GB2234248A

GB2234248A - Improved lactone-treated dispersant additives derived from amido-amine adducts

Info

Publication number: GB2234248A
Application number: GB9011381A
Authority: GB
Inventors: Antonio Gutierrez; Robert Dean Lundberg
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 1989-05-30
Filing date: 1990-05-22
Publication date: 1991-01-30
Also published as: GB9011381D0

Abstract

A lactone modified dispersant additive comprises at least one adduct of (A) a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.7 (e.g., from about 1 to 4) mono- or dicarboxylic acid producing moieties (preferably acid or anhydride moieties) per polyolefin molecule, (B) an amido-amine or thioamido-amine characterized by being a reaction product of at least a polyamine and an alpha, beta-unsaturated compound of the formula: <IMAGE> wherein X is sulfur or oxygen, Y is -OR<4>,-SR<4>, or -NR<4)<R<5>), and R<1>, R<2>, R<3>, R<4> and R<5> are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl, and a C5 - C9 lactone material. The additives may be post-treated for example by boration.

Description

IMPROVED LACTONE-TREATED DISPERSANT ADDITIVES DERIVED FROM AMIDO-AMINE ADDUCTS This invention relates to improved oil soluble dispersant additives useful oleaginous compositions, including fuel and lubricating oil compositions, and to concentrates containing said additives.

This application is also related to the following applications filed by the inventors herein: Serial No. GB-A-29197312, Serial No. EP-A-0263706, Serial No. EP-A-0263702, Serial No. EP-A-026703, Serial No.

GB-A-2211849 and Serial No. GB-A-2201678, all of which were filed on October 7, 1986. All of the above applications are expressly incorporated herein by reference in their entirety.

U.S. Patent 2,921,085 relates to the preparation of beta-aminopropionamides by reaction of an alkyl amine with an acrylate to form an alkyl aminopropionate and reaction of the latter compound with an amine. The resulting compounds are disclosed to have utility as surface active agents, specifically as emulsifying, wetting, foaming and detergent agents.

U.S. Patent 3,337,609 relates to adducts of hydroxyalkyl alkylene polyamines and acrylates. The resulting adducts are added to polyepoxides to provide compositions which are suitable for use as a barrier coating for polyethylene surfaces, and for additional end uses, such as in molding. In addition, the adducts are disclosed to be useful as catalysts in resin preparation and as corrosion inhibitors in water systems for ferrous metals.

U.S. Patent 3,417,140 relates to the preparation of amido-amine compositions, which are useful as epoxy resin curing agents, by reacting a polyalkylene polyamine and a fatty amine (comprising a moho- or diamine having as one of the substituents on a nitrogen atom a hydrocarbyl radical having 8 to 24 carbon atoms) with an alpha-beta unsaturated carbonylic compound. It is disclosed that this reaction occurs through the Michael addition of an amine group across the unsaturated group of the carbonylic compound and through the condensation of an amine group with the carbonylic group.

U.S. Patent 3,247,163 also relates to curing agents for polyepoxide compositions, which curing agents are prepared by reacting an organic amine and an acrylate.

U.S. Patent 3,445,441 relates to amino-amido polymers characterized by being a reaction product of at least a polyamine and an acrylate type compound, such as methyl or ethyl acrylate, and methyl or ethyl methacrylate. The patent states that the polymers are useful in a wide variety of applications, such as floculating agents, water clarifying additives, corrosion inhibitors in oil and gas wells, and as lube oil additives. The patent further discloses that the polymers may be derivitized, including acylation with monocarboxylic acids and polycarboxylic acids, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, for example, diglycolic, phthalic, succinic, etc., acids.

U.S. Patent 3,903,003 relates to lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer which is formed by reacting a terminally carboxylated substantially completely hydrogenated polyisoprene having an average molecular weight between about 20,000 and 250,000 and a nitrogen compound of the group consisting of polyalkylene amines and hydroxyl polyalkylene amines.

U.S. Patent 4,493,771 relates to scale inhibiting with compounds containing quaternary ammonium and methylene phosphonic acid groups. These compounds are derivatives of polyamines in which the amine hydrogens have been substituted with both methylene phosphonic acid groups or their salts and hydroxypropyl quaternary ammonium halide groups. The patent discloses that any amine that contains reactive amino hydrogens can be utilized, for example, polyglycol amines, amido-amines, oxyacylated amines, and others.

U.S. Patent 4,459,241 contains a similar disclosure to U.S. Patent 4,493,771.

It is known that polymers of 6 to 10 membered lactones such as valerolactone or epsiloncaprolactone, hereinafter 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:

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 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 high 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 Ecaprolactone with a diamine wherein one of the diamine groups is a tertiary amine and the other amine group is a primary or secondary amine to form a polycaprolactone polymer having a tertiary amine group at one end and a primary hydroxyl group at the other end. The polycaprolactone polymer would be used to neutralize polymeric acids.

It has now been found that oil soluble dispersant additives, useful in fuel and lubricating oil compositions, including concentrates containing the additives, can be prepared by polymerizing a 6 to 10 membered lactone using as the initiator those lactone-reactive functions contained within a known class of oil soluble dispersants, namely: dicarboxylic acids, anhydrides, esters, etc. that have been substituted with a high molecular weight hydrocarbon group. Typical examples of one such initiator are polyalkylene succinimides wherein the polyalkylene moiety has a number average molecular weight of about 700 to about 5,000 and wherein the ratio (functionality) of succinic acid producing moieties to each equivalent weight of the polyalkylene moiety is from about 0.70 to about 2.0.

Exemplary of the patent literature which relates to lactone polymerization processes and/or to oil soluble dispersant additives are the following U.s. Patents: 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 45% by weight of units of hydroxycarboxylic acids obtained from aliphatic alcohols, aliphatic, cycolaliphatic or aromatic carboxylic acids, and lactones of aliphatic C5-C12 hydroxycarboxylic acids.

The synthetic ester oils are suitable for the preparation of lubricants and lubricant compositions.

U.S. Patent 3,202,678 discloses as oil additives, N-polyamine substituted alkenyl succinimides, wherein the alkenyl radical is obtained by polymerizing a C2 -C5 olefin to form a hydrocarbon having a molecular weight ranging from about 400 to about 3,000. The number of dicarboxylic acid producing moieties per hydrocarbon radical in the succinimides is not disclosed, but the mole ratio of polyolefin to maleic anhydride used to obtain the alkenyl succinimides is from 1:1 to 1:10.

U.S. Patent 3,219,666 discloses as dispersing agents in lubricants, derivatives of polyalkenyl succinic acids and nitrogen compounds, including polyamines. The preferred molecular weight of the polyalkenyl moieties is 750-5,000.

U.S. Patent 4,234,435 discloses as oil additives, polyalkylene substituted dicarboxylic acids derived from polyalkylenes having a Mn of 1300 to 5,000 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.

U.S. Patent 3,381,022 relates to ester derivatives of substantially saturated polymerized olefin-substituted succinic acid wherein the polymerized olefin substituent contains at least about 50 aliphatic carbon atoms and has a molecular weight of about 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 disclosed to be useful as additives in lubricating compositions, fuels, hydrocarbon oils and power transmission fluids. A related application, i.e., U.S.

Patent No. 3,522,179, relates to 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.

U.S. Patent 4,502,970 discloses lubricating oil compositions useful in both gasoline engines and diesel engines. The compositions contain a polyisobutenyl succinicimide as a supplemental dispersant-detergent in combination with another conventional dispersant. The polyisobutenyl group has a Mn of about 700-5,000.

U.S. Patent 4,379,914 and its continuation-inpart (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.

U.S. Patent 3,169,945 discloses the preparation of lactone polyesters which are useful as plasticizers and as intermediates 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, amine or amino alcohol.

U.S. Patent 4,532,058 discloses as a motor oil dispersant, a spirolactone condensation product formed by heating alkenyl succinic anhydrides in the presence of a basic catalyst, and then heating the resulting bicyclic spirodilactone condensation product with a polyamine or polyamine alcohol. It should be emphasized that this patent describes the intermolecular decarboxylation of an alkenyl succinic anhydride at elevated temperatures to form a condensation product and carbon dioxide as a by-product.

This prior art is not concerned with polymerizable lactones which are the subject of the instant invention.

U.S. Patent 4,113,639 and 4,116,876 disclose an example of alkenyl succinic anhydride having a molecular weight of the alkenyl group of 1,300 and a Saponification Number of 103 (about 1.3 succinic anhydride units per hydrocarbon molecule). This alkenyl succinic anhydride may be reacted with polyamine and then boric acid (U.S.

4,113,639), or may be reacted with an amino alcohol to form an oxazoline (4,116,876) which is then borated by reaction with boric acid.

U.S. Patent 4,062,786 in Example 13 shows a polyisobutenylsuccinic anhydride of molecular weight of about 1300 and a Saponification Number of about 100 (about 1.25 succinic anhydride units per alkenyl group).

U.S. Patent 4,123,373 in Example 3 shows a polyisobutenylsuccinic anhydride of about 1,400 molecular weight having a Saponification Number of 80 (about 1.07 succinic anhydride units per polyisobutylene units).

Additional exemplary prior art disclosures which are expressly incorporated herein by reference in their entirety are U.S. Patents: 3,087,936i 3,131,150; 3,154,560; 3,172,892; 3,198,736; 3,215,707; 3,219,666; 3,231,587; 3,325,484; 3,269,946; 3,272,743; 3,272,746; 3,278,550; 3,284,409; 3,284,417; 3,288,714; 3,361,673; 3,390,086; 3,401,118; 3,403,102; 3,455,827; 3,562,159; 3,576,743; 3,632,510; 3,684,771; 3,792,061; 3,799,877; 3,836,470; 3,836,471; 3,838,050; 3,838,052; 3,879,308; 3,912,764; 3,927,041; 3,950,341; 4,110,349; 4,113,639; 4,116,875; 4,151,173; 4,195,976; 4,517,104; 4,536,547 and Re. 26,330.

