitrogen heteroatoms).
• a localization of such groups, particularly as exemplified by fiillerenes, is extremely desirable, as such structures have a greater NO x trapping capacity, and hence, capability to sludge formation.
• Substituents and groups that do not interfere with the reactivity of the carbon-carbon unsaturation with NO x or with ofthe overall solubility ofthe molecule in the lube oil also may be present and those that promote reactivity of the unsaturated sites with NO x are desirable.
• Hydrocarbons suitable for use as the tail portion of the antinoxidant molecule can have an absence of unsaturation and are oil soluble aliphatic and aromatic hydrocarbyl groups that are essentially inert to oxidation at engine conditions.
• the minimum number of carbon atoms in the hydrocarbyl portion of the molecule is affected by the number and relative polarity of the NO x -reactive centers in order to maintain oil solubility ofthe molecule. Thus fewer hydrocarbyl chains of reduced length are required for less polar NO x -reactive centers. In all cases, the minimum chain length is typically at least C , more preferably at least C ⁇ up to a maximum chain length of per head group.
• chains containing from at least C ⁇ up to C 1 40 aliphatic and aromatic hydrocarbyl groups per NO x -reactive head group or center are suitable, more preferably from C ⁇ 2 to C 1 00, most preferably C ⁇ « to C j chains per NO x reactive moiety (head group) depending on the identity of the head group or center.
• polythiophene requires at least one C ⁇ , preferably Cg aliphatic hydrocarbyl tail per thiophene moiety; phenol requires at least one Cig aliphatic hydrocarbyl chain.
• Base oils for grafting as tail portions are suitably any lube basestock, i.e., any hydrocarbon boiling in the lube oil range, examples of which include S 150N, S600N, and polymerized alpha- olefins ("PAOs"). Hydrocarbon polymers (polyolefins) can also be used as tail portions.
• a NO x -reactive center is bonded to the aliphatic hydrocarbyl center by a carbon to carbon bond.
• the resulting antinoxidant molecule must contain sites of unsaturation in the head portion(s) capable of reacting with or immobilizing NO x to form oxidatively stable, non-oxidizable moieties and suitable hydrocarbyl tail portion(s) to maintain the oil solubility of the molecule at the conditions present in engines.
• a lower limit also exists on the characteristics ofthe head group, because sites or head groups having a lower concentration of NO x -reactive carbon-carbon unsaturation (e.g., monoalkenes and monoalkynes) will immobilize less NO x per weight or volume of oil.
• NO x -reactive carbon-carbon unsaturation e.g., monoalkenes and monoalkynes
• an upper limit exists on the number, length and structure of the aliphatic and aromatic hydrocarbyl center(s) which is related to the number, size and structure ofthe NO x reactive center(s) and vice versa. Dilution ofthe activity of the NO x -reactive centers) is undesirable, as is dilution of the solubility promoting effect ofthe aliphatic hydrocarbyl centers).
• head and tail groups may be varied within the parameters established herein.
• suitable combinations include Ceo or CTM grafted to a C 3 o to C 4 s aliphatic hydrocarbyl lube oil basestock, ethylene-propylene copolymer (“EP”) bound to hydroquinone, ethylene-propylene copolymer bound to phenol ethylene-butene copolymer (“EB”), poly n-butenes, polythiophene (and other unsaturated, heteroatom containing cyclic moieties) bound to Cg to C 4 j alkylhydrocarbons.
• EP ethylene-propylene copolymer
• EB phenol ethylene-butene copolymer
• poly n-butenes polythiophene (and other unsaturated, heteroatom containing cyclic moieties) bound to Cg to C 4 j alkylhydrocarbons.
• these sludge mitigation compounds include a major amount of lubricating oil containing an effective amount of at least one compound selected from the group consisting of (A) at least one alkyl substituted hydroxyaromatic compound formed by alkylation of at least one polymer selected from the group consisting of (i) unsaturated ethylene alpha olefin copolymer, (ii) poly(alpha olefin) homopolymer and copolymer, (iii) polybutenes, (iv) polybutadiene polymers and copolymers, wherein said ethylene alpha olefin copolymer contains from about 20 to about 70% ethylene and at least 15% of the polymer chains contain terminal ethyleneidene unsaturation, and wherein said polybutadiene polymers and copolymers contain one or more unsaturation sites prior to said alkylation, and wherein said polymers are alkylated with compounds of the formula H-Ar-(OH) c where Ar is selected from the group
