CA1284145C

CA1284145C - Diesel lubricants and methods

Info

Publication number: CA1284145C
Application number: CA000517724A
Authority: CA
Inventors: David E. Ripple; Jack Lee Karn; Daniel M. Vargo
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1985-09-19
Filing date: 1986-09-08
Publication date: 1991-05-14
Anticipated expiration: 2008-05-14
Also published as: AU591710B2; EP0240516A1; EP0240516B1; ZA867071B; DE3689473D1; ES2001974A6; FI872181A0; AU6338286A; MX169871B; BR8606979A; WO1987001722A1; JPS63501018A; DE3689473T2; FI872181A

Abstract

Title: DIESEL LUBRICANTS AND METHODS

Abstract of the Disclosure A diesel lubricant exhibiting improved ability to minimize undesirable viscosity increases when used in diesel engines is described. More particularly, in accordance with the present invention, a diesel lubricant is described which comprises a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising (A) at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -NH- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of at least about 1200 and an Mw/Mn ratio of at least about 1.5, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each equivalent weight of substituent groups, and (B) at least one basic alkali metal salt of at least one acidic organic compound having a metal ratio of at least about 2. The diesel lubricant also may contain (C) at least one oil-soluble neutral or basic alkaline earth metal salt of at least one acidic compound.

Preferably, the basic alkali metal salt (B) contained in the diesel lubricants of the invention is at least one sodium or potassium salt and more preferably, a sodium salt of a sulfonic acid.
Optionally, the diesel lubricants of the invention can contain (C) at least one neutral or basic alkaline earth metal salt of an acidic organic material. The invention also includes methods for preparing the alkali metal salts, particularly the potassium salts, and methods for operating diesel engines which comprises lubricating said engines during operation with the diesel lubricants of the invention.

Description

L4~i Title. DIESEL LUBRICANTS AND METHODS

Backqround o~ the Invention The present invention relates to diesel lubricants, and more paxticularly to diesel lubricants containing additives which are ef~ective to minimize undesirable viscosity increases of the lubricant when the lubricant is used in diesel engines. The invention also relates to methods o~ preparing basic alkali metal sulfonates, particularly basic potassium sulfonates, and a method of operating diesel engines which comprises lukricating said engines during operation with the diesel lubricants o~ the invention.
It is well known that lubricating oils tand to deteriorate under conditions of use in present day internal combustion engines resulting in the formation of sludge, lacquer, carbonaceous materials and resinous materials which tend to adhere to the various engine parts, in particular, the engine rings, grooves and skirts. Furthermore, diesel angines operated at low-speed and high-torque such as under prolonged idle and stop-and-go conditions have experienced extensive and undesirable thicXening of the lubricant. It has been suggested in the prior art ~hat t~e undesirable thickening of the oil is caused by the high levels of insolubles (soot).

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, - -- .: :-'. ' ' '' . ' :, One class of compounds which has been suggested ~or use in lubricating oils, particularly diesel oils, are the normal and overbased sul~urized calcium alkyl phenolates such as described in U.g.
Patents 3,474,035; 3,528,917; and 3,706,632~ These materials function as detergents and dispersants, and also are reported to exhibit antioxidant and anti-thickening properties. Another multi-purpose additive for lubricating oils having antioxidant, anti-thickening, anti-corrosion and detergent proparties is described in U.S. Patent 3,897,352. The additive described in this patent comprises a sulfurizPd, Group II me~al nitrated alkyl phenolate.
As will ba dascribed more fully h~reinafter, the present invention relates to a diesel lubricant containing certain speci~ied types of carboxylic derivative compositions as dispersants and certain basic alkali metal salts. This combination of specific dispersant and detergent is effectiv2 to minimize undesirable viscosity increases of diesel lubricants when used in diesel engines.
Lubricating oil formulations containing oil-soluble carboxylic acid derivatives, and in particular, those ob~ained by the reaction of a carboxylic acid with an amino compound have been described previously such as in U.S. Patents 3,018,250; 3,0~4,195;
3,172,892; 3,216,936; 3,219,666; and 3,272,746. Many of the above-identified patents also describe the use of such carboxylic acid deriva~ives in lubricating oils in combinat-on with ash-containing detergents including basic metal salts o~ acidic organic materials such as sulfonic acids, carboxylic acids, etc~

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~ he particular type of carboxylic acid derivative composition utilized in the diesel lubricant o~ the present invention are described generally in U.S. Patent 4,234,435. This patent also descrlbe~
lubricating compositions containing said carboxylic acid derivative compositions in combination with other additives such as fluidity modifiers, auxiliary detergents and dispersants of the ash-producing or ashless-type, oxidation inhibitors, etc. A lubricating !~ composition containing the carboxylic acid deri~ative, a basic calcium sulfonate, and other traditional additives is described in the '435 patent in Col. 52, lines 1-8.
The second critical component of the diesel ~l lubricants of the present invention is at least one basic alkali metal salt of at least one acidic organic compound having a metal ratio of at least about 2.
Such compositions generally are referred to in the art as metallic or ash-detergents, and the use of such -~ detergents in the lubricating oil formulations has been suggested in many prior art patents. For example, Canadian Patent 1,055~700 describes the use of basic alkali sulfonate di~persions in crankcase lubricants for both spark-ignited and compression-ignited internal combustion engines. The Canadian patent suggests that the basic alkali sulfonate disperæions can be used alone or in combination with other lubricant additives ~nown in the art such as ashless dispe~sants including esters or amides o~ hydrocarbon-substituted succinic acids.
Even though detergents and dispersants, both of the ash and the ashless-type have been utilized previously in diesel lubricants, many of these ~ . .
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lubricants have continued to exhibit undesirable thickening, especially under low-speed, high-torque operation unles~ relatively large amounts o~ khe detergents and dispersanks are incorporated in~o khe diesel lubricants. The use o~ large amounts o~
detergents and dispersants generally is undesirable because of the added~cost.
In order to constitute an acceptable diesel lubricani, a lubricant must achieve two performance levels: Classi~ication CC(Caterpillar l-H) and Clas~i~ication CD(Caterpillar 1-&), with the l-G level representing more severe, highly super-charged engine operation. There continues to be a need in the industry for compositions which can be added to diesel lubricants which will minimize, i~ not prevent, undesirable vi~cosity increase of the lubricant when used in diesel engines, and when formulated into diesel lubricants, the lubricants are capa~le of achieving Caterpillar l-H and Caterpillar l-G level par~ormancs without signi~icantly adding to the cost of the diesel lubricant.
Summary of the Invention A diesel lubricant e~hibiting improved ability to minimize undesirable viscosity increases when used 1~ in diesel engines is described. ~ore particularly, in accordance with the present invention, a diesel lubricant is descri~ed which comprises a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising (A) at lPast one carboxylic derivative composition produced by reacting at least one substitu~ed succinic acylating agent with at least . , .. .

one amino compound containing at least one -NH- group wherein said acylating agent consists o~ sub~tituent groups and succinic groups wherein th~ substituent groups are derived from polyalkene characterized by an Mn value of a~ least about 1200 and an Mw/Mn ratio o~
at least about 1.5, and wherein said acylating agents are characterized by the presence within their structure o~ an average of at least about 1.3 succinic groups for each equivalent weight of substituent groups, and (B) at least one basic alkali metal salt of at least one acidic organic compound having a metal ratio of at least about 2. The diesel lubricant also may contain (C) at least one oil-soluble neutral or basic alkaline earth metal salt of at least one acidic compound.
Preferably, the basic alkali metal salt (B) contained in the diesel lubricants of the invention is at least one sodium salt and more prefarably, a sodium salt of a sulfonic acid. The inven~ion also includes methods for preparing basic metal salts, particularly potassium salts, and methods for operating diesel engines which comprise lubricating aid engines during operation with the die~el lubricants o~ the invention.
Description o~ the Pre~erred Embodiments The diesel lubricants of the present invention comprise a ma;or amount of an oil of lubricating viscosity and a minor amount, su~ficient to minimiza undesirable viscosity increase~ of the lubricant when used in diesel engines, of a composition comprising a combination of (A) at least one carboxylic derivative composition as defined more ~ully below, and (B) at least one basic alkali metal salt of at least one acidic organic compound.

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The oil o~ lubricating viscosity which i5 utilized in the preparation of the diesel lubricants of the invention may be based on natural oils, synkhetlc oils, or mixture~ thereof.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solventotreated or acid-treated mineral lubricating oils of the para~finic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.~; poly(l-hexenes), poly(l-octenes), poly(l-decenes), e~c. and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes, tetra-decylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etheri~ication, etc., constitute another class of known synthetic lubricating oils that can be used. These are exemplified by the oils prepared through polymerizatlon of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight o~ about 1000, dlphenyl ether of .
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4~L45 polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono~
and polycarboxylic esters khereof, ~or example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the C13Oxo acid diester of tetraethylena glycol.
Another suitable class of synthetic lubricating oils that can be used comprises the esters of dicar~oxylic acids (e.g , ph~ha~.ic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2~ethylhexy1 alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etcl) Specific examples of these esters include dibutyl adipate, di(~-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacata, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles o~ 2-ethylhexanoic acid and the l.ike.
Esters useful as synthetic oils also include those made ~rom C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaery-thritol, tripentaerythritol, etG.
Silicon-based oils such as the polyalkyl-, polyaryl-~ polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another use~ul class of ' ~28~

synthetic lubricant~ (e.g., tetraethyl silicake, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butyl-phenyl)silicate, hexyl~(4-methyl-2-pentoxy)dlsiloxane, poly(methyl) 5il oxanes, poly(mekhylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters o~ phosphorus-containing acids ~e.g., tricresyl phosphate, trioctyl phosphate~ diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, re~ined and rere~ined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed herein-above can be used in the concentrates of the present invention. Unrefined oils are those obtained dir2ctly from a natural or synthetic source without further purification txeatment~ For example, a shale oil obtained dixectly ~rom retor~ing ~perations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils ara similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more pxoperties. Many such purification techniques are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, ~iltration, percolation, etc~
Rerefined oils are obtained by processes similar to those used to obtai~ re~ir.ed oils applied to re~ined oils which have baen already used in service. Such rerefined oils are also known as reclaim~d or reprocessed oils and often are additionally processQd ,.- ` .