SUMMARY OF THE INVENTION In one embodiment, the present invention is directed to a dispersant additive comprising at least one adduct of (A) an amido-amine characterized by being a reaction product of at least a polyamine and an alpha, beta unsaturated compound of the formula:

wherein X is sulfur or oxygen, Y is -OR4, -SR4, or -NR4(R5) and R1, R2, R3, R4 and.R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl, (B) a polyolefin of 300 to 10,000 number average molecular weight substituted with at least 0.3 (e.g., from about 1 to 4) mono- or dicarboxylic acid producing moieties (preferably acid or anhydride moieties) per polyolefin molecule, and (C) a C5 to Cg lactone material.

The materials of the invention are different from the prior art because of their effectiveness and their ability to provide enhanced lubricating oil dispersancy.

Therefore, the present invention is also directed to novel processes for preparing the dispersant adducts of his invention.

It is a principal object of one aspect of this invention to provide a novel class of poly (C5-Cg lactone) adduct dispersants. Another object of this aspect of the invention is to provide a process for preparing a novel class of dispersants from C5-C9 lactones and hydrocarbyl substituted mono- and dicarboxylic acids, anhydrides, esters, etc. which contain lactone-reactive amine functionality.

A further object is to provide lubricant compositions and concentrates containing the novel poly (CS-Cg lactone) adducts of this invention.

Yet another object is to provide a novel class of oil soluble dispersants from polyalkylene substituted acylating agents which have at least one lactone-reactive amino group in their structure.

Still another object is to provide poly (C5-Cg lactone) adducts from derivatives of polyalkylene substituted succinic acylating agents which contain at least one lactone-reactive amino group, as well as lubricant compositions and concentrates containing such adducts.

Still another object is to provide metal complexes and other post-treated derivatives, e.g., borated derivatives, of the novel poly (C5-Cg lactone) adducts of this invention, as well as lubricant compositions and concentrates containing such posttreated derivatives.

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 this invention, one or more of the above objects can be achieved by initiating the polymerization of a C5-C9 lactone by means of an amino function contained in a polyolefin substituted dicarboxylic acylating agent, wherein the polyolefin has a number average molecular weight of about 300 to about 10,000, wherein the acylating agent has been neutralized with a polyfunctional amine, and wherein the polyolefin substituted, neutralized acylating agent contains from about 0.70 to about 2.0 dicarboxylic acid producing moieties, preferably acid anhydride moieties, per equivalent weight of polyolefin.

In another aspect, one or more of the objects of this invention can be achieved by heating a C5-C9 lactone such as E-caprolactone at a temperature of at least about 80 C, and preferably from about 90 C, to about 180* C with a polyalkylene succinimide initator wherein the polyalkylene is characterized by a number average molecular weight of about 300-10,000 and wherein the initiator is characterized by the presence within its structure of from about 0.70 to about 2.0 succinic acid or succinic acid derivative moieties for each equivalent weight of polyalkylene; and, in a further aspect, one or more objects of this invention are achieved by providing poly (C5-Cg lactone) adducts produced by such a process.

One or more additional objects of this invention are achieved by reacting E-caprolactone with a polyalkylene succinic acylating agent which has been post-treated to introduce into the structure thereof at least one lactone-reactive amino group; one or more additional objects are accomplished by providing poly (E-caprolactone) adducts produced by such a process.

One or more additional objects can be illustrated in connection with the reaction between E-caprolactone and a polyalkylene succinimide initiator having secondary amine functionality, such as a polyisobutenyl bis-succinimide, as follows (Eq. 4):

where x is a number from 1 to 4, and m has a value of up to about 100, preferably from 1 to about 20, most preferably from 1 to about 5, R represents polyisobutylene having a number average molecular weight of from about 700 to about 5,000, and the functionality of succinic acid producing moieties is from about 0.7 to about 2.0 per equivalent weight of polyisobutylene.

The novel poly (C5-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 prior art derivatives of polyalkenyl succinic acids and nitrogen compounds are used as dispersant/detergents in lubricants, especially lubricants intended for use in the crankcase of internal conbustion engines, gears, and power transmitting units. Accordingly, 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-Cg 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 providing concentrate compositions 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 poly (C5-Cg lactone) adduct, as mentioned above and described in more detail hereinafter.

DETAILED DESCRIPTION OF THE INVENTION PREPARATION OF AMTDO-AMINE REACTANT A As described above, the amido-amine comprises a reaction product of at least one polyamine and an alpha, beta ethylenically unsaturated compound.

The polyamines useful in this invention comprise polyamines, most preferably polyalkylene polyamines, of about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to 12, and most preferably at least 5 (e.g., 5 to 9) nitrogen atoms ip the molecule. These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful.Preferred amines are aliphatic saturated amines, including those of the general formulas:

wherein R, R', 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; C2 to C12 hydroxy amino alkylene radicals; and C1 to C12 alkylamino C2 to C6 alkylene radicals; and wherein R"' can additionally comprise a moiety of the formula:

wherein R' is as defined above, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or different and are numbers of from 0 to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t' is not greater than 15.To assure a facile reaction, it is preferred that R, R', R", R"', s, s', t and t' be selected in a manner sufficient to provide the compounds of Formulas II and III with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R" or R''' groups to be hydrogen or by letting t in Formula III be at least one when R"' is H or when the IV moiety possesses a secondary amino group. The most preferred amine of the above formulas are represented by Formula III and contain at least two primary amine groups and at least one, and preferably at least three, secondary amine 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 triamine; triethylene tetramine; tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine; di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aniinoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAN); diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.

Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula (V):

wherein p1 and p2 are the same or different and are each integers of from 1 to 4, and nl, n2 and n3 are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2-pentadecyl imidazoline: N- (2-aminoethyl) piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an 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, triethylenetetramine, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalkylene polyamines such as those of the formulae:

where m has a value of about 3 to 70 and preferably 10 to 35; and

where "n" has a value of about 1 to 40 with the provision that the sum of all the nts is from about 3 to about 70 and preferably from about 6 to about 35, and R is a polyvalent saturated hydrocarbon radical of up to ten carbon atoms wherein the number of substituents on the R group is represented by the value of "a", which is a number of from 3 to 6. The alkylene groups in either formula (VI) or (VII) may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.

The polyoxyalkylene polyamines of formulas (VI) or (VII) above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from about 200 to about 4,000 and preferably from about 400 to about 2,000. The preferred polyoxyalkylene polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2,000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc.

under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.

Additional amines useful in the present invention are described in U.S. Patent 3,445,441, the disclosure of which is hereby incorporated by reference in its entirety.

Thus, any polyamine, whether aliphatic, cycloaliphatic, aromatic, heterocyclic, etc., can be employed provided it is capable of adding across the acrylic double bond and amidifying with for example the carbonyl group (-C(O)-) of the acrylate-type compound of formula I, or with the thiocarbonyl group (-C(S)-) of the thioacrylate-type compound of formula I.

The alpha, beta ethylenically unsaturated compounds employed in this invention comprise at least one member selected from the group consisting of alpha, beta ethylenically unsaturated compounds of the formula:

wherein X is sulfur or oxygen, Y is -OR4, -SR4, or -NR4(R5) , and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.

When R1, R2, R3, R4 or R5 are hydrocarbyl, these groups can comprise alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic, which can be substituted with groups which are substantially inert to any component of the reaction mixture under conditions selected for preparation of the amido-amine. Such substituent groups include hydroxy, halide (e.g., C1, F1, I, Br), -SH and alkylthio. When one or more of through R5 are alkyl, such alkyl groups can be straight or branched chain, and will generally contain from 1 to 20, more usually from 1 to 10, and preferably from 1 to 4, carbon atoms. Illustrative of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. When one or more of R1 through R5 are aryl, the aryl group will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).

When one or more of R1 through R5 are alkaryl, the alkaryl group will generally contain from about 7 to 20 carbon atoms, and preferably from 7 to 12 carbon atoms.

Illustrative of such alkaryl groups are tolyl, m-ethylphenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R1 through R5 are aralkyl, the aryl component generally consists of phenyl or (C1 to C6) alkyl-substituted phenol and the alkyl component generally contains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbon atoms. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and 4-isobutylbenzyl. When one or more of R1 and R5 are cycloalkyl, the cycloalkyl group will generally contain from 3 to 12 carbon atoms, and preferably from 3 to 6 carbon atoms. Illustrative of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, and cyclododecyl.When one or more of R1 through R5 are heterocyclic, the heterocyclic group generally consists of a compound having at least one ring of 6 to 12 members in which on oe more ring carbon atoms is replaced by oxygen or nitrogen. Examples of such heterocyclic groups are furyl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyl and 1,4-oxazinyl.

The alpha, beta ethylenically unsaturated carboxylate compounds employed herein have the following formula:

wherein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate compounds of formula VIII are acrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl, and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid, 2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid, 3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid, 3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid, 2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid, 2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pentenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate, methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl 2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propeno-ate, dodecyl 2-decenoate, cyclopropyl 2 , 3 2, 3-dimethyl-2-butenoate, methyl 3-phenyl-2-propenoate, and the like.