• R" is independently a halogen radical or hydrocarbyl radical containing from 1 to about 10 carbon atoms
• b is independently an integer from 0 to 2
• c is an integer from 0 to 2
• B a compound formed by alkylation of any of said polymers (i)-(iv) with a compound selected from the group consisting of (v) fiillerenes, acetylenes, thiophenes, conjugated dienes, aryls aromatics and heterocyclic aromatics.
• the ethylene alpha olefin copolymer will have an ethyleneidene content of from about 50 to about 100.
• the hydroxyaromatic compounds include an effective amount of at least one alkyl substituted hydroxyaromatic compound formed by alkylation of at least one polymer selected from the group consisting of (i) unsaturated ethylene alpha olefin copolymer, (ii) poly(alpha olefin) homopolymer and copolymer, (iii) polybutenes, (iv) polybutadiene polymers and copolymers, wherein said ethylene alpha olefin copolymer contains from about 20 to about 70% ethylene and at least 15% of the polymers chains contain terminal ethyleneidene unsaturation, and wherein said polybutadiene polymers and copolymers contain one or more unsaturation sites prior to said alkylation, and wherein said polymers are alkylated with compounds of the formula H-Ar-(OH) c where Ar is selected from the group consisting of
• R" is independently a halogen radical or hydrocarbyl radical containing from 1 to about 10 carbon atoms
• b is independently an integer from 0 to 2
• c is an integer from 0 to 2 is added to said lubricating oil.
• alkyl substituted hydroxyaromatic compounds may be selected from the group consisting of a phenol or hydroquinone alkylation product substituted with a poly(alphaolefin) polymer preferably selected from the group consisting of ethene butene, poly n-butene, polyisobutene, ethene propene, and mixtures thereof.
• Ethene butene phenol is a more preferred alkyl substituted hydroxyaromatic compound.
• the hydroxyaromatic compound is a phenol
• the percent of ortho and para groups varies from 100% ortho to 100% para and mixtures thereof, but preferably 100% para.
• the polymers desirably have an Mn of from about 300 to 100,000, preferably, 800 to about 2,000.
• Mn is from about 800 to about 5,000, most preferably 800 to about 2,000.
• the molecule will be soluble (i.e., soluble or stably dispersible) in the lube oil both before and on reaction with NO x and compatible with other additives present over the range of operating conditions at which the lube is used. Sludge reduction of at least two times, preferably at least ten times, that of untreated basestock can be achieved.
• PAO Mobil SHF 61
• Ceo Ceo
• the solution was heated at 160°C and 0.8 ml of t-butyl peroxide was added dropwise under nitrogen. The reddish- brown solution was allowed to stir at that temperature for 1 hour. After cooling to room temperature, the solution was mixed with 100 ml of heptane and filtered. The solvent was evaporated on rotary evaporator.
• the product was characterized by the Gel Permeation Chromatography (GPC).
• GPC Gel Permeation Chromatography
• IR spectra ofthe product revealed new peaks appearing at 3620 and 1400 cm-1 (indicating a change in the nature ofthe hydroxyl groups on the aromatic ring that would indicate the presence of a substituent) and disappearance ofthe double bond peaks of the EP polymer at 3065, 1645 and 885 cm “1 (indicating the loss ofthe polymer unsaturation). This indicates that the dihydroxyaromatic was alkylated.
• the presence ofthe antinoxidant additives had a beneficial effect on sludge mitigation.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=24199742

Family Applications (1)

Country Status (5)

Families Citing this family (4)

Citations (2)

Family Cites Families (3)

• 1996
  • 1996-10-30 EP EP96937847A patent/EP0863965A4/de not_active Withdrawn
  • 1996-10-30 JP JP9517566A patent/JPH11515053A/ja active Pending
  • 1996-10-30 AU AU75296/96A patent/AU717669B2/en not_active Ceased
  • 1996-10-30 WO PCT/US1996/017507 patent/WO1997016510A1/en not_active Application Discontinuation
  • 1996-10-30 CA CA 2233210 patent/CA2233210A1/en not_active Abandoned

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events