CA1271592A - Lactone modified polymeric amines useful as oil soluble dispersant additives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Hydroxyl terminated polymeric C5-C9 lactone adducts are made by reacting a C5-C9 lactone with the reaction product of a C2 - C10 olefin polymer or a halogenated derivative thereof having a number average molecular weight of 300 to about 10,000, with an amine containing from 2 to 60 total carbon atoms and from 1 to 12 nitrogen atoms. The resulting adducts are useful per se as oil soluble dispersant additives. They are also useful in fuel and lubricating oil compositions, as well as in concentrates and additive packages.

Description

~:71592 aACKGROUND OF THE INVENTION

FIELD OF THE INvE~TION

This invention relates to oil sol~ble hydroxyl terminated additives useful in fuel and lubricating oil compositions, including concentrates containing said additives, and methods for their manufacture and use. The hydroxyl terminated additives are poly~C5-Cg lactone) adducts which have been prepared by reacting a C5-Cg lactone with a polyalkylene amine having a number average molecular weight of from about 300 to about 10,000. The hydroxyl terminated products are effective as dispersants and HD
additives.

.

~L~'7~

PRIOR ART

Polyalkylene amines are well known lubricating additives. These agents act to keep sludge and varnish dispersed in engine oils and have been successful commercially.
It is also known that polymers of 6 to 10 membered lactones such as valerolactone or E-caprolactone can be prepared by reacting the lactone monomer with a hydroxyl or amine initiator. When reacting E-caprolactone, for example, the polymerization reaction may be illustrated by the following equations:

O
Ro~ R~oc~(c~)s~

R'NH2 ~ R t~H~c(c~5~ 2 The reactions are known to be catalyzed by various esterification catalysts such as stannous octanoate, and a variety of different molecular weight products are feasible depending upon the ratio of lactone to initiator. Molecular weights on the order of from a few hundred up to about 5,000 are .

5~

reproducably achievable.

Caprolactone can also be polymerized to a very high molecular weight, e.g., on the order of 100,000 or more. Typically such hi~h molecular weight polymers do not employ initiators and preservation of functionality is not a requirement.
It is also known to react a lactone such as E-caprolactone with a diamine wherein one of the amine groups is a tertiary amine and the other amine group is a primary or secondary amine to form a polymer having a terminal hydroxyl group and a terminal tertiary amine group. The polymeric products are useful for neutralizing polymeric acids.
It has now been found that improved oil soluble dispersant additives, useful in fuel and lubricating oil compositions, including concentrates containing the additives, can be prepared by reacting a 6 to 10 membered lactone with a polyalkylene amine, such as a polyisobutylene amine ! having a number average molecular weight on the order of about 300 to about 10,000.
While there are a number of prior art disclosures relating to adducts of lactones and polyamines, to polyalkenyl amine lubricating additives and to lactone polymerization reactions, in general, little or no prior art of direct pertinence -appears to have surfaced in regard to the present dispersants. Exemplary of the patent literature which relates to lactone polymerization processes and/or to oil soluble dispersant additives are the following U.S. Paten~s: U.S. 4,362,635 discloses synthetic ester oils which are esterification products of monoalcohols and dicarboxylic acids or of polyhydric alcohols and monocarboxylic acids respectively, containing 5 to 4S% by weight of units of hydroxycar~oxylic acids obtained from aliphatic alcohols, aliphatic, ~ycloaliphatic or aromatic carboxylic acids, and lactones of aliphatic Cs-C12 hydrocar~oxylic acids. The synthetic ester oils are suitable for the preparation of lubricants and lubricant compositions.
U.S. Patent 2,890,2~8 discloses a process for polymerizing la~tones to form lactone polyesters that are useful as plasticizers.
U.S. Patent 2,898,301 discloses alkyl hydroxyamide lubricating fluid additives derived from monoamines, including polymerized fatty acid amines, and gamma-lactones such as gamma-butyrolactane.
U.s: Patent 4,168,278 discloses adducts o f primary amines, especially hydroxy amines, and oaprolactam. The adducts are useful as depolymerization inhibitors. A similar disclosure is contained in U.S. Patent 3,R92,806, which relates to polycaprolactam adducts that are formed by reaction between an N-alkyl alkylene diamine and caprolactam.
The adducts are useful as antimicrobial agents.

U.S. Patent 3,832,367 discloses alkoxylated hydroxyamide detergen~s which are prepared ~y reacting a beta, gamma, delta or epsilon type C8-C40 lactone with an alkanolamide to form an intermediate hydroxyalkanolamide, and ~hen reacting the intermediate hydroxyalkanolamide with an alkylene oxide.

U.S. Patent 3,373,112 discloses lubricant additives derived from polyalk~lene polyamines, including polyisobutylene polyamines and non-l~ctone acylating agents.

~L27159~

U.S. Patent 3,062~631 discloses condensation products of beta-lactones, particularly C3-C6 beta-lactones, and amines as corrosion inhibiting additives.
U.S. Patent 3,169,945 discloses the preparation of lactone polyesters which are use~ul as plasticizers and as interme~iates for preparing elastomers and foams. The polyesters can be prepared by reacting a lactone such as E-caprolactone with an initiator such as an alcohol, ~nine or amino alcohol.
A similar disclosure is contained in U.S. Patent 3,284,417. This latter patent also discloses the use of a stannous octanoate polymerization catalyst.
U.S. Patent 4,379,914 and its continuation-in-part (U.S. Patent 4,463,168) disclose the preparation of polycaprolactone polymers by reacting E-,caprolactone with a diamine wherein one of the amine groups of the diamine is a tertiary amine and the other is a primary or secondary amine. The polycaprolactone polymers are disclosed as being useful for neutralizing certain sulfonic acid-containing polymers to form amine-neutralized, sulfonated derivatives which can be combined with an alkyl benzene sulfonic acid to give a surfactant which contains ester groups, hydroxyl groups and amine-neutralized sulfonate groups.
U.S. Patent 3,436,463 discloses N-substituted gamma hydroxycarboxylic acid amides which are useful as nematocides and insecticide~. The compounds of this patent are prepared by reacting an organic primary amine with a lactone such as gamma-butyrolactone or gamma-valerolactone.
U.S. Patent 4,397,750 teaches the preparation of hydroxy substituted pyrrolidone esters from butyrolactones and polyhydroxyamines. Corresponding 59~