The alpha, beta ethylenically unsaturated carboxylate thioester compounds employed herein have the following formula:

wherein R1, R2, R , and RI are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate thioesters of formula IX are methylmercapto 2-butenoate, ethylmercapto 2 -hexenoate, isopropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiary butylmercapto 2-propenoate, octadecylmercapto 2-propenoate, dodecylmercapto 2-decenoate, cyclopropylmercapto 2, 3-dimethyl-2-butenoate, methylmercapto 3 -phenyl -2-propenoate, methylmercapto 2-propenoate, methylmercapto 2-methyl-2-propenoate, and the like.

The alpha, beta ethylenically unsaturated carboxyamide compounds employed herein have the following formula:

wherein R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated carboxyamides of formula X are 2-butenamide, 2-hexenamide, 2-decenamide, 3-methyl-2-heptenamide, 3-methyl-2-butenamide, 3-phenyl-2-propenamide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide, 2-propyl-2-propenamide, 2-isopropyl-2-hexenamide, 2 , 3 - dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl 2-butenamide, N,N-diethyl 2-hexenamide, N-isopropyl 2-decenamide, N-phenyl 2-pentenamide, N-tertiary butyl 2-propenamide N-octadecyl 2-propenamide, N-N-didodecyl 2-decenamide, N-cyclopropyl 2,3-dimethyl-2-butenamide, N-methyl 3-phenyl-2-propenamide, 2-propenamide, 2-methyl-2-propenamide, 2-ethyl-2-propenamide and the like.

The alpha, beta ethylenically unsaturated thiocarboxylate compounds employed herein have the following formula:

wherein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxylate compounds of formula XI are 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid, 3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid, 3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid, 2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid, 2-isopropyl-2-hexenthioic acid, 2, 3-dimethyl-2-butenthioic acid, 3-cyclohexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl 2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-butenthioate, ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate, tertiary butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl 2-decenthioate, cyclopropyl 2 , 3 2, 3-dimethyl-2-butenthioate, methyl 3-phenyl-2-propenthioate, and the like.

The alpha, beta ethylenically unsaturated dithioic acid and acid ester compounds employed herein have the following formula:

wherein R1, R2, R3, and R4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated dithioic acids and acid esters of formula XII are 2-butendithioic acid, 2-hexendithioic acid, 2-decendithioic acid, 3-methyl-2-heptendithioic acid, 3-methyl-2-butendithioic acid, 3-phenyl-2-propendithioic acid, 3-cyclohexyl-2-buten dithioic acid, 2-methyl-2-butendithioic acid, 2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid, 2,3-dimethyl-2-butendithioic acid, 3-cyclo hexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid, methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl 2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate, phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl 2-propendithioate, dodecyl 2-decendithioate, cyclopropyl 2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate, and the like.

The alpha, beta ethylenically unsaturated thiocarboxyamide compounds employed herein have the following formula:

wherein R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxyamides of formula XIII are 2-butenthioamide, 2-hexenthioamide, 2-decenthioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-butenthioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-buten thioamide, 2-methyl-2-butenthioamide, 2 -propyl - 2 -propenthioamide, 2-isopropyl-2-hexenthioamide, 2,3-dimethyl-2-butenthioamide, 3 -cycl ohexyl-2 -methyl-2-pententhioamide, N-methyl 2-butenthioamide, N,N-diethyl 2-hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl 2-pententhioamide, N-tertiary butyl 2-propenthioamide, N-octadecyl 2-propenthioamide, N-N-didodecyl 2-decenthioamide, N-cyclopropyl 2,3-dimethyl-2-butenthioamide, N-methyl 3 -phenyl-2 -propenthioamide, 2 -propenthioamide, 2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamide and the like.

Preferred compounds for reaction with the polyamines in accordance with this invention are lower alkyl esters of acrylic and (lower alkyl) substituted acrylic acid. Illustrative of such preferred compounds are compounds of the formula:

where R3 is hydrogen or a C1 to C4 alkyl group, such as methyl, and R4 is hydrogen or a C1 to C4 alkyl group, capable of being removed so as to form an amido group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl, hexyl, etc. In the preferred embodiments these compounds are acrylic and methacrylic esters such as methyl or ethyl acrylate, methyl or ethyl methacrylate.When the selected alpha, beta-unsaturated compound comprises a compound of formula I wherein X is oxygen, the resulting reaction product with the polyamine contains at least one amido linkage (-C(O)N < ) and such materials are herein termed "amido-amines." Similarly, when the selected alpha, beta unsaturated compound of formula I comprises a compound wherein X is sulfur, the resulting reaction product with the polyamine contains thioamide linkage (-C(S)N < ) and these materials are herein termed "thioamido-amines.n For convenience, the following discussion is directed to the preparation and use of amido-amines, although it will be understood that such discussion is also applicable to the thioamido-amines.

The type of amido-amine formed varies with reaction conditions. For example, a more linear amido-amine is formed where substantially equimolar amounts of the unsaturated carboxylate and polyamine are reacted.

The presence of excesses of the ethylenically unsaturated reactant of formula I tends to yield an amido-amine which is more cross-linked than that obtained where substantially equimolar amounts of reactants are employed. Where for economic or other reasons a cross-linked amido-amine using excess amine is desired, generally a molar excess of the ethylenically unsaturated reactant of about at least 10%, such as 10-300%, or greater, for example, 25-200%, is employed. For more efficient cross-linking an excess of carboxylated material should preferably be used since a cleaner reaction ensues. For example, a molar excess of about 10-100% or greater such as 10-50%, but preferably an excess of 30-50%, of the carboxylated material. Larger excess can be employed if desired.

In summary, without considering other factors, equimolar amounts of reactants tend to produce a more linear amido-amine whereas excess of the formula I reactant tends to yield a more cross-linked amido-amine. It should be noted that the higher the polyamine (i.e., in greater the number of amino groups on the molecule) the greater the statistical probability of cross-linking since, for example, a tetraalkylenepentamine, such as tetraethylene pentamine

has more labile hydrogens than ethylene diamine.

These amido-amine adducts so formed are characterized by both amido and amino groups. In their simplest embodiments they may be represented by units of the following idealized formula:

wherein the R's, which may be the same or different, are hydrogen or a substituted group, such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl, etc., and A is a moiety of the polyamine which, for example, may be aryl, cycloalkyl, alkyl, etc., and n is an integer such as 1-10 or greater. The amido-amine adducts preferably contain an average of from 1 to 3 amido groups per molecule of the amido-amine adduct.

The above simplified formula represents a linear amido-amine polymer. However, cross-linked polymers may also be formed by employing certain conditions since the polymer has labile hydrogens which can further react with either the unsaturated moiety by adding across the double bond or by amidifying with a carboxylate group.

Preferably, however, the amido-amines of this invention are not cross-linked to any substantial degree, and more preferably are substantially linear.

Preferably, the polyamine reactant contains at least one primary amine (and more preferably from 2 to 4 primary amines) group per molecule, and the polyamine and the unsaturated reactant of formula I are contacted in an amount of from about 1 to 10, more preferably from about 2 to 6, and most preferably from about 3 to 5, equivalents of primary amine in the polyamine reactant per mole of the unsaturated reactant of formula I.

The reaction between the selected polyamine and acrylate-type compound is carried out at any suitable temperature. Temperatures up to the decomposition points of reactants and products can be employed. In practice, one generally carries out the reaction by heating the reactants below 100*C, such as 80-900C, for a suitable period of time, such as a few hours. Where an acrylic-type ester is employed, the progress of the reaction can be judged by the removal of the alcohol in forming the amide.

During the early part of the reaction alcohol is removed quite readily below 100'C in the case of low boiling alcohols such as methanol or ethanol. As the reaction slows, the temperature is raised to push the polymerization to completion and the temperature may be raised to l500C toward the end of the reaction. Removal of alcohol is a convenient method of judging the progress and completion of the reaction which is generally continued until no more alcohol is evolved. Based on removal of alcohol, the yields are generally stoichiometric. In more difficult reactions, yield of at least 95% are generally obtained.

Similarly, it will be understood that the reaction of an ethylenically unsaturated carboxylate thioester of formula IX liberates the corresponding HSR4 compound (e.g., H2S when R4 is hydrogen) as a by-product, and the reaction of an ethylenically unsaturated carboxyamide of formula X liberates the corresponding HNR4(R5)# compound (e.g., ammonia when R4 and R5 are each hydrogen) as by-product.

The reaction time involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. In general, lower temperature demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to 10 hours will be employed.

Although one can employ a solvent, the reaction can be run without the use of any solvent. In fact, where a high degree of cross-linking is desired, it is preferably to avoid the use of a solvent and most particularly to avoid a polar solvent such as water. However, taking into consideration the effect of solvent on the reaction, where desired, any suitable solvent can be employed, whether organic or inorganic, polar or non-polar.

As an example of the amido-amine adducts, the reaction of tetraethylene pentaamine (TEPA) with methyl methacrylate can be illustrated as follows:

PREPARATION OF CARBOXYLfC-PROWCING REACTANT B-l The long chain hydrocarbyl polymer-substituted mono- or dicarboxylic acid material, i.e., acid, anhydride or acid ester used in this invention, includes the reaction product of a long chain hydrocarbon polymer, generally a polyolefin, with a monounsaturated carboxylic reactant comprising at least one member selected from the group consisting of (i) monounsaturated C4 to C10 dicarboxylic acid (preferably wherein (a) the carboxyl groups are vicinyl, (i.e. located on adjacent carbon atoms) and (b) at least one, preferably both, of said adjacent carbon atoms are part of said mono unsaturation); (ii) derivatives of (i) such as anhydrides or C1 to C5 alcohol derived mono- or di-esters of (i); (iii) monounsaturated C3 to C10 monocarboxylic acid wherein the carbon-carbon double bond is conjugated to the carboxy group, i.e, of the structure

and (iv) derivatives of (iii) such as C1 to C5 alcohol derived monoesters of (iii). Upon reaction with the polymer, the monounsaturation of the monounsaturated carboxylic reactant becomes saturated. Thus, for example, maleic anhydride becomes a polymer substituted succinic anhydride, and acrylic acid becomes a polymer substituted propionic acid.

Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferably from about 1.0 to about 2.0, and most preferably from about 1.1 to about 1.7 moles of said monounsaturated carboxylic reactant are charged to the reactor per mole of polymer charged.

Normally, not all of the polymer reacts with the monounsaturated carboxylic reactant and the reaction mixture will contain non-acid substituted polymer. The polymer-substituted mono- or dicarboxylic acid material (also referred to herein as "functionalized" polymer or polyolefin), non-acid substituted polyolefin, and any other polymeric by-products, e.g. chlorinated polyolefin, (also referred to herein as "unfunctionalized" polymer) are collectively referred to herein as "product residue" or "product mixture". The non-acid substituted polymer is typically not removed from the reaction mixture (because such removal is difficult and would be commercially infeasible) and the product mixture, stripped of any monounsaturated carboxylic reactant is employed for further reaction with the amine or alcohol as described hereinafter to make the dispersant.

Characterization of the average number of moles of monounsaturated carboxylic reactant which have reacted per mole of polymer charged to the reaction (whether it has undergone reaction or not) is defined herein as functionality. Said functionality is based upon (i) determination of the saponification number of the resulting product mixture using potassium hydroxide; and (ii) the number average molecular weight of the polymer charged, using techniques well known in the art. Functionality is defined solely with reference to the resulting product mixture. Although the amount of said reacted polymer contained in the resulting product mixture can be subsequently modified, i.e. increased or decreased by techniques known in the art, such modifications do not alter functionality as defined above.The terms "polymer substituted monocarboxylic acid material" and "polymer substituted dicarboxylic acid material" as used herein are intended to refer to the product mixture whether it has undergone such modification or not.

Accordingly, the functionality of the polymer substituted mono- and dicarboxylic acid material will be typically at least about 0.5, preferably at least about 0.8, and most preferably at least about 0.9 and will vary typically from about 0.5 to about 2.8 (e.g., 0.6 to 2), preferably from about 0.8 to about 1.4, and most preferably# from about 0.9 to about 1.3.

Exemplary of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 alkyl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, etc.

Preferred olefin polymers for reaction with the monounsaturated carboxylic reactants to form reactant A are polymers comprising a major molar amount of C2 to C10, e.g. C2 to C5 monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-l, 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 isobutylene; etc. Mixtures of polymers prepared by polymerization of mixtures of isobutylene, butene-l and butene-2, e.g., polyisobutylene wherein up to about 40% of the monomer units are derived from butene-l and butene-2, is an exemplary, and preferred, olefin polymer.Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C4 to C18 non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of 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 weight.

The olefin polymers used in the formation of reactant B will have number average molecular weights within the range of about 300 to 10,000, generally from about 700 and about 5,000, preferably from about 1000 to 4,000, more preferably between about 1300 and about 3,000.

Particularly useful olefin polymers have number average molecular weights within the range of about 1500 and about 3000 with approximately one terminal double bond per polymer chain. An especially useful starting material for highly potent dispersant additives useful in accordance with this invention is polyisobutylene, wherein up to about 40% of the monomer units are derived from butene-l and/or butene-2. The number average molecular weight for such polymers can be determined by several known techniques. 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. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.

The olefin polymers will generally have a molecular weight distribution (the ratio of the weight average molecular weight to number average molecular weight, i.e. Rw/Rn) of from about 1.0 to 4.5, and more typically from about 1.5 to 3.0.

The polymer can be reacted with the monounsaturated carboxylic reactant by a variety of methods. For example, the polymer can be first halogenated, chlorinated or brominated to about 1 to 8 wt.

%, preferably 3 to 7 wt. % chlorine, or bromine, based on the weight of polymer, by passing the chlorine or bromine through the polymer at a temperature of 60 to 250eC, preferably 110 to l600C, e.g. 120 to 140it, for about 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer may then be reacted with sufficient monounsaturated carboxylic reactant at 100 to 250it, usually about 180 to 235eC, for about 0.5 to 10, e.g. 3 to 8 hours, so the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patents 3,087,436; 3,172,892; 3,272,746 and others.Alternatively, the polymer and the monounsaturated carboxylic reactant are mixed and heated while adding chlorine to the hot material. Processes of this type are disclosed in U.S. Patents 3,215,707; 3,231,587; 3,912,764 t 4,110,349; 4,234,435; and in U.K. 1,440,219.

Alternately, the polymer and the monounsaturated carboxylic reactant can be contacted at elevated temperature to cause a thermal "ene" reaction to take place. Thermal "ene" reactions have been heretofore described in U.S. Patents 3,361,673 and 3,401,118, the disclosures of which are hereby incorporated by reference in their entirety.

Preferably, the polymers used in this invention contain less than 5 wt%, more preferably less than 2 wt%, and most preferably less than 1 wt% of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300, as determined by high temperature gel premeation chromatography employing the corresponding polymer calibration curve. Such preferred polymers have been found to permit the preparation of reaction products, particularly when employing maleic anhydride as the unsaturated acid reactant, with decreased sediment.In the event the polymer produced as described above contains greater than about 5 wt% of such a low molecular weight polymer fraction, the polymer can be first treated by conventional means to remove the low molecular weight fraction to the desired level prior to initiating the ene reaction, and preferably prior to contacing the polymer with the selected unsaturated carboxylic reactant(s). For example, the polymer can be heated, preferably with inert gas (e.g., nitrogen) stripping, at elevated temperature under a reduced pressure to volatilize the low molecular weight polymer components which can then be removed from the heat treatment vessel.The precise temperature, pressure and time for such heat treatment can vary widely depending on such factors as as the polymer number average molecular weight, the amount of the low molecular weight fraction to be removed, the particular monomers employed and other factors. Generally, a temperature of from about 60 to 100*C and a pressure of from about 0.1 to 0.9 atmospheres and a time of from about 0.5 to 20 hours (e.g., 2 to 8 hours) will be sufficient.

In this process, the selected polymer and monounsaturated carboxylic reactant and halogen (e.g., chlorine gas), where employed, are contacted for a time and under conditions effective to form the desired polymer substituted mono- or dicarboxylic acid material.

Generally, the polymer and monounsaturated carboxylic reactant will be contacted in a unsaturated carboxylic reactant to polymer mole ratio usually from about 0.7:1 to 4:1, and preferably from about 1:1 to 2:1, at an elevated temperature, generally from about 120 to 260it, preferably from about 160 to 240'C. The mole ratio of halogen to monounsaturated carboxylic reactant charged will also vary and will generally range from about 0.5:1 to 4:1, and more typically from about 0.7:1 to 2:1 (e.g., from about 0.9 to 1.4:1). The reaction will be generally carried out, with stirring for a time of from about 1 to 20 hours, preferably from about 2 to 6 hours.

By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g. polyisobutylene will normally react with the monounsaturated carboxylic acid reactant. Upon carrying out a thermal reaction without the use of halogen or a catalyst, then usually only about 50 to 75 wt. 5 of the polyisobutylene will react. Chlorination helps increase the reactivity. For convenience, the aforesaid functionality ratios of mono- or dicarboxylic acid producing units to polyolefin, e.g., 1.1 to 1.8, etc. are# based upon the total amount of polyolefin, that is, the total of both the reacted and unreacted polyolefin, used to make the product.

The reaction is preferably conducted in the substantial absence of 2 and water (to avoid competing side reactions), and to this end can be conducted in an atmosphere of dry N2 gas or other gas inert under the reaction conditions. The reactants can be charged separately or together as a mixture to the reaction zone, and the reaction can be carried out continuously, semi-continuously or batchwise. Although not generally necessary, the reaction can be carried out in the presence of a liquid diluent or solvent, e.g., a hydrocarbon diluent such as mineral lubricating oil, toluene, xylene, dichlorobenzene and the like.The polymer substituted mono- or dicarboxylic acid material thus formed can be recovered from the liquid reaction mixture, e.g., after stripping the reaction mixture, if desired, with an inert gas such as N2 to remove unreacted unsaturated carboxylic reactant.

If desired, a catalyst or promoter for reaction of the olefin polymer and monounsaturated carboxylic reactant (whether the olefin polymer and monounsaturated carboxylic reactant are contacted in the presence or absence of halogen (e.g., chlorine) can be employed in the reaction zone. Such catalyst of promoters include alkoxides of Ti, Zr, V and Al, and nickel salts (e.g., Ni acetoacetonate and Ni iodide) which catalysts or promoters will be generally employed in an amount of from about 1 to 5,000 ppm by weight, based on the mass of the reaction medium.

AMINE NEUTRALIZATION OF THE POLYMER SUBSTITUTED MONO- OR DICARBOXYLIC ACID MATERIAL In order to form the poly (C5-Cg lactone) adduct dispersants of the present invention, the polymer-substituted mono- or dicarboxylic material must be neutralized with the selected amido-amine material. This will result in the formation of an imide or amide linkage, or a mixture of imide and amide linkages, in the polymer-substituted dicarboxylic material and in amide linkages in the polymer-substituted monocarboxylic materials and will add a lactone-reactive amino group thereto. The lactone-reactive amino group will initiate the subsequent lactone polymerization to provide the novel dispersants of this invention.

