CA2233210A1 - Antinoxidant sludge control additives - Google Patents
Antinoxidant sludge control additives Download PDFInfo
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- CA2233210A1 CA2233210A1 CA 2233210 CA2233210A CA2233210A1 CA 2233210 A1 CA2233210 A1 CA 2233210A1 CA 2233210 CA2233210 CA 2233210 CA 2233210 A CA2233210 A CA 2233210A CA 2233210 A1 CA2233210 A1 CA 2233210A1
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a process for mitigating NOx-induced sludge formation in engine oils by dissolving in an engine oil of lubricating viscosity an effective amount of a molecule having at least one head portion enriched in NOx reactive carbon-carbon unsaturation and at least one oil soluble hydrocarbyl, preferably aliphatic, tail portion having an absence of carbon-carbon unsaturation of suitable chain length in an optimum ratio of head to tail sufficient to reduce NOx-induced sludge formation in the engine oil. The invention also relates to formulated lube oil compositions containing the antinoxidant additive. The 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.
Description
W O 97/16510 PCTrUS96/17507 -ANTrNo~DANT SLUDGE CONTROL ADDmVES
This is a co~ ;Qn-in-part of U.S. Serial No. 551,076 filed October 31, 1995, which is based on PM 94CL 033.
FIELD OF THE INVENTION
The present invention relates to control of sludge formation in lubes.
BACKGROIJND OF THE INVE~NTION
Oxides of nitrogen, also referred to as NOx, are by-products of the operation of internal combustion çngin~s These oxides are emitter~ for example, as exhaust gas from the comhl-stion of hydrocarbon fuels. They react even at relatively low tCl"~ e~ res (e.g., 70~ - 120~C) with colllponcnls of motor oils, such as additives, to form sludge and contribute to lube oil degradation. It would be adv~nt~geolls to develop additives, lube oil forrnulations, and methods that can address lube oildegradation and ...;~ e sludge formation particularly in the pl~sel1ce of NO".
Applicants' invention addresses these needs.
SVMMARY OF THE INVENTION
The present invention provides for a method for miti~ting sludge formation in engine oils by adding to an engine oil of lubricating visco~ily an effective, minor ~rnollnt 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 I,~droc~l"rl tail portion having an absence of carbon-carbon unsaturation of suitable chain length in an optimum ratio of head to tail sufficient to reduce NOx-in~ ced sludge formation in the engine oil. Plert;ll~,d examples of such molecules include polyethylene propylene copolymer- and polyisobutylene-grafted hydroquinone polyalkylthiophenes, W O 97/16~10 PCTrUS96/17507-fulle.~,lc-grafted lube oil b~sto~ ethylene propylene polymer-grafted phenol andethylene butylene polymer-grafted phenol The present invention also provides for lube oil compositions and additive conc~.l.dl~s for mitig~ting sludge r~ ~lion co..~ g the foregoing ~le lles The present invention may suitably comprise, consist or consist c ~ lly of the el~ s or steps ~icclosed herein and may be practiced in the iqbs~ce of an ~ .1 or step not specifically disclosed DETAILED DESCRIPTION OF THE INVENTION
The present invention provides for methorls for controlling sludge (i e., insolubles) formation, particularly that indt~ced by NOX, in lube oils and the lube degradation r~s-llting from the combustion of hydrocarbonaceous fuels using NOx-reactive sludge control additives (also referred to herein as "~ntinoxitls~nt additives"), and provides for form~ ted lube oil co-l-posiLions and additive conct~ tes c~ ;..g these additives Examples of such fuels include those typically used for internal co..-bu:~lion engines such as cr~nkc~ce lubricating fuels for spark-ignited and con~ ,ion-ignited internal combustion ~ngin--~, 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 i..le....c.l;~les of their reactions ("NOx") are produced in internal combustion engines from a variety of sources such as blowby gases and thermal degradation of o.~ o~ les As used herein the term " NOx-reactive" in~ es reactivity to nitrous oxides and to the products of reactive organonitrate species such as sludge p--,~,u.~o.~ The most typical oxide of nitrogen is NO2, however, other reactive nitrogen oxides may also be present and the present invention also may be effectively carried out in the p.t;sence of such oxides CA 022332l0 l998-04-24 W O 97/16510 PCT~US96/17507-Lube oils and additives typically present therein degrade in the engine in the presence of NO", oxygen and heat to form sludge precursors and sludge. Applicants have disco~w-ed novel additives and methods for re~-cing the occurrence of such degradation ch~ y. These additives can be used to preserve the lifetime of current additives by p.~;re,~,nlially reacting with NOx. Thus Applicants' invention provides a method for mitig~ting sludge formation associated with certain currently available additives by rendering them ltiai~ to degradation into insolubles, i.e., sludge. The invention is also useful in the design of new additives sl~it~hle for use to ...ioi...;~e 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 o~Lilllulll relationship of both carbon-carbon ullaalulaLed Nox-reactive portions and oil soluble alc,---&~ic, p-erelably ~liph~tic, hydrocarbyl portions having a chain length sufficient to ...~i..l,.;.~ solubility of the NOx-reactive and NOx-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 r~ dil,g or controlling sludge formation and lube oil degradation which colll~liaes cG---bi~ g with an engine oil of lubricating viscosi~y an effective amount of at least one sludge mitigation compound having at least one first moiety or portion enriched in NOx-reactive carbon-carbon unsaturation and at least one second moiety or portion deficient in NOx-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 molecllle NOx-reactive and lube oil soluble. Aliphatic hydrocarbyl groups are pler~lably e~centi~lly free of carbon-carbon unsaturation. These moieties also are, lespe.,li~ely, referred to herein as "head"
or " NOx''-reactive head," and "tail" or "aliphatic hydrocarbyl tail" portions or "centers"
or moieties for convenience. These terms are meant to indicate a localization orconce..l.aLion of the particular structure or feature identified. For example, a molecule useful in the present invention will have, in co...binaLion, at least one head and tail portions, provided that the number, structure and col~l,n~alion are sufflcient to impart NO,~-reactivity to the head portion and to impart oil solubility to the tail portion and to the mole 1l~ as a whole both in its NOx-reactive and NOx-reacted forms. The dualcharacter of the mole- le as being NOx-reactive and oil soluble are ~Cs~nti~l to the invention.