hydroxyamide side-products are also disclosed. The disclosed esters are useful as additives for lubricants and fuels.
U.S. Patent 3,493,568 discloses diol amides prepared from caprolactone and a monohydroxy amino alcohol. The diol amides can be cyclodehydrated to form oxazolines and oxazines wh:Lch can be polymerized to yield crosslinked polymeric structures.
U.S. Patent 4,512,903 discloses lubricant compositions containing amides of lactones, such as beta-propiolactone or gamma-bul:yrolactone, and fatty amines.
U.S. Patent 4,234,435 discloses as oil additives, polyalkylene substituted dicarboxylic acids derived from poly-alkylenes having a Mn of 1300 to 5000 and containing at least 1.3 dicarboxylic acid groups per polyalkylene. In Example 34 of that patent, a polyisobutene-substituted succinic acylating agent is reacted with caprolactam in the presence of mineral oil and sodium hydroxide. That patent also discloses lubricant additives derived from high molecular weight hydrocarbyl amines. The hydrocarbyl amines can prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or an amine.
U.S. Paten~ 3,38i,022 relates to ester derivatives of substantially saturated polymerized olefin-substituted succinic acid wherein the polymerized olefin substitutuent contains at least about 50 aliphatic carbon atoms and has a molecular weight of abou~ 700 to 5,000. The esters include the acidic esters, diesters, and metal salt esters wherein the ester moiety is derived from monohydric and polyhydric alcohols, phenols and naphthols. The ester derivatives are useful as additives in 12~
, lubricating compositions, fuels, hydrocarbon oils and power transmission fluids. A related patent, i.e., U.SO Patent ~o. 3,522,179, discloses lubricating compositions comprising a major amount of a lubricating oil and a minor proportion of an ester derivative of a hydrocarbon-substituted succinic acid sufficient to improve the detergency of the lubricating composition. The ester derivatives are similar to those described in U.S. Patent 3,381,022 and contain at least about 50 aliphatic carbon atoms.
The hydrocarbon substituent may be derived from a polymerized lower monoolefin having a molecular weight of from about 700 to about 5,000.

Additional exemplary prior art disclosures, include U.S. Patents 3,025,323;
4,062,786; 4,086,294; 4,247,671; 4,2~1,871;
4,292,184; and 4,448,905.

SUMMARY OF THE INVENTION

Despite the efficacy of prior art dispersant and oleaginous compositions, there is a need for more efficient and less costly dispersants which can either perform better, or perform well at lower dispersant levels. Accordingly, it i5 a principal object of this invention to pro~ide novel lactone adduct based dispersznts which are effec~ive, and readily prepared under typical dispersan~
manu~acturing conditions.
~nother object is to provide a novel class of `~

59~

poly (C5-Cg lactone) adduct dispersan~s.
Another object is to provide a process for preparing efficient dispersants by reacting a Cs-Cg lactone with a polyalkylene amine having a number average molecular weight of from about 300 to about 10, 000.

A further object is to provide lubricant compositions and concentrates containing the novel C5-Cg lactone based dispersant:s of this invention.
Yet another object is to provide a novel class of oil soluble hydroxyl te!rminated adducts from polyalkylene amines and C5-Cg lactones, as well as lubricant compositions and concentrates containing such adducts.
Yet another object is to provide metal ~omplexes and o~her post-treated derivatives, e.g., borated derivatives, of the novel C5-Cg lactone based dispersan~s of this inention, a~ well as lubricant compositions and concentrates containing such adducts.
The manner in which these and other objects can be achieved will be apparent from the detailed description of the invention which appears hereinbelow.
In one aspect of ~hi~, inven~ion, one or more of the above objects can be achieved by initiating the polymerization of a C5-Cg lactone by means of an amino function contained in a polyalkylene amine, such as polyisobutylene amine, wherein the poLyalXylene amine has a number average molecular weight of about 300 to about 10,000.
In another ~spect, one or more of the objects of this invention can be achieved by heating a Cs-Cg lactone such as E-caprolactone at a temperature of at ~7~
g least about 50C, and preferably from about 90C to about 180C with a polyalkylene amine initiator wherein the polyalkylene is characterized by a number average molecular weight of about 700-5,000; and, in a further aspect, one or more objects of this invention are achieved by providing poly (Cs-Cg lactone) adducts produced by such a process.

One or more additional objects of this invention are achieved by reacting a molar excess of E-caprolactone with a polyisobutylene amine to form a hydroxyl terminated dispersant adduct which contains an amida group and a repeating sequence of ester groups between the amide group and the terminal hydroxy group; one or more additional objects of this invention can be illustrated in connection with the ~eaction between E-caprolactone and a polyisobutenyl amine initiator having available primary amine functionality as follows:

m ~ + PIB-N~, r Pla -~ ~ C (~.)5 0 ~ 3 where m has an average value of from about 0.2 to about 100, preferably from about 1 to about 20, most preferably from 1 to about 5, and PIB represents polyisobutylene having a number average molecular --` 10 weight of from about 700 to about 5,000. The above polymerization can be conducted with or without a catalyst. However, it is preferred to employ a catalyst such as stannous octanoate in an amount of from about 50 to about 10,000 parts by weight of catalyst per one million parts by weight of total reaction mixture.