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by techni~ues direc~ed to removal of spent additives and oil breakdown products.
Component (A) which is utilized in the diesel lubricants o~ the present invention is at least one caxboxylic derivative aomposition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -N-H- group wherein said acylating agent con~ists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of at least about 1200 and an Mw/Mn ratio of at l~ast about 1.5, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each e~uivalent weight of substituent group~.
The substituted succinic acylating agent utilized the preparation of the carboxylic deri~ative can be characterized by the presence within its structure of ~wo groups or moieties. The first group or moiety i~ referred to hereinafter, for conv~nience, as the "su~stituent group(s) 19 and is derived ~rom a polyalkene. The polyalkene from which the substituted groups are derived is characterized by an Mn (number average molecular weight) value of at least 1200 and more generally from about 1500 to about 5000, and an Mw/Mn value of at least about 1.5 and more generally from about 1.5 to about 6. The abbreviation Mw represents the weight average molecular weight. The number average molecular weight and the weight average molecular weight of the polybutenes can be measured by well known techniques of vapor phase osmometry (VPO~, membrane osmometry and gel permeation c~romatography ~2~4~5 (GPC). These techniques are well known to thoae skilled in the art and need not be described herein The second group or moiety is re~e~red ~o herein as the "succinic group(s)". The succinic groups are those groups characterized by the structure O ~ I o X- - ~ C ~ C C X' (I) wherein X and X' are the same or different provided at least one of X and X' is such ~hat the substituted succinic acylating agent can function as carboxylic acylating agents. That is, at least one of X and X' must be such that the substituted acylating agent can form amides or amine salts with, and otherwise function as a conventional carboxylic acid acylating agents.
Transesterification ~nd tran~amidation reactions are considered, for purposes of this invention, as conventional acylating reactions.
Thus/ X and/or X' is usually -OH, -O-hydrocarbyl, ~O-~ where M~ represents one equivalent of a metal, a~monium or amine cation, -NH2, -Cl, -Br, and together, X and X' can be -O- so a~ to form the anhydride. The specific idantity of any X or X' group which is not one of the above is not critical so long as its presence does not prevent the remaining group from entering into acylation reactions. Preferably, however, X and X' are each uch that both rarboxyl functions of the succinic group (i.e., both -C~Q)X and -C(O~X' can enter in~o acylation reactions.
One of the unsatisfied valences in the grouping rC_~_ - ~, ' . ' ,' ' ; .
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of Formula ~ forms a carbon-to-carbon bond with a carbon atom in the substituent group. While other such unsatisfie~ valence may be satisfied by a similar bond with the same or different substituent group, all but the said one such valence is usually sakis~ied by hydrogen; i.e., -H.
The substituted succinic acylating agents are characterized by the presence within their structure o~
1.3 succinic groups ~that is, groups corresponding to Formula I) for each equivalent weight of substituent groups. For purposes of this inventlon, the number of equivalent weight of substituent groups is deemed to be the number corresponding to the quotient obtained by dividing the Mn value of the polyalkene from which the substituent is derived into the total weight of the substituent groups present in the substituted succinic acylating agents. Thus, if a substituted succinic acylating agent is characterized by a total weight of substituent group of 40,000 and the Mn value for the polyalkene from which the substituent groups are derived is 2000, then that substituted succinic acylating ~gent is characterized by a total of 20 (40,00Q/2000=20) equivalent weights of substituent groups. Therefore, that particular succinic acylating agent must also be characterized by the presance within its structure of at least 26 succinic groups to meet one of the requirements of the novel succinic acylating agents of this invention.
Another requirement for the substituted succinic acylating agents within this inven~ion is that the substituent groups mus~ have bsen derived rom a polyalkene characterized by an Mw/Mn value of at least about 1.5.

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Polyalkenes having the Mn and Mw values discussed above are known in the art and can be prepared according to conventional proc~dures~ Sevaral such polyalkenes, especially polybutenes, are commercially available.
In one preferred embodiment, the succinic groups will normally correspond to the formula CH C(O)R
CH~ -C~O)RI (II) wherein R and R~ are each independently selected from the group c3nsisting o~ -OH, -Cl, -O-lower alkyl, and when taken together, R and Rl are -O-. In the latter case, the succinic group is a succinic anhydride group. All the succinic groups in a particular succinic acylating agent need not be the same, but they can be the same. Preferably, the succinic groups will correspond to Q O
- CH - C ~ OH - CH ~ ~
~H2 C ~ OH I / (III) C~2--C~
o (A) (B) and mixtures of (III(A)) and (IIItB)). Providing substituted succinic acylating agents w~erein the succinic group~ are the same or different is within the ordinary skill of the art and can be accomplished through conventional procedures such as treating the substituted succinic acylating agents themselves (for ~ .

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example, hydrolyzing the anhydride to the free acid or converting the free acid to an acid chloride with thionyl chloride) and/or selecting the appropriate maleic or fumaric reactants.
As previously mentione~, the minimum number o~
succinic groups for each equivalent weight o~
substituent group is 1.3. The maximum number generally will not exceed 6. Preferably the minimum will be 1.4;
usually 1.4 to about 6 succinic groups for each eguivalent weight of substituent group. A range based on this minimum is at least 1.5 to about 3.5, and more generally about 1.5 to about 2.5 succinic yroups per equivalent weight of ~ubstituent groups.
From the foregoing, it is clear that the substituted succinic acylating agents of this invention can be represented by the symbol Rl(R2)y wherein Rl represents one equivalent weight of substituent group, R2 represents one succinic group corresponding to Formula (I~, Formula (II~, or Formula (III), as discussed above, and y is a number equal to or greater than 1,3. The more preferred embodiments of the invention could be similarly represented by, for example, letting Rl and R2 represent more preferred substi~uent groups and succinic groups, respectively, as discussed elsewhere herein and by letting the value of y vary as discussed above.
In addition to preferred substituted succinic groups where the preference depends on the number and identity of succinic groups for each e~uivalent weight o~ subs~ituent groups, still ~urther preferences are based on the identity and characterization of the polyalkenes ~rom which the subs~ituent groups ara derived.

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With respect to the value of Mn for example, minimum of about 1200 and a maximum of abouk 5000 are preferred with an Mn value in the range of from about 1300 or 1500 to about 5000 also being preferred.
more preferred Mn value is one in the range ~ from about 1500 to about 2800. A most preferred range of Mn values is from about 1500 to about 2400. With polybutenes, an especially preferred minimum value for Mn is abou~ 1700 and an especially preferred range of Mn values is from about 1700 to about 2400.
As to the values of the ratio ~Iw/Mn, there are also several pre~erred values. A minimum ~w/~n value of about 1.8 is preferred with a range of values of about 1.8 up to about 3.6 also being preferred. A
s~ill more preferred minimum value o~ Mw/Mn is about

2.0 with a preferred range of values of from about 2.0 to about 3.4 also being a preferred range. An especially preferred minimum value o~ Mw/Mn is about 2.5 with a range of values of about 2.5 to about 3 2 also being especially preferred.
Before proceeding to a further discussion of the polyalkenes from which the substituent groups are derived, it should be pointed out that these prefarred characteristics of the succinic acylating agents are intended to be understood as being both independent and dependent. They are intended to be independent in the sense that, for example, a preference for a minimum of 1.4 or 1.5 succinic groups per equivalent weight of substituent groups is not tied to a more preferred value of ~n or Mw/Mn. They are intended to be dependent in the sense ~hat, for example, when a preference for a minimum of 1.4 or 1.5 succinic groups is combined with more preferred values of Mn and/or , : ' ' ~2~

Mw/Mn, the combination of preferences does in fact describe still ~urther more pre~erred embodiments of the invention. Thus, the various parameters ax~
intended to stand alone with respeat to the particular parameter being discussed but can also be co~bined wlth other parameters to identify further preferences. This same concept is intended to apply throughout the specification with respect to the description of preferred values, rangesl ratios, reactants, and the like unless a contrary intent is clearly demonstrated or apparent.
The polyalkenes from which the substikuen~
groups are derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, usually 2 to about 6 carbon atoms. The interpolymers ara those in which two or more olefin monomers are inkerpolymerized according to well-known conventional procedures to form polyalXenes ha~ing units within their structure derived from each of said two or more olefin monomers. Thus, I'intexpolymer(s) as used herein is inclusive of copolymers, terpolymers, tetrapolymers, and the like. As will be apparent to those of ordinary s~ill in the art, the polyalkenes from which the substituent groups are derived are often conventionally referred to as "polyolefin(s)!'.
The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsakurated groups (i.e.l >C=CX2~);
that is, they are monoolefinic monomers such as ekhylene, propylene, butene-l, isobutene, and octene-l or polyolefinic monomers (usually diolefinic monomers) such as butadiene-11,3 and isoprene.

~Z;8~5 These olefin monomers are usually polymeriz~
able terminal olefins; that is, olefins charackerized by the presence in their structure o~ the group >C=CH2. However, polymerizable inkernal ole~in monomers (sometimes referred to in the literature as medial olefins~ characterized by the presence within their structure of the group --C-C=~

can also be used to form the polyalkenesO When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For purposes of this invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal ole~in. Thus, pentadiene-1,3 ~i.e., piperylene) is deemed to be a te~minal olefin for purposes of this invention.
While the polyalkenes from which the substituent groups of the succinic acylating agen~s are deri~ed generally are hydrocarbon groups such as lower alXoxy, lower alkyl mercapto, hydroxy, mercapto, oxo, as keto and aldehydro groups, nitro, halo, cyano, carboalkoxy, (where alkoxy is usually lower alkoxy), alkanoyloxy, and khe like provided the non~hydrocarbon substituents do not substantially interfere with ~ormation of the substituted succinic acid acylating agents of this invention. When present, such non-hydrocarbon groups normally will not contribute more than about 10% by weight of the total weight of the polyalkenes. Since the polyalkene can contain such ' - ' . , - ' ' .