Other embodiments are form~ tion~ that contain a ma~or portion or amount of a basestock boiling in the lube oil range and a minor portion of the sludge mitig~tion/control (A..~ nt) additive. The effect of using the compound is to reduce p-u~,n~,ily of NO, in the base oil to react forrn insolubles, i.e., sludge. The minor portion or ~tnollnt of the additive is an amount effective to mitig7te or control sludge formation and lube oil degradation. Typically, this may be achieved in amounts from about 0.1 to about 10 wt%, p,er~,~bly ~om about 0.2 to about 5 wt% ofthe additive co.l"~o~ d. The formulation may optionally contain other additives such as visco~ily modifiers, antioxidants, dis~ ls, detergents, a,-Li~.,ar agents, friction modifiers, corrosion hlhil,ilol~" d~mlllcifi~o~s, pour point depr~ ts and ~ntifoam agents.
It is believed that the additive can ~ ;CA1IY immobilize NOx by reaction of the NOx-reactive carbon-carbon uns&lu~led portion(s) of the molecule with NOXwhile ,~ soluble in the lube oil. This result is unexpected because other additives used in lube oils typically react with NO" to form sludge precursors and sludge rather than oil soluble species Applicants' invention mhig~tes this result.
The starting materials disclosed herein may be purchased commercially or ~ C;,~d using known procedures. Fullerene grafted hydrocarbons may be p,epaled as known in the art. Fullerene ~dd~lctc of base oils may be p, ~pared similarly.
NOx-reactive moieties suitable for use as head portions include reactive carbon-carbon unsaturated bonds that react with NOx and reaction products thereof to form oxidatively stable reaction products. Other reactive carbon-carbon u.~s&Lu~Lion int~ des reactive acetylenic, olefinic, conjug~ted dienes, aryl and heteloal~.,.la~ic groups (aromatic ring co..l~ p sulfur, oxygen, nitrogen h~leroalollls) A localization of such groups, particularly as exemplified by fullerenes, is extremely desirable, as such W O 97/16510 PCTrUS96/17507-structures have a greater NOx Ll ~ppil-g capacity, and hence, capability to sludge formation. Substit~l~nte and groups that do not interfere with the reactivity of the carbon-carbon uns~lulalion with NOx or with of the overall solubility of the molecule in the lube oil also may be present and those that promote reactivity of the unsaturated sites with NOx are de.,;. ~ble.
Hydrocarbons suitable for use as the tail portion of the a-Li-~ idant molecule can have an ~hsence of ulls~lul~Liol and are oil soluble aliphatic and aromatic hydrocarbyl groups that are eSsenti~lly inert to oxidation at engine conditions. The unlber of carbon atoms in the hydrocarbyl portion of the molecule is a~cled by the llulllI,er and relative polarity of the NOx-reactive centers in order to l~n;~ oil solubility of the molecule. Thus fewer h~d,Oca-l"~l chains of reduced length are l~yuh~,d for less polar Nox-reactive centers. In all cases, the miniml1m chain length is typically at least C~, more preferably at least C6 up to a m~iml1m chain length of C~40 per head group. More typical1y, chains cor.~ from at least C6 up to Cl40 aliphatic and aromatic hydrocarbyl groups per NOx-reactive head group or center are suitable, more p~re~ly from Cl2 to C10O, most p-ere~bly Cls to C45 chains per NOx reactive moiety (head group) depe,-di--g on the identity of the head group or center. For example, polythiophene requires at least one C6, preferably C8 aliphatic hydrocarbyl tail per thiophene moiety; phenol requires at least one Cl8 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 1 50N, S600N, and polymerized alpha-olefins ("PAOs"). Hydrocarbon polymers (polyolefins) can also be used as tail portions.
A NOx-reactive center is bonded to the aliphatic hydrocarbyl center by a carbon to carbon bond.
After grafting of the head and tail groups, the res111ting antinoxidant molecule must contain sites of unsaturation in the head portion(s) capable of reacting with or immobilizing NOx to form oxidatively stable, non-oxidizable moieties and suitable hydrocarbyl tail portion(s) to ...~;..l~;.. the oil solubility of the molecule at the conditions present in Pn~in~s A lower limit also exists on the characteristics of the head group, bec~use sites or head groups having a lower co~c~ Lion of Nox-reactive carbon-carbon unsaturation (e.g., mono~lkenes and monoallynes) will immobilize less NOX per weight or volume of oil. In practical terms an upper limit exists on the number, length and structure of the ~liph~tic and aromatic hydrocarbyl center(s) which is related to the --I,el, size and structure of the NOx reactive center(s) and vice versa. Dilution of the activity of the NOx-reactive center(s) is u~1de~i~le, as is dilution of the solllkility plolllolillg effect ofthe aliphatic hydrocarbyl center(s).
The actual co-..l,il.aLion of head and tail groups may be varied within the -..Glers established herein. Examples of suitable combinations include C60 or C~0 grafted to a C30 to C45 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 co.~ g cyclic moieties) bound to C8 to C45 alkyll.~ ,al bons.
Preferably, these sludge mitigation compounds include a major amount of lubricating oil co.~ -i.-g an effective amount of at least one compound selected from the group co~ g of (A) at least one alkyl substituted hydrox~lo...~lic compound formed by alkylation of at least one polymer selected from the group col-~;slillg of (i) unsalul~lled ethylene alpha olefin copolyrner, (ii) poly(alpha olefin) homopolymer and copolymer, (iii) polybutenes, (iv) polybutadiene polymers and copolymers, wherein said ethylene alpha olefin copolymer co--lail-s from about 20 to about 70% ethylene and at least 15% of the polymer chains contain terminal ethylen~ one 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 s~lected from the group CO~ ;..g of WO 97/16510 PCT~US96tl7507-R"
a , R"b /R'b 1 and ..
Rb R"
whele;n a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical c(s..~ g from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2, and (B) a compound formed by alkylation of any of said polymers (i)-(iv) with a compound selected from the group con~i~ting of (v)fullerenes, acetylenes, thiophenes, conjugated dienes, aryls aromatics and heterocyclic ~o-"alics. More plt;relably, the ethylene alpha olefin copolymer will have an ethylPnpi~lçnp~ content of from about 50 to about 100. Also more preferably, thehydro~yalolllalic compounds include an effective amount of at least one allyl substituted hyd~o~yalolnaLic compound formed by alkylation of at least one polymer selected from the group coll~;s~il,g of (i) unsaturated ethylene alpha olefin copolymer, (ii) poly(alpha olefin) homopolymer and copolymer, (iii) polybutenes, (iv) polyb~.lt?~-liPn~P.