The novel poly(CS-Cg lactone) adducts of this invention are useful per se as an additive, e.g., a dispersant additive, for example, in the same manner as disclosed in U.S. Patent 3,219,666 where prlor art derivatives of polyalkenyl succinic acids and nitrogen compound~ are used as dispersant/detergents in lubricants, especially lubricants intended for use in the crankcase of internal combustion engines, gears, and power transmitting units. Accordlngly, one or more objects of the invention are achieved by providing lubricating oil compositions, e.g., automatic transmission fluids, heavy duty oils suitable for use in the crankcases of gasoline and diesel engines, etc.
containing the novel poly(C5-C9 lactone) adducts of this invention. Such lubricating oil compositions may contain additional additives such as viscosity index improvers, antioxidants, corrosion inhibitors, detergents, pour point depressants, antiwear agents, etc.
Still further objects are achieved by producing concentrate conpositions comprising from about 20 to about 80 wt % of a normally liquid, substantially inert, organic solvent/diluent, e.g., mineral lubricating oil, or other suitable solvent diluent and from about 20 to about 80 wt % of a (Cs-Cg lactone) adduct, as mentioned above and described in more de~ail hereinafter.

THE POLYALKYLENE AMINE

The polyalkylene amines used in the invention include a lon~ ohain hydrocarbon, generally a polyolefin~ substituted with 1 to about 12, preferably 1 to about 5 amino groups, preferably primary amino groups, per mole of polyolefin.

The preferred polyolefins are polymers comprising a major molar amount of C2 to C1o~ e.g., C2 to Cs monoolefin. Such olefins include ethylene, propylene, butylene, pentene, octene-1, styrene, etc.
The polymers can be homopolymers such as polyisobutylene, as well as copolymers of two or more of such olefins such as copolymers of: ethylene and propylene; butylene and isobutylene; propylene and isobitylene; etc. Other copol~mers include those in which a minor molar amount of the copolymer monomers, e.g., a copolymer of iso~utylene and butadiene; or a copolymer o~ ethylene, propylene and 1,4-hexadiene;
etc.
In some cases, the olefin polymer may be completely saturated, for example, an ethylene~
propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular w~ight .
The olefin pol~mers usually will have a number average molecular weight (~n) within the range of about 300 and about 10,000, more usually between about 700 and about 5,000. Particularly useful olefin polymers have a n~er average molecular weight within the range of about 900 and about 2,500 wi~h approximately one terminal double bond per polymer . .,. ~

chain. An especially useful starting material for a highly potent dispersant additive made in accordance with this invention is polyisobutylene. The number average molecular weight for such polymers can be determined by several known technigues. A convenient method for such determination is by gel permeation chromatography (GPC~ which additionally provides molecular weight distribution information. See W.W. Yau, J.J. Kirkl nd and D.D. Ely, "Modern Size Exclusion Liquid Chromatography", ~ohn Wiley and Sons, New York, New York 1979.
Processes for substituting the olefin polymer with amino groups are known in the ar~. For example, the olefin polymer can be first halogenated, for example, chlorinated or brominated to about 1 to 8, preferably 3 to 7 wt.% chlorine or bromine, based on the weight of polymer, by passing the chlorine or bromine through the polyolefin at a temperature of 100 to 250C, e.g., 140 to 220C for about 0.5 to 10 hours preferably 1 to 7 hours. The halogenated polymer then may be reacted with sufficient alkyl amine at 100 to 150C, usually about 140 to 180C, for about 0.5 to 10, e.g., 3 to 8 hours, and neutralized with an alkaline hydroxide so that the product obtained will contain about 1 to 10, preferably 1 to 5 e.g., 2 moles of the primary amine per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patent 3,373,112 and others.
Alternatively, the olefin polymer, and the alkyl amine can be mixed and heated while adding chlorine to the ho~ material.
By the use of halogen, about 50 to 80 wt.~ of the polyolefin, e.g., polyisobutylene normally will react with the alkyl amine material. Upon carrying out a thermal reaction without the use of halogen or a catalyst, then u~ually only about 5 to 10 wt.~ of the polyisobutylene will react. Chlorination helps increase the reactivity.
Suitable amines for reaction with the polyolefin or halogenated polyolefin include mcnoamines and polyamines of about 2 to 60, e.g., 3 to 20, most preferably 3 to 10 total carbon atoms in the molecule.
These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other non-interfering groups, e.g., alkoxy groups, amide groups, nitrile groups, imidazoline groups, and the like. Preferxed amines are aliphatic saturated amines, including those of the general formula:

~ R - N ---(CH2)s ~ N--(CH2)s ~ R' where R and R' are independently selected from the group consisting of hydrogen, C1 to C25 straight or branched chain alkyl radicals, C1 to C12 alkoxy C2 to C6 alkylene radicals, and C1 to C12 alkylamino C2 to C6 alkylene radicals; each s is the same or a different number of from 2 to 6, preferably 2 to 4; and t is a number of from 0 to 10, preferably 2 to 7. If t=0, then R or R' must be H such that there are at least 2 of either primary or secondary amino groups.
Non-limiting examples of suitable amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane;
polyethylene amines such as diethylene ~riamine;
tri~thylene tetramine; tetraethylene pe~tamine;
polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene) triamine; di-(1,3-propylene) triamine;
N,N-dimethyl-1,3-diamino propane; N,N-di-(2-aminoethyl) ethylene diamine; N-dodecyl-1,3-propane diamine; di-, 7~;9~

1~
and tri-tallow amines; amino morpholines such as N-(3-aminopropyl) morpholine; etc.
Other useful æmine com~ounds include:
alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic compounds such as imidazolines, morpholines, and N-aminolakyl piperazines of the general formula:

~ CH2 - CH2 ~
NH2 ~ (CH2)p - N \ / N - G

wherein G is independently selected from the group consisting of hydrogen and omega-(nontertiary)-aminoalkylene radicals of from 1 to 3 carbon atoms, and p is an integer of from 1 to 4. Non-limiting examples of such amines include 2-pentadecyl imidazoline, N-(2-aminoethyl) piperazine, etc.
Commercial mixtures of amine compounds advant~geously may be used. For example, one process for preparing al~ylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenete~ramine, tetraethylene pe~tamine and isomeric piperazines.
low cost mixture of polylethyleneamLne) compounds averaging about S to 7 nitrogen atoms per molecule are available commercially under trade marks such as "Polyamine ~", "Polyamine 400:, "Dow Polyamine E-100", etc.
Useful amines also include polyoxalkylene polyami~es such as those of the ormu1as:

~ , , .