The amido-amine is readily reacted with the selected mono- or dicarboxylic acid material, e.g. poly alkenyl succinic anhydride or poly alkenyl substituted propionic acid, by heating an oil solution containing 5 to 95 wt. % of the mono- or dicarboxylic acid material to about 100 to 250#C., preferably 125 to 175 C., generally for 1 to 10, e.g. 2 to 6 hours until the desired amount of water is removed. The heating is preferably carried out to favor formation of imides, amides or mixtures of imides and amides, rather than salts. Generally from 0.5 to 5 (e.g., 0.75 to 3), preferably from about 1.5 to 2.5 moles of monoor dicarboxylic acid moiety content (e.g., grafted maleic anhydride content or grafted acrylic acid content) is used per equivalent of amido-amine reactant, e.g., amine.

An example of the reaction of an amido-amine reactant with a polymer substituted dicarboxylic acid producing reactant is the reaction of polyisobutylene succinic anhydride (PIBSA) with a poly amido-amine having two terminal -NH2 groups, which can be illustrated as follows:

wherein x and y are each integers of from 1 to 10; preferably the sum of x + y is at least 3, e.g., 4 to 20.

An example of the reaction of an amido-amine reactant with a polymer-substituted monocarboxylic acid producing reactant is the reaction of polyisobutylene propionic acid (PIBA) with a poly amido-amine having two terminal -NH2 groups, which can be illustrated as follows:

wherein x and y are each integers of from 0 to 10, with the proviso that the sum of x + y is at least 1, e.g., 1 to 20 and wherein Z1 and z2 are the same or different and are each moieties of the formula:

It will be understood that the amido-amine reactant B can be employed alone or in admixture with any of the above described amines, such as the polyalkylene polyamines, useful in preparing the amido-amine reactant.

Preferably, the polymer substituted mono- or dicarboxylic acid producing material and amido-amine will be contacted for a time and under conditions sufficient to react substantially all of the primary nitrogens in the amido-amine reactant. The progress of this reaction can be followed by infra-red analysis.

The dispersant-forming reaction can be conducted in a polar or non-polar solvent (e.g., xylene, toluene, benzene and the like), and is preferably conducted in the presence of a mineral or synthetic lubricating oil.

LACTONE POLYMER CAPPING OF THE AMIDO-AMINE NEUTRALIZED POLYMER SUBSTITUTED MONO- OR DICARBOXYLIC MATERIAL In an aspect of invention, the novel poly (CS-Cg lactone) adducts are prepared by polymerizing the lactone using at least one residual amine functionality on the neuralized polymer substituted mono- or dicarboxylic acid material as the ring opening and polymerization initiator.

Useful lactone compounds for this process include polymerizable lactones having at least five carbon atoms in the lactone ring, e.g. 5 to 9 carbon atoms, and preferably at least 6 carbon atoms in the lactone ring, e.g. 6 to 9 carbon atoms. The lactones may be substituted or unsubstituted and the subtituents, if any, may comprise, for example, C1 to C25 straight or branched chain alkyl; aryl, aralkyl, or cycloalkyl having 6 to 60 total carbon atoms; C1 to C12 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-deltavalerolactone, E-caprolactone, methyl-E-caprolactone, dimethyl-E-caprolactone, methoxy-E-caprolactone, cyclohexyl-E-caprolactone, 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 neutralized polymer substituted mono- or dicarboxylic acid material may be carried out, with or without a catalyst, simply by heating a mixture of the lactone and polymer-substituted acid material in a reaction vessel in the absence of a solvent at a temperature of from about 30etc. to about 2000C., more preferrably at a temperature of about 75it. to about 180it., and most preferably about 90' to about l60#C., for a sufficient period of time to effect polymerization. Optionally, a solvent for the monomer and/or polymer can be employed to control viscosity and/or reaction rates.

In one preferred embodiment of the invention, the C5-C9 lactone is reacted with a polyisobutenyl succinimide which has been prepared by neutralizing polyisobutenyl succinic acid with an aliphatic diamine as outlined above. This reaction can be depicted generally by the following equation when the succinimide has available primary amino functionality (Eq. 5)::

where x and y are each numbers from 1 to 10, m has an average value of from about 0.1 to about 100, preferably from 0.2 to about 20, z is from 4 to 8, PIB represents polyisobutylene having a number average molecular weight of from about 700 to about 5,000, preferably about 900 to about 3,000, and the ratio (functionality) of succinic acid moietien is from about 0.7 to about 2.0 per equivalent weight of polyisobutylene, and more preferably from about 1.00 to about 1.5 per equivalent weight of polyisobutylene.

When the succiminide has available secondary amino functionality, the reaction can be depicted generally by the following equation (Eq. 6):

where x and y are each numbers from 1 to 4, z is a number from 4 to 8, and m has an average value of from zero to about 100, preferably from 1 to about 20.

Catalysts useful in the promotion of the above-identified reaction 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 may be added to the reaction mixture at any effective concentration level. However, the catalyst generally is added at a concentration 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 initiator molecule and form a polymer adduct containing the polylactone 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 groups. In the presence of a catalyst, such as stannous octanoate, it is believed that the lactone preferably will react somewhat more readily with the terminal hydroxyl group than with a secondary amino group thus producing a polylactone ester adduct.If the stoichiometry of the initiator is such that very few primary amino groups are available, secondary amino groups will be converted to polylactone adducts. This preferance towards reaction with the primary amino groups results in an added benefit in those specific applications where the presence of primary amines is considered to be deleterious to performance (such as in diesel dispersancy). In those cases, the present invention provides a means for replacing the deleterious amine group with an amide function and a desirable hydroxyl group.

In the reactions shown above in Equation 6, the values of m and n or the average degree of polymerization (DP) (wherein DP=(m+n)/2) of the lactone monomers may vary depending upon the intended application. At DP's of much greater than about 10, e.g., greater than about 50, the polylactone adducts can exhibit crystallinity; a characteristic 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 neutralized hydrocarbyl substituted dicarboxylic acid material, the average degree of polymerization (DP) should be between about 1 and about 100, more preferably between about 1 and about 50, and most preferably between about 0.2 and about 20.

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-C9 lactone derived dispersant materials. Complex forming metal reactants include the nitrates, thiocyanates, halides, carboxylates, phosphates, thio-phosphates, sulfates, 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 those formed by reacting the novel additives of the present invention with one or more post-treating reagents, usually selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters, boron acids, sulfur, sulfur chlorides, phosphorous sulfides and oxides, carboxylic acid or anhydride acylating agents, epoxides and episulfides and acrylonitriles. The reaction of such posttreating 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-C9 lactone derived additive compound with a boron oxide, halide, ester or acid. Treatment may be carried out by adding about 1-3 wt.S of the boron compound, preferably boric acid, and heating and stirring the reaction mixture at about 135so to 165it for 1 to 5 hours followed by nitrogen stripping and filtration, if desired. Mineral oil or inert organic solvents facilitate the process.

Other dispersants which can be employed in admixture with the novel amido-amine dispersants of this invention include those derived from the aforesaid long chain hydrocarbyl substituted dicarboxylic acid material and the aforesaid amines, such as polyalkylene polyamines, e.g., long chain hydrocarbyl substituted succinimides.

Exemplary of such other dispersants are those described in co-pending Serial No. 95,056, filed September 9, 1987.

A preferred group of ashless dispersants are those derived from polyisobutylene substituted with succinic anhydride groups and reacted with amido-amine adducts formed by reacting polyethylene amines, e.g., tetraethylene pentamine, pentaethylene examine, polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with an acrylate-type compound of formula (XIV) above.One particularly preferred dispersant combination involves a polyisobutene substituted with succinic anhydride groups and reacted with (1) an amido-amine adduct which has been formed by the reaction of (1) a polyalkylene polyamine, and (b) an acrylate-type reactant selected from the group consisting of lower alkyl alky-acrylates (e.g., methyl, ethyl, iso-propyl, propyl, iso-butyl, n-butyl, tert-butyl, etc , esters of methacrylic acid, acrylic acid, and the like), and (2) a Cg-Cg (preferably C6-Cg) lactone material (e.g., delta-valerolactone, methyl-deltavalerolactone, E-caprolactone, methyl-E-caprolactone, dimethyl-E-caprolactone, methoxy-E-caprolactone, cyclohexyl-E-caprolactone, methylbenzyl-E-caprolactone, caprylolactone, methyl-caprylolactone and the like).

The dispersants of the present invention can be incorporated into a lubricating oil in any convenient way.

Thus, these mixtures can be added directly to the oil by dispersing or dissolving the same in the oil at the desired level of concentration of the dispersant. Such blending into the additional lube oil can occur at room temperature or elevated temperatures. Alternatively, the dispersants can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then blending the concentrate with a lubricating oil basestock to obtain the 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 those formed by reacting the novel additives of the present invention with one or more post-treating reagents, usually selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron esters, boron acids, sulfur, sulfur chlorides, phosphorous sulfides and oxides, carboxylic acid or anhydride acylating agents, epoxides and episulfides and acrylonitriles. The reaction of such posttreating 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-C9 lactone derived additive compound with a boron oxide, halide, ester or acid.Treatment may be carried out by adding about 1-3 wt.% of the boron compound, preferably boric acid, and heating and stirring the reaction mixture at about 135it to 165'C for 1 to 5 hours followed by nitrogen stripping and filtration, if desired. Mineral oil or inert organic solvents facilitate the process.