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 ethylçnPidçne. unsaturation, and wherein said polyb~lt~l1iPne 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 isselected from the group COIlsi ,~il,g of R"
J a R"b and ..
wherein a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical cc,..~ from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2 is added to said lubricating oil.
More p,erGlably alkyl substituted hydlO~y~lulllaLic compounds may be s~1ecte~ from the group co~ ing of a phenol or hydroquinone alkylation product s~bsl;l..led with a poly(alphaolefin) polymer prerc..~bly selected from the group col~c ~l ;ilg of ethene butene, poly n-butene, polyisobutene, ethene propene, and mixtures thereof. Ethene butene phenol is a more pre~,l~d alkyl substit~lted hydloxy~ lalic compound. When the hydl~y~ llaliC compound is a phenol, the percent of ortho andpara groups varies from 100% ortho to 100% para and mixtures thereof, but p,~rel~bly 100% para. The polymers desirably have an Mn of from about 300 to 100,000, prtr~;lably, 800 to about 2,000. For ethene butene the more p[~relled range of Mn is from about 800 to about 5,000, most pl~rt;l~bly 800 to about 2,000.
For use as a lubricant additive the molecule will be soluble (i.e., soluble or stably di:~Jtl ~;ble) in the lube oil both before and on reaction with NO" and co,..palible with other additives present over the range of operating conditions at which the lube is used.
CA 022332l0 l998-04-24 W O 97/16510 PCTrUS96/17~07-_g _ Sludge reduction of at least two times, preferably at least ten times, that of unl~Led b~cçstor~ can be achieved.
The following examples illustrate the invention:
~. Sample Procedures for Synthesis of Antinoxidant Molecules Example 1: Free-radical Graftin~ of Fullerenes to Poly(alphaolefins) "PAO"
100 g of PAO (Mobil SH~ 61) was mixed with 1 g of C60 in a 500 ml round bottom flask equipped with con~1en~r and a nitrogen bubbler. The solution was heated at 1 60~C and 0. 8 ml of t-butyl peroxide was added dropwise under nitrogen. The reddish-brown solution was allowed to stir at that te,-lpe-~ re for 1 hour. After cooling to room t~,l.p~ .t;, 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). In the C60 grafted PAO, a new peak corresponding to apprc ~ tely 2 and 3 molecules of PAO are ~tt~çhec~ to C60 molecule were observed along with the peaks due to PAO.
Example 2: Alkylation of Ethylene Propylene copolyrner with Phenol In a 250 ml round-bottom flask were charged 4.3 g of phenol and 50 ml of heptane. To this was added 6 g of Amberlyst- 15 and the mixture was heated to 90~C.
Added to this was 20 g of an EP polymer (mw = 870~ and the solution was ...~i.,l ~;..~c~ at 90~C for another 8 hours. The reaction mixture was then filtered, the filtrate evaporated, and the res~llt~rlt product redissolved in heptane. The heptane solution was filtered and the filtrate evaporated under vacuum to obtain the product.
WO 97/16510 PCT~US96/17507-IR spectra of the product revealed new peak apped~ , at 3612 cm~l (inrlic~tinF~ a change in the nature ofthe hydlu~yl groups on the aromatic ring that would in-lic~te the presence of a ~b5~ çnt) and disal)pe~ ~lce of the double bond peaks of the EP polymer at 3065, 1645 and 885 cm~' (inflic~tin~ the loss of the poly~ner unsaturation).
This in~iic~tes that the phenol was alkylated.
FY~rnple 3: Alkylation of Ethylene Propylene Copolymer with Hydro4uh~ c In a 250 ml round-bottom flask were chalged 6.32 g (0.0575 moles) of hydro~uhlone (mw = 110) and 50 ml of heptane. To this was added 10 g of Alllbelly~L-15 and the lnixLule was heated to 90~C. Added to this was 50 g of an EP polymer (mw = 870) and the solution was ...~ ;..ed at 90~C for another 2 hours. The reaction llfixLule was then filtered, the filtrate evaporated, and the l ~ product redissolved in heptane. The hep~le solution was itself filtered and the filtrate evaporated under vacuum to obtain the product.
IR spectra ofthe product revealed new peaks appearing at 3620 and 1400 cm- 1 (in~lic~ting a change in the nature of the h~/dl oxyl groups on the aromatic ring that would intli~te the pl-,sellce of a substituent) and d;sappealance ofthe double bond peaks of the EP polymer at 3065, 1645 and 885 cm~' (in~ ting the loss ofthe polymer un~Lu~Lion). This indicates that the dihydloxy~uolllaLic was alkylated.
B. General Procedure for Bench Tests Bench tests were conrl~cted to llleasule the impact of the sludge control additives described in this invention on sludge formation in lubricating oils. In the sludge ~im-ll~tion test NO2 gas, delivered into the lube oil at a predetermined fixed rate, or a model organonitrate compound was contacted with the idPnfified lubricant co..l~ the sludge control additive of the present invention. The lube oil was allowed to react with NO2 or the organonitrate compound, in the presence of 1 g of myrcene, a diene. The reaction was carried out at tt~ alule~ of 95~C to ~ e Seql~çnce VE sump or of 150~C to cim~ te Se~lu ~-~ e IIIE sump, each for 2 hrs.
Ex~ ?le 1: VE Sump Simulation S~ . ' were removed from the reaction "~lule and analyzed by h~.~ed ,~e~ scol)y to follow the change in sludge formation as a function of time in the pr~ sellce of NO2. At the end ofthe test the reaction l~lule was filtered and the total ~mo-lnt of sludge produced was weigLcd. The following three samples were tested:
Sample Contents A R~cestorL + NO2 + ~yl-.t;lle (Col"~ e Example) B 20% Basestock grafted with C60 in a 5:1 ratio + A
C C60 (ungrafted) + A (Coc,pa,~ e Example) The results are shown in Table I below.