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non-hydrocarbon subs~ituent, it is apparent that the olefin monomers from which the polyalkenes are made can also contain such substltuents. Normally, however, as a matter o~ practicality and expense, ~he ole~in monomers and the polyalkenes will be free from non-hydrocarbon groups, except chloro groups which usually facilitate the formation of the substituted succinic acylating agents of this invention. (As used herein, the term "lower" when used with a chemical group such as in "lower alkyl" or "lower alkoxy" is intended to describe groups having up to 7 carbon atoms).
Although the polyalkenes may include aromatic groups ~eæpecially phenyl groups and lower alkyl-and/or lower alkoxy-substituted phenyl groups such as para-(tert-butyl)phenyl) and cycloaliphatic groups such as would be obtained from polymerizable cyclic ole~ins or cycloaliphatic substituted-polymerizable acyclic olefins, the polyalkenes usually will be free from such groups. Nevertheless, polyalkenes derived from interpolymers of both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or para-(tert-butyl)styrene are exceptions to this generalization. Again, because aromatic and cycloaliphatic groups can be present, the olefin monomers from which the polyalkenes are prepared can contain aromatic an~ cycloaliphatic groups.
From what has been described hereinabove in regard to the polyalkene, it i clear that there is a general pre~erence for aliphatic, hydrocarbon polyalkenes free from aromatic and cycloaliphatic groups (other than the diene-styrene interpolymer exception already noted). Within this general preference, there is a further preference for polyalkenes which are derived from the group consis~ing .: -~L28~4~;

of homopolymers and interpolymers of terminal hydrocarbon ole~ins o~ 2 to about 16 carbon atoms.
This further pre~erence is qualified by the proviso that, while interpolymers o~ terminal olefins are usually preferred, interpolymors optionally contalning up to about 40~ of polymer units derived Prom internal olefins of up to about 16 carbon atoms are also within a preferred group. A more preferred class o~
polyalkenes are those sPlected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 6 carbo~ atoms, more preferably 2 to 4 carbon atoms. However, another preferred class of polyalkenes are the latter more preferred polyalkenes optionally containing up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms.
Specific examples o~ terminal and internal olefin monomers which can be used to prepare the polyalkenes according to conventional, well-known polymerization techniques include ethylene; propylene;
butene-l; butene-2; .isobutene; pentene-l; hexene-l;
heptene-l; octene-l; nonene-l; decene-l; pentene-2;
propylene-tetramer; diisobutylene; isobutylene trimer;
butadiene-1,2; butadiene-1,3; pentadiene-1,2; penta-diene-1,3; pentadiene-1,4; isoprene; hexadiene-1,5;
2-chloro-butadiene-1,3; 2-methyl-heptene-1; 3-cyclo-hexylbutene-l; 2-methyl-pentene-1; styrene; 2l4-dichloro styren~; divlnylbenzene; vinyl acetate; allyl alcohol; l-methyl-vinyl acetate; aarylonitrile; ethyl acrylate; methyl methacrylate; ethyl vinyl ether; and methyl vinyl ketone. 0~ these, the hydrocarbon polymerizable monomers are preferred and of these hydrocarbon monomers, the terminal olefin monomers are particularly preferred.

~Z1~4~45 Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, styrene-isobutene copolymers, isobutene-butadiene-1,3 copolymer~, propana-isoprene copolymers, isobutene-chloroprene copolymers, isobutene-~para-methyl)styrene copolymers, copolymers o~ hexene~l with hexadiene-1,3, copolymers of octene-l with hexene-l, copolymers of heptene-l with pentene-l, copolymers of

3-methyl butene-l with octene-l, copolymers o~ 3,3-dimethyl-pentene-l with hexene-l, and terpolymers of isobutene, styrene and piperylene. More specific examples of such interpolymers include copolymer of 95%
(by weight) of isobutene with 5~ ~by weight) of styrene; terpolymer of 98~ of isobutene with 1~ of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of butene-l and 3% of hexene-l;
terpolymer of 60% of isobutene with 20~ of pentene-l and 20% of octene-l; copolymer of 80% of hexene-l and 20~ of heptene-l; texpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propylene; and copolymsr of 80% of ethylene and 20~ of propylene. A preferred source of polyalkenes are the polyti~obutene)s obtained by polymerization of C4 refinery stream having a butene content of about 35 to about 75~ by weight and an isobutene content of about 30 to about 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride. These polybutenes contain predominantly (greater than about 80% of the total repeating units) of isobutene repeating units of the con~iguration ~H3 ,. -:

~28~S

Obviously, preparing polyalkenes as described above which meet the various criteria for Mn and Mw/Mn is within the skill of the art and does not compri~e part of the present invention. Techniques readily apparent to those in the art include controlling polymerization temperatures, regulating the amount and type of polymerization initiator and/or catalyst, employing chain terminating groups in the polymerization procedure~ and the like. Other conventional techniques such as stripping (including vacuum stripping) a very li~ht end and/or oxidatively or mechanically degrading high molecular weight polyalkene to produce lower molecular weight polyalkenes can also be used.
In preparing the substituted succinic acylatin~ agents of this invention, one or more of the above described polyalkenes is reacted with one or more acidic reactants selacted from the group consisting of maleic or fumaric reactants of the general formula X(O)C-CH=~-C(O)X' (IV) wherein X and X' are as defined hereinbefore.
Preferably the maleic and fumaric reactants will be one or more compounds corresponding to the formula RC(O)-CH=CH-C(O)R' (V) wherein R and R' are as previously defined herein.
Ordinarily, the maleic or fumaric reactants will be maleic acid, ~umaric acid, maleic anhy~ride, or a mixture of two or more of~these. The maleic reactants are usually preferred over ~he fumaric reac~ants .

- ` ~
~. :
.

s because the former are more readily aYailabl~ and are, in general, more readily reacted with the polyalkenes (or derivatives thereof) to prepare the substituked succinic acylating agents o~ the pre6ent invention, The especially pre~erred reaatants are maleic acid, maleic anhydride, and mixtures of these. Due to availability and ease of reaction, maleic anhydride will usually bP employed.
The one or more polyalkenes and one or more maleic or fumaric reac~al~,s can be reacte~ according to any of saveral known procedules in order to produce the substituted succinic acyl~ti~g agents o~ the present invention. Basically, th~a procedures are analogous to procedures used to prepa~e the high molecular weight succinic anhydrides and other equi~alent succinic acylating analogs thereof e~cept that the polyalkenes (or polyolefins) of the prior art are replaced with the particular polyalkenes described above and the amount of maleic or fumaric reactant used must be such that there is a~ least 1.3 succinic groups for each equivalent weight of the substituent group in the flnal substituted succinic acylating agent produced~
For conv~nience and brevlty, the term "maleic reactant" is often used hereafter. When used, it should be unders~ood ~hat the tarm is generic to acidic reactants selected from maleic and fumaric reactan~s corresponding to Foxmulae (IV) and (V) above including a mixture of such reactants.
One procedure ~or preparing the substituted succinic acylating agents of this invention is illustrated, in part, in U.S. Paten~ 3~219,666.

en~. This procedure is conveni~ntly designated as the "two-step procedure". It involves first chlorinating the polyalkene until khere ig an average of at least about one chloro group ~or each molecular weight of polyalkene. (For purposes of this invention, the molecular weight of the polyalkPne is the weight corresponding to the Mn ~alue.) Chlorination involves merely contacting the polyalkene with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyalkene. Chlorination is generally carried out at a temperature of about 75C
to about 125C. If a diluent is used in the chlorination procedure, it should be one which is not itself readily sub;ect to further chlorination. Poly-and perchlorinated and/or ~luorinated alkanes and benzenes are examples of suitable diluents.
The second step in the two-skep chlorination procedure, or purpos~s of this inventionl is to react the chlorinated polyalkene with the maleic reactant at a temparature usually within the range of about 100C
to about ~00C. The mole ratio of chlorinated polyalkene to malei~ -reactan~ i~; usually about 1:1.
(For pur~oses of this invention, a mole of chlorinated polyalkene is that weight of chlorinatad polyalkene correspondin~ to the Mn value of the unchlorinated polyalkene.) However, a stoichiometric excess of maleic reactant can be used, ~or example, a mole ratio of 1:2. If an average of more th~n about one chloro group per molecule of polyalkene is introduced during the chlorina~ion step, then more than one mole o~
maleic reactant can react per molecule of chlorinated polyalkene. Because of such situations, it is bPtter to describe th~ ratio of chlorinated polyalkene to :

' .

~2~34~

maleic reactant in terms of equivalents. (An equivalent weight of chlorinated polyalkene, for purposes of this invention, is the weight corresponding to the Mn value divided by the averags number o~ chloro groups per molecule of chlorinated polyalkene while the equivalent weight of a maleic reactant is its molecular weight.) Thus, the ratio of chlorinated polyalkene to mal~ic reactant will normally be such as to provide about one equivalent of maleic reactant for each mole of chlorinated polyalkene up to about one equivalent of maleic reactant for each equivalent of chlorinated polyalkene with the understanding that it is normally desirable to provide an excess of maleic reactant; for example, an excess of about 5% to about 25% by weight.
Unreacted excess maleic reactant may be stripped from the reaction product, usually under vacuum, or reacted during a further stage o~ the process as explained below.
The resulting polyalkPnyl-substituted succinic acylating agent is, optionally, again chlorinated if the desired number of succinic groups are not present in ~he product If there is present, a~ the time of this subsequent chlorination, any excess maleic reactant from the second step, the exces~ will react as additional chlorine i5 introduced during the su~sequent chlorination. Otherwise, additional maleic reactant is introduced during and/or subsequent to the additional chlorination step. This technique can be repeated until the total number of succinic groups per equivalent weight of substituent groups reaches the desired level.
Another procedure for preparing substituted succinic acid acylating agents of the in~ention - . :
.' . ' , - . .

utilizes a process described in U.S. Patent 3,912,764 and U.K. Patent 4,440,21~. According to that process, the polyalkene and the maleic reactant are first ~eacted by heating them together in a "direct alkylation" procedure.
When the direct alkylation step is completed, chlorine i5 introduced into the reaction mixture to promote reaction of the remaining unreacted maleic reactants. According to the patents, 0.3 to 2 or more moles of maleic anhydride are used in the reaction for each mole of olefin polymer; i.e., polyalkene. The direct alkylation step is conducted at temperatures of 180C to 250C. During the chlorine-introducing stage, a temperature of 160C to 225C is employed. In utilizing this process to prepare the substituted succinic acylating agents of this invention, it would be necessary to use sufficient maleic reactant and chlorine to incorporate at least 1.3 succinic groups into the final product for each equivalent weight of polyalkene.

The process presently deemed to be best for preparing the substituted succinic acylating agents utilized in this invention from the standpoint of efficiency, overall economy, and the performance of the acylating agents thus produced, as w211 as the performance of the derivatives thereof, is the so-called "one-step" process. This process is described in U.S. Patents 3,215,707 and 3,231,587.

Basically, the one-step process involves preparing a mixture of the polyalkene and the maleic .