A preferred group of ashless dispersants are those derived from polyisobutylene substituted with succinic anhydride groups and reacted with amido-amine adducts formed by reacting polyethylene amines, e.g., tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof, with an acrylate-type compound of formula (XIV) above.One particularly preferred dispersant combination involves a polyisobutene substituted with succinic anhydride groups and reacted with (1) an amido-amine adduct which has been formed by the reaction of (1) a polyalkylene polyamine, and (b) an acrylate-type reactant selected from the group consisting of lower alkyl alky-acrylates (e.g., methyl, ethyl, iso-propyl, propyl, iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid, acrylic acid, and the like), and (2) a Cg-Cg (preferably C6-Cg) lactone material (e.g., delta-valerolactone, methyl-deltavalerolactone, E-caprolactone, methyl-E-caprolactone, dimethyl-E-caprolactone, methoxy-E-caprolactone, cyclohexyl-E-caprolactone, methylbenzyl-E-caprolactone, caprylolactone, methyl-caprylolactone and the like).

Thus, these mixtures can be added directly to the oil by dispersing or dissolving the same in the oil at the desired level of concentration of the dispersant. Such blending into the additional lube oil can occur at room temperature or elevated temperatures. Alternatively, the dispersants can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then. blending the concentrate with a lubricating oil basestock to obtain the final formulation. Such dispersant concentrates will typically contain (on an active ingredient (A.I.) basis) from about 20 to about 60 wt.%, and preferably from about 10 to about 40 wit.*, dispersant additive, and typically from about 30 to 90 wt.%, preferably from about 40 to 60 wit.8, base oil, based on the concentrate weight.

The lubricating oil basestock for the dispersant typically is adapted to perform a selected function by the incorporation of additional additives therein to form lubricating oil compositions (i.e., formulations).

LUBRICATING 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 liquid petroleum fuels such as middle distillates boiling from about 65 to 430 C., including kerosene, 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 about 0.5, and preferably 0.005 to about 0.1 weight percent, based on the total weight of the composition, will usually be employed.

The distillate fuel oils will generally boil within the range of about 1200C to about 500 C, e.g. 150 to about 400#C. The fuel oil can comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates, etc. The most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels and heating oils. The heating oil may be a straight atmospheric distillate, or it may frequently contain minor amounts, e.g. 0 to 35 wt.%, of vacuum gas oil and/or of cracked gas oils. The low temperature flow problem is most usually encountered with diesel fuels and with heating oils.

Oil soluble, as used herein, means that the additives are soluble in the fuel at ambient temperatures, e.g., at least to the extent of about 0.1 wt.% additive in the fuel oil at 25'C.

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.

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 compressionignited 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 power transmitting fluids such as automatic transmission fluids, tractor 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 invention may be suitably incorporated into synthetic base oils such as alkyl esters of dicarboxylic acids, polyglycols and alcohols, polyalphaolefins, alkyl benzenes, organic esters of phosphoric acids, polysilicone oils, etc.

The lubricating oil base stock conveniently has a viscosity of typically about 2.5 to about 12, and preferably about 2.5 to about 9 cs. at lOO#C.

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, 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 sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular dispersant, if desired.

Lubricating oil compositions, e.g. automatic transmission fluids, heavy duty oils suitable for gasoline and diesel engines, etc., can be prepared with the additives of the invention. Universal type crankcase oils wherein the same lubricating oil compositions can be used for both gasoline and diesel engine can also be prepared.

These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations.

Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, friction modifiers, etc. All is described in U.S. Patent 4,797,219, the disclosure of which is hereby incorporated by reference in its entirety. 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.

In the preparation of lubricating oil formulations it is common practice to introduce the additives in the form of 10 to 80 wt. %, e.g. 20 to 80 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually these concentrates may be diluted with 3 to 100, e.g. 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g.

crankcase motor oils. The purpose of concentrates, of course, is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend. Thus, a dispersant would be usually employed in the form of a 40 to 50 wt. % concentrate, for example, in a lubricating oil fraction.

The ashless dispersants of the present invention will be generally used in admixture with a lube oil basestock, comprising an oil of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. 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 to the absence of the additive.

Additional conventional additives selected to meet the particular requirements of a selected type of lubricating oil composition can be included as 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.g., 0.1 to 10, and preferably from about 0.1 to about 7 wt.%, based on the weight of said composition.

Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters and C13 Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.

Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.

Compositions when containing these conventional additives are typically blended into the base oil in amounts effective to provide their normal attendant function. Representative effective amounts of such additives (as the respective active ingredients) in the fully formulated oil are illustrated as follows: Wt.% A.I. Wt.% A.I.

ComPositions (Preferred) (Broad) Viscosity Modifier .01-4 0.01-12 Detergents 0.01-3 0.01-20 Corrosion Inhibitor 0.01-1.5 .01-5 Oxidation Inhibitor 0.01-1.5 .01-5 Dispersant 0.1-8 .1-20 Pour Point Depressant 0.01-1.5 .01-5 Anti-Foaming Agents 0.001-0.15 .001-3 Anti-Wear Agents 0.001-1.5 .001-5 Friction Modifiers 0.01-1.5 .01-5 Mineral Oil Base Balance Balance When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or disper PreparatiOn of Polyisobutylene Succinic Anhydride (PIBSA) EXAMPLE 1 A polyisobutenyl succinic anhydride having a succinic anhydride (SA) to polyisobutenylene mole ratio ( i . e., a SA::PIB ratio) of 1.04 is prepared by heating a mixture of 100 parts of polyisobutylene (940 Rn; RW/Rn = 2.5) with 13 parts of maleic anhydride to a temperature of about 220 C. When the temperature reaches 1200C., the chlorine addition is begun and 10.5 parts of chlorine at a constant rate are added to the hot mixture for about 5.5 hours. The reaction mixture is then heat soaked at 220 C. for about 1.5 hours and then stripped with nitrogen for about one hour. The resulting polyisobutenyl succinic anhydride has an ASTN Saponification Number of 112. The PIBSA product is 90 wt.% active ingredient (A. I . ), the remainder being primarily unreacted PIB.

EXAMPLE 2 A polyisobutenyl succinic anhydride (PIBSA) having a SA:PIB ratio of 1.24, is prepared by heating a mixture of 100 parts of polyisobutylene (1320 Rn; Rw/Rn n 2.5) with 11 parts of maleic anhydride to a temperature of about 220 c. When the temperature reaches 120 C., the chlorine addition is begun and 10 parts of chlorine at a constant rate are added to the hot mixture for about 5 hours. The reaction mixture is then heat soaked at 220#C. for about 1.5 hours and then stripped with nitrogen for about one hour. The resulting polyisobutenyl succinic anhydride was diluted with S150 mineral oil to obtain a product having an ASTM Saponification Number of 69.The PIBSA product is 59 wt.% active ingredient (A. I . ), the remainder being primarily unreacted PIB and mineral oil.

EXAMPLE3 A polyisobutenyl succinic anhydride having a SA:PIB ratio of 1.13 is prepared by heating a mixture of 100 parts of polyisobutylene (2225 R n ; Rw/Rn = 2.5) with 6. 14 parts of maleic anhydride to a temperature of about 220it. When the temperature reaches 1204C., the chlorine addition is begun and 5.07 parts of chlorine at a constant rate are added to the hot mixture for about 5.5 hours. The reaction mixture is then heat soaked at 220*C. for about 1.5 hours and then stripped with nitrogen for about one hour. The resulting polyisobutenyl succinic anhydride has an ASTM Saponification Number of 54.The PIBSA product is 80 wt.% active ingredient (A.I.), the remainder being primarily unreacted PIB.

Preparation of Amido Amine - PIBSA Adducts A series of dispersants are prepared according to the method disclosed in our copending application Serial No. 126,405, filed November 30, 1987, by reacting the selected PIBSA, prepared as in Examples 1-3 above, with one of two amido-amines or with a polyalkylene polyamine, tetraethylene pentamine (TEPA). Amido-amine I is prepared by reacting TEPA with methyl acrylate at a 2:1 TEPA:methyl acrylate molar ratio, to form a product mixture having 30.1 wt.% total N, 8.2 wt.t primary N, and containing about 50 wt.% unreacted TEPA. Amido-amine II is prepared similarly, except that a 1.5:1 TEPA:methyl acrylate molar ratio is employed, to form a product mixture containing 28.3 wt.% total N, 6.1 wt.S primary N, and about 25 wt.% unreacted TEPA.

The amination reactions are carried out as follows: EXAMPLE 4 A mixture of 200 parts by weight of the PIBSA product formed in Example 1 and 188 parts of S150 mineral oil is heated to 150*C. under N2. Then 32.3 parts of amido-amine I are added dropwise while stirring and light nitrogen sparging. The mixture is nitrogen stripped at 150'C for 3 hours and then filtered.

EXAMPLE 5 A mixture of 200 parts by weight of the PIBSA product formed in Example 1 and 200 parts of S150 mineral oil is heated to 150so. under N2. Then 43.4 parts of amido-amine II are added dropwise while stirring and light nitrogen sparging. The mixture is nitrogen stripped at 150*C for 3 hours and then filtered.

EXAMPLE 6 A mixture of 200 parts by weight of the PIBSA product formed in Example 2 and 55 parts of S150 mineral oil is heated to 1500C. under N2. Then 21 parts of amido-amine I are added dropwise while stirring and light nitrogen sparging. The mixture is nitrogen stripped at 150it for 3 hours and then filtered.

EXAMPLE 7 A mixture of 200 parts by weight of the PIBSA product formed in Example 2 and 62 parts of S150 mineral oil is heated to 150 C. under N2. Then 28.2 parts of amido-amine II are added dropwise while stirring and light nitrogen sparging. The mixture is nitrogen stripped at 150*C for 3 hours and then filtered.

EXAMPLE 8 A mixture of 200 parts by weight of the PIBSA product formed in Example 3 and 126 parts of S150 mineral oil is heated to l50#C. under N2. Then 15.9 parts of amido-amine I are added dropwise while stirring and light nitrogen sparging. The mixture is nitrogen stripped at 150it for 3 hours and then filtered.