1~7~

NH2--~kylene ~ O-alkylene ~ NH2 IrI

where m has a value of about 3 to 70 and preferably 10 to 3 5; and R ~ alkylene ~ O-al~cylene ~ NH2 ~ a IV

where n has a value of a~out 1 to 40 with the prov.ision that the sum of all the n ' s is from about 3 to about 70 and preferably from about 6 to about 35, R is a substituted saturated hydrocarbon radical of up to 10 carbon atoms, whecein the number of substituents on the R group is ~epresented by the value of na", which is a nu~ber from 3 to 6.
The alkylene groups in either formula ( III or IV) may be straight or branched chain containing about

- 2 to 7, and pref erably about 2 to 4 carbon a~oms .
The abo~e polyoxyalkylene polyamines, prefera~ly polyoxyalkylene diamines and polyoxyalkyLene triamines, ma,y have average molecular weights ranging from about 200 to 4,000 and pref~rably from about 400 to about 2,000. The preferred polyoxyalkylene include the polyoxyethylene and polyoxypropylene diamines and the pol~oxypropylene triamines. The polyoxyalkylene polyamines are conunercially available and may be obtained, for exa~ple, from the Jefferson Chemical Company, Inc. under the trade marks "Jefamines D-230, D-400, D-lOOG, D-2000, T-403", etc.

LAC~ONE CAPPING OF THE POLY~IENE AMINE

In a~ aspect of invention, the novel poly ~ Cs-Cg lactone ) a~:lducts are prepared by polymerizi~g a iactone using ae lease ~ne residual amine functionality ',~
.. . .

.

~L~"7159 on an amine substituted lon~ chain hydrocarbon as the ring opening and polymerization initiator.
Useful lactone compounds for this process include lactones having at least five carbon atoms in the lactone ring, e.g. 5 to 9 carbon atoms. The lactones may be substituted or u~substituted and the substituents, if any, may comprise, for example, alkyl, aryl, aralkyl, cycloalkyl, alkoxy or other groups which would not interfere with the ring opening reaction and adduct formation. The preferred lactones have no more than two substituent groups, and the more preferred lactones are unsubstituted.
Non-limiting examples of the useful lactone include delta-valerolactone, methyl-delta-valerolactone, E-caprolactone, methyl-E-caprolactone, dimethyl-E-caprolactone, methoxy-E-caprolactone, cyclohexyl-E-caprolacton~, methylbenzyl-E-caprolactone, caprylolactone, methyl~caprylolactone, and the like, with E-caprolactone being particularly preferred.
The ring opening polymerization of the lactone by reaction with the amine substituted long chain hydrocarbon material may be carried out, with or without a catalyst, simply by heating a mixture of the lactone and material in a reaction vessel iA the absence of a solvent at a temperature of from about 30C to about ~00C, more preferably at a temperature of about 75C to abou~ 180C, and most preferably about 90C to about 160C,for a sufficient period of time ~o effe~t polymerization. Optionally, a solvent for ~he monomer and/or polymer can be employed to control viscosity and/or reaction rates.
In one preferred embodiment of the invention, the C5-Cg lactone is reacted with a polyisobutylene amine which has been prepared by reac~ing a polyisobutylene with an alkyl amine such as 1,3-~2 7~ ~9 " 17 diaminopropane, followed b~ neutralization with analkali metal hydroxide, such as sodium hydroxide or potassium hydroxide. This reaction can be.depicted by the following equation:
o ~C,~ ~I O
PIB- ~2 ~ ~ PIB- N~ o~H