:.
- . - .: .

~L2~

reactant containing the necessary amounts of both to provide the desired substituted succinic acylating agents of this invention. This means that there must be at least 1.3 moles of maleic reactant for each mole o~ polyalkene in order that there can be at lea~t 1.3 succinic groups for each equivalent weight o~
substituent groups. Chlorine is then introduced into the mixture, usualy by passin~ chlorine gas through the mixture with agitation, while maintaining a temperature of at least about 140C.
A variation on thls process in~olv~s adding additional maleic reac~ant duriny or subsequent to the chlorine introduction but, ~or reasons explained in U.S. Patents 3,215,707 and 3,231,587, this variation is presently not as preferred as the situation where all the polyalkene and all the maleic reactant are first mixed before the introduction of chlorine.
Usually, where the polyalkene is sufficiently fluid at 140C and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-step process. How~ver, as explained hereinbe~ore, if a solvent/diluent is employed, it is preferably one that resists chlorination. Again, the poly- and per-chlorinated and/or -fluorinated alkanes, cycloalkanes, ~nd benzenes can be used for this purpose.
Chlorine may be introduced continuously or intermittently during the one-step process. The rate of introduction of the chlorine i~ not critical although, for maximum utilization of the chlorine, the rate should he about the same as the rate of consumption of chlorine in the cour~e of the reaction.
When the introduction rate of chlorine exceeds the rate ., ., " ~ . ~ ' - ' ' ~. . - :

8~

of consumption, chlorine is evolved from the reaction mixture. It is often advantageous to use a alosed system, including superatmospheric pressure, in order to prevent loss o~ chlorine so as to maxlmizs chlorine utilization.
The minimum temperature at which the reaction in the one-step process takes place at a reasona~le rate is about 140C. ~hus, the minimum temp~rature at which the process is normally carried out is in the neighborhood of 140C. The pre~erred temperature range is usually between about 160~C and about 220C. Higher temperatures such as 250C or even higher may be used but usually with litle ad~antage.
In fact, temperatures in excess of 220C are often disadvantageous with respect to preparing the particular acylated succinic compositions o~ this invention because they tend to l'crack" the polyalkenes (that is, reduce their molecular weight by thermal degradation) and/or decompose the maleic reactant. For this reason, maximum temperatures o~ about 200C to about 210C are normally not exseeded. The upper limit of the useful temperature in the one-step process is determined primarily by the decomposition point o~
the components in the reaction mixture includiny the reactants and the desired products. The decomposition point is that temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired products.
In the one-step process, ~he molar ratio of male.ic reactant to chlorine is such that there is at least about one mole of chlorin~ for each mole of maleic reactant to be incorporated into the product.
Moreover, for practical reasons, a slight excess, ,- . , ' . . ' usually in the neighborhood of about 5% to about 30% by weight of chlorine, is utilized in order to offset any loss of chlorine from the reaction mixture. Larger amounts of excess chlorine may be used but do not appear to produce any beneficial results.
As mentioned previously, the molar ratio of polyalkene to maleic reactant is such that there is at least about 1.3 moles of maleic reactant for each mole of polyalkene. This is necessary in order that there can be at least 1.3 succinic groups per equivalent weight of substituent group in the product.
Preferably, however, an excess of maleic reactant is used. Thus, ordinarily about a 5% to about 25~ excess of maleic reactant will be used relative to that amount necessary to provide the desired number of succinic groups in the product.
A preferred process for preparing the substituted acylating compositions of this invention comprises heating and contacting at a temperature of at least about 140QC up to the decomposition temperature (A) Polyalkene characterized by Mn value of about 1200 to about 5000 and an Mw/Mn value of about 1.5 to about 4, (B) One or more acidic reactants of the formula XC(O)-CH=CH-C(O)X' wherein X and X' are as defined hereinbefore, and (C~ Chlorine wherein the mole ratio of (A):(B) is such that there is at least about 1.3 moles of (B~ for each mole of (A) wherein the number of moles of (A) is the quotient of - . . . . .
.
::; . : . .
. . . - :
- . .
: .' : ', . . . .

~L28~ S

the total weight of (A) di~ided by the value o~ Mn and the amount of chlorine employed is such as to provide at least about 0.2 mole (preferably at least about 0.5 mole) of chlorine for each mole of (B) to be reacted with (A), said substituted acylating compositions being characterized by the presence within their structure of an average o~ at least 1.3 groups derived from (B) for each equivalent weight of the subst.ituent groups derived from (A). The substituted acylated compositions as produced by such a process are, likewise, part of this invention.
As will be apparent, it is intended that the immediately preceding description of a preferred process be generic to both the process involving direct alkylation with subsequent chlorination as described in U.~. Pa~ent 3,912,764 and U.K a Patent 1,4~0,29 and to the comple~ely one-s~ep process described in U~S.
Patents 3,215,707 and 3,231,587. Thus, said description does not require that the initial mixture of polyalkene and acidic reactant contain all of the acidic reactant ultimately ~o be incorporated into the substituted acyiating composition to be prepared. In other words, all of the acidic reactant can be present initially or only part thereof with subsequent addition of acidic reactant during the course of the reaction.
~ikewise, a direct alkylation reaction can precede the introduction of chlorine. Normally, however, the original reaction mixture will contain the to~al amount of polyalkene and acidic raactant to be utilized.
Furthermore, the amount of chlorine used will normally be such as to provide about one mole of chlorine for each unreacted mole of (B) present at the ~ime chlorine introduction is commenced. Thus, if the mole ratio of , ' . '. ~ ' ' .~

(A):(B) is such that there is about 1.5 moles of (B) for each mole of (A) and if direct al~ylation results in half of (B) being incorporated into the product, then the amount of chlorine introduced to complete reaction will be based on the unreac~ed 0.1~ mole o~
(B); that is, at least about 0.75 mole of chlorine (or an excess as explained above) will then be introduced.
In a more preferred process for prepariny the substituted acylating compositions of this invention, ~here is heated at a tempera~ure of a~ least about 140C a mixture comprising:
(A) Polykene characterized by an ~n value of about 1200 to about 5000 and an Mw/Mn value of about 1.3 to about 4, (B) One or more acidic reactants of the formula RC(O)-CH-CH-C(O)R' wherein R and R' are as defined above, and (C) Chlorine wherein the mole ratio of (A):(B) is such that there is at least about 1.3 moles of (B) for each mole of (A) where the nu~ber of moles of (A) is a quotient of the total weight of (A) divided by the valu~ of Mn, and the amount of chlorine employed is such as to provide at least about one mole of chlorine or each mole of (B) reacted with (A), the substituted acylating compositions being fur~her charact~rized by the presence within their structure of at least 1.3 groups derived from (B) for each equivalent weight of the subs~ituent groups derived from (A). This process/ as described, includes only the one-step process; tha~ is, . ~: . . . : .
' ' :,'':' ~ ' ~

~L2~

a process where all of both (A) and tB) are present in the initial reaction mixture The substitut2d acylaked composition as produced by such a proce5s are, likewise, part of this invention.
The terminology "substituted succinic acylating agent(s)" is used in describing the substituted succinic acylating agents regardless of the process by which they are produced. Obviously, as discussed in more detail hereinbefore, several processes are available for producing the substituted succinic acylating agents. On the other hand, the terminology "substituted acylating composition(s)", is used to describe the reaction mixtures produced by the specific preferred processas described in detail herein. Thus, the identity of particular substituted acylating compositions is dependent upon a particular process of manufacture. It is believed that the novel acylating agents used in this invention can best be described and claimed in the alternative manner inherent in the use of this ~erminology as thus explained. This is particularly true because, while the products o~ this inven~ion are clearly substitutad succinic asylating agen~s as defined and discussed above, their structure cannot be represented by a single specific chemical formula. In fact, mixtures of products are inherently present.
With respect to the pre~erred processes described above, preferences indicated hereinbefore with respect to (a) the substituted succinic acylating agents and (b) the values of Mn, ths values of the ratio ~w/Mn, the identity and composition of the polyalkenes, the identity of the acidic reactant ~that is, the maleic and/or fumaric reactants~, the ratios of ~Z8~5 reactants, and the reac~ion temperatures also apply.
In like manner, the same preferences apply to the substituted acylated compositions produced by these pre~exred processes.
For example, such processe~ wherein the reaction temperature is from about 160C to abouk 220C are preferred. Likewise, the use of polyalkenes wherein the polyalkene is a homopolymer or interpolymer of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 40% of the polymer units derived from internal olefins of up to about 16 carbon atoms, constitutes the preferred aspect of the process and compositions prepared by the process. In a more preferred aspect~ polyalkenes for use in the process and in preparing the compositions of the process are the homopolymers and interpolymers of terminal olefins of 2 to 6 carbon atoms with the proviso that said interpolymers can optionally contain up to about 25% of polymer units derived from internal olefins of up to about 6 carbon atoms. Especially preferred polyalkenes are polybutenes, ethylene-propylene copolymers, polypropylenes with the polybutenes being particularly preferred.
In the same manner, the succinic group content of the substituted acylating compositions thus produced are preferably the same as that describe~ in regard to the substituted succinic acylating agents. Thus, the substituted acylating compositions characterized by the presence within their structure of an average of a~
least 1~4 succinic groups derived fro~ (~) for each e~uivalent weight of the substituent groups derived from (A) are preferred with those containing at least - ' ' `

~Z~ 5 ~32 1.4 up to about 3.5 succinic groups derived from (B) for each e~uivalent weight of substituent group~
derived from (A) being 9till more pre~erred. In khe same way, those substituted acylating composikions characteri~ed by the presence within their structure of at least 1.5 succinic groups derived from (B) for each equivalent weight of substituent group derived from (A) are still fuxther prsferred, while those containing at least 1.5 succinic groups derived from (B) for each equivalent weight of substituent ~roup derived from (A) being especially preferred.
Finally, as with the description of the substituted succinic acylating agents, the substituted acylating compositisns produced by the preferred processes wherein the succinic groups derived from (B) correspond to the formula CH - C - OH - CH ~ C
~0 ' l /o o and mixtures of these constitute a preferred class.
An especially preferred process for preparing the substituted acylating compositions comprises heating at a temperature of about 160C to about 220C a mixture comprising:
~ A) Polybutene characterized by an Mn value of about 1700 to about 2400 and an Mw/Mn value of about 2.5 to about 3.2, in which at least 50% of the total units derived from butenes is derived from isobutene, ~2841~5 (B) One or more acidic reactants of the ~ormula RC(O)-CH-C~-C(O)R' wherein R and R' are each -OH or when taken together, R
and R' are -O-, and (C) Chlorine wherein the mole ratio of (A)~(B) is such that there is at least 1.5 moles of (B) ~or each mole of (A) and the number of moles of (A) is the quotient of the total weight of (A) divided by the value of Mn, and the amount of chlorine employed is such as to provide at least ahout one mole of chlorine for each mole of (B) to be reacted with (A), said acylating compositions being chara~terized by the presence within their structure of an average of at least 1.5 groups derived ~rom (B) ~or each equivalent weight o~ the substituent groups derived from (A)- In the same manner, substituted acylating compositions produced by such a process constitute a preferred ~-lass of such compositions.
For purposes of brevity, the terminology "acylating reagent(~)" is often used hereafter ~o re~er, collectively, to both the substituted succinic acylating agent and to the substituted acylating compositions used in this invention.
The acylating reagents of this i~vention are intermediates in processes for preparing the carboxylic deri~ati~e compositions (A) comprising reacting one or more acylating reagents with an amino compound characterized by the presence with~n its structure of at least one group.

