CA2657538A1 - Ashless controlled release gels - Google Patents

Abstract

The present invention relates to a control release gel for delivery of additives free of producing ash to substantially free of producing ash into a lubricant. Further, the invention provides for a method of controlled release of additive(s) into the lubricant.

Description

Title: ASITLI~SS CONTROLLED RELEASE GELS
FIELD OF THE INVENTION
'I'he present invention relates to a controlled release gel that release additives iBito a lubricant wherein there is substantially ash free to an ash free production of ash in the lubrie,atit. Furkiierrraore, the present inventioxg relates to a gel that control releases additives into a lubricaiit without the addition of ash-containing components or substatitially free of ash-eontaixgiug components.

BACKGROUND OF THE INVENTION
Lubricant compositions, in particular, crankcase motor oils are desired to provide ashless lubricants, that is those which do not contain metals which f m-i sulfated ash. Ashless lubricants are advantageous because they reduce combustion cban-iber deposits. Additionally, the use of ash free, acid neutralizing additives would eliininate the fortnation of sulfate ash in the oil.
The eond entioBial means of rfle-La.tralizing acids that form in oil due to the eotiabustiori process is by engployirig basic additive eoilafsorietits such as detergelits in the lubricant. Detergents generally contain some ash-f rniing metal element, such as calcium or magnesium. It is thought that sulfated ash from the oil contributes to particulate emissions and to Fluggirflg diesel particulate filters, and thus regulated limits on sulfated ash in the oil are expected. Therefore, the use of ash free acid neutralizing additives in the lubricant would eliminate sulfate ashes in the oil, tlius allowing regulatory c n-iplianee.
The present invention provides for ari ashless additive liibriearit.
Lubricant additives are slowly degraded by the ten-iFerature aBid chemically liarsb environment of the oil as the etggitge or otlger power equifsment operates.
'I'herefi~re, as the oil ages, it loses its performance effectiveness upon its degradation.
The incorporation of additives into a lubricai-it gel protects the additive components from degradation until release, thus improving the lubricant's Ferfertnanee efficiel'iey.

The present invention provides for a controlled release of all ashless gel farrrfl-La.lation with improved acid ne-La.tralizatien perforrrflance, efficiency and reduced emgssioxgs.
SIJMMARY OF THE li"YVEN'I'I()N

The invention provides for a lubricant additive gel eoinprising:
1} an ashless dispersant;

2) an acid selected from the group consisting of acid fortned from a polymer containing acidic groul.~s in the backbone, a polyacidic eongpotirad and rnixttires tlgereof; and 3) optionally other l-La.bricaBit additives;

resulting in a lubrieaiit additive coBitralled release gel that does not produce substaiitially any ash to no ash.

The present illvelltion provides for a controlled release process for supplyiilg one or more desired additives to a lubricant by contracting the lubricant with a lubricant additive controlled release gel without the addition of producing ash containing components and in another embodiment with the addition of additives being substantially free of ash producing eainlioneiits.
The controlled release gel eata be used in any lubricating eoitditioning device including, but not limited to, iaiternal combustion engines, natural gas engines, stationary erigiues, ngariiie diesel engines, power equipment, hydraulic systems, lubricated mechanical systems, transmission systems, gears, differentials, metal working coolant systems, industrial lubricated systems and the like.

DETAILED DESCRIPTION OF THE INVENTION
'I'he present invention provides a lubricant additive gel that control releases the e n-iponents into a lubrgcal'it, which components are specifically formulated in the gel to meet desired performariee requirements of the gels aiid the lubricant that the gel is releasing its desired additives iBito. The controlled release gel comprises:
1) an ashless dispersant;

2) an acid selected frong the g-roiip eorisisting of acid formed from a polymer coBitairfling acidic greulis in the backbone, ap lvaeidic eongpotirad and rnixttires tlgereof; and 3) optionally lubricant additives.
The weight ratio of component I above i.e., ashless disl.~ersaiit to component 2 above i.e., acid is about 0.1 to about ] 00 and in another embodiment about I to about 50.
The additive composition is in the form of a gel. Tbe composition is a mixture of an ashless dispersant and an acid when combined form a gel. The controlled release gel is substaiitially free of ash producing eoml."?onetgts and in aBiother en-ib dimerit has the absence of ash producing components. The weight ratio of the ashless dispersant to the acid is abotit 0.1 to about 100 aiid in aiiotiier embodiment about I to about 50.
Gels are materials that comprise mixtures of two or more substances and which exist in a semi-solid state more like a solid than a liquid. The gel exists in a sen-ii-solid state more like a solid than a liquid, see Parker, Dictioiiarv of Scientific and Teehtgieal Terms, Fifth Editioii, MeCsraiv f3ill, 1994. See, also, Larson, "The Stra.cture aBid rheology of Complex Fluids", Chapter 5, Oxford University Press, New York, New York, 1999, each which is incorporated herein by reference.
The rheological properties of a gel can be rneastared by small amplitude oscillatory shear testing. This teehniqtje measures the structural character of the gel and produces a term called the storage modulus which represents storage of elastic energy and the loss modulus which represents the viscous dissipation of that energy. The ratio of the loss modulusistorage modulus, which is called the loss tangent, or "tan delta'', is >1 for materials that are licl-Lgid-like al'id <1 for materials that are solid-like. The additive gels have tan delta values in one eiiabodiment of about 5 0.75, in another ernbodirneiit of ab ta.t < 0.5 aBid in aBiother embodiment of about < 0.3. The gels have tan delta valiies in oiie embodiment of about < 1, in otge engbodingerit of about <.
0.75, in one einbadignent of about < 0.5 or in one embodiment of about < 0.3.
The additive gel eoinl.-~rises at least tivo additives when combined form a gel.
'l'he additive gel includes combining a dispersant and an acid to form a gel.
In one en-ibodimellt, the additive gel does not contain any ash c olltainirgg detergents ineluditig, biit tiot liiiaited to, over based metal sulforiated detergents.
In one egnbadignerlt, a gel which finds paatie,ular use are those ill which gellation occurs through the combination of an acid arid an ashless succinimide dispersant. In oxge ernbodirneiit, the ratio of the ashless dispersaiit to the acid is from about 1:1 to about 1:100, in another embodirrgel'it from about 100:1 to about 1:1 from about 4:1 to about 1:1 and in another embodiment from about 4:1 to about 2:1.
The ashless dispersant ii-ieludes Mallriieh disl.-~ersal-its, polymeric dispersants, carboxylie, dispersants, amine dispersants, and combinations and mixtli.res thereof, all of which are substaBitially free of forming ash to completely free of forming ash.
Ira otie embodiment the preferred dispersarit is polyisobutenyl stieciiiimide dispersant.
Ashless typ. e dispersants are characterized by apalar group attached to a relatively high molecular iveight liydroearbon chain. Typical ashless dispersants include N-substituted long chain alkerlyl succinimides, having a variety of chemical structures including typically:
R, R, H
n N /N NH2 4~1 O
0 JR2 n and/or R, R, N-[R2NH]x-R2N

whereil'i each R' is iiidepelldelltly al'i a.lkyl group, frequently a polyisobutyl group, with amoleeular weight of 500-5000, and lk`'' are alkenylene groups, commonly ethylelle (C2144)gr ups. Succinimide dispersants are inore fiilly described in U.S.