TABLE - I Sludge weight in grams BASESTOCK _ _ C
PAO 2.1 2 0.4 1 1.44 S150N 2.45 0.35 4.01 The results in~ic~te that only B produced cignific~nt dec,~ases in sludge formation.
W O 97/16510 PCT~US96/17507-Example 2: Sequence m E Sump Sim~ tion Each of the five tests listed below was c~ n~ çted using the model sludge ~,~u-~or, C8HI7NO3 under id~ntiç~l con~iti~?n~ in the p,~,sence of 100/mmol C8HI7NO3/kg of lube. !~mples were removed for i- rl~ed spectral analysis and at the end of the test the lube solutions were filtered and the total sludge weighed. The results are shown in Table II.
TABLE - II Sludge weight in grams/100~ of lube SAMPLE SLIJI)GE Wt (~) S150N + ~y~ene (Co---pa-~Li~/e Example) 2.12 SlSON + 20% S1 50N grafted C60 + .. y.cenc 0.90 S1250N + C60 (un~,-~led) + ~--y~ielle (Con-l)a-~ e Example) 1.70 The results in-lic~te that only the lube oils co..ln;..;l~g the ~ntinoxid~nt mo'ee~-les produced cignific~nf de~.eases in sludge forrnation Fxample 3: VE Sump Simulation A test was run using poly(C6-thiophene) and poly(C8-thiophene) as antinoxidant co...pa,ison, but in which the formation of organic nitrate and nitro species and the buildup of a carbonyl species also were measured periodically using infra-red spectroscopy Samples were taken periodically from the reaction m-ixture and analyzed using FTIR to fo110w the composition change The total amount of thesludge was collected, rinsed with ~,en~e, dried and weighed at the end of each test.
The NO,~ pe-rc,----ance data co---pa-t;d with the base case and are shown below in Table IV.
TABLE IV
SAMPLE SLUDGE RN02 RONO2 fC=O MYRCENE
~ WT (~e) DECAY
Base case SlSON 1.81 11.8 2.7 2.5 -99%
Base case S150N +1.12 13.9 3.1 3.2 -98%
0.8 wt% Poly(C6-thiophene) Base case S150N +0.32 18.4 3.7 3.5 -48%
0.8 wt% Poly(C8-ILophene) The ple~e-lce of the ~lhlo~idant additives had a beneficial effect on sludge miti~tion E~ )le 4: VE Sump ~im~ tion EP-bound phenol as well as EP-bound hydroquinone were evaluated in the NOx test diccllssed above. The pe-ru,..~ .e data co~paled to the Base Case and are shown in Table V.
TABLE V
SAMPLE SL~)GE Wt Base case (S150N) 1.81 EP-phenol 0.83 EP-hydroquinone 0.54 The sludge mitigation in the presence of the antinoxidant additives is evident.
This is a co~ ;Qn-in-part of U.S. Serial No. 551,076 filed October 31, 1995, which is based on PM 94CL 033.
FIELD OF THE INVENTION
The present invention relates to control of sludge formation in lubes.
BACKGROIJND OF THE INVE~NTION
Oxides of nitrogen, also referred to as NOx, are by-products of the operation of internal combustion çngin~s These oxides are emitter~ for example, as exhaust gas from the comhl-stion of hydrocarbon fuels. They react even at relatively low tCl"~ e~ res (e.g., 70~ - 120~C) with colllponcnls of motor oils, such as additives, to form sludge and contribute to lube oil degradation. It would be adv~nt~geolls to develop additives, lube oil forrnulations, and methods that can address lube oildegradation and ...;~ e sludge formation particularly in the pl~sel1ce of NO".
Applicants' invention addresses these needs.
SVMMARY OF THE INVENTION
The present invention provides for a method for miti~ting sludge formation in engine oils by adding to an engine oil of lubricating visco~ily an effective, minor ~rnollnt 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 I,~droc~l"rl tail portion having an absence of carbon-carbon unsaturation of suitable chain length in an optimum ratio of head to tail sufficient to reduce NOx-in~ ced sludge formation in the engine oil. Plert;ll~,d examples of such molecules include polyethylene propylene copolymer- and polyisobutylene-grafted hydroquinone polyalkylthiophenes, W O 97/16~10 PCTrUS96/17507-fulle.~,lc-grafted lube oil b~sto~ ethylene propylene polymer-grafted phenol andethylene butylene polymer-grafted phenol The present invention also provides for lube oil compositions and additive conc~.l.dl~s for mitig~ting sludge r~ ~lion co..~ g the foregoing ~le lles The present invention may suitably comprise, consist or consist c ~ lly of the el~ s or steps ~icclosed herein and may be practiced in the iqbs~ce of an ~ .1 or step not specifically disclosed DETAILED DESCRIPTION OF THE INVENTION
The present invention provides for methorls for controlling sludge (i e., insolubles) formation, particularly that indt~ced by NOX, in lube oils and the lube degradation r~s-llting from the combustion of hydrocarbonaceous fuels using NOx-reactive sludge control additives (also referred to herein as "~ntinoxitls~nt additives"), and provides for form~ ted lube oil co-l-posiLions and additive conct~ tes c~ ;..g these additives Examples of such fuels include those typically used for internal co..-bu:~lion engines such as cr~nkc~ce lubricating fuels for spark-ignited and con~ ,ion-ignited internal combustion ~ngin--~, 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 i..le....c.l;~les of their reactions ("NOx") are produced in internal combustion engines from a variety of sources such as blowby gases and thermal degradation of o.~ o~ les As used herein the term " NOx-reactive" in~ es reactivity to nitrous oxides and to the products of reactive organonitrate species such as sludge p--,~,u.~o.~ The most typical oxide of nitrogen is NO2, however, other reactive nitrogen oxides may also be present and the present invention also may be effectively carried out in the p.t;sence of such oxides CA 022332l0 l998-04-24 W O 97/16510 PCT~US96/17507-Lube oils and additives typically present therein degrade in the engine in the presence of NO", oxygen and heat to form sludge precursors and sludge. Applicants have disco~w-ed novel additives and methods for re~-cing the occurrence of such degradation ch~ y. These additives can be used to preserve the lifetime of current additives by p.~;re,~,nlially reacting with NOx. Thus Applicants' invention provides a method for mitig~ting sludge formation associated with certain currently available additives by rendering them ltiai~ to degradation into insolubles, i.e., sludge. The invention is also useful in the design of new additives sl~it~hle for use to ...ioi...;~e 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 o~Lilllulll relationship of both carbon-carbon ullaalulaLed Nox-reactive portions and oil soluble alc,---&~ic, p-erelably ~liph~tic, hydrocarbyl portions having a chain length sufficient to ...~i..l,.;.~ solubility of the NOx-reactive and NOx-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 r~ dil,g or controlling sludge formation and lube oil degradation which colll~liaes cG---bi~ g with an engine oil of lubricating viscosi~y an effective amount of at least one sludge mitigation compound having at least one first moiety or portion enriched in NOx-reactive carbon-carbon unsaturation and at least one second moiety or portion deficient in NOx-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 molecllle NOx-reactive and lube oil soluble. Aliphatic hydrocarbyl groups are pler~lably e~centi~lly free of carbon-carbon unsaturation. These moieties also are, lespe.,li~ely, referred to herein as "head"
or " NOx''-reactive head," and "tail" or "aliphatic hydrocarbyl tail" portions or "centers"
or moieties for convenience. These terms are meant to indicate a localization orconce..l.aLion of the particular structure or feature identified. For example, a molecule useful in the present invention will have, in co...binaLion, at least one head and tail portions, provided that the number, structure and col~l,n~alion are sufflcient to impart NO,~-reactivity to the head portion and to impart oil solubility to the tail portion and to the mole 1l~ as a whole both in its NOx-reactive and NOx-reacted forms. The dualcharacter of the mole- le as being NOx-reactive and oil soluble are ~Cs~nti~l to the invention.