: -~: .

:
: . - . , .

.

34~4~

The amino compound characteri~ed by the presence within its structure of at least one -NH-group can be a monoamine or polyamine compound. For purposes of this invention, hydrazine and substituted hydrazines containiny up to khree substituents are included as amino compounds suitable for preparing carboxylic derivative compositions. Mixtures o~ two or more amino compounds can be used in the reaction with one or more acylating reagents of this invention.
Preferably, the amino compound contains at least one primary amino group (i.e., -NH2) and more preferably the amine is a polyamine, especially a polyamine containing at least ~wo -NH- groups, either or both of which are pximary or secondary amines. The polyamines not only result in carboxylic acid derivative compositions deriv~d from monoamines, but these pre~erred polyamines result in carboxylic derivative compositions which exhibi~ more pronounced V.I.
improving properties.
The monoamines and polyamines must be characterized by the presence within their structure of at least one -NH- group. Therefor~, they have at least one primary (i.e., H2N-3 or secondary amino (i.e., H-N=) group. The amines can ~e aliphatic, cyclo-aliphatic, aromatic, or heterocyclic, including aliphatic-substituted cycloaliphatic, aliphatic-substituted aromatic, aliphatic-substituted hetero-cyclic, cycloaliphatic-substituted aliphatic, cyclo-aliphatic-substituted heterocyclic, aromatic-substi-tuted aliphaticl aromatic-substituted cycloaliphatic, aromatic-substituted he~erocyclic, heterocyclic-substi-tuted aliphatic, heterocyclic-substituted alicyclic, and heterocyclic-substituted aromatic amines and may be , , ~2~

saturated or unsaturated. If unsaturated, the amine will be free from acetylenic unsaturation. The amines may also contain non-hydrocarbon substituents or groups as long as these groups do not signi~icantly inkerfere with the reaction o~ the amines with thQ acyla~ing reagents of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl mercapto, nitro, interrupting groups such as -o-and --S- (e.g., as in such groups as -CH2CH2 X-C~2CH2- where X is -0- or -S-).
With the exception of the branched polyalkylene polyamine, the polyoxyalkylene polyamines, and the high molecular weight hydrocarbyl-substituted amines described more fully hereafter, the amines ordinarily contain less than about 40 carbon atoms in total and usually not more than about 20 carbon atoms in total.
Aliphatic monoamines include mono-aliphatic and di-aliphatic substituted amines wherein the aliphatic groups can be saturated or unsaturated and straiyht or branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono-and di-alkenyl-substituted amines, and amines having one N-alkenyl substituent and one N-alkyl substituent and the like. Ths total number of carbon atoms in these aliphatic monoamines will, as mentioned before, normally will not exceed about 40 and usually not exceed abou~ 20 carbon a~oms. Specific examples of such monoamines include ethylamine, diethylamine, n-butylamine, di-n-butylammine, allylamine, isobutyl-amine, G~coamine, stearylamine, laurylamine, methyl-laurylamine, oleylamine, N-methyl-octylamine, dodecyl-. .

', . ,. :.

' '.`, ' ... ' ~: .

~%334~5 amine, octadecylamine, and the like. Examples o~
cycloaliphatic-substituted aliphatic amines, aromatic substituted aliphatic amin~s, and heterocyclic-sub ti-tuted alipha~ic amines, include 2-(cyclohexyl)-ethyl-amine, benzylamine, phenekhylamine, and 3-(~urylpropyl) amine~
Cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure. Examples o~
cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentyl-amines, N-ethyl-cyclohexylamine, dicyclohexylamines, and the like. Examples o~ aliphatic-substitut~d, aromatic-substituted, and heterocyclic- ubstituted cycloaliphatic monoamines include propyl-substituted cyclohexylamines, phenyl-substituted cyclopentylamines, and pyranyl-substituted cyclohexylamine.
Aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The aromatic ring will usually be a mononuclear arom~tic ring (i.e., one deri~ed from benzene) but can include fused aromatic rings, especially those deriv~d ~rom naphthalene. Examples of aromatic monoamines include aniline, di(para-methylphenyl) amine, naph~hylamine, N-(n-butyl)aniline, and the like. Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines are para-etho~yaniline, para-dodecylaniline/ cyclohexyl-substituted naphthylamine, and thienyl-substituted aniline.

~Lf~8'9L1~L5 Polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to the above~described monoamines except ~or the presence within their structure o~ another amino nitrogen. The other amino nitrogen can be a primary, secondary or terkiary amino nitrogen. Examples o~ such polyamines include N-amino-propyl-cyclohexylamines, N,N'-di-n-butyl-para-phenylene diamine, bis-~para-aminophenyl)methane, 1,4-diamino-cyclohexane, and the like.
Heterocycic mono- and polyamines can also be used in making the carboxylic derivative compositions of this invention. As used herein, the terminology "heterocyclic mono- and polyamine(s)" is intended to describe those heterocyclic amines containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in ~he heterocyclic ring.
However, as long as there is present in the heterocyclic mono- and polyamines at least one primary or secondary ~mino group, the hetero-N atom in the ring can be a ter~iary amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen. Heterocyclic amines can be saturated or unsaturated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, al~yl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about 20. Hsterocyclic amines can contain hetero atoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen hetero a~om. ~he five- and six-membered heterocyclic rings are preferred.
Among the suitable heterocyclics are aziridine~, azetidines, azolidines, tetra- and di-hydro ~;28~4~

pyridines, pyrroles, in~oles, piperidines, imidazoles, di- and tetrahydroimidazoles, piperazines, isaindoles, purines, morpholines, thiomorpholines, N-aminoalk~l-morpholines, N-aminoalkylthiomorpholines, N-aminoalkyl~
piperazines, N,N'-di-aminoalkylpiperazines, azeplnes, azocines, azoninec, azecines and tetra-, di- and perhydro derivatives of each of the above and mixtures Qf two or more of these heterocyclic amines. Preferred heterocyclic amines are the saturated 5- and 6~membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl-substituted piperidines, pipera~ine, aminoalkyl~
substituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especially preferred.
Usually the aminoalkyl substltuents are substituted on a nitrogen atom forming part of the hetero ring.
Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-di-aminoethylpipera2ine.
Hydroxyamines both mono- and polyamines, analogous to those described above arP also useful as (a) provided they contai~ at leas~ one primary or secondary amino group. Hydroxy-substituted amines having only terkiary amino nitro.~en such as in tri-hydroxyethyl amine, are thus excluded as (a) (but can be used as (b) as disclosed hereafter). The hydroxy-substituted amines contamplated are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, th~y have hydroxy groups capable of functioning as alcohols. Examples of such hydroxy-suhstituted amines ~2~

include ethanolamine, di-(3-hydroxypropyl)-amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanol-amine, di-(2 hydroxypropyl) amine, N-(hydroxypropyl)-propylamine, N (2-hydroxyethyl)-cyclohexylamine, 3-hy-droxycyclopentylamine, para-hydroxyaniline, N-hydroxy-ethyl piperazine, and the like.
Hydrazine and substituted-hydrazine can also be used. At least one of the nitrogens in the hydrazine must rontain a hydrogen directly bonded thereto. Prefera~ly there are at least two hydro~ens bonded directly to hydrazine nitrogen and, more preferably, both hydrogens are on the same nitrogen.
The substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alXyl, especially lower alkyl, phenyl, and substi~uted phenyl such as lower alkoxy substituted phenyl or lower alkyl substituted phenyl. Specific examples of substituted hydrazines are methylhydrazine, N,N-dimethyl-hydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-p~enyl-N' ethylhydra~ine~ N-(para-tolyl)-N'-(n-b.utyl)-hydrazine, N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methyl-hydrazine, N,N'-di(para--chlorophenol)-hydra-zine, N~phenyl-N'-cyclohexylhydrazine, and the like.
Th~ high molecular weight hydrocarbyl amine~, both mono-amines and polyamine~, which can b~ u~ed as (a) are generally prepared by reacting a chlorinated polyole~in having a molecular weight o at leask about 400 with ammonia or amine. Such amines are known in the art and described, ~or example, in U.S. Patents 3,275,554 and 3,438,757, ;' ~ ' ' '' ~28A~LAS

All that is required for use of these amines is that they possess at least one primary or secondary amino group.
required for use of these amines 15 ~nat tney possess at least one primary or secondary amino group.
~ nother group of amines suitable ~or use are branched polyalkylene polyamines. The branched polyalkylene polyamines are polyalkylene polyamine~
wherein the branched group iR a side chain containing on the average at least one nitrogen-bonded aminoalkylene rH -i (i.e., NH2 - R t N - RJ x group per nine amino units present on the main chain, for example, 1-4 of such branched chain~ per nine units on the main chain units. Thus, these polyamines contain at .l.east three primary amino groups and at least one tertiary amino group.
Suitable amines also include polyoxyalkylene polyamines, e.g., polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecular weights ranging from about 200 to 4000 and preferably from about 400 to 2000. Illustrative examples of these polyoxyalkylene polyamines may be charac~erized ~y the formulae N~2-Alkylene ~O-Alkylene t NH2 (~I) wherein m has a value of about 3 to 70 and preferably about 10 to 35.

R-~-Alkylene t O-AlkYlen~ ~-nNH2)3-6 (VII) ,`i~,_ .