Patent 4,234,435 which is incorporated herein by reference. The dispersants described in this pateiit are particularly effective for producing a gel in accordance witli the presetgt inventiori.
The ashless dispersant includes, but is not limited to, an ashless dispersant such as a polyisobutenyl suecinin-iide ai-id the like. Polyisobutenyl succii-tirnide ashless dispersants are commercially available products which are typically made by reactii-ig together polyisobutylene having a ii-Lan-iber average molecular weight ("Mn") of about 300 to 10,000 with maleic anhydride to form polyisobutenyl sueeinie anhydride (`:PIBSA") and then reacting the product so obtained with a polyamine typically eoiitair,~ixgg I to 10 etbylexge aniiiio groups per inoleeule. The disl.~?ersaxgt so obtained is tyliically formed from a mixture of different compounds and can be characterized by a variety of different variables including the degree of its amixge substitution (i.e., the ratio of the ecluizalents of amino groups to carbonylic groups, or the N:CO ratio), its maleie anhydride eol-iversion level (i.e., its molar ratio of maleie anhydride to 13I13, as defined in IJ.S. Patent 4,234,435, ineorp-orated herein by reference), the Mn of its PIB group, al-id its n-i de of preparation (tbem-ial assisted sueeination vs. 0z-assisted sueeiraatioxg). Analogous compounds inade with other polyamines (e.g. polypropenyl) can also be used. Ashless dispersants of this type are described, for example, in U.S. Patent 4,234,435, which is incorporated herein by reference.
Normally, the N:C'0 ratio of these polyisobuteiiyl succinimide ashless dispersants will be about 0.6 to 1.6 more typically about 0.7 to 1.4 or even 0.7 to 1.2.
In addition or altematively, the maleic anhydride conversion level of these polyisobutenyl succinimide ashless dispersants will norgnally be about ].3, more typically at least 1.5 or even 1.6 or above. In addition or altema.tively, the Mn of the 1.~?olyisobtitexgyl segments of these polyisobuteiiyl succinimide ashless dispersaiits are riormally> > about 350, more typically at least 1200, at least about 1500 or even 1800 or above. In additiori or alterraatively, these polyisobutenyl siieeinirrlide ashless dispersants are also made using Glz-assisted succination rather than therBnal assisted succination, since this produces PISAs of higher conversion than thermally produced PI B SAs (the latter known as DA or direct addition PII3SA-s).

The Maiiuiela dispersant are the reaction products of alkyl Phenols in which the alkyl g,-reuli contaiBis at least about 30 carbon atoms with aldehydes (especially fomgaldelayde) atgd amines (especially polyalk-ylene Polyarrlitges). Mannich bases having the following general structure (including a variety of different isomers and OH OH
CH2-NH-{R2-NH]x-R2-NH-CH2 I I ~
Rl Rl the like) are especially interesting.

and/or Ri Ri H H

~ R2 n n OH

Another class of ashless dispersants is nitrogen eaiitainirflg carboxylic dispersants. Exanil.~?les of these "carboxylic dispersaxgts" are described in Patent U.S.
Patent 3,'~19,666.
Amine dispersants are reaction 1.~?rodtiets of relatively high molecular weight aliphatic halides and agnines, preferably polyalkylene P lvagnines. Exan-iPles thereof are deseribed, in U.S. Patent 3,565,804.
holvgnerie, dispersants are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.,,,., amino alk.wl acrylates or acrylamides aBid Palv-(oxyetlidlene)-substituted aea-ylates. Examples of polymer dispersants thereof are disclosed in the followiiig U.S. Patents: 3,329,658 and 3,702,300.