Other embodiments are form~ tion~ that contain a ma~or portion or amount of a basestock boiling in the lube oil range and a minor portion of the sludge mitig~tion/control (A..~ nt) additive. The effect of using the compound is to reduce p-u~,n~,ily of NO, in the base oil to react forrn insolubles, i.e., sludge. The minor portion or ~tnollnt of the additive is an amount effective to mitig7te or control sludge formation and lube oil degradation. Typically, this may be achieved in amounts from about 0.1 to about 10 wt%, p,er~,~bly ~om about 0.2 to about 5 wt% ofthe additive co.l"~o~ d. The formulation may optionally contain other additives such as visco~ily modifiers, antioxidants, dis~ ls, detergents, a,-Li~.,ar agents, friction modifiers, corrosion hlhil,ilol~" d~mlllcifi~o~s, pour point depr~ ts and ~ntifoam agents.
It is believed that the additive can ~ ;CA1IY immobilize NOx by reaction of the NOx-reactive carbon-carbon uns&lu~led portion(s) of the molecule with NOXwhile ,~ soluble in the lube oil. This result is unexpected because other additives used in lube oils typically react with NO" to form sludge precursors and sludge rather than oil soluble species Applicants' invention mhig~tes this result.
The starting materials disclosed herein may be purchased commercially or ~ C;,~d using known procedures. Fullerene grafted hydrocarbons may be p,epaled as known in the art. Fullerene ~dd~lctc of base oils may be p, ~pared similarly.
NOx-reactive moieties suitable for use as head portions include reactive carbon-carbon unsaturated bonds that react with NOx and reaction products thereof to form oxidatively stable reaction products. Other reactive carbon-carbon u.~s&Lu~Lion int~ des reactive acetylenic, olefinic, conjug~ted dienes, aryl and heteloal~.,.la~ic groups (aromatic ring co..l~ p sulfur, oxygen, nitrogen h~leroalollls) A localization of such groups, particularly as exemplified by fullerenes, is extremely desirable, as such W O 97/16510 PCTrUS96/17507-structures have a greater NOx Ll ~ppil-g capacity, and hence, capability to sludge formation. Substit~l~nte and groups that do not interfere with the reactivity of the carbon-carbon uns~lulalion with NOx or with of the overall solubility of the molecule in the lube oil also may be present and those that promote reactivity of the unsaturated sites with NOx are de.,;. ~ble.
Hydrocarbons suitable for use as the tail portion of the a-Li-~ idant molecule can have an ~hsence of ulls~lul~Liol and are oil soluble aliphatic and aromatic hydrocarbyl groups that are eSsenti~lly inert to oxidation at engine conditions. The unlber of carbon atoms in the hydrocarbyl portion of the molecule is a~cled by the llulllI,er and relative polarity of the NOx-reactive centers in order to l~n;~ oil solubility of the molecule. Thus fewer h~d,Oca-l"~l chains of reduced length are l~yuh~,d for less polar Nox-reactive centers. In all cases, the miniml1m chain length is typically at least C~, more preferably at least C6 up to a m~iml1m chain length of C~40 per head group. More typical1y, chains cor.~ from at least C6 up to Cl40 aliphatic and aromatic hydrocarbyl groups per NOx-reactive head group or center are suitable, more p~re~ly from Cl2 to C10O, most p-ere~bly Cls to C45 chains per NOx reactive moiety (head group) depe,-di--g on the identity of the head group or center. For example, polythiophene requires at least one C6, preferably C8 aliphatic hydrocarbyl tail per thiophene moiety; phenol requires at least one Cl8 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 1 50N, S600N, and polymerized alpha-olefins ("PAOs"). Hydrocarbon polymers (polyolefins) can also be used as tail portions.
A NOx-reactive center is bonded to the aliphatic hydrocarbyl center by a carbon to carbon bond.
After grafting of the head and tail groups, the res111ting antinoxidant molecule must contain sites of unsaturation in the head portion(s) capable of reacting with or immobilizing NOx to form oxidatively stable, non-oxidizable moieties and suitable hydrocarbyl tail portion(s) to ...~;..l~;.. the oil solubility of the molecule at the conditions present in Pn~in~s A lower limit also exists on the characteristics of the head group, bec~use sites or head groups having a lower co~c~ Lion of Nox-reactive carbon-carbon unsaturation (e.g., mono~lkenes and monoallynes) will immobilize less NOX per weight or volume of oil. In practical terms an upper limit exists on the number, length and structure of the ~liph~tic and aromatic hydrocarbyl center(s) which is related to the --I,el, size and structure of the NOx reactive center(s) and vice versa. Dilution of the activity of the NOx-reactive center(s) is u~1de~i~le, as is dilution of the solllkility plolllolillg effect ofthe aliphatic hydrocarbyl center(s).