where PIB represents polyisobutylene having a number average molecular weight of from about 700 to about 5,000, m is a number which has an average value of from about 0.2 to about 100, preferably from 1 to 20, and z is a number from 4 to 8.
Catalysts useful in the promotion of the above-identified reac~ion are selected from the group consisting of stannous octanoate, stannous hexanoate, stannous oxalate, tetrabutyl titanate, a variety of metal organic based catalysts, acid catalysts and amine catalysts, as described on page 266, and forward in a book chapter authored by R. D. Lundberg and E. F. Cox entitled, "Kinetics and Mechanisms of Polymerization:
Ring Opening Polymerization"; edited by Frisch and Reegen, published by Marcel Dekker in 1969, wherein stannous octanoate is an especially preferred catalyst.
The catalyst is added to the reaction mixture at a concentration level which is effective to ensure complete reaction of the lactone and polyisobutylene 7~L592 amine within about 3 to about 7 hours. Generally speaking, the catalyst is added to the reaction mixture at a concen~ration level of about 50 to about 10,000 parts of catalyst per one million parts by weight of total reaction mixture.
When initiating the polymerization of the lactone monomer under the conditions described herein, the lactone will react selectively first with primary amino groups present in the in:itiator molecule and form a polymer adduct containing a Lactone ester group and a terminal hydroxyl group. In the absence of a catalyst, any excess lactone monomer will either react with a secondary amino group present in the initiator molecule or with the hydroxyl group formed via the reaction of the lactone with the primary amino group. In the presence of a catalyst, such as stannous octanoate, it ,is believed that the lactone preferably will react somewhat more rapidly with the tenminal hydroxyl group than with a secondary amino group thus producing a polylactone estPr adduct.
If the stoichiometry of the polyalkylPne amine initiator is such that very few primary amino groups are available, secondary amino groups will be converted to polylactone adducts. The preference towards reaction with primary amino groups results in an added benefit in those applications where the presence of primary amino groups is considered to be - deleterious to performance (such as in diesel dispersancy). In such cases, the present invention provides a means of replacing the deleterious amine group with an amide function and a desirable hydroxyl group.
In the reaction shown above, the average value of m or the degree of polymerization (DPJ of the lactone monomer may vary depending upon the intended application. At DP's of much greater than abou~ 10 the polylactone adducts can exhibit crystallinity; a characteris~ic which is undesirable in an oil soluble dispersant due to the consequent high viscosity, or even solid, oil products which can be obtained.
However, at lower DP's, oil soluble adducts possessing low viscosity and desirable sludge and varnish inhibition characteristics are obtained. Accordingly, regardless of the identity of the lactone and amine substituted long chain hydrocarbon ma~erial, ~he value of m, or the average degrele of polymerization (DP) should be between about 0.2 and about 100, more preferably between about 1 and about 50, and most preferably between about 1 and about 20. For dispersant uses, a DP of about 1 to about 5 is particularly preferred.
Further aspects of the present invention reside in the formation of metal complexes and other post-treatment derivatives, e.g., borated derivatives~
of the novel additives prepared in accordance with this invention. Suitable metal complexes may be formed in accordance with known techniques of employing a reactive metal ion species during or after the formation of the present C5-Cg lactone derived dispersant materials. Complex-forming metal reactants include the nitrates, thiocyanates, halides, carboxylates, phospha~es, thio-phosphates, sulfa~es, and borates of transition metals such as iron, cobalt, nickel, copper, chromium, manganese, molybdenum, tungsten, ruthenium, palladium, platinum, cadmium, lead, silver, mercury, antimony and the like. Prior art disclosures of these complexing reactions may be found in U.S. Patents 3,306,908 and Re. 26,433.
Post-treatment compositions include reacting the novel additives of the present invention with one or more post-reacting reagents, usually selected from the group consisting of boron oxicle, boron oxide hydrate~ boron halides, boron acids, sulÇur, sulfur chlorides, phosphorous sulfides and oxides, carboxylic acid or anhydride acylating agents, epoxides and episulfides and acrylonitriles. The reaction of such post-treating agents with the novel additives of this invention is carried out using procedures known in the art. For example, boration may be accomplished in accordance with the teachings of U.S. Patent 3,254,025 by treating the C5-Cg lactone derived additive compound with a boron oxide, halide, ~ster or acid. Treatment may be carried out by addin~ about 1-3 wt.% of the boron compound, preferably boric acid, and heating and stirring the reaction mixture at about 135C,to 165C
for 1 to S hours followed by nitrogen stripping and filtration, if desired. Mineral oil or inert organic solvents facilitate the process.

THE COMPOSITIONS

The lactone derived additives of the present invention have been found to possess very good dispersant properties as measured herein in a wide variety of environments.
Accordingly, the lactone derived adducts are used by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils.
When the dispersants of this invention are used in normally liq~id petrol~um fuels such as middle distillates boiling frnm about 150 ~o 800F., including kerose~e, diesel fuels, home heating fuel oil, jet fuels, etc., a concentration of the additive in the fuel in the range of typically from about 0.001 to abou~ 0.5, and preferably 0.001 to about 0.1 weight ~1 percent, based on the total weight of the composition, will usually be employed.
The lactone derived dispersants find their primary utility in lubricating oil compositions which employ a base oil in which the additives are dissolved or dispersed.
Such base oils may be natural or synthetic although the natural base oils will derive a greater benefit.
Thus, base oils suitable for use in preparing lubricating compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like. Advantageous results are also achieved by employing the dispersant additives of the present invention in base oils conventionally employed in and/or adapted for use as pow~r transmitting fluids such as automa~ic transmission fluids, tractox fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids,power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additives of the present invention.
Thus, the additives of the present inv~ntion may be suitably incorporated into synthetic base oils such as alkyl esters of dicarboxylic acids, polyglycols and alcohols; polyalphaolefins, alkyl benæenes, organic esters of phosphoric acids, polysilicone oils, etc.
Natural base oils include mineral lubricating oils which may vary widely as to their crude source, e.g., whether paraffinic, naphthenic, mixed, paraffinic-naphthenic, and the like; as well as ~o ~L27 their foxmation, e.g., distillation range, straight run or cracked, hydrofined, solvent extracted and the like.
More specifically, the natural lubricating oil base stocks which can be used in the compositions of this invention may be ~traight mineral lubricating oil or distillates derived from paraffinic, naphthenic, asphaltic, or mixed base crudes, or, if desired, various blends oils may be employed as well as residuals, particularly those from which asphaltic constituents have been removed. The oils may be refined by conventional methods usin~ acid, alkali, and/or clay or other agents such as aluminum chloride, or they may be extracted oils produced, for example, by solvent extrac~ion with solvents of the type of phenol, sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene, crotonaldehyde, etc.
The lubricating oil base stock conveniently has a viscosity of typically about 2.5 to about 12, and preferably about 2.5 to a~out 9 cs. at 100C.
Thus, the lactone derived additives of the present invention can be employed in a lubricating oil composition which comprises lubricating oil, typically in a major amount, and the dispersant additive, typically in a minor amount, which is effective to impart enhanced dispersancy, relative ~o the absence of the additive. Addi~ional conventional additives selected to me2t the particular requirements of a selected type of lubricating oil composition can be included as desired.
The dispersants of this invention are oil-soluble, dissolvable in oil with the aid of a suitable solvent, or are stably dispersible materials~ Oil-soluble, dissolvable, or stably dispersible as that terminology is used herein does not necessarily indicate that the materials are soluble, dissolvable, 27~S~;~