Disl.?ersaxgts can also be post-treated by reaetioxg with any of a variety of agents. Ani rflg these are urea, thi -Larea, dimercapt tliiazoles, carbon disulfide, aldebydes, ketoties, carboxylic acids, hydroearbon-siibstituted succinic anhydrides, nitriles, expoxides, boron cempeuBids, and phosphorus compounds.
The ashless dispersants can be used alone or in combination. The disl.~ersai-it is present in the range from about 0.02 -,Nt% to about 99.5 wt% gel, in another embodiment in the range from about 1v4 ,% to about 70 wt% gel, al'id in another embodiment in the range from about 5 wt% to about 50 wt% total weight of the gel.
The acid includes apelymer containing acidic groups in the back-bone, for exanil.~?le, polymers derived fTom styrene arid maleie atiliydride, polyrngers derived from acrylates including acrylic acid, acrylic acid esters, methacrylic acid and its esters, polymers derived from high molecular iveight (Cn wbereill n < 12) esters and acids, polymers derived from esterified maleie anhydride styrene copolymers, polymers derived from esterified ethylene diene monomer copolymer; surfactants with acidic groups in the backbone; emulsifiers with acidic groups in the backbone;
polyacidic compounds, for exan-iple, polyacidic surfactants and/or polyacidic dispersants; funetiotialized derivatives of each eoinliolgerit listed bereiig and ngixtures tbere f.
In otge engbodingerit, the acid is fc~iTned from the polymerazatiolg of styrene aBid maleic anhydride. In one embodiment, the copolymer is partially esterified with oxge or ngore C6 to C32 alcohol or mixture of alcohols and in another einbodiment Cg toCig aleohols. 'The equivalent ratio of alcohol to acid groups is from about 0.1w-t o to about 0.99 wt % and in another embodiment about 0.45 w-t% to about 0.95 uTt i;,.
In one embodiment, the p lvacidie sli.rfaetants include a maleinated OC13 (olefin eop lyiner of ethylene and propylene). In another embodiment, the polyacidic siirfaetants include di-isobutenyl sueeari froiyi the reaction of di-isobutylene and maleic anhydride. In one embodiment, the polyacidic dispersants include a succinimide restiltitig froiii reaction of <1 equivalent of an ethylene diamille polyamirie with the maleinated OCP. In another embodiment, the polyacidic dispersants include a succinimide resulting fr m reaction of <1 eq-Lgivalent of an ethylene diamine p lvagnine with di-isobutenyl succan. 'I'he TAN is > 1, in another en-ibodimel-it the TAN is > 3 (e.g. koH/g al'id the oil blend viscosity at about 10% oil is 75 cSTO 1QflC atgd in atgotlger engbodingerit 1fleST olflOC. In one embodiment, the acid nlust have residual acid groups with a total acid iiunlber > I and in another embodiment > 3.
The acids can be used alone or in combination. The acid is present in the range from about 0.02 wt% to about 99.5 w-t%, in one errgbodirrgel'it in the ral-ige from about 0.1 w-t /a to about 90 wt%, and in another embodiment in the range from about 1 4% to about 80 uTt i;,.
Typieally, the additive gel further contains at least one desired additive for controlled release into the lubricant fluid. The additive gel desired components include viscosity modifier(s), frgetion modifier(s), ashless detergent(s), cloud point depressant(s), pour point depressant(s), demulsifier(s), flow improver(s), anti static agent(s), ashless dispersaiit(s), ashless antioxidant(s), antifoaiii(s), eorrosioti/rust inhibitor(s), extreme pressure/antiwear agent(s), seal swell agent(s), lubricity ai d( s), antimisting agel-it(s), and mixtures tbere f; resulting in a controlled release gel that over time releases the desired additive(s) into the lubricant when the gel is contacted with the lubricant. The desired additive component is further determined by the lubricant formulation, performanee characteristics, fiiraetioxg and the like and what additive is desired to be added for depleted additives arld!'er added new depending on the desired fLxnetions.
The desired additive optional components of the ashless detergeBit, ashless dispersant, and;'or asbless antioxidants are compounds that contain a base et~~polient which is an acid neutralizing component that is free of ash containing components.
Exan-iples include, but are not limited to, high nitrogen to carbonyl (> 1:1) dispersants; nitrogen containing antioxidants such as substituted biphenyl amines, organic an-iines such as C 5 to C 36 amines, ethoxylated an-iines and the like. The asbless detergents, ashless dispersaiits and/or ashless antioxidants have a TBN which is = 1, in another embodiment the TBN is > 10 and in another embodiment the TBN
is>50.
Ashless antioxidants include alkyl-substituted phenols such as 2, 5-di-teatiary butel-4-methyl pbenol, phenate sulfides, phosphosulfurized terpeiies, sulfuiized esters, aromatic amines, diphenyl amines, alk-ylated diphenyl amines and hindered phenols, bis-nonylated dipbenylainine, nonyl dipbenylainine, octyl diphenylan-iine, bis-oetylated dipbenylainirae, bis-decylated diphenylamine, decyl difSlienyrlamixge and mixtures thereof.
The asbless axgtioxidarat fuxgction ixgcludes sterically hixgdered phenols and includes but is not limited to 2,5-di-teat-butylpberial, 4-metbyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylpbenol 2,6-dfl-tert-butylhhenol, 4-perltyl-2-6-di-tert-butylphen l, 4-hexyl-2,6-di-tert-butylphenol, 4-heptyl-2,6-di-tert-butylphenol, 4-(2-etbylbexyl)-2,6-di-tert-butylpherflol, 4-octyl-2,6-di-tert-butylphenol, 4-n nvl-2,6-di-tert-butylhliegiol, 4-deeyl-2,6-di-tert-bta.tylhlien l, 4-ta.ndee,yl-2,6-di-tert-butylpberflol, 4-dodeeyl-2,6-di-tert-bukylpheraol, 4-trideeyl-2,6-di-tert-btitvlphenol, 4-tetradeevl-2,7-di-tert-butylpberflol, methylene-bridged sterically hindered phenols include but are not limited to 4,4-ngethyrlenebis(6-tert-btityl-o-eresol), 4,4-metliyleraebis(2-tert-arnyl- -eresol), 2,2-methylenebis(4-metyl-6-tert-butvlplienol), 4,4-methylene-bis(2,6-di-tertbutylphen l) and mixtures thereof Yknother example of an asbless antioxidant is a hindered, ester-su:bstituted phenol, which can be prepared by heating a 2,6-diallylphenol with an acrylate ester uxgder based eonditiotgs, such as adiieoti.s KOI-le Ashless antioxidants may be used alone or in combination. The arltioxidaBits are typically present in the range of about 0.01 Nvt % to abotit 95 wt ia, in one egnbadignerlt in the range from about 0.Q1 -,vt % to 95 -wt %, and in another embodiment in the range from about 1~~t % to about 70 wt % and in another embodiment in the range from about 5 N-t % to about 60 wt % total weight of the gel.
The extreme pressure/anti-wear agents include a sulfiar or chlorosulphur EP
agent, a chlorinated hydrocarbon EP agent, or a phosphorus EP agent, or mixtures thereof. Exan-iples of such EP agel-its are amine salts of phosphorus acid acid, chlorinated wax, organic sulfYdes and polysulfides, such as benzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid sulfurizecl alkylphenol, sulfurized dipetttene, sulfuri_zed terpene, aBid sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reactiol'i product of phosphorus sulfide with tur~.-~entine or methyl oleate, phosphorus esters such as the dihydr carbon and trihydrocarbon phosphate, i.e., dibutyl phosphate, diheptyl phosphate, dicyclohexyl phosphate, pentylphenyl pbosl.~hate, dipentyll.~?lgeriyl phosphate, tridecyl phosphate, distearyl phosphate atid polypropylene s-Labstituted phenol phosphate, metal thiocarbamates, such as zinc dioetyldithioearbamate arid baritim heptylpheraol diacid, such as zilie dicyclohexyl phosphorodithioate and the zinc salts of aphosphoroditliiaic acid cognbination may be used and mixtures thereof.
In one embodiment the antiwear agent/extreme presslire agent comprises an amine salt of a phosphorus ester acid. The ainine salt of aphosphorus ester acid includes phosphoric acid esters and salts tbereof; dialkyldithiophosphoric acid esters and salts thereof; phosphites; and phospherus-e,ontairiing carboxylic esters, ethers, and atraides; attd mixtures thereof.
In one embodiment the phosphorus compound further eomlirises a sulfur atom in the molecule. In one embodingerit the angiue salt of the phosphorus compound is ashless, i.e., metal-free (pri r to being mixed with other eomponerlts~.
The amines which may be suitable for use as the ainine salt include primary agnines, secondary amines, tertiarti, amines, and mixtli.res thereo#: 'The amines include those with at least one hydrocarbyl group, or, in certain embodiments, two or three hydrocarbyl groul.?s. The hydrocarbyl groups may colgtain about 2 to about 30 carbon atoms, or in other embodirneiits about 8 to about 26 or about 10 to ab -Lflt 20 or about 13 to about 19 earbott atoms.
Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylangirie, octylamitie, and dodeevlarnirae, as well as such fatty angiiies as n-oetylamine, n-decylarrline, n-dodecylamine, rfl-tetradeeylagnine, n-hexadeeylamine, n-oetadeeylamil'ie and oleyla.rrgiiie. Other useful fatty ainines include corlln-iereially available fatty amines such as ' ~`~rmeeg~ '" amines ~r~ducts available from Akzo Cbemicals, Chicago, Illinois), such as Armeen C, Armeen 0, Ain-ieen OL, Am-leen T, Armeeti I-IT, A-rmeeri S and Ariiieen SD, wherein the letter desigraatioxg relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
Exarnfsles of suitable secondary amines include dimetliylatlaine, dietliylarrline, dipropylamine, dibutylamine, diamylainine, dihexylamine, diheptylamine, methyletlielarriine, ethylbutyla.rrgiiie and ethylan-iylalnineo The seeondaly a.rrgiiies may be cyclic amines such as piperidine, piperazine and morpholine.

The aniiiie ngay also be a tertiary-aliphatie primary angiue. The aliphatic group in this case may be an alkyl gr -La.p caiitaining abaut ' to about 30, or about 6 to abotit 26, or about 8 to about 24 carbon atoins. Tertiary alkyl amixges ineliide monoamines such as tert-butylainirle; tert-hexylamine, 1-methyl-l-agnirlen eyclohexai-te, tert-octylamine, tert-deeylainine, tei-t-dodeeylamine, tert-tetradecylamine, tert-hexadee,ylamirfle, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
Mixtures of amines may also be used in the invention. In one embodiment a useful mixture of amines is "PrimeneC 8 1 R` and "Prignerlelk) JMT." Primene and Primene JMT (both produced arid sold by Rolitn & Iiaas) are mixtures of C
l 1 to G 14 tertiary alkyl primary arniBies and G 18 to C22 tertiary al-yl primary amines respectively.
Suitable hydrocarbyl amine salts of alk-ylphosphoric acid may be represented by the following formula:

R3-0 \ /O- R\ R6 ~P~ ~~

whereil'i R3 and R4 are independently hydrogen or hydrocarbyl groups such as a.llk-yl groups; for the phosphorus ester acid, at least one of R ' and 1e will be hydrocarbyl.
R3 and R 4 may contain about 4 to about 30, or about 8 to about 25, or about 10 to abotit 20, or about 13 to about 19 carbori atoms. R ', R6 alacl R ' may be indehendeBitly hydrogen or liydrecarbyl groups, such as alkyl branched or linear alk-yl chains with I to about 30, or about 4 to about 24, or about 6 to about 20, or about 10 to about 16 carbon atoms. '1'hese 1k5,R 6 and R ' grotips may be branched or lil'iear groul.~s, and in eei-tain einbodiments at least one, or alternatively tivo of R5, Rs and R 7 are hydrogen. Examples of alkyl groups suitable for R5, R6 and lk7 include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl groups and mixtures tbere f.