EXAMPLE 9 A mixture of 200 parts by weight of the PIBSA product formed in Example 3 and 132 parts of S150 mineral oil is heated to 1500C. under N2. Then 21.3 parts of amido-amine II are added dropwise while stirring and light nitrogen sparging. The mixture is nitrogen stripped at 150it for 3 hours and then filtered.

EXAMPLES 10 - 21 In a series of runs, the PIBSA-maido-amine adduct products of Examples 4 - 9 are contacted with E-caprolactone, in the amounts indicated in the Table below, to form caprolactone modified PIBSA-amido-amine adducts of this invention. In each run, the indicated quantity of E-caprolactone, and 0.25 grams of stannous octanoate. This reaction mixture is heated to 150'C and held at this temperature for 2 hours while stirring under a nitrogen blanket. The resulting polycaprolactone adduct is stripped with a mild stream of nitrogen for one half hour and collected. Infrared analysis of the polycaprolactone adduct indicates complete opening of the lactone ring.

TABLE A EXAMPLE PIBSA-AMIDO-AMINE ADDUCT E-CAPROLACTONE EXAMPLE EXAMPLE NO. MOLE {mole) 10 4 0.1 0.1 11 4 0.1 0.05 12 5 0.1 ' 0.1 13 5 0.1 0.05 14 6 0.06 0.06 15 6 0.06 0.03 16 7 0.06 0.06 17 7 0.06 0.03 18 8 0.048 0.048 19 8 0.048 0.024 20 9 0.048 0.048 21 9 0.048 0.024 The following lubricating oil compositions are prepared using the lactone modified amido-amine dispersants of Examples 10-21. The resulting compositions are then tested for sludge inhibition (via the SIB test) and varnish inhibition (via the VIB test), as described below.

The SIB test has been found, after a large number of evaluations, to be an excellent test for assessing the dispersing power of lubricating oil dispersant additives.

The medium chosen for the SIB test is a used crankcase mineral lubricating oil composition having an original viscosity of about 325 SUS at 38'C that had been used in a taxicab that is driven generally for short trips only, thereby causing a buildup of a high concentration of sludge precursors. The oil that is used contained only a refined base mineral lubricating oil, a viscosity index improver, a pour point depressant and zinc dialkyldithiophosphate anti-wear additive. The oil contained no sludge dispersant. A quantity of such used oil is acquired by draining and refilling the taxicab crankcase at 1000-2000 mile intervals.

The SIB test is conducted in the following manner: the aforesaid used crankcase oil, which is milky brown in color, is freed of sludge by centrifuging for one hour at about 39,000 gravities (gs.). The resulting clear bright red supernatant oil is then decanted from the insoluble sludge particles thereby separated out. However, the supernatant oil still contains oil-soluble sludge precursors which on heating under the conditions employed by this test will tend to form additional oil-insoluble deposits of sludge. The sludge inhibiting properties of the additives being tested are determined by adding to portions of the supernatant used oil, a small amount, such as 0.5, 1 or 2 weight percent, of the particular additive being tested.Ten grams of each blend being tested are placed in a stainless steel centrifuge tube and are heated at 135it for 16 hours in the presence of air. Following the heating, the tube containing the oil being tested is cooled and then centrifuged for about 30 minutes at room temperature at about 39,000 gs. Any deposits of new sludge that form in this step are separated from the oil by decanting the supernatant oil and then carefully ishing the sludge deposits with 25 ml of heptane to remove all remaining oil from the sludge and further centrifuging.

The weight of the new solid sludge that has been formed in the test, in milligrams, is determined by drying the residue and weighing it. The results are reported as amount of precipitated sludge in comparison with the precipitated sludge of a blank not containing any additional additive, which blank is normalized to a rating of 10. The less new sludge precipitated in the presence of the additive, the lower the SIB value and the more effective is the additive as a sludge dispersant. In other words, if the additive gives half as much precipitated sludge as the blank, then it would be rated 5.0 since the blank will be normalized to 10.

The VIB test is used to determine varnish inhibition. Here, each test sample consisted of 10 grams of lubricating oil containing a small amount of the additive being tested. The test oil to which the additive is admixed is of the same type as used in the above-described SIB test. Each ten gram sample is heat soaked overnight at about 140iC and thereafter centrifuged to remove the sludge. The supernatant fluid of each sample is subjected to heat cycling from about 1500c to room temperature over a period of 3.5 hours at a frequency of about 2 cycles per minute. During the heating phase, gas which is a mixture of about 0.7 volume percent SO2, 1.4 volume percent NO and balance air is bubbled through the test samples. During the cooling phase, water vapor is bubbled through the test samples. At the end of the test period, which testing cycle can be 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 imposed on the walls is rated to values of from 1 to 11 with the higher number being the greater amount of varnish, in comparison with a blank with no additive that is rated 11.

10.00 grams of SIB test oil are mixed with 0.05 grams of the products of the Examples as described in Table II and tested in the aforedescribed SIB and VIB tests.

The above data thereby obtained show that the lactone modified amido-amine dispersants of this invention have excellent SIB/VfB performance and sludge and varnish inhibiting properties.

EXAMPLE 22 A series of lubricating formulations were prepared in which the dispersant comprises the lactone modified amido-amine dispersant of Examples 10-21. Each lubricating composition contains 6 vol% of the dispersant product mixture formed in Examples 10-21, respectively. Each lubricating composition also contained in equal proportions, mineral lubricating oil, a mixture of overbased Mg sulfonate detergent inhibitor and overbased Ca sulfonate detergent inhibitor, zinc dialkyl dithiophosphate antiwear agent, antioxidant and ethylene propylene viscosity index improver.

EXAMPLE 23.

To a stirred reaction vessel is added 1.5 moles of tetraethylene pentaamine (TEPA) at room temperature, followed by 1 mole of ethyl acrylate, under a N2 blanket. The resulting exothermic reaction raises the reaction mass' temperature to about 75it. Then an infra-red analysis (IR) is made of the reaction mass, which shows the disappearance of the double bond of the ethyl acrylate, but reveals ester groups to be still present. A gas chromatographic analysis of the reaction mass is also then taken, which shows unreacted TEPA still present.

An esterification catalyst, stannous octanoate, is then added (1 drop) to the reaction mass, and the temperature of the reaction vessel is increased to 130 to 135-C with mild N2 sweeping. The by-product alcohol (ethanol) is removed as a vapor from the reaction vessel with the sweep N2, and the progress of the reaction is followed by IR until the ester absorption band disappears.

The reaction mass is stirred for additional 1 hour at 130 to 135'C to ensure completion of the reaction. A total reaction time of 6 hours is used. The resulting product mixture containing the amido-amine is analyzed and is found to contain 4.8 milliequivalents of primary amine per gram of amido-amine and a nitrogen content of 30.1 wt%.

To the reaction mass obtained above is added 1.5 moles of E-caprolactone, to form a polycaprolactoneamido-amine adduct. No additional catalyst is added; rather, the catalyst used in formation of the polycaprolactone-amido-amine adduct is allowed to function as the catalyst for the caprolactone ring opening reaction. This reaction mixture is heated to 1500C and held at this temperature for 2 hours while stirring under a nitrogen blanket. The resulting polycaprolactone adduct is stripped with a mild stream of nitrogen for one half hour and collected. Infrared analysis of the polycaprolactone adduct indicates complete opening of the lactone ring.

To the polycaprolactone-amido-amine product obtained above is added 3 mole of the PIBSA formed as in Example 1 above, using the reaction conditions described in Example 4 to form a product mixture containing the desired PIBSA-polycaprolactone-amido-amine adduct.

EXAMPLE 24.

The procedure of Example 11 was repeated except that the esterification catalyst comprised titanium tetrabutoxide, and similar results were obtained.

It will be understood that the reactants (A), (B) and (C) can be contacted for reaction in any order. While the above illustrative examples exemplify methods wherein the long chain hydrocarbyl substituted dicarboxylic acid producing material is first reacted with the amido-amine and the resuling adduct modified by reaction with the polymerizable lactone (Examples 1 - 21) and the method wherein the polymerizable lactone and amido-amine are first contacted to form an adduct followed by contacing the lactone-amido-amine adduct with the the long chain hydrocarbyl substituted dicarboxylic acid producing material (Examples 22 - 24), any other order of addition can be used. Alternatively, the reactants can be charged to the reaction zone simultaneously.

The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.

Claims

CLAIMS:

1. A poly (C5 to Cg) adduct of an aminated hydrocarbyl substituted dicarboxylic acid producing material useful as an oil additive and formed by reacting (A) a long chain hydrocarbyl substituted C4 to C10 monounsaturated mono- or dicarboxylic acid producing material formed by reacting an olefin polymer of C2 to C10 monoolefin having a number average molecular weight of about 300 to 10,000 and a C4 to C10 monounsaturated acid material, said acid producing material having an average of at least about 0.5 mono- or dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material; (B) an amido-amine or a thioamido-amine characterized by being a reaction product of at least a polyamine and an alpha, beta-unsaturated compound of the formula::

wherein X is sulfur or oxygen, Y is -OR4, -SR4, or -NR4(R5) , and R1 R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl; and (C) a C5 to Cg lactone material, said poly (C5 to Cg) adduct containing the unit (C(O)(CH2)zO)#m wherein m has an average value of from 0.1 to 100 and z is 4 to 8.

2. The poly (C5 - Cg) adduct according to claim 1, wherein reactants (A) and (B) are first contacted, followed by addition of reactant (C).

3. The poly (C5 - Cg) adduct according to claim 1, wherein reactants (B) and (C) are first contacted, followed by addition of reactant (A).