. : :

~Z~4~L~LS

wherein n is such that the total value i5 ~rom about 1 to 40 wi~h ~he proviso that the sum o~ all o~ the n's is from about 3 to about 70 and generally from about 6 to about 35 and R is a polyvalent saturated hydroc~rbon radical o~ up to 10 carbon atoms having a val~nc~ Or 3 to 6. The alkylene groups may ~e straight or branch~d chains and contain from 1 to 7 carbon atoms and usually from 1 to 4 carbon atoms. The various alkylene group~
present within Formulae (VI) and (VII) may be th2 sa~e or differentO
The pxeferr~d polyoxyalkyl~ne polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyox~propylene triamines ha~ing a~erage molecular weights ranging from ahout 200 to 2000. The polyoxyalkylene polyamines are commercially available and ~ay be ob~ained, for example, from the Je~ferson C~emical Company, Inc. under the trade nam~
"~effamines D-230, D-400, D-1000, D-2000, T-403, etc~".
U.S. Patents 3,804,763 and 3,948,800 are p~rticularly relevant for their disclosure of such polyoxyalkylene polyamines and pxocess for acylating them with carboxylic acid acylating agents which processes can be applied to their reaction with the acylating reagents of this invention.
The most preferred amines are the alkylene polyamines, including the polyalkylene polyamines, as de~cribed in more detail hereafter. The alkylene polyamines include those conforming to the formula ~3 - N- (U-N3n R3 (VIII) R3 ~3 , ,.~, ~z134~

wherein n is from 1 to aboui 10; each R3 is independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substitute~ hydrocarbyl group having up ~o about 30 atoms, with ~ha proviqo that at least one R3 group is a hydrogen atom and u is an alkylene group of about 2 to about 10 carbon atoms. Pre~erably u ls ethylene or propylene. Especially pre~erred are the alkylene polyamines where each R3 is hydrogen with tne ethylene polyamines and mixtures o~ ethylene polyamines being the most preferred. Usually n will have an average value of ~rom about 2 to about 7~ Such alkylene polyamines include methylene polyamine, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, etc. The higher homologs of such amines and related amino alXyl-substituted piperazines are also included.
Alkylene polyamines useful in preparing the carboxylic derivative compositions include ethylene diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, deca methylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di~heptamethylene~
triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaekhylene hexamine, di(trimethylene)triamine, N--(2-amino-ethyl)piperazine, 1,4-bis(2,aminoethyl)pipera7ine, and the like. Higher homologs as are obtained by condensing two or more of the above-illustra~ed alXylene amines are useful as (a) a~ are mixtures of two or more of any of the afore-described polyamines.
Ethylene polyamines, such as those mentioned above, are especially use~ul for reasons of cosk and ~LZ~ 5 effectiveness. Such polyamines are described in detail under the heading ~'Diamines and Higher Amines" in The Encyclopedia of Chem~cal Technology, Second Edltion, Kirk and Othmer, Volume 7, pages 27-39, Interscience Publishers, Division of John Wiley and Sons, 1965. Such compounds are prepared most conveniently by the reaction o~' an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc. These reactions result in the production of the somewhat complsx mixtures of alkylene polyamines, including cyclic condensation products such as piperazines. The mixtures are particularly useful in preparing novel sulfur-containing compositions of matter of this invention. On the other hand, quite satisfactory products can also be obtained by the use of pure alkylene polyamines.
Other useful types of polyamine mixtures are those resulting from stripping of the ~bove-described polyamine mixturesO In ~his instance, lower molecular weight polyamines and volatile contaminan~s are removed from an alkylene polyamin~ mixture to leave as residue what is often termed l'polyamine bottoms". ~n general, alkylene polyamine ~ottoms ~an be characterized as having less than two, usually lsss than one percent (by weight) material boiling below about 200C. In the lnstance of ethylens polyamine bo~toms, which are readily available and found to be quite u~eful, the bottoms contain lees than about two percen~ (by weight) total diethylene triamine (DETA) or triethylene tetramine (TETA). A typical sample of suGh ethylene polyamine bottoms obtained from the Dow Chemical .
. .

;.
--~L2~4~5 Company o~ Freepor~, Texas designated "E-100" showed a specific gravity at 15.6C of 1.0168, a pe~cent nitrogen by weight o~ 33.15 and a viscos~ty at 40C
of 121 centistokes. Gas chromatography analysis of such a sample showed it to contain about 0.93% "~ight Ends" (DETA?), 0.72~ TETA, 21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and higher (by weight~. These alkylene polyamine bottoms includa cyclic condensation products such as piperazine and higher analogs of diethylene triamine, triethylene tetramine and the like.
These alkylene polyamine bottoms can be reacted solely with the acylating agent, in which case the amino reactant consists essentially of alkylene polyamine bottoms, or they can be used with other amines and polyamines, or alcohols or mixtures thereof. In these latter cases at least one amino reactant comprises alkylene polyamîne bottoms.
Hydroxylalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing derivatives of the afore-described olefinic carboxylic acids. Preferred hydroxylalkyl-subs~ituted alkylene polyamines are those in which the hydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less than eight carbon atoms.
Examples of such hydroxyalkyl-substi~uted polyamines include N-(2-hydroxyethyl)ethylene diamine,N,N-bis~2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl~
piperazine, monohydroxypropyl-~ubstituted diethylene triamine, dihydroxypropyl-substituted tetraethylene pentamine, N-(2-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained by condensation o~ the above-illustrated hydroxy alkylene polyamines 8Al4!~

through amino radicals or through hydroxy radicals are likewise useful as (a). Condensation through amino radicals results in a higher amine accompanied by removal o~ ammonia and condensation ~hrough the hydroxy radicals results in products containing ether linkages accompanied by removal of water.
The carboxylic derivative compositions (A) produced ~rom the acylating reagents and the amino compounds described hereinbefore produce acylated amines which include amine salts, amides, imides and imidazolines as well as mixtures thereof. To prepare carboxylic acid derivatives ~rom the acylating reagents and the amino compounds, one or more acylating reagents and one or more amino compounds are heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, at temperatures in the range o~ about 80C up to the decomposition point (where the decomposition point is as previously defined) but normally at temperatures in the range o~
about 100C up to about 300C provided 300C does not exceed the decomposition point. ~emperatures of about 125C to a~out 250C are normally used. The acylating reagent and the amino compound are reacted in amounts sufficient to provide from about one-hal~
equivalent to about 2 moles of amino co~pound per equivalent of acylating reagent. For purposes of this invention an eguivalent of amino compound is that amount of the amino compound corresponding to the total weight of amino compound divided by the total number of nitrogens present. Thus, oc~ylamine has an equivalent weight equal to its molecular weight; ethylene diamine has an equivalent weight equal to one-hal~ its molecular weight; and aminoethylpiperazine has an ' ' ' `. ., - ` ::

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;

equivalent weight equal ko one-third its molecular weight.
The numbers of equivalents o~ acylati~g reagent depends on the number o~ carbo~ylic function~
(e.g., -C(o)X, -CtO)X', -C(O)R, and -C(O)R', wherein X, X', R and Rl are as defined above) present in the acylating reagent. Thus, the number of e~uiYalents of acylating reagents will vary with the number o~
succinic groups present therein. In determining the number of eguivalent~ of acylating reagents, those carboxyl function which are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there are two equivalents o~
acylating reagent for each succinic group in the acylating reagents or, from ano~her viewpoin~, two equivalents for each group in the acylating reagents d~rived from (~); i.e., the maleic reactant from which the acylating reagent is prepared. conventional techniques are readily available ~or determining the number of carboxyl functions (e.g., acid num~er, saponification number) a~d, thus, the number of equivalents of acylating reagent available to react with a~ine.
Because the acylating reagents can be used in the same manner as the high mol~cular weight acylatt~g agents o~ the prior art in preparing acylatad amines suitable for use a3 component (A) in the diesel lubr~cants o~ this i~ention, U.S. Patents 3,172!892;
3,219,666; 3,272,746; and 4,234,435 are particularly relevant for their disclosure with respect to the procedures applicable to reacting the acylating reagents with the amino compounds as described above. In applying the disclosures of these ~.~8~5 patents to the acylating reagents, the latter can be substituted for the high molecular weight carboxylic acid acylating a~ents disclosed in these pakents on an equivalent basis. That is, where ons equivalent o~ khe high molecular weight carboxylic acylating ayenk disclosed in these incorporated patents is utilized, one equivalent of the acylating reagent of this invention can be used.
In order to produce carboxylic derivative composition~ exhibiting viscosity index improving capabilities, it has been found generally necessary to react the acylating reagents with poly~unctional reactants. For example, polyamines having two or more primary and/or secondary amino groups are preferred.
It is believed that the polyfunctional reactants serve to provide "b~ridges" or cross-linking in the carboxylic derivative compositions and this, in turn, is somehow responsible for the viscosity index-improving properties. However, the mechanism by which viscosity index improving properties is obtained is not understood and there is no intention to be bound by thls theory.
Obviously, howaver, it is not necessary that all of the amino compound reacted with the acylating reagents b~ polyfunctional. Thus, co~bina~ions of mono- and polyfunctional amino compounds be used.
While the paxameters have not been fully determined as yet, it is believed that acylating reagents of this invention should be reacted with amino compounds- which contain sufficient polyfunctional reactant, (e.g., polyamine) so that at least about 25%
of the total number of carboxyl groups (from the succinic groups or from the groups derived from the ~2~34~

maleic reactant) are reacted with a polyfunctional reactant. Better results, insofar as the viscosity index-improving facilities o~ ~he carboxylic derivative compositions is concerned, appear to be obtained when at least 50% of the carboxyl groups are involved in reaction with such polyfunctional reactants. In mos~
instances, the best viscosity index improving properties seem to be achieved when the acylating reagents of this invention are reacted with a sufficient amount of polyamine to react with at least about 75% of the carboxyl group. It should be understood that the foregoing percentages are "theoretical" in the sense that it is not required that the stated percentage of carboxyl functions actually react with polyfunctional reactant. Rather these percentage~ are used to charac~erize the amounts of polyfunctional reactants desirably "available" to react with the acylating reagents in oxder to achieve the desired viscosi~y index improving properties.
Another optional aspect o~ this illvention involves the post-treatment of the carboxylic derivative compositions (A). The process for post-treating thP carboxylic acid deriv~tive compositions is again analogous to the post treating processes used with respect to similar derivatives o~ the high molecular weight carboxyllc acid acylating a~ents of the prior art. Accordingly, the same reaction conditions, ratio of reactants and the like can be used.
Acylated nitrogen compositions prepared by reacting the acylating reagents with an amino compound as dascribed above are post-treated by contacting tha acylated nitrogen compositions thus formed (e.g., the ~Z8~