In otge engbodingetit the hydrocarbyl amine salt of ari alkylphosl.?lgorie acid ester is the reaction product of a C 14 to C 18 alkylated phosphoric acid with I'rimerie 81 RTm (produced atid sold by Rohin & Iiaas) whieh is a mixture of C l1 to C

tertiary alkyl primary amines.
Similarly, hydrocarbyl an-iine salts of dia.-yldithiolahosphoric acid esters of the invention used in the rust inhibitor package may be represented by the formula:

R3 0\ /g R\ R6 P;~\ S H ~ +

wherein tlie various R groups are as defined above, although typically both R
groul.~s are hydrocarbyl or alkyl. T;xarnliles of hydrocarbyl arnine salts of dialkyldithiophosphoric acid esters include the reaction product(s) of hexyl, heptyl or octyl or raotiyl, 4-methyl-2-fsentyl or 2-ethy1hexyl, isopropyl dithiophosphoric acids with ethylene diamine, merp. holirie, or Primene 8 1 RTm, and mixtures thereof.
In one embodiment the dithiophosphoric acid may be reacted with an epoxide or a glycol. 'I'his reaction product is further reacted with a phosphorus acid, anl-iydride, or lower ester. The epoxide includes al'i aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide and the like. In one embodiment the epoxide is Propylene oxide. The glyeols may be aliphatic glyreols having from I
to about 12, or from about 2 to about 6, or about 2 to about 3 carbon atoms.
The dithiophosphoric acids, glyeols, epoxides, itgorganie phosphorus reagents axgd methods of reacting the same are described in U.S. l3atent numbers 3,197,405 and 3,544,465. The resulting acids may then be salted with ainines. An example of suitable dithiophosphoric acid is prepared by adding phosphorus pentoxide (about 64 grams) at about 58T over aperi d of about 45 minutes to about 514 grarns of liydroxypropyl 0,0-di(4-metllvl-2-perityrl)pliosphoroditllioate (prepared by reaetillg di(4nmethyl-2-pentyl)-pbesphoredithi ic acid with about 1.3 moles of propylene oxide at about 25 C ). The mixtiire is heated at about 75 C', for about 2.5 hours, mixed with a diatornaeeotis eartli and filtered at about 70 T. The filtrate colgtains about 11.8% by weight pbasphora.s, about 15.2% by weight sulfur, and an acid riumber of 87 (bromopheraol blue).
The EP i aritiwear agents are present in the range of about 0 dv-t % to ab -La.t 50 uTt i;,, in one embodiment in tlie range fronl about 0.25 wt % to about 25 I %
and in another embodiment in the range from about 0.5 IN-t % to about 10 'A%t%
total weight of the gel.
The antifoams include organic silicones such as poly dignethyl siloxane, poly ethyl siloxane, polydiethyl siloxane, polyacrylates and polyn-iethacrylates, trimetliyl-triflouro-profsyrlmetlgyl siloxane atid the like.
The aBitifeams may be used alone or in combination. The antif ams are used in the range of about Qwt % to about 20 wt %, in otie embodiment in the range of about 0.02 wt % to about 10 w-t % and in another embodiment in the range of 0.05 NN,t % to about 2.5 uTt % total weight of the gel.
'I'he viscosity modifier provides both viscosity improving properties and dispersant properties. Examples of dispersant-viscosity inodifiers iiiclude vinyl l.~?yriditie, N-vinyl pyrrolidone and N,N'-dimethylainiraoetbyl inethacrylate are examples of nitrogen-containing monomers and the like. Polyacrylates obtained from the polymerizatiotg or copolymerization of one or inore alkyl acrylates also are useful as viscosity modifiers.
Funetiotialized polymers can also be used as viscosity modifiers. Among the common classes of such polymers are olefin e polvgners and aerylate or methacrylate copolymers. Functionalized olefin eopolyn-iers can be, for instanee, interpolymers of ethylene and propylene which are grafted with an active monomer such as maleic anl-iydride and then derivatized with an alcohol or an ainine.
Other siieb eopolyriners are copolymers of ethylene arid propyletie which are reacted or grafted with nitrogen compounds. Derivatives of polyacrylate esters are well krleNvn as dispersant viscosity index ngodifiers additives. Dispersarit acrylate or polyn-iethacrylate viscosity modifiers such as AcryloidTM985 or ViscoplexTM 6-054, from RohMax, are particularly useful. Solid, oil-soluble l.-~olyiners such as the PIB
(polvisobutylene), gnethaervlate, polyalk.wstyrerfle, ethylene;'propvlene and ethylene%rol.~ylene/ 1,4-bexadiene polyn-iers and rrgaleic anhydride-styrene interl.~?olymer atgd derivatives thereof, can also be used as viscosity index improvers.
The viscosity n-iodifiers are known and caingnercially available.
The viscosity inoditiers ngay be used alone or in conghiuation. The viscosity modifiers are present in the range of about flwt % to 80 Nv-t %, in one embodiment in the range from about 0.25 wt % to about 50 wt % and in another embodiment in the range from about 0.5 wt % o to about 10 wt % total weight of the gel.
The friction modifiers include organo-molybdenum compounds, including molybdenum dithiocarbamates, and fatty acid based materials, including those based on oleic acid, including glycerol inono-oleate, those based on stearic acid, and the like.
In one embodiment, the friction modifier is a phosphate ester or salt incliiding a monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl phosphate, wherein each hydrocarbyl group is saturated. In several embodiments, each hydrocarbyl group contains from about 8 to about 30, or from about 12 up to about 28, or from about 14 up to about 24, or from about 14 up to about 18 carbons atoms. ln another embodiment, the hydrocarbyl groul.~s are alkyl groups. Examples of liydrocarbyl groiips include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups and mixha.res thereof.
In otge engbodingerit, the phosphate salts may be prepared by reacting an acidic phosphate ester with an agnine compound or a metallic base to form an amine or a metal salt. The ainines may be monoamities or polyangiues. IJsefLxl amiues include those amines disclosed in U.S. Patent 4,234,435 at Col. 21, line 4 to C' l. 27, lil'ie 50.
Useful amines include prirnarv ether amines, such as those represented by the formula, R"((3R')Y-hTI-12, wherein R' is a divaleiit a.-ylene groul.~
having about 2 to abotit 6 carbon atoms; x is atauniber frorn one to abotit 150, or from about one to about five, or oBie; and R" is a hydrocarbyl group of about 5 to ab ta.t 150 carbon atoms.
The phosphate salt may be derived from apelyarnine. The polyamines include alkoxylated diamines, fatty polyan-iine diainines, allylenepolyalnines, hydroxy containing p lvagnines, condensed polyamines, arylpolyamines, and heterocyclic polyamines.