4. The poly (C5 - Cg) adduct according to claim 1, wherein said polyamine comprises amines containing from 2 to 60 carbon atoms and from 3 to 12 nitrogen atoms per molecule.

5. The poly (C5 - Cg) adduct according to claim 4, wherein said amine comprises a polyalkylenepolyamine wherein said alkylene groups each contain from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to about 9 nitrogen atoms per molecule.

6. The poly (C5 - Cg) adduct according to claim 1, wherein said hydrocarbyl substituted C4 to C10 monounsaturated dicarboxylic acid producing material comprises polyisobutylene of about 900 to 5000 number average molecular weight substituted with succinic anhydride moieties, said polyamine comprises polyalkylenepolyamine wherein said alkylene groups each contain from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to 9 nitrogen atoms per molecule, and said alpha, beta-unsaturated compound comprises at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.

7. The poly (C5 - Cg) adduct according to claims 1 or 5, wherein said polyamine comprises polyethylenepolyamine or polypropyleneamine and said poly (C5 - Cg) adduct is borated.

8. The poly (C5 - Cg) adduct according to claim 7, wherein said poly (C5 - C9) adduct contains about 0.05 to 2.0 weight percent boron.

9. The poly (C5 - Cg) adduct according to claim 7, wherein said olefin polymer comprises polyisobutylene.

10. The poly (C5 - Cg) adduct of claim 9 wherein the ratio of acid producing moieties per molecule of olefin polymer in said poly (C5 - Cg) adduct is from about 0.9 to 1.3.

11. The poly (C5 - Cg) adduct of claim 10, wherein said number average molecular weight of said olefin polymer is from about 1300 to 4,000.

12. The poly (C5 - Cg) adduct according to claims 1 or 5 wherein about 0.5 to 5 moles of said acid producing material dicarboxylic acid moiety content are employed per primary nitrogen equivalent of said amido-amine.

13. The poly (C5 - Cg) adduct according to claims 1 or 5 wherein said polyamine contains an average of at least 2 primary nitrogen atoms per molecule, said X group is oxygen and said polyamine and said alpha, beta-unsaturated compound are contacted in an amount of from about 3 to 5 equivalents of said polyamine (based on said primary amine content) per mole of said alpha, beta unsaturated compound.

14. The poly (C5 - Cg) adduct according to claim 13 wherein said amido-amine contains an average of from 1 to 3 amido groups per molecule of said amido-amine.

15. The poly (C5 - Cg) adduct according to claims 1 or 5 wherein said polyamine contains an average of at least 2 primary nitrogen atoms per molecule, said X group is sulfur and said polyamine and said alpha, beta-unsaturated compound are contacted in an amount of from about 3 to 5 equivalents of said polyamine (based on said primary amine content) per mole of said alpha, beta unsaturated compound.

16. The poly (C5 - Cg) adduct according to claim 15 wherein said amido-amine contains an average of from 1 to 3 amido groups per molecule of said amido-amine.

17. The poly (C5 - Cg) adduct according to claim 1 wherein said C5 to Cg lactone material is E-caprolactone.

18. The poly (C5 - C9) adduct according to claim 1 wherein said C5 to Cg lactone material comprises at least one member selected from the group consisting of delta-valerolactone, methyl-delta valerolactone, E-caprolactone, methyl-E-caprolactone, dimethyl-E-caprolactone, methoxy-E-caprolactone, cyclohexyl-E-caprolactone, methylbenzyl-E-caprolactone and caprylolactone, methyl-caprylolactone.

19. A process for producing a poly (C5 - cg) adduct useful as an oil additive which comprises: (a) providing a hydrocarbyl substituted C4 to C10 monoolefin having a number average molecular weight of about 700 to 10,000 and a C4 to C10 monounsaturated acid material, said acid producing material having an average of at least about 0.8 dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material; (b) providing an amido-amine compound having at least one primary amino group prepared by reacting at least one polyamine with at least one alpha, beta-unsaturated compound of the formula::

wherein X is sulfur or oxygen, Y is -oR4, -SR4, or -NR4(R5) and R1 R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl; (c) contacting the said acid producing material with said amido-amine compound under conditions sufficient to effect reaction of at least a portion of the primary amino groups on said amido-amine compound with at least a portion of the acid-producing groups in said acid producing material, to form a first adduct; and (d) contacting said first adduct with a C5 to Cg lactone material under conditions sufficient to ring open the lactone ring of said lactone material to form said poly (C5 - C9) adduct containing the unit #(C(O)(CH2)zO)#m wherein m has an average value of from 0.1 to 100 and z is 4 to 8.

20. The process according to claim 19 wherein said polyamine comprises amines containing from 2 to 60 carbon atoms and from 3 to 12 nitrogen atoms per molecule.

21. The process according to claim 20, wherein said amine comprises a polyalkylenepolyamine wherein said alkylene groups each contain from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to about 9 nitrogen atoms per molecule.

22. The process according to claim 19, wherein said hydrocarbyl substituted C4 to C10 monounsaturated dicarboxylic acid producing material comprises polyisobutylene of about 900 to 5000 number average molecular weight substituted with succinic anhydride moieties, said polyamine comprises polyalkylenepolyamine wherein said alkylene groups contain from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to 9 nitrogen atoms per molecule, and said acrylate-type compound comprises at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.

23. The process according to claims 19 or 22, wherein said polyamine comprises polyethylenepolyamine and wherein poly (C5 - Cg) adduct is borated.

24. The process according to claims 19 or -22, wherein said poly (C5 - Cg) adduct is borated to provide from about 0.05 to 2.0 weight percent boron in said borated poly (C5 - Cg) adduct.

25. The process according to claim 19, wherein said olefin polymer comprises polyisobutylene.

26. The process of any one of claims 19 to 22, wherein the ratio of acid producing moieties per molecule of olefin polymer in said poly (C5 - Cg). adduct is from about 0.9 to 1.3.

27. The process or claim 24, wherein said number average molecular weight of said olefin polymer is from about 1300 to 4,000.

28. The process of claim 19, wherein said monounsaturated acid material comprises maleic anhydride.

29. A concentrate containing from about 3 to 45 wt. % of the poly (C5 - Cg) adduct of claim 1.

30. A concentrate containing from about 10 to 35 wt. % of the poly (C5 - Cg) adduct of claim 4.

31. A lubricating oil composition containing from about 0.1 to 20 wt. % of the poly (C5 - Cg) adduct prepared according to claim 19.

32. A process for producing a dispersant useful as an oil additive which comprises: (a) providing a hydrocarbyl substituted C4 to C10 monoolefin having a number average molecular weight of about 700 to 10,000 and a C4 to C10 monounsaturated acid material, said acid producing material having an average of at least about 0.8 dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said acid producing material; (b) providing an amido-amine compound having at least one primary amino group prepared by reacting at least one polyamine with at least one alpha, beta-unsaturated compound of the formula::

wherein Y is -OR4, -SR4, or -NR4 (R5) , and R1, R2, R3, R4 and R5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl; (c) contacting the said acid producing material with said amido-amine compound under conditions sufficient to effect reaction of at least a portion of the primary amino groups on said amido-amine compound with at least a portion of the acid-producing groups in said acid producing material, to form a first adduct; and (d) contacting said first adduct with a C6 to Cg lactone material under conditions sufficient to ring open the lactone ring of said lactone material to form said poly (C6 - C9) adduct containing the unit [ C(O)(CH2)zO)#m wherein m has an average value of from 0.1 to 100 and z is 4 to 8.

33. The process according to claim 32 wherein said polyamine comprises amines containing from 2 to 60 carbon atoms and from 3 to 12 nitrogen atoms per molecule.

34. The process according to claim 32, wherein said hydrocarbyl substituted C4 to C10 monounsaturated dicarboxylic acid producing material comprises polyisobutylene of about 900 to 5000 number average molecular weight substituted with succinic anhydride moieties, said polyamine comprises polyalkylenepolyamine wherein said alkylene groups each contain from 2 to 6 carbons and said polyalkylenepolyamine contains from 5 to 9 nitrogen atoms per molecule, and said acrylate-type compound comprises at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.

35. The process according to claims 32 or 33, wherein said polyamine comprises polyethylenepolyamine and wherein said dispersant is borated.

36. The process according to claims 32 or 34, wherein said dispersant is borated to provide from about 0.05 to 2.0 weight percent boron in said borated dispersant.

37. The process according to claim 31, wherein said olefin polymer comprises polyisobutylene.

38. The process of claim 37, wherein the ratio of acid producing moieties per molecule of olefin polymer in said dispersant is from about 0.9 to 1.3.

39. The process of claim 34, wherein said number average molecular weight of said olefin polymer is from about 1300 to 4,000.

40. The process of claims 32 or 34, wherein said monounsaturated acid material comprises maleic anhydride.

41. The process of claim 32 wherein said C5 to Cg lactone material is E-caprolactone.

42. The process of claim 32 wherein said C5 to Cg lactone material comprises at least one member selected from the group consisting of delta-valerolactone, methyl-del tavalerolactone, E-caprolactone, methyl -E-caprolactone, dimethyl-E-caprolactone, methoxy-E-caprolactone, cyclohexyl-E-caprolactone, methylbenzyl-E-caprolactone and caprylolactone, methyl-caprylolactone.

43. A lubricating oil composition containing from about 0.1 to 20 wt. % of the dispersant prepared according to claim 31.

44. The poly (C6 - Cg) adduct of claim 1, wherein said monounsaturated acid material comprises maleic anhydride.

45. The process according to claim 32, wherein said amine comprises a polyalkylenepolyamine wherein said alkylene groups each contain from 2 to 40 carbons and said polyalkylenepolyamine contains from 5 to about 9 nitrogen atoms per molecule.