miscible, or capable of being suspended in oil in all proportions. It does mean, however, that the dispersant additives, for instance, are soluble or stably dispersible in oil to an extent su~ficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other aclditives may also permit incorporation of higher levels of a particular dispersant, if desired.
Accordingly, while! any effective amount of the dispersant additives can be incorporated into the lubricating oil composition, it is contemplated that such effective amount be sufficient to provide said lube oil composition with an amount of the additive of typically from about 0.10 to about 15 e.gO, 0.1 to 10, and preferably from about 0.1 to about 7 wt.%, based on the weight of said composition~
The dispersant additives of the present invention can be incorporated into the lubricating oil in any convenien~ way. Thus, they can be added directly to the oil by dispersing, or dissolving the same in the oil at the desired level of concentration typically with the aid of a suitable solvent such as toluene, or tetrahydrofuran. Such blending can occur at room temperature or elevated temperatures.
Alternatively, the dispersant additives may be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then blending the concentrate with lubricating oil base stock to obtain the final formulation. Concentrates will typically contain from about 20 to about 60 wt.%, by weight dispersant additive, and typically from about 80 to about 20%, preferably from about 60 to about 20% by weight, base oil, based on the concentrate weight.
The lubricating oil base s~ock for the . 12~5g~

dispersant additives of the present invention typically is adapted to perform a seLected function by the incorporation of additives therein to form lubricating oil compositions (i.e., formulations).
Representative additives typically present in such formulations include viscosit~ modifiers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants, anti-foaming agen~s, anti-wear agents, pour point depressants, detergents, rust inhibitors and the like.
Viscosity modifiers impart high and low temp~rature operability to the lubricating oil and permit it to remain she~ar stable at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures.
Viscosity modifiers are generally high molecular wei~ht hydrocarbon polymers inoluding . polyesters. The viscosity modifiers may also be derivatized to include other properties or functions, such as the ~ddition of dispersancy properties.
These oil soluble viscosity modifying polymers will generally have number average molecular weights of from 103 to 106, preferably 104 to 106, e.g., 20,000 to 250,000, as determined by gel permeation chromatography or membrane osmometry.
Representative examples of suitable viscosity modifiers are any of the types known to the art including polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and vinyl compound, interpolymers of styrene and acrylic esters, and styrene/isoprene copolymers.
Corrosion inhi~itors, also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricating oil composition. Illustrative of corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfuri~ed hydro-carbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide. Phospho-sulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C2 to C6 olefin polymer such as polyisobutylene, with f~om 5 to 30 wt.~ of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in the range of 150 to 600F.
Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner taught in U.S. Patent No. 1,969,324.
Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces, and by viscosity growth. Such oxidation inhibitors include alkaline earth metal salts of alkylphenolthioesters having preferably Cs to C12 alkyl side chains, e.g., calcium nonylphenol sulfide, barium t-octylphenyl sulfide, dioctylphenyl-amine, phenylalphanaphthylamine, phosphosulfurized or sulfurized hydrocarbons, etc.
Friction modifiers serve to impart the proper friction characteristics to lubricatin~ oil compositions such as automatic transmission fluids.
Representative examples o~ suitable friction modifiers are found in U.S. Patent No. 3,933,659 which discloses fatty acid esters and amides; U.S. Patent No .
4 ,176, 074 which describes molybdenum complexes of polyisobutyenyl succinic anhydride-amino alkanols; U.S.
Paten~ No. 4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S. Patent No. 3,779,928 which discloses alkane phosphonic acid salts; U. S. Patent NoO 3,778,375 which discioses reaction products of a phosphona~e with an oleamide; U. S~ Patent No.

3,852,205 which discloses S-carboxyalkylene hydro-carbyl succinimide, S-car~o~ralkylene hydrocarbyl succinamic acid and mixtures thereof; U. SO Patent No.
3,879,306 which discloses N-(hydroxyalkyl) alkenyl succinamic acids or succinLmides; U. S. Patent No.
3,932,290 which discloses reac:tion products of di-(lower alkyl) phosphites and epoxides; and U. S. Patent No. 4,028,258 which discloses the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl succinimides. The most ~ preferred friction modifiers are succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis alkanols such as described in U. S. Patent No. 4,344,853.
Dispersants maintain oil insolubles, resulting from oxidation during use, in suspension in the fluid thus preventing sludge flocculation and precipitation or deposition on metal parts. Suitable dispersants include high molecular weight alkyl succinates, the reaction product of oil-soluble polyisobutylene succinic anhydride with ethylene amines such as tetraethylene pentamine and borated salts thereof.
Pour poi~t depressants lower the temperature at which the fl~id will flow or can be poured. Such depressants are well known. Typically of those - addi~ives which usefully optimize the low ~emperature fluidity of the fluid are C8-C18 dialkylfumarate vinyl acetate copolymers, polymethacrylates, and wax naphthalene. Foam control can be provided by an anti~oamant of the polysiloxan~ type, ~.g., silicone oil and polydimethyl siloxane.

P~ ' Anti-wear a~ents, as their name implies, reduce wear of metal parts. R~presentatives of conventional -anti-wear agents are zinc dialkyldithiophosphate and zinc diaryldithiosphate.
Detergents and metal r-lst inhibito~s include the metal salts of sulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, naphthenates and other oil soluble mono- and di-carboxylic acids~ Highly basic ~viz, overbased) metal salts, such as highly basic alkaline ea~th metal sul~onates (especially Ca and Mg salts) are frequently used as detergents. Representative examples o~ such materials. and their methods o~ preparation, are found in Patent N~. 1,262,721, issued November 7, 1989.