The metal salts of the phosphorus acid esters are prepared by the reaction of a metal base with the acidic phosphon.as ester. The metal base may be any metal coiiafsouxgd capable of forming angetal salt. Exainliles of metal bases include metal oxides, hydroxides, carboBiates, borates, or the like. Suitable metals include alkali metals, alkaline earth metals al'id transition metals. In one embodiment, the metal is a Group lIA metal, such as calcium or magnesium, Group IIB metal, such as zinc, or a Group VIIB metal, such as manganese. Exan-iples of metal coinl.-~ourgils which may be reacted Nvith the ph sphorus acid include zinc hydroxide, zinc oxide, copper hydroxide or copper oxide.
In oxge engbodingerit, the friction modifier is apbosphite aiid may be a monohydrocarbyl, dihydrocarbyl or a triliydrecarbyl phosphite, wherein each liydrocarbvl group is saturated. In several embodiments each hydrocarbyl group independently contains from about 8 to about 30, or from about 12 up to about 28, or from about 14 up to about 24, or from about 14 up to about 18 carbons atoms.
In one embodiment, the hydr carbyl groups are alkyl groups. Examples of hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groiips and mixtures thereof.
In one embodiment, the friction modifier is a fatty imidazoline comprising fatty substituents containing from 8 to about 30, or from about 12 to about 24 carbon atoms. The substituent may be saturated or unsaturated, preferably saturated.
In one aspect, the fatty imidazoline may be prepared by reactilig a fatty carboxylic acid with a p lvalkylerlep lyagnine, such as those discussed above. A suitable fatty in-iidazoline includes those described in US Patel'it 6,482,777.
'I'he friction modifiers can be used alone or in combination. 'I'he friction reducing agents are present in the range of about 0v4 ~'% to 60 wi%, or from about 0e25 wt % o to abotit 40 wt ~'ia, or frorn about 0.5 wt % to about 10 aArt %
total weic'llt of the gel.
The anti-inisting agerits include very high (>100,00OMra) polyolefiiis sticb as 1.5 Mn palvisobtatylerie (for exagnp. le the material of the trades name VistaBlexf""), or polyn-iers containing 2-~T-a.crylarnido), 2-methyl propane sulfonic acid (also known as AMPSO"), or deridatives thereof, and the like.

The anti-inisting agerits can be tised alone or in eombinatiori. The anti-misting agents are present in the range of about 0NV-t % to 10 wt %, or from ab -La.t 0.25 1At % to abotit 10 wt ia, or froin about 0.5 wt % to about 2.5 wt %
total weight of the gel.
The eorrosiol'i inhibitors iiielude alkylated succinic acids al-ld anhydiides derivatives thereof, organo phosphonates and the like. Tbe rust inhibitors may be used alone or in con-ibil-tation. The nast inhibitors are present in the range of about 0 wt % to about 20 w-t %, and in one embodiment in the range from about 0.0005 wt % to about 10 dv-t % and in another embodiment in the range from about 0.0025 N'V-t % to about 2.5 aAt % total weight of the gel.
The ashless metal deactivators include derivatives of benzotriazoles such as tolyltriazole, N,N-bis(beptyl)-ar-metbyl-lI-I-bexizotriazole-l-methananiiiie, N,N-bis(rl rflyl)-ar-rnethyl-1H-I3enzotriazole-l-methanamirfle, _N,N-bis(dee,vl)ar-rnetlIyl-lH-Benzotriazole-l-methanarrgiiie, hT,N-(undeeyl)a.r-rrietliel-lll-benzotriazole-1-methanamine, N,N-bis(d deeyl)ar-gnetbyl-1 H-13enz triazo le-l-gnethanamine N,:N-bis(2-ethy1hexyl)-ar-methyl-lH-Benz iriazole-l-methana.rrgiile and mixtures thereoI'.
In oiie embodiment the ngetal deactivator is N,N-bis(1-ethylhexyl)ar-metliyl-ll-1-berizotriazele-l-metlianamirfle;l,2,4-triazeles, benzimidazoles, 2-alkylditbiobenzirnidazoles;2-alkyldithiobenzotlgiazoles; 2-N,N-dialkvldithio-earbameyl)berizothiazeles;2,5-bis(alkyl-ditliio)-1,3,4-tbiadiazeles such as 2,5-bis(tert-oetvlditliio)-1,3,4-thiadiazole 2,5-bis(tert-nonylditlgio)-1,3,4-thiadiazole, 2,5-bis(tert-dee,yldithio)-1,3,4-tliiadiaz le, 2,5-bis(tert-undeeyldithi )-1,3,4-thiadiazole, 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-trideeylditbio)-1,3,4-thiadiazole, 2,5-bis(tert-tetradeeyldithio)-1,3,4-tliiadiaz le, 2,5-bis(tert-eta.decyldithio)-1,3,4-thiadia.zole, 2,5-bis(tert-nonadecyldithio)-1,3,4-tbiadiazole, 2,5-bis(tert-eieosyldithio)-1,3,4-thiadiazole and mixtures tbereof; 2,5-bis(N,N-dia-yldithieearbamoyl)-1,3,4-thiadiazeles; 2-alkvditbio-5-merealito thiadiazoles;
and the like.
The ashless metal deactivators may be used alone or in combination. The ashless metal deactivators are l.~resel-it in the range of about 0 wt % to about 50 'A't %, or from about 0.0005 -,Nt % to about 25 wt %, or from about 0.0025 wt % to about 10 w,t % total weiglit of the gel.

The dengulsifiers iraeliide polyethylene and polypropylene oxide copolymers aBid the like. The demulsifiers may be used alone or in combination. The deiiaa.dsifiers are presetit in the range of about 0 wt 'I/o to about ?Q IArt %, or from about 0.0005 N~v-t % to about 10 dv-t %, or from ab -Lflt 0.001-5 -VNt % to about 2.5 wt %
total weight of the gel.
'I'he lubricity aids include glycerol mono oleate, sorbitan mono oleate and the like. The lubricity additives may be used alone or in con-ibination. The lubricity additives are present in the range of about 0 wt % to about 50 NN-t %, or from about 0.0005 wt % to about 25 -,Nt %, or from ab -Lflt 0.001-5 -wt % to about 10 Nvt % total weight of the gel.
The flow improvers include ethylene vinyl acetate copolymers and the like.
The flow irrll.~?rovers may be used alone or in o,ombiriation. The flow ingprovers are present in the range of about 0-,Nt % to about 50 wt %, or from about 0.0005 wt % to about 25 vvt %, or from about 0.0025 wt % to about 5 vvt % total weight of the gel.
'I'he cloud point depressants include alk.Tvlphenols and derivatives thereof, ethylene vinyl acetate eopolen-iers and the like. The cloud point depressants may be used alone or in combination. The cloud l.?oiut depressatits are l.?resetgt in the rarige of about Q-vNt % to about 50 Nvt %, or from about 0.0005 -VNt % to about 25 NN-t %, or from ab~ut.QQ25% to about 5 wt % total iveight of the gel.
The pour point depressants include alkylphenols and derivatives thereof, ethylene vinyl acetate copolymers and the like. The pour poitit depressatit may be used alone or in combination. 'I'he pour point depressant are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 sv-t %, or from about 0.0025 Nvt % to about Swt % o total weight of the gel.
The seal swell agents include organo sulfur compounds such as thiophene, 3-(deeyloxy)tetralgvdro-1, 1-dioxide, pbtlgalates atid the like. The seal swell agelits may be used alone or in combination. The seal swell agents are preseBit in the range of about 0 ivt ')/o to about 50 wt %, or from about 0.0005 wt % to abotit 25 wt ~'ia, or from about 0.0025 Nvt % to about 5 wt % total weight of the gel.
Optionally, other eoinl.-~oiiel-its can be added to the gel which includes base stock oils, inert carriers, dyes, bacteriostatic agents, solid particulate additives, and the like so long as these components do not have a detrimental effect on the gel.