The actual co-..l,il.aLion of head and tail groups may be varied within the -..Glers established herein. Examples of suitable combinations include C60 or C~0 grafted to a C30 to C45 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 co.~ g cyclic moieties) bound to C8 to C45 alkyll.~ ,al bons.
Preferably, these sludge mitigation compounds include a major amount of lubricating oil co.~ -i.-g an effective amount of at least one compound selected from the group co~ g of (A) at least one alkyl substituted hydrox~lo...~lic compound formed by alkylation of at least one polymer selected from the group col-~;slillg of (i) unsalul~lled ethylene alpha olefin copolyrner, (ii) poly(alpha olefin) homopolymer and copolymer, (iii) polybutenes, (iv) polybutadiene polymers and copolymers, wherein said ethylene alpha olefin copolymer co--lail-s from about 20 to about 70% ethylene and at least 15% of the polymer chains contain terminal ethylen~ one 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 s~lected from the group CO~ ;..g of WO 97/16510 PCT~US96tl7507-R"
a , R"b /R'b 1 and ..
Rb R"
whele;n a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical c(s..~ g from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2, and (B) a compound formed by alkylation of any of said polymers (i)-(iv) with a compound selected from the group con~i~ting of (v)fullerenes, acetylenes, thiophenes, conjugated dienes, aryls aromatics and heterocyclic ~o-"alics. More plt;relably, the ethylene alpha olefin copolymer will have an ethylPnpi~lçnp~ content of from about 50 to about 100. Also more preferably, thehydro~yalolllalic compounds include an effective amount of at least one allyl substituted hyd~o~yalolnaLic compound formed by alkylation of at least one polymer selected from the group coll~;s~il,g of (i) unsaturated ethylene alpha olefin copolymer, (ii) poly(alpha olefin) homopolymer and copolymer, (iii) polybutenes, (iv) polyb~.lt?~-liPn~P.
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 ethylçnPidçne. unsaturation, and wherein said polyb~lt~l1iPne 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 isselected from the group COIlsi ,~il,g of R"
J a R"b and ..
wherein a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical cc,..~ from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2 is added to said lubricating oil.
More p,erGlably alkyl substituted hydlO~y~lulllaLic compounds may be s~1ecte~ from the group co~ ing of a phenol or hydroquinone alkylation product s~bsl;l..led with a poly(alphaolefin) polymer prerc..~bly selected from the group col~c ~l ;ilg of ethene butene, poly n-butene, polyisobutene, ethene propene, and mixtures thereof. Ethene butene phenol is a more pre~,l~d alkyl substit~lted hydloxy~ lalic compound. When the hydl~y~ llaliC compound is a phenol, the percent of ortho andpara groups varies from 100% ortho to 100% para and mixtures thereof, but p,~rel~bly 100% para. The polymers desirably have an Mn of from about 300 to 100,000, prtr~;lably, 800 to about 2,000. For ethene butene the more p[~relled range of Mn is from about 800 to about 5,000, most pl~rt;l~bly 800 to about 2,000.
For use as a lubricant additive the molecule will be soluble (i.e., soluble or stably di:~Jtl ~;ble) in the lube oil both before and on reaction with NO" and co,..palible with other additives present over the range of operating conditions at which the lube is used.
CA 022332l0 l998-04-24 W O 97/16510 PCTrUS96/17~07-_g _ Sludge reduction of at least two times, preferably at least ten times, that of unl~Led b~cçstor~ can be achieved.
The following examples illustrate the invention:
~. Sample Procedures for Synthesis of Antinoxidant Molecules Example 1: Free-radical Graftin~ of Fullerenes to Poly(alphaolefins) "PAO"
100 g of PAO (Mobil SH~ 61) was mixed with 1 g of C60 in a 500 ml round bottom flask equipped with con~1en~r and a nitrogen bubbler. The solution was heated at 1 60~C and 0. 8 ml of t-butyl peroxide was added dropwise under nitrogen. The reddish-brown solution was allowed to stir at that te,-lpe-~ re for 1 hour. After cooling to room t~,l.p~ .t;, 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). In the C60 grafted PAO, a new peak corresponding to apprc ~ tely 2 and 3 molecules of PAO are ~tt~çhec~ to C60 molecule were observed along with the peaks due to PAO.
Example 2: Alkylation of Ethylene Propylene copolyrner with Phenol In a 250 ml round-bottom flask were charged 4.3 g of phenol and 50 ml of heptane. To this was added 6 g of Amberlyst- 15 and the mixture was heated to 90~C.
Added to this was 20 g of an EP polymer (mw = 870~ and the solution was ...~i.,l ~;..~c~ at 90~C for another 8 hours. The reaction mixture was then filtered, the filtrate evaporated, and the res~llt~rlt product redissolved in heptane. The heptane solution was filtered and the filtrate evaporated under vacuum to obtain the product.
WO 97/16510 PCT~US96/17507-IR spectra of the product revealed new peak apped~ , at 3612 cm~l (inrlic~tinF~ a change in the nature ofthe hydlu~yl groups on the aromatic ring that would in-lic~te the presence of a ~b5~ çnt) and disal)pe~ ~lce of the double bond peaks of the EP polymer at 3065, 1645 and 885 cm~' (inflic~tin~ the loss of the poly~ner unsaturation).
This in~iic~tes that the phenol was alkylated.
FY~rnple 3: Alkylation of Ethylene Propylene Copolymer with Hydro4uh~ c In a 250 ml round-bottom flask were chalged 6.32 g (0.0575 moles) of hydro~uhlone (mw = 110) and 50 ml of heptane. To this was added 10 g of Alllbelly~L-15 and the lnixLule was heated to 90~C. Added to this was 50 g of an EP polymer (mw = 870) and the solution was ...~ ;..ed at 90~C for another 2 hours. The reaction llfixLule was then filtered, the filtrate evaporated, and the l ~ product redissolved in heptane. The hep~le solution was itself filtered and the filtrate evaporated under vacuum to obtain the product.