Some of these numerous additives can provide a multiplicity of effects, e.g., a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
Compositions when containing these conventional additives are typically blended into the base oil in amounts which are effective to provide their nonmal attendant function~ Representative effective amounts of such additives are illustrated as follows:

~:7~
. 27a Additive Vol % Wt % a.i Viscosity Modifier .01-4 .01-4 Corrosion Inhi~itor O.01-1 .01-1.5 Oxidation inhibitor 0.01-1 .01-1.5 Dispersant 0.1 -7 0.1 -8 Pour Point Depressant O.Q1-1 .01-1.5 Anti-~oaming A~ents 0.001-0.1 .O01-0.15 Anti-Wear Agents 0.001-1 .001-1.5 Friction Modifiers 0.01 - l .01 - 1.5 Detergents/Rust Inhibitors .01-2.5 .01-3 Mineral Oil Base Balance BalancP
When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solu~ions or dispersio~s of the dispersant (in concentrate amounts hereinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several ~8 additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The concentrate or additive-package will typically be formulated to contain the dispersant additive and optional additional additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant. Thus, the dispersant of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages containing active ingredients in collective amounts of typically from about 2.5 to about 90%, and preferably from about 5 to about 75%, and most preferably from about 8 to about 50% by weight additives in the appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 wt.~ of the additive-package with the remainder being base oil.
All of said weight percents expressed herein are based on active ingredient (a.i.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will ~e the sum of the a.i. weight of each additive plus the weight of total oil or diluent.
This invention will be further understood by reference to the following examples, wherein all parts are parte by weight and all molecular weights are number averag~ molecular weights unless otherwise noted, and which include preferred embodiments of the invention.

~ ;715~

EXAMPLE 1 - Prepaxation of Polyisobutylene-Amine About 1250 g of a chlorinated polyisobutylene (4.2% C1) of a number avera~e molecular weight of 940 was charged into a 2 liter reaction flask. Thereafter, 400 g of 1,3-diaminopropane were added slowly and the reaction mixture was heated to 150C for S hours. The reaction mixture was cooled to room temperature and neutralized with sodium hydroxide (105.7 g at 50%
solution). The water and excess amine were stripped off from the reaction flask and the residue was diluted in excess heptane. The heptane solution was filtered and rotoevaporated at 100C. The product analyzed for 62.5% active ingredient and 1.68 wt. % nitroqen.

EXAMPLES 2-S - Lactone Capping of PIB-Amine About 80 g (O.05 moles) of the PIB-Amine prepared in accordance with EXAMPLE 1 were mixed in a 2 liter reaction ~lask with 5.7 g (0.05 moles) of E-caprolactone and 0.05 g of stannous octanoate. The reaction mixture was heated to 140C for 3 hours.
Infrared analysis of the reaction mixture indicated that the reaction was completed.

The procedure of EXAMPLE 2 was followed, except that 28.5 g (0.25 moles) of E-caprolactone were reacted with the PIB-Amine.

~L~'7~5 The procedure of EXAMPLE 2 was followed except that 57 g (0.5 moles) of E-caprolactone were reacted with the PI~-Amine.

The procedure of EiXAMPLE 2 was followed except that 171 g (1.5 moles) of E-caprolactone were reacted with the PI~-Amine.

Table I, which follows summarizes the characteristics of the dispersant materi~ls prepared in accordance with EXAMPLES 2-5.

TABLE I
EXAMPLE PIB,M 1 Amine2 PIB-Amine/CL3 2 9401,3-diaminopropane1.0:1.0 3 940 " 1.0:5.~

4 940 " 1.0:10.0 9~0 " 1.0:30.0 1 = number average molecular weight of polyisobutylene (PIB) 2 = amine used to prepare PIB-Amine 3 = moles of PIL-Amine reacted with moles of E-caprolactone (CL) SLUDGE INHIBITION AND VARNISH INHIBITION
BENCH TEST

Samples of the polycaprolactone adducts prepared on accordance with EXAMPLES 2 and 3 were subjected to a 3L~7159~

standard sludge inhibition bench test (SIB) and a standard varnish inhibition bench test (VIB). The adduct prepared in accordance with EX~MPLE 4 (mole ratio of Cl to PIB-Amine of 10:1) showed some evidence of insolubility in the oil used to run the SIB and VIB
tests and, therefore, was not tested. The adduct prepared in accordance with E~MPLE 5 was even less soluble than tha~ adduct prepared in accordance with EXAMPLE 4, and it too was no~ tested. A control sample ~the PI8-Amine of EXAMPLE 1) also was tested to provide a basis of comparison between the polycaprolactone adducts of this invention and the corresponding prior art PI~-Amine dispersants.
The SI~ and VIB tests forecast the performance of a lubricant in a gasoline engine. These tests are described below:
The SIB Test employs a used crankcase mineral lubricating oil composition having an oriqinal viscosity of about 325 SSU at 37.8C that has bPen used in a taxicab driven generally for shout trips only thereby causing a buildup of a high concentration of sludge precursors. The oil contains only a refined ~ase mineral oil, a viscosity index improver, a pour point depressant an a zinc dialkyldithiophosphate anti-wear additive. The oil contains no sludge dispersants. Such used oil is acquired by draining and refilling taxicab crankcases at about 1,000-2,000 mile intervals.
The SI~ Test is conducted in the following mannar: The used crankcase oil is freed of sludge by centrifuging for one half hour at about 39,000 gravities (gs). The resulting clear bright red oil is then decanted from the insoluble sludge particles, However, the supernatant oil still contains oil-soluble sludge precursors which, under the conditions employed ~y this test, tend to fonm additional oil-insoluble ~L~'7~55~

deposits of sludge. The sludge inhibiting properties of the additives being tested are determined by adding to portions of the used oil 0.5 wt. %, on an active basis, of the particular additive being tested. Ten grams of each oil sample being tested is placed an a stainless steel centrifuge tube and is heated at 140C for 16 hours in the presence of air. Following the heating, the tube containing the oil being tested is cooled and then centrifuged for 30 minute!s at about 39,000 gs. Any deposits of new sludge that form in this step are separated from the oil by decalnting supernatant oil and then carefully washed with 15 ml of pentane to remove all remaining oils from the sludge. The weight, in milligrams, of the new solid sludge that forms in the test is determined by drying the residue and weighing it. The results are reported as milligrams of sludge per ten grams of oil, thus measuring differences as small as one part per ten thousand. The less new sludge formed, the more effective is the additive as a dispersant. In other words, if the additive is effective, it will hold at least a portion of the new sludge that forms on heating and oxidation, stably suspended in the oil so that i~ does not precipitate during the centrifuging period.
In the VIB Test, a test sample consisting of ten grams of lubricating oil containing 0.5 wt.%, on an active basis, of the additive being evaluated is used. The test oil is a commercial lubricating oil obtained from a taxi after about 2000 miles of driving with the lubricating oll. Each sample is heat soaked overnight at about 140C and thereafter cen~rifuged to remove the ~ludge. The supernatant fluid of each sample is subjected to heat cycling from about 150C to room temperature over a period of 3.5 hours at a frequency of about two cycles per minute. During ~he heating phase, L5~3~