In otge engbodingetit the inventiotg provides a method for lubricating a mechanical device. Typ. ically the oil-soluble gel is delivered from within an oil filter, but any means by whieh the gel can be brought itgto contact with the lubricant can be used e.g., container/delivery device within the oil pan, or within a fluid by-pass loop.
The gel is positioned within the lubricating system, anywhere the gel will be in contact with the lubricant including, but not limited to, lubricating oil, motor oil, hydra.ulie fluid, transmission driveline fluid, metal workiiig fluid al-ld the like. The gel is positioned anywhere that the circulating lubricant contacts the gel such as full flow of oil, bypass of the oil in the reserN7oir or cognbiriations therein.
The location of the gel in the lubricating system includes, but is tgot limited to, a filter, drain pati, oil bypass loop, canister, housing, reservoir, pockets of a filter, canister in a filter, inesh in a filter, canister in a bypass system, mesh in a bypass system and the like.
One or more locations can contain the gel. Fli.rtber, if more than one gel is used it eal'i be idel-itieal, silnilar and/or a different gel.
In one embodiment, the gel is positioned anywhere in the filter. 'l'he filter is a desirable location to place the gel because the gel and/or spent gel can easily be reiiaoved, and thexg replaced with a new and/or recycled gel.
The gel Bieeds to be in coBitact with the engine oil, in one en-ib dimerit the gel is in contact with the oil in the range of about 100% to about 1% of the oil system, in aBiother en-ibodimeBit the gel is in contact with the oil in the raBige of ab tat 75 % to about 25% of the oil system and in another embodimetgt the gel is in coritaet with the oil in the range of about 50% of the oil system.
The release rate of the additive eoinp nel'its in the gel is detelinined primarily by the gel formulation. The release rate is also dependent on the form of the gel and/or the mode of addition. The gel is positioned in a location desirable for the specified atgd desirable dissolution rate of the specified additives. The gel's farinulatian may be composed of one or more components that selectively dissolve eonipletely or a portioti of the components remain till the end of its service life or combinations thereof.
The gel is added to the lubrication system by any knowl-i method depending on the desired form of the gel, the desired speed of addition, the desired release rate, the desired mode of operatiol'i and/or aiiy of the combinations of the above.
In one embodimeiit the additive coml.~?ositiori is a gel and is added to the lubricating system by means of aii injector pump, or a container in the oil filter. In one embodirneiit the gel is added to the lubraeatiiig system by ngeans of an addition device stieb as an auger system.
In one errgbodirrgel'it the propelties iinl.~arted by the desired additives include dispersancy, antioxidance, corrosion inhibition, wear prevention, seuffing prevention, pitting prevention ineluding micro and macro pitting, frictioii modifying properties including increased and/ r decreased friction coefficients, detergency, viscosity control using viscosity modifiers, faagn control or mixtures thereo In accordance with the present invention, a coxgtrolled release gel is provided for fluid e, rflditioBiirig devices. The present invention of a gel cagi be used in any fluid e,onditioiiing device ixgcluding interrial combustion engines which include mobile and stationatv engines, natural gas engines, marine diesel engines, generators, on highway and/or off highway engines, hydraulic systems, automatic traiismissions, gear boxes which include marlual transmissions and differentials (e.g., front and rear drive axles and industrial speed increasers or reducers), metalworking fluids, puin1.-~s, siisl.~?eiision systems, other lubricated meehaxgieal systengs, industrial lubrieated system and the like.

SPECIFIC EMBODIMENTS
'I'he controlled release of the ashless base-containing gel f rrnulation has been demonstrated along with corresponding improvement in acid neutralization l.?erforniaiiee effieiexgcy.
Gel 1 is formed of the following composition:
Cor~poiient % wt ia) Partly esterified maleic anhydride i styrene copolymer 2.4 %
ib) Noiiyl I)il.-~hel-tel an-iine asheldd antioxidant 10.0%
ii) DA P II3SA / TE1'A ashless dispersant 87.6%
aDeiived from Maleic al-ihydride-styrene copolymer (0.69RSV)/C8-10 AleohoL/C

18 Ale hol,/MeS04H(catalyst) (2.9:0.87:1.7:0.1 l)eqin S1JAQ Oil to 60%, Total Acid Nuniber =__= 23meq K(31-1/g.
b Derived from alykylation of diphenylagnirle with nonene using AIC 12 catalyst, Total Base Number = 156 gneq KC)El/g.
c Derived from 850-1600 Mn high vinylidene polyisobutylene, maleic anhydride and tetraethylene pentamine, Total Base Number = 100 The polynaer and half of the antioxidant are mixed to foma Colraporiellt A.
The dispersaiit and the other half of the antioxidant are inixed to ferBn Component B.
Component B was tlgexg added to Component A with stirring and the resulting mixture heated at about 100C for about 12 hours. The resulting Gel (Gel 1) was used in Example 2 and 3.
ExaMle 2. Controlled Release Base Gel 1Release - Lab '1'est The Gel 1(about 50 g) was loaded into the bottom of a 1-L beaker and about 500 g of Valvoline 10W-30 added. The resulting mixture was heated at about and oil samples were taken at regular interN7als over 13 days and the total base number measured by ASTM Test Method D2896. The results are shoWn in Table 1.
Table I ExaMhle 2 (100% TBN release = 14 TBN added) % Theory Test lioiirs TBN added TBN TBN added 0 0.0% 7.4 0 4 11% 9.0 2.4 7.5 19% 10.1 2.7 24 37% 12.6 5.2 54 55% 15.1 7.7 62 64% 16.4 9.0 80 74% 17.8 10.4 312 94% 20.5 13.1 These resiilts show that coxgtrolled release of ashless base can be achieved using a gel of the composition described herein.
Exa~l.~le 3. Gel I Field Test. Gel 1(about 71 g) was loaded into a cylindrical cul), with about 2 mm holes located on the top face. The container was placed at the crown end of an oil filter of the saine size and fittings as aFrarn PI-13387A oil filter, and itistalled ota a 2002 Pontiac Urarid Prix. The car was then driven under rlerrnal stop-and-go conditions for about 500 miles, with oil san-iples taketl at regtilar itltervals and the total base ntimber analyzed by ASTM
D2896 aild the total acid riugnber analyzed by ATMS method D664A. The results are shown in Table 2.