IR spectra ofthe product revealed new peaks appearing at 3620 and 1400 cm- 1 (in~lic~ting a change in the nature of the h~/dl oxyl groups on the aromatic ring that would intli~te the pl-,sellce of a substituent) and d;sappealance ofthe double bond peaks of the EP polymer at 3065, 1645 and 885 cm~' (in~ ting the loss ofthe polymer un~Lu~Lion). This indicates that the dihydloxy~uolllaLic was alkylated.
B. General Procedure for Bench Tests Bench tests were conrl~cted to llleasule the impact of the sludge control additives described in this invention on sludge formation in lubricating oils. In the sludge ~im-ll~tion test NO2 gas, delivered into the lube oil at a predetermined fixed rate, or a model organonitrate compound was contacted with the idPnfified lubricant co..l~ the sludge control additive of the present invention. The lube oil was allowed to react with NO2 or the organonitrate compound, in the presence of 1 g of myrcene, a diene. The reaction was carried out at tt~ alule~ of 95~C to ~ e Seql~çnce VE sump or of 150~C to cim~ te Se~lu ~-~ e IIIE sump, each for 2 hrs.
Ex~ ?le 1: VE Sump Simulation S~ . ' were removed from the reaction "~lule and analyzed by h~.~ed ,~e~ scol)y to follow the change in sludge formation as a function of time in the pr~ sellce of NO2. At the end ofthe test the reaction l~lule was filtered and the total ~mo-lnt of sludge produced was weigLcd. The following three samples were tested:
Sample Contents A R~cestorL + NO2 + ~yl-.t;lle (Col"~ e Example) B 20% Basestock grafted with C60 in a 5:1 ratio + A
C C60 (ungrafted) + A (Coc,pa,~ e Example) The results are shown in Table I below.
TABLE - I Sludge weight in grams BASESTOCK _ _ C
PAO 2.1 2 0.4 1 1.44 S150N 2.45 0.35 4.01 The results in~ic~te that only B produced cignific~nt dec,~ases in sludge formation.
W O 97/16510 PCT~US96/17507-Example 2: Sequence m E Sump Sim~ tion Each of the five tests listed below was c~ n~ çted using the model sludge ~,~u-~or, C8HI7NO3 under id~ntiç~l con~iti~?n~ in the p,~,sence of 100/mmol C8HI7NO3/kg of lube. !~mples were removed for i- rl~ed spectral analysis and at the end of the test the lube solutions were filtered and the total sludge weighed. The results are shown in Table II.
TABLE - II Sludge weight in grams/100~ of lube SAMPLE SLIJI)GE Wt (~) S150N + ~y~ene (Co---pa-~Li~/e Example) 2.12 SlSON + 20% S1 50N grafted C60 + .. y.cenc 0.90 S1250N + C60 (un~,-~led) + ~--y~ielle (Con-l)a-~ e Example) 1.70 The results in-lic~te that only the lube oils co..ln;..;l~g the ~ntinoxid~nt mo'ee~-les produced cignific~nf de~.eases in sludge forrnation Fxample 3: VE Sump Simulation A test was run using poly(C6-thiophene) and poly(C8-thiophene) as antinoxidant co...pa,ison, but in which the formation of organic nitrate and nitro species and the buildup of a carbonyl species also were measured periodically using infra-red spectroscopy Samples were taken periodically from the reaction m-ixture and analyzed using FTIR to fo110w the composition change The total amount of thesludge was collected, rinsed with ~,en~e, dried and weighed at the end of each test.
The NO,~ pe-rc,----ance data co---pa-t;d with the base case and are shown below in Table IV.
TABLE IV
SAMPLE SLUDGE RN02 RONO2 fC=O MYRCENE
~ WT (~e) DECAY
Base case SlSON 1.81 11.8 2.7 2.5 -99%
Base case S150N +1.12 13.9 3.1 3.2 -98%
0.8 wt% Poly(C6-thiophene) Base case S150N +0.32 18.4 3.7 3.5 -48%
0.8 wt% Poly(C8-ILophene) The ple~e-lce of the ~lhlo~idant additives had a beneficial effect on sludge miti~tion E~ )le 4: VE Sump ~im~ tion EP-bound phenol as well as EP-bound hydroquinone were evaluated in the NOx test diccllssed above. The pe-ru,..~ .e data co~paled to the Base Case and are shown in Table V.
TABLE V
SAMPLE SL~)GE Wt Base case (S150N) 1.81 EP-phenol 0.83 EP-hydroquinone 0.54 The sludge mitigation in the presence of the antinoxidant additives is evident.
Claims (26)
1. A lubricating oil for mitigating sludge formation in engine oils comprising: a major amount of a lubricating oil in admixture with 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 consisting of and wherein a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical containing from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2, and (B) a compound formed by alkylation of any of said polymers (i)-(iv) with a compound selected from the group consisting of (v) fullerenes, acetylenes, thiophenes, conjugated dienes, aryls aromatics and heterocyclic aromatics.
2. The lubricating composition of claim 1 wherein 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 ethyleinedene 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)o where Ar is selected from the group consisting of , and wherein a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical containing from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2 is added to said lubricating oil.
3. The lubricating oil of claim 1 wherein the alkyl substituted hydroxyaromatic compound is selected from the group consisting of a phenol or hydroquinone alkylation product substituted with a polymer selected from the group consisting of ethene butene, poly n-butene, polyisobutene, and ethene propene, benzoquinone and anisol and mixtures thereof.
4. The lubricating oil of claim 1 wherein the alkyl substituted hydroxyaromatic compound is ethene butene phenol.
5. The lubricating oil of claim 2 wherein the polymers have an Mn of from about 300 to about 100,000.
6. The lubricating oil of claim 3 wherein the polymers have an Mn of 800 to about 2,000.
7. The lubricating oil of claim 3 wherein when the polymer is an ethene butene polymer the Mn is from about 800 to about 5,000.
8. The lubricating oil of claim 1 wherein when the hydroxyaromatic compound is a phenol, the phenol has a percent of ortho and para groups of from 100%
ortho to 100% para.
ortho to 100% para.
9. The lubrication oil of claim 1 wherein the ethylene alpha olefin copolymer has an ethyleneidene content of from about 30 to about 100 mole percent.
10. The lubricating oil of claim 1 further comprising detergents, dispersants, anti-wear agents, viscosity modifiers, antioxidants, surfactants and pour point depressants.