a gas containing a mixture of 0.7 volume percent S02, 1.4 volume percent NO and the balance, air, is bubbled through the test samples and during the cooling phase, water vapor is bubbled through the test samples. At the end of the test period, which testing cycle is repeated as necessary to determine the inhibiting effect of any additive, the wall surfaces of the test flasks in which the samples are contained are visually evaluated as to the varnish inhibition. The amount of varnish deposited on the walls is rated at values of ~rom one to eleven with the higher number being the greatsr amoun~
of varnish. It has been found that this test forecasts the varnish results obtained as a conseguence of carrying out the ASTM MS sequence ~D engine test, which test is well known in the automotive industry.
The test is described in the ASTM Document for Multigrade Test Sequence for Evaluating Automotive Engine Oil, Sequence VD, Part 3 of STP 315H.

Table II, which follows, summarizes the compositions tested and the test results.

TABLE II
SAMPLE TESTEDCL;PIB-Aminel SIB2 VIB3 EXAMPLE Z 1:1 5.1 7 EXAMPLE 3 5:1 9.91 5 ~PIB-Amine~ 0 7.40 8 1 = moles caprolac one per mole of polyisobutylene-amine 2 = mg sludge per 10 g oil (1 to 10, 1 the best) 3 = varnish rating - visually determined ~1 to 11, 1 the best) The data in Table II demonstrate that the varnish performance of the present polyisobutyl amine-caprolactone adducts is superior to that of the polyisobutylene amine control. The data also show that the sludge inhibi~ion properties of the dispersants are enhanced when E-caprolactone is reacted with the PIB-Amine at a 1:1 ratio, but that slightly poorer, although still acceptable, sludge inhibition properties are obtained when the amount of E-caprolactone is increased to a 5:1 ratio.
As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in light of the foregoing disclosure and illustrative examples, tables and discussion, without departing from the spirit and scope of the disclosure or from the scope of the invention as set forth in the following claims.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A hydroxyl terminated polymeric adduct of a C5-C9 lactone and a polyalkylene amine material useful as an oil additive, said adduct being formed by reacting a C5-C9 lactone with a polyalkylene amine, said polyalkylene amine, in turn, being formed by reacting an olefin polymer material comprising a major molar amount of a C2-C10 monoolefin and having a number average molecular weight of about 300 to about 10,000 or a halogenated derivative thereof with an amine compound that is reactive therewith to add amino groups onto said olefin polymer material, and said adduct containing the unit where z is a number from 4 to 8 and m is an average number from about 0.2 to about 100.

2. The hydroxyl terminated polymeric adduct material according to Claim 1, wherein said C5-C9 lactone is E-caprolactone.

3. The hydroxyl terminated polymeric adduct material according to Claim 2, wherein said olefin polymer is selected from polyisobutylene and halogenated polyisobutylene.

4. The hydroxyl terminated polymeric adduct material according to Claim 3, wherein said amine compound is selected from the group consisting of amines of about 2 to 60 total carbon atoms and about 1 to 12 nitrogen atoms in the molecule.

5. The hydroxyl terminated polymeric adduct material according to Claim 4, wherein said amine compound is an aliphatic saturated amine having the formula:
wherein R and R' independently are selected from the group consisting of hydrogen, C1 to C25 straight or branched chain alkyl radicals, C1 to C12 alkoxy C2 to C6 aldylene radicals, and C1 to C12 alkylamino C2 to C6 alkylene radicals; each s is the same or a different number of from 2 to 6; and t is a number of from 0 to 10, provided, however, that when t=0, at least one of R
and R' must be hydrogen.

6. The hydroxyl terminated polymeric adduct material of Claim 5, wherein said amine compound is selected from the group consisting of 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;
1,6-diaminohexane; diethylene amine; triethylene tetramine; tetraethylenepentamine; 1,2-propylene diamine; di-(1,2-propylene)triamine; di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl)ethylene diamine; and N-dodecyl-1,3-propane diamine.

7. The hydroxyl terminated polymeric adduct material according to Claim 4, wherein said amine compound is selected from the group consisting of alicylcic diamines, imidazolines, morpholines, and N-aminoalkyl piperazines of the general formula:

wherein G is selected from the group consisting of hydrogen and omega-(nontertiary) aminoalkylene radicals of 1 to 3 carbon atoms, and p is a number from 1 to 4.

8. The hydroxyl terminated polymeric adduct material according to Claim 4, wherein said amine compound is a mixture of poly(ethyleneamines) averaging about 5 to 7 nitrogen atoms per molecule.

9. The hydroxyl terminated polymeric adduct material according to Claim 4, wherein said amine compound is a polyoxyalkylene polyamine having the formulae:
NH2 - alkylene - (o-alkylene)m - NH2 where m has a value of above 3 to 70; or R ?alkylene - (o-alkylene)n - NH2]a where n has a value of about 1 to 40 with the provision that the sum of all the n's is from about 3 to about 70, R is a substituted saturated hydrocarbon radical of up to 10 carbon atoms, wherein the number of substituents on the R group is represented by the value of "a", which is a number from 3 to 6.

10. The hydroxyl terminated polymeric adduct material according to claim 1, which has been post-treated with a borating agent selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters and boron acids.

11. An oleaginous composition comprising an oleaginous material selected from the group consisting of fuels and lubricating oil and the adduct of any one of claims 1-10.

12. A lubricating oil composition comprising a major amount of lubricating oil and about 0.01 to 15 wt. % of the adduct of any one of claims 1-10.