Table 2 ExaD~iple 3 100% TBN release :::: 2.8 TBN added) Miles 0 100 500 % TBN Release 0 7% 21%
TBN-TAN 5.6 5.8 6.2 TBN added 0 0.2 0.6 These results show that eontrt~lled release of ashless base can be achieved in a vehicle uiider actual driving conditions using a gel of the eoinl.~osition described above.
Example 4. Controlled Release Base Ge12 In another speeifio, eiiabodament, Gel 2 is fomged pursuant to Examl.~?le 1 but with the following components:
Component % 'Alt ial I)A1'IBSAdispersant 84.1%
ib) MSC, esterified polymer a 9.4 ,%
ii) Tri(2-etbylliexyl) borate 6.5%
The polymer and half of the borate are mixed to form Component A. The dispersarit and the other half of the borate are mixed to forr~~~
~oluliolgerit B.
Component B was then added to GognpoBierit A with stirring and the resulting inixtiire heated at 1O0C for 12 h~urs. The resulting Gel (Gel 2) was used in Example S.
Exa~-~le 5. Controlled Release Base Gel 2 Release - Lab Test '1'he Gel 5 (about 50~l) was loaded into the bottom of a] -L beak-er and 500 g fValv line 10W-30 added. The resulting mixture was heated and oil sainples were tak-en at regular intervals over 13 days and the total base ntimber measiired by ASTM Test Method D2896. The results are shown in Table 3.
Table 4 Example 5 (100`%b =__:5.5 TBN added) Test 1-fours 0 24 148 72 96 168 192 % Release 0% 0% 25% 22% 38% 102% 95%
TBN 7.3 7.3 8.7 8.5 9.4 12.9 12.5 TBN added 0 0 1.4 1.2 2.1 5.6 5.2 These results show that controlled release of ashless base eatg be achieved using a gel of the composition described herein.
Example 6. Gel 2 Field Test. Gel 2, (about 71 g) was loaded itito a cyliiidrical c-Lap; with about 2 mm holes located on the top face. The eoiitainer was placed at the crown ei-id of ai-i oil filter of the same size and fittings as aFrain 4967 oil filter, and installed on a 1998 4-cylinder Tov ta Camry. The car was then driven under normal stop-and-go conditions for about 500 rniles, with oil samples takeil at regular intervals and the total base rflum ber analyzed by AST M D4730 and the total acid n-La.rnber analyzed by ATMS method D664A. The results are compared to the same analyses for the car when driven without the gel in the filter (Conil.~?arative Exagnple) and are shown in Table 4.
Table 5ExaMple 6(100% TBN release - 2.8 TBN added) Change in base or acid uBiits Miles 0 500 1000 1500 2000 3000 3500 er 1C~00 nii T13N --- baseline 5.9 6.2 5.5 5.3 4.4 4.0 3.7 -0.73 TAN - baseline 2.4 1.9 2.5 1.9 3.0 2.6 4.3 +0.46 TBN - Gel 3 6.0 5.8 4.5 -0.73 TAN - Uel 3 2.0 1,7 2.1 1.8 +-0,050 These results show that the controlled release ashless gel of the composition described in Exan-iple 5 reduces acid build-up in an engine under actLgal driving conditions.

Example 7. Controlled lkelease Base Gel 3 In another specific embodiment, Gel 3 is fomied of the composition below:
Component % NN't ia) DA PIBSA dispersargt 84.1%
ib) Maleinated OCP d 9.4% i;, ii) Tri(2-etlgyllgexyl) borate 6.5~'i~
d Mitsui Lucant A-5320H

by the mixing proeedtire used for Gel 2, Example 4.

ExatUle 8. Coxgtrolled Release Base Ge13 Release - Lab Test The gel 3 (5 g) was loaded iuto ainetal 2-oz jar cap and placed in the bottong of a 1017-gnL beaker and ab ta.t 50 g of Valvoline 1OW-30 added. The resulting inixture was heated and oil sainples were taken at regular intervals over 13 days and the total base number measured by AS7"M Test Method D2896. The results are shown in Table 5.

Table 6 Ex~LiTle 8 (100~'% release = 8.2 TBN added) Test 14 tars 0 48 72 96 % Release 0% 58% 73% 74%
TBN 7.4 12.2 13.4 13.5 TI3-N added 0 4.8 6.0 6.1 These results show that controlled release of ashless base can be achieved using a gel of the composition described herein.

Example 9. Ash Less Controlled Release Viseosit Modifier Gel (VM ~'~elGe14 is fdriied by the following eomponexgts:

Component % wt ia) DA 1'IBSA dispersant 44%
ib) MSC, esterified polyiiier' 10%
ii) Molybdenum dithioearbamate (Modet)h 45%
ii) Tri(2-etlgyllgexyl) borate' l%

hAkeda Saukuralube 100 friction ngodifier (p'M) 'Liquid Corrosioll Inhibitor The components are mixed per the procedure used for Ge12 in Exan-iple 6.

ExatUle 9. Coxgtrolled Release FM Gel R_elease - Lab Test The gel (5 g) was loaded irito a metal 2-oz jar cap and placed in the bottom of a 100-m-I., beaker and 40 b f Valvoline 10Wm30 added. The resulting mixture was heated arid oil sarnl.~?les were taken at regular intervals over 8 days atgd the 'No Mo measure by inductively e,oupled plasma (lC1') analysis. '1'he results are shown in Table 16. These results show that controlled release of Mo FM gel can be achieved using an ash less FM gel of the composition described irl '1'able 16.

'I'able 7 Example 9 (100% Mo FM release = 0.4146% Mo in oil) Test lIotirs 0 48 72 96 120 144 192 % FM 0% 16% 35% 40% 46% S9 /'~ 75%
Release % Mo in 0% 0.0682E'ib 0.1441% 0.166% 0.1913% 0.2428% 0.3102E'ib oil U;xaMle 10. Ash Less Controlled Dis ersant/Anti xidarlt Gel "I)1S/A~Q Gel) In another specific emboditnerat, an ash less I3IS/AC7 gel is formed of the following component (CBe15):
Corailiotgerit 'NO wt ia) DA PIBSA dispersarit 2.5%
ii) OSP PIBSA disl.~ersai-it 11.0%
ii) C)Sf' PIBSA dispersant 31.0%
ib) MSC, esterified l.~olyiner' 8.5%
ii) Molybdenum dithiocarbamate (Modtc)h 5.0%
ii) Nonyl DPA arfltiaxidanrb 21.0%
ii) 2,6-dit-butylphenolic antioxidatitk 21.0%
ii) hAkeda Sak-.a.raluve 100 friction modifier (FM) 'Liqtjid Corrosioti frahibitor iDerived from 850-1600 Mn high vinylidene polyisobutylene, maleic anhydride and 1~2,6dimtert-hutyl, 4-(3 butylpropanoyl) phenol In another specific embodiment, ari ash less VM gel is formed of the following components (Gel 6):
Cornpotaerit ~'ia aNrt ia) DA PIBSA dispersarit 2.4%
o ib) MSG, esterified polymera 9.6%
ii) E.PL 147e 113.2 %
Group II Mineral Oil (Dil Oil) 74.8%
eh,thvlene-pr~pylene e polymer, MW=105-106.

The EPDl~'1 and the dil oil are niixed and half of the resultiug solution is mixed with dispersant to ferBn C n-iponerflt A. The other half of the EPDM/dil oil solution is mixed with MSC to form Coml.~?onexgt B. Coiiafsorieiit A and B are theri mixed and the resulting gnixha.re heated at 117OC for 12 li -La.rs. The resulting Gel 6 (VM Gel) was used in Exainple 9.