. -4~

carboxylic deri~ative compositions) with one or more post-treating reagents selected ~rom th~ group consisting of boron oxide, bcron oxide hydrate, boron halides, boron acids, esters o~ boron acid~, carbon disulfide, sul~ur, sulfur chlarides, alkenyl cyanides, carboxylic acid acylating agents, ald~hydes, ketone~, urea, thiourea, guanidine, dicyanodiamide, hydrocar~yl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphi~es, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl lsothiocyanates, epoxides, episulfid~s, formaldehyde or formaldehyde-~roducing compounds plus phenols, and sul~ur plus phenols.
Slnc~ post-treating processes involving the use of these post-treating re~gents are known inso~ar as application to reaction products of high molec~lar weight carb~.~lic acid acylating agents o~ the prior art and amlne~ and/or alcoholq, de~ail~d descrip~ions o~ these processe~ herein are unn~.cessary. In order to apply the prior art processes to the carboxylic derivati~e compositions of this invention, all that is necessary is that reaction conditions, ratio reactants/ and the like as da~cribed in the prior art, be applied to the carboxylic derivativ.e compositions (A). In particular, U.S. Patent 4,234,435 is particularly relevant for its disclosure of post-treating procasses and post-treating reagents applicable to the carboxylic derivative compositions (A). The following U.S. patents also describe post-treating processes and post treating reagents applicable to ~the carboxylic derivative compositions (A): U. S . Patents 3, 200 ,107; 3, 254, 025:
3,2561185;

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.

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~28~4~;

3,282,955; 3,284,410; 3,366,569; 3,403,102; 3,428,561;
3~502,677; 3,639,242; 3,708,522; 3,865,813; 3,865,7~0;
3,954;639.
The preparation of khe acylating agent and the carboxylic acid derivakive composition~ (A), as well as the post-treated carboxylic acid derivative compositions i5 illustra~ed by the following examples.
These examples illustrate presently pre~erred embodiments. In the ~ollowing examples, and elsewhere in ths specification and claims, all percentages and parts are ~y weight unless otherwise clearly indicated, Example A-l A mixture of 510 parts (0.28 mole) of polyisobutene (Mn-1845; Mw=5325) and 5g parts (O.59 mole) of maleic anhydride is heated to 110C. This mixture is heated to 190C in 7 hours during which 43 parts (0.6 mole) of gaseous chlorine is added beneath the surface. At 190-192C an additional 11 parts (0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is stripped by heating at 190-193C
with nitrogen blowing for 10 hours. The residue is the desired polyisobutene-substi~uted succinic acylating agent having a saponification equiva}ent number o~ 87 as determined by ASTM procedure D-94.
Example A-2 A mixture of lO00 parts (0.495 mole) of polyisobutene ~Mn-2020; ~w-6049) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C. This mixture is heated to 184C in 6 hours durin~ which 85 paxts (1.2 moles) of gaseous chlorine is added beneath the surface. At 184-189C an additional 59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is stripped by heating at 186-190C

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-~L2~34~

with nitrogen blowing for ~6 hours. The residue is the desired polyisobutene-substituted succinic acylating agent having a saponification equivalenk number o~ ~7 as determined by ASTM procedure D~94.
Example A-3 A mixture o~ 3251 parts o~ polyisobukene chloride, prepared by the addition of 251 parts of gaseous chlorine to 3000 parts of polyisobutene (Mn=1696; Mw-6594) at 80C in 4.66 hours, and 345 parts of maleic anhydride is heated to 200C in 0.5 hour. The reaction mixture is held at 200-224C for 6.33 hours, stripped at 210C under vacuum and filtered. The filtrate is the desired polyisobutene-substituted succinic acylating agent having a saponification equivalent number of 94 as determined by ASTM procedure D-94.
Example A-4 A mixture o~ 3000 parts (1.63 moles) of polyisobutene (Mn=1845: Mw=5325) and 344 parts (3.51 moles) of maleic anhydride is heated to 140C. This mixturs is hPated to 201C in 5.5 hours during which 312 parts (4.3~ moles) of gaseous chlorine is added beneath the surface. The reackion mixture ls heated at 201-236C with nitrogen blowing for 2 hours and stripped under vacuum at 203c. The reaction mixture is filtered to yield the ~iltrate as the desired polyisobutene-substituted succinic acylating agent having a saponi~ication e~uivalent number of 92 as determined by ASTM procedure D-94.
Example A-5 A mixture of 3000 parts (1.49 moles~ of polyisobutene (Mn=2020; Mw=6049) and 364 parts ~3.71 moles) of maleic anhydride is heatsd at 220C for 8 .

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hours. The reaction mixture is cooled to 170C. At 170-190C, 105 parts (1.48 moles) of gaseous chlorine is added beneath the sur~ace in 8 hours. The reackion mixture is heated at 190C with nitrogen blowing ~or Z hours and then stripped under vacuum at 190C. The reaction mixture is filtered to yield the ~iltrate as the desired polyisobutene-substi~uted succinic a?ylating agent.
Example A 6 A mixture of 800 parts of a polyisobutene falling wi~hin the scope of the claims of the presant invention and having an Mn of about 2000, 646 parts of mineral oil and 87 parts of maleic anhydride is heated to 179~ in 2.3 hours. At 176-180C, 100 parts of gaseous chlori.ne is added beneath the surface over a l9-hour period. The reaction mixture is stripped by blowing with nitrogen for 0.5 hour at 180~. The residue is an oil-containing solution of the desired polyisobutene-substituted succinic acylating agent.
Example A-7 The procedure for Example A-l is repeated except the polyisobutene (Nn-1845; Mw=5325) is replaced on an equimolar basis by polyisobutene (~n=1457, Mw=5808).
Example A-8 The procedure for Example A-l is repeated except the polyisobutene (Mn=1845; Mw=5325) is replaced on an equimolar ba~is by polyisobutene (Mn=2510;
Mw=5793)-~xample A-g The procedure for Example A-l is repeated except the polyisobutene (Mn-1845; ~w=5325) is replaced on an equimolar basis by polyisobu~ene (Mn=32~0;
~w=5660).

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o53 Example A-10 A mixture is prepared by the addition of 10.2 parts (O.25 equivalent) of a commercial mixture of ethylene polyaminss having from about 3 to about 10 nitrogen atoms per molecule to 113 parts o~ mineral oil and 161 parts (0.25 equivalent) o~ the subst1tuted succinic acylating agent prepared in Example A-l at 138C. The reaction mixture is heated to 150C in 2 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution o~ tha desired product.
Example A-ll A mixture is prepared by the addition o~ 57 partC (1.38 equivalents) of a commercial mixture of athylene polyamines having from about 3 to 10 nitrogen atoms per molecule to 1067 parts of mineral oil and 893 parts (1.38 ~equivalents~ of the substituted succinic acylating agent prepared in Example A-2 at 140-145C. Tha reaction mixture is heated to 155C
in 3 hours and strippQd by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product.
Example A-12 A mixture is prepared by the addition of 18.2 parts ~0.433 equivalent) of a commercial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms per molecule to 3~2 parts of mineral oil and 34~
parts (O.52 equivalent~ of the substituted succinic acylating agent prepared in Example A 2 at 1~0C.
The reaction mixture is heated ~o 150C in 1.8 hours and stripped by blowing wi~h nitrogen. The reaction mixture is filtered ~o yield the ~iltrate as an oil solution of the desired product.

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Example A-13 A mixture is prepared by the addition of 5500 parts of the oil solution of the substituted succinic acylating agent prepared in Example A-7 to 3000 paxts of mineral oil and 236 parts o~ a commercial mixture o~
ethylene polyamines having an average of about 3-10 nitrogen atoms per molecule at 150C over a one-hour period. The reaction mixture is heaked at 155-165C
for two hours, then stripped by blowing wikh nitrogen at 165C for one hour. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired ni~rogen~containing product.
Examples A-14 through A-27 are prepared by following the general procedure set forth in Example A-lO.

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Ratio of Sub-stituted Suc-cinic Acylating Example Agent To Percent Number Reactant~s) Reactants _ Diluent A-14 Pentaeth~lene 1:2 equi~alents 40%
hexamine A-15 Tris(2-aminoethyl) 2:1 moles 50%
amine A-16 Imino-bis-propyl- 2:1 moles` 40 amine A-17 Hexamethylene 1:2 moles 40%
diamine A-18 1-(2-Aminoethyl)- 1:1 equivalents 40%
2-methyl-2-imidazoline A-l9 N-aminopropyl- 1:1 moles 40%
pyrrolidone a A commercill mixture of ethylene polyamines corresponding in empirical ~ormula to pentaethylene hexamine.
b A commercial mixture of ethy}ene polyamines corresponding in empirical formula to diethylene triamine.
c A commercial mixture of ethylene polyamines corre~ponding in empirical formula to triethylene tetramine.

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. ' ~ . ': ~ , s Ratio of Sub-stltuted Suc-cinic Acylatlng Example Agent To Percent Number ReactantLsL ~eactants Diluent A-20 N,N-dimethyl-1,3- l:l equivalents 40%
Propane diamine A-21 Ethylene diamine 1:4 equivalents 40%
A-22 1,3-Propane l:l moles 40%
diamine A-23 2~Pyrrolidinone 1:1.1 moles 20%
A-24 Urea 1:0.625 moles 50%
A-25 Dieth~lenetri- 1:1 moless 50 amine A-26 Triethylene- 1:0.5 moles 50%
amine ~-27 Ethanolamine l:l moles 4g%

a A commercial mixture of ethylene polyamines corresponding in empirical formula to pentaethylene hexamine.
b A comm~rcial mixture of ethylene polyamines corresponding in empirical ~ormula to diethylene triamine.
c A commercial mixture of ethylene polyamines corresponding in empirical formula to triethylene tetramine.