11. A method for mitigating sludge formation in engine oils, comprising:
dissolving in an engine lubricating oil an effective minor amount of a sludge mitigation compound having at least one head portion enriched in NOx reactive carbon-carbon unsaturation and at least one oil soluble aliphatic hydrocarbyl tail portion having an absence of carbon-carbon unsaturation of suitable chain length in ratio of head to tail portion sufficient to mitigate sludge formation in the engine oil.
dissolving in an engine lubricating oil an effective minor amount of a sludge mitigation compound having at least one head portion enriched in NOx reactive carbon-carbon unsaturation and at least one oil soluble aliphatic hydrocarbyl tail portion having an absence of carbon-carbon unsaturation of suitable chain length in ratio of head to tail portion sufficient to mitigate sludge formation in the engine oil.
12. The method of claim 11 wherein sludge mitigation compound is 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)o where Ar is selected from the group consisting of , and wherein a is 1 or 2, R" is independently a halogen radical or hydrocarbyl radical containing from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2, and (B) a compound formed by alkylation of any of said polymers (i)-(iv) with a compound selected from the group consisting of (v)fullerenes, acetylenes, thiophenes, conjugated dienes, aryls aromatics and heterocyclic aromatics.
13. The method of claim 12 wherein 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 ethyleinedene 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 , and wherein a is 1 or 2, R" is independently a halogen radical or hydrocarbon radical containing from 1 to about 10 carbon atoms, and b is independently an integer from 0 to 2 and c is an integer from 0 to 2 is added to said lubricating oil.
14. The method of claim 12 wherein the alkyl substituted hydroxyaromatic compound is selected from the group consisting of a phenol or hydroquinone alkylation product substituted with a polymer selected from the group consisting of ethene butene, poly n-butene, poly isobutene, and ethene propene, benzoquinone and anisol and mixtures thereof.
15. The method of claim 12 wherein the alkyl substituted hydroxyaromatic compound is ethene butene phenol.
16. The method of claim 12 wherein the polymers have an Mn of from about 300 to about 100,000.
17. The method of claim 13 wherein when the polymer is ethene butene and the Mn is from about 800 to about 5,000.
18. The composition of claim 13 wherein when the hydroxyaromatic compound is a phenol, the phenol has a percent of ortho and para groups of from 100%
ortho to 100% para.
ortho to 100% para.
19. The method of claim 12 wherein the ethylene alpha olefin copolymer has an ethyleneidene content of from about 30 to about 100 mole percent.
20. The method of claim 11 wherein the aliphatic hydrocarbyl tail portion is at least one C6 aliphatic hydrocarbyl group per head portion.
21. The method of claim 11 wherein the tail portion is at least one C12 to C100 aliphatic hydrocarbyl group per head portion.
22. The method of claim 11 wherein the additive is present in an amount of from about 0.2 to about 5 wt%.
23. The method of claim 11 wherein the tail portion is a base oil selected from the group consisting of S15ON, S600N, mineral oils and the synthetic base stocks.
24. The method of claim 11 wherein the compound is selected from the group consisting of ethylene propylene copolymer-grafted hydroquinone, fullerenegrafted lube oil basestock, ethylene propylene copolymer-grafted phenol.
25. The method of claim 11 wherein the head portion is selected from the group consisting of reactive acetylenic, olefinic, conjugated dienes, aryl and aromatic heterocyclic groups.
26. The method of claim 11 wherein the compound is selected from the group consisting of C60 grafted to a C30 to C45 aliphatic hydrocarbyl lube oil base stock and polythiophene bound to C8 to C45 alkylthiophenes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55107695A | 1995-10-31 | 1995-10-31 | |
| US08/551,076 | 1995-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2233210A1 true CA2233210A1 (en) | 1997-05-09 |
Family
ID=24199742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2233210 Abandoned CA2233210A1 (en) | 1995-10-31 | 1996-10-30 | Antinoxidant sludge control additives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0863965A4 (en) |
| JP (1) | JPH11515053A (en) |
| AU (1) | AU717669B2 (en) |
| CA (1) | CA2233210A1 (en) |
| WO (1) | WO1997016510A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111278956B (en) * | 2017-10-25 | 2022-11-04 | 昭和电工株式会社 | Lubricating oil composition and method for producing same |
| CN113710780B (en) * | 2019-04-24 | 2023-05-12 | 株式会社力森诺科 | Lubricating oil composition and method for producing same |
| CN113710782B (en) * | 2019-04-24 | 2022-11-18 | 昭和电工株式会社 | Method for producing lubricating oil composition and lubricating oil composition |
| WO2020218386A1 (en) * | 2019-04-24 | 2020-10-29 | 昭和電工株式会社 | Lubricating oil composition, method for producing same and vacuum apparatus |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737301A (en) * | 1985-10-11 | 1988-04-12 | Exxon Chemical Patents Inc. | Polycyclic thiophene lubricating oil additive and method of reducing coking tendencies of lubricating oils |
| US4800032A (en) * | 1987-07-08 | 1989-01-24 | The Lubrizol Corporation | Aliphatic hydrocarbon substituted aromatic hydrocarbons to control black sludge in lubricants |
| EP0589107A1 (en) * | 1992-09-23 | 1994-03-30 | Nippon Oil Co. Ltd. | Lubricating oil composition and process for preparing the same |
| US5454961A (en) * | 1994-04-19 | 1995-10-03 | Exxon Research & Engineering Co. | Substituted fullerenes as flow improvers |
| EP0709447A1 (en) * | 1994-10-25 | 1996-05-01 | Exxon Research And Engineering Company | Multiring aromatics for enhanced deposit control |
-
1996
- 1996-10-30 JP JP9517566A patent/JPH11515053A/en active Pending
- 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
- 1996-10-30 EP EP96937847A patent/EP0863965A4/en not_active Withdrawn
- 1996-10-30 AU AU75296/96A patent/AU717669B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11515053A (en) | 1999-12-21 |
| AU717669B2 (en) | 2000-03-30 |
| EP0863965A1 (en) | 1998-09-16 |
| WO1997016510A1 (en) | 1997-05-09 |
| EP0863965A4 (en) | 1999-02-10 |
| AU7529696A (en) | 1997-05-22 |
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