Exam le 11. Controlled Release VM Gel Release - Lab Test The above gel (Gel 6) (about 18g) was loaded into a plastic cylinder 2 inch high and 1 inch in diameter with 18 equally spaced 0.25 inch square openings.
'The loaded gel container was placed in the bottom of a 250-mL beaker aBid about 90 g of Valvoline 1OW-30 oil added. The resultirac, mixture was heated at 100C and oil samples were taken at regular iiitervals over 4 days and the kinematic viscosity ineasured at 1O0C by ASTM Test Method D445 1QQ. The results are shoWn in Table 9. These results show that eoiitrolled release of ashless viscosity modifier can be achieved usiiig a gel of the con-ipositi n described iii Table 7 below.

Table 8Exanaple 10 (100% release =_= 28.3 cSt aclde(l) Test Hours 0 48 72 96 % VM lkelease 0% 20% 32% 39%
Kin Visc~. 10OC, cSt 10.2 15.8 19.1 21.3 A Kirl Visc~. I OOC, cSt 0 4.8 6.0 6.1 Exarnhle 12. Ash Less Controlled Release Friction Modifier Gel (FM Gel) In axgotlger specific embodimetit, ari ash less FM gel is formed from the following cognpalient.
The disfsersarits arid the plieriolie antioxidant are mixed with lialf of the diphenylamine antioxidant to f rni Component A. The MSC and the Saukuralube are inixed with the other half of the diFhenylainine antioxidant to fom-i Component B. Component A was then added to C'omponent B with stirring and the resulting mixture heated at 10OC for 12 hours.
The resiilting Gel (DIS/AO Gel) was ti.sed in Example 13.
ExaMhle 13. Controlled Release DIS/AO Gel Release - Lab Test The gel (5g) was loaded into a metal 2-oz jar cap arid placed in the bottong of a 100-rnL, beaker and 50 g of Valvoline 117W-30 added. The resulting mixture was heated and oil san-iples were taken at regular inteivals over 8 days al-ld the % Mo measure by inductively e,ouFled plasma (ICI') analysis. 'I'he results are shown in Table 8.
'I'hese results show that controlled release of the DIS/AO Gel components can be achieved using an ash less DIS/AO Gel of the composition described in example I2.
Table 9 ExaMFle 14 (100% DISIACI Gel release =17.fl461% Mo in oil) Test Hours 0 120 144 168 192 % Mo Release 0% 0 61% 0 66% 0 76% o 86%
% Mo in Oil 0.0002 o0.0283 o 0.0:305 o 0.0:352 o 0.0:394%

Although only a few embodiments of the present invention have been described above, it should be appreciated that ngatiy modifieatiotis call be made without departing from the spirit and scope of the invention. All such modifications are ixgtended to be itieltjded within the scope of the present in-ven-tiora, which is to be limited only by the following claims:

Claims (10)

1. A lubricant additive gel comprising:
1) a dispersant;

2) an acid selected from the group consisting of an acid formed from a polymer containing acidic groups in the backbone, a polyacidic compound, surfactants with acidic groups in the backbone, emulsifiers with acidic groups in the backbone and mixtures thereof; and

3) optionally lubricant additives;
wherein the gel is substantially free of ash producing components and resulting in a lubricant additive gel that control releases the components into a lubricant wherein the weight ratio of the ashless dispersant to the acid formed from the polymerization is about 0.1 to about 100 and wherein a tan delta value is >= 1.

2. The composition of claim 1 wherein the dispersant is selected from the group consisting of mannich dispersants, polymeric dispersants, carboxylic dispersants, amine dispersants, and combinations thereof and wherein the dispersant is substantially free of forming ash to completely free of forming ash; and wherein the acid is selected from the group consisting of polymers derived from the polymerization of styrene and maleic anhydride, polymers derived from acrylates, polymers derived from acrylic acid, polymers derived from acrylic acid esters, polymers derived from methacrylic acid, polymers derived from methacrylic acid esters, polymers derived from high molecular weight (CN
wherein n <=12) esters and acids, esterified maleic anhydride styrene copolymers, polymers derived from esterified ethylene diene monomer copolymers, a polyacidic compound, surfactants with acidic groups in the backbone, emulsifiers with acidic groups in the backbone and mixtures thereof.

3. The composition of claim 2 wherein the dispersant is a polyisobutenyl succinimide dispersant and wherein the acid is selected from the group consisting of an acid formed from the polymerization of styrene and maleic anhydride; a copolymer that is partially esterified with one or more C6 to C32 alcohol or mixture of alcohols, and mixtures thereof.

4. The composition of claim 1 wherein the additive gel further contains at least one desired additive selected from the group consisting of viscosity modifer(s), friction modifier(s), detergent(s), cloud point depressant(s), pour point depressant(s), demulsifier(s), flow improver(s), anti static agent(s), dispersant(s), antioxidant(s), antifoam(s), corrosion/rust inhibitor(s), extreme pressure/antiwear agent(s), seal swell agent(s), lubricity acid(s), antimisting agent(s), and mixtures thereof, and wherein the additive gel is substantially free of ash producing components, and wherein at least one of the desired additive(s) is control released over time into a lubricant when the gel is in contact with the lubricant.

5. The composition of claim 1 wherein other components can be added to the gel comprising base stock oils, inert carriers, dyes, bacteriostatic agents, solid particulate additives or combinations thereof.

6. A process for lubricating mechanical devices comprising a) supplying one or more lubricant gels to a lubricant and b) contacting the lubricant with an additive gel wherein the lubricant gel comprises 1) a dispersant; 2) an acid selected from the group consisting of an acid formed from a polymer containing, acidic groups in the backbone, a polyacidic compound, surfactants with acidic groups in the backbone, emulsifiers with acidic groups in the backbone and mixtures thereof;
and 3) optionally lubricant additives resulting, in a controlled release of additives into a lubricant substantially free of the addition of ash into the lubricant wherein the use of the additive gel is completely free of the production of ash.

7. The process of claim 6 wherein the release rate of the additive components from the gel is determined by the gel formulation and wherein the gel formulation comprises one or more additives that selectively dissolve completely or partially into the lubricant over time.

8. The process of claim 6 wherein the controlled release gel is provided for lubricant conditioning devices selected from the group consisting of internal combustion engines, mobile combustion engines, stationary engines, natural gas engines, marine diesel engines, generators, on high-way engines, off-high-way engines, hydraulic, systems, automatic transmissions, gear boxes, gears, manual transmissions, differentials, metalworking fluids, axles, pumps, suspension systems, industrial lubricated systems and combinations thereof.

9. An oil filter for an engine comprising a housing, a filter for removing particulate matter from the oil passing through the filter, an oil and a lubricant additive gel comprising 1) an ashless dispersant; 2) an acid selected from the group consisting of an acid formed from a polymer containing acidic groups in the backbone, a polyacidic compound, surfactants with acidic groups in the backbone, emulsifiers with acidic groups in the backbone and mixtures thereof; and 3) optionally lubricant additives and resulting in a lubricant additive gel that control releases the components into the lubricant of the engine without the addition of ash.

10. A lubricated system comprising a lubricant, an ashless lubricant additive gel comprising 1) an ashless dispersant; 2) an acid selected from the group consisting of an acid formed from a polymer containing acidic groups in the backbone, a polyacidic compound, surfactants with acidic groups in the backbone, emulsifiers with acidic groups in the backbone and mixtures thereof, and 3) optionally lubricant additives resulting in a lubricant additive gel substantially free of ash producing components that control releases a desirable additive into the lubricant.