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Example A-28 A mixture is prepared by the addi~ion o~ 31 parts of carbon disulfide over a period o~ 1.66 hours to 853 parts o~ the oil solution of the produck prepared in Example A-14 at 113-145C. The reackion mixture is held at 145-152C for 3.5 hours, then filtered to yield an oil solution o~ the desired product.
~xample A-29 A mixture of 62 parts of boric acid and 27~0 parts of the oil solution of the product prepared in Example A-10 is heated at 150C under nitrogen for 6 hours. The re~ction mixture is filtered to yield the filtrate as an oil solution of the desired boron-containing product.
Example A-30 An oleyl ester of boric acid is prepared by heating an equimolar mixture of oleyl alcohol and boric acid in toluene at the reflux temparature while water is removed azeotropically. The reaction mixture is then heated to 150C under vacuum and the residue is the ester having a boron content of 3.2% and a saponification number of ~2. A mixture of 344 parts o~
the heater and 2720 parts of the oil solution of the product prepared in Example A-10 is heated at 150C
~or 6 hours and then filtered. The filtrate is an oil solution of the desired boron-containing product.
Example A 31 Boron trifuoride (34 parts) is bubbled into 2190 parts of the oil solution o~ the product prepared in Example A-11 at 80C within a period of 3 hours.
The re~ulting mixture is blown with nitrogen at 70-80C for 2 hours to yield the residue as an oil solution o~ ~he desired product.

,~ .

-5~-Example ~-32 A mixture of 3420 parts of the oil-containing solution of the product prepared in Example A-12 and 53 parts of acrylonitrile is heaked at reflux temperature from 125-145C for 1.25 hours, at 145C ~or 3 hours and then stripped at 125C under vacuum. The residue is an oil solution of the desired productO
Example A-33 A mixture is prepared by the addition of 44 parts of ethylene oxide over a period of one hour to 1460 parts of the oil solution of the product prepared in Example A-ll at 150C. The reaction mixture is held at 150C for on2 hour, then filtered to yield the filtrate as an oil solution of the desired product.
Example A-34 - A mixtur~ Qf 11~0 parts of the oil solution of the product of ~xample A-10 and 73 pax~s of terephthalic acid is heated at 150-160C and filtered. The filtrate is an oil solution of the desired product.
Example A-35 A decyl ester of phosphoric acid is prepared by adding one mole of phosphorus pentaoxide to three moles of decyl alcohol at a temperature within the range of 32-55C and then heating the mixture at 60-63C until the reaction is ~omplete. The product is a mixture of the decyl esters of phosphoric acid having a phosphorus content of 9.9% and an acid number of 250 (phenolphthalein indicator). A mixture of 1750 parts of the oil solution of the product prepared in Example A-10 and 112 parts of the above decyl ester is heated at 145-159C for one hourO The reaction mixture is filtered to yield the filtrate as an oil solution o~ the desired product.

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~59-Example A-36 A mixture of 2920 parts of the oil solution of the product prepared in Example A-ll and ~9 parts o~
thiourea is heated to 80C and held at 80C ~or 2 hours. The reaction mixture is then heated at 150-155C for 4 hours, the last o~ which the mixture is blown with nitrogen. The reaction mixture is ~iltered to yield the filtrate as an oil solution of the desired product.
Example A~37 A mixture of 1460 parts of the oil solution of the product prepared in Example A-ll and 81 parts of a 37~ aqueous formaldehyde solution is heated at reflux ~or 3 hours. The reaction mixture is stripped under vacuum at 150C. The residue is an oil solution of the desired product.
Example A-38 A mixture o~ 1160 parts of the oil solution of the product prepared in Example A-10 and 67 parts o~
sul~ur monochloride is heated for one hour at 150C
under nitrogen. The mixture is filtered to yield an oil solution of ~he desired sulfur-containing product.
Example A-39 A mixtura is prepared by the addition of 11.5 parts of formic acid to 1000 parts o~ the oil solution of the product prepared in Example A-ll at 60~C. The reaction mixture is heated at 6Q-100C for 2 hour , 92-100C for 1 A 75 hours and then filtared to yiald an oil solution of the desired product.
Example A-40 An appropriate size flask fitted with a stirrer, nitrogen inlet tube, addition funnel and Dean-Stark trap/condenser is charged with a mixture of 2483 .

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~2~34~a~5 parts acylating agent (4.2 e~uivalents) as described in Example A-3, and 11~4 parts oil. This mixture is heated to 210C while nitrogen was 510wly bubbled through it. Ethylene polyamine bottoms (134 parts, 3.1~ equivalents) is slowly added over about one hour at this temperature. The temperature i5 maintained at about 210C for 3 hours and then 3688 parts oll is added to decrease the temperature to 125Co After storaye at 138C for 17.5 hours, the mixt~re is filtered through diatomaceous earth to provide a 65%
oil solution o~ the desired acylated amine bottoms.
Component (B) of the diesel lubricants of this invention is at least one basic alkali metal salt of at least one acidic organic compound. Thi~ component is among those art-recognized metal-containing composi-tions variously refered to by such names as "ba~ic", "super~ased" and "overbased" salts or complexes. The method for their preparation is commonly referred to as "overbasing". The ~erm "metal ratio" is often used to define tke quantity of metal in these salts ox co~plexes relative to the quantity of organic anion, and is defined as the ratio of the number of equivalents thereof which would be present in a normal salt based upon the usual stoichiometry o~ the compounds involved.
The alkali metals present in the basic alkali metal salt~ includa principally lithium, sodium and potassium, with sodium and potassium being prefexred.
The most useful acidic organic compounds are sulfur acids, carboxylic acids, organic phosphorus acids and phenols.

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- ,. , ~Z84~S

The sulfur acids include sul~onic, sulf~mic thiosulfonie, sulfinic sulfenic, partial ~ster sulfuric, sul~urous and ~hlosul~urlc acids. Generally the sulfur acid is a sul~onic acid.
The sulfonic acids axe preferred as component (B) in the diesel lubricants of the invention. They include those represented by the formulae Rl(S03H)r and (R2)XT(so3H~y~ In these formulae, Rl is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essentially hy~rocarbon radical free ~rom acetylenic unsaturation and containing up to about 60 carbon atoms. When Rl is aliphatic, it usually contains at least about 15 carbon atoms: when it is an aliphatic-substituted cycloaliphatic radical, the aliphatic substituents usually contain a to~al of at least about 12 carbon atoms. Examples of Rl are alkyl, alkenyl and alkoxyalkyl radicals, and aliphatic-substituted cycloaliphatic radicals wherein the aliphatic substituen~s axe alkyl, alkeny~, alkoxy, alkoxyalkyl, carboxyalkyl and the like. Generally, the cycloaliphatic nucleus is derived from a cycloalkane ox a cycloalkene such as cyclopentane, cyclohexane, cyclohexene or cyclopentane. Speci~ic examples of are cetylcyclohexyl, laurylcyclohe~yl, cetylo~yethyl, octadecenyl, and radicals derived from pet~oleum, saturated and unsaturated paraffin wax, and olefin polymers including polymerized monoolefins and diolefin~ containing about ~-8 car~on a~oms ~per olefinic monom~r unit. Rl can also con~ain o~her substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso; lower alkoxy, lower al~ylmercapto, carboxy, carbalkoxy, oxo or thio, , .. .

.
. ' - , : ~' ' -, .

.

~ILZ84 11 ~S

or interrupting groups such as -NH-, -O- or -S-, as long as the essentially hydrocarbon character thereo~
is not destroyed.
R2 is generally a hydrocarbon or e~sentlally hydrocarbon radical free ~rom acetylenic un~aturation and containing from about ~ to about 60 aliphatic carbon atoms, pre~erably an aliphatic hydrocarbon -radical such as alkyl or alkenyl. It may also, however, contain substituents or interrupting groups such as those enumerated above provided the essentially hydrocarbon character thereof is retained. In general, any non-carbon atoms present in Rl or R2 do not account for more than 10% of the total weight thereof.
~ is a cyclic nucleus which may be derived from an aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or from a heterocyrllic compound such as pyridine, indole or isoindole. Ordinarily, T is an aromatic hydrocarbon nucleus, Pspecially a benzene or naphthalene nucleus.
The subscript x is at leas~ 1 and is generally 1~3. The subscripts r and y hav~ an average value of about l-4 per molecule and are generally also 1.
The following are speaific examples of sulfonic acids useful in preparing the salts (B). It is to be understood that such examples serve also to illustrate the salts of such sulfonic acids useful as component (B). In other words, for every sulfonic acid enumerating, it is intended that the corresponding basic alkali metal salts thereo~ are also under tood to be illustrated. (~he same applies to the lists of other acid materials listed below, i.e., the carbo~ylic acids, phosphorus acids and phenols~) Such sulfonic acids include mahogany sul~onic acids, bright stock lZ~A~S
-63~

sul~onic acids, pe~rolatum sul~onic acids, mono- and polywax substituted naphthalene sulfonlc acids, cekyl-chlorobenzene sulfonia acids, ~etylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxy-capryl benzene sulfonic acids, dicetyl thianthrene sulfonic acids, dilauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic acids~ saturated paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-sukstituted paraffin wax sul~onic acids, tetraisobutylene sulfonic acids, tetra-amylene sul~onic acids, chloro-substituted paraffin wax sulfonic acids, nitroso-substi~uted paraffin wax sulfonic acids, petroleum naphthene sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl cyclohexyl sulfonic acids, mono- and polywax-substi-tu~ed cyclohexyl sulfonic acids, postdodecylbenzene sulfonic acids, "dimer alkylate" sulfonic acids, and the like.
Alkyl-substituted ~enzene sulfonic acids wherein the alkyl group contains at least 8 carbon atoms including dodecyl ben7ene "bottoms" sulfonic acids are particularly useful The latter are acids derived from benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1, 2, 3, or more branched-chain C12 substituents on the benzene ring. Dodecyl benzene bottoms, principally mixtures of mono- and di dodecyl benzenes, are available as by-products from the manufacture of household deterg~nts. Similar products obtained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also useful in making the sul~onates used in this inv~ntion.

~284L~

The production of sulfonates from detergent manufacture by-products by reaction with, e.g., SO3, is well known to those skilled in thQ art. S~e, ~o~
example, the article "Sul~onates" in Kirk-Othm~r "Encyclopedia of Chemical Technology", Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley &
Sons, N.Y. (1969).
O~her descriptions of basic sulfonate salts and techniques ~or making them can be found in the following U.S. Patents: 2,17~,110; 2,202,781;
2,239,974; 2,319,121; 2,337,552; 3,4~8,284; 3,595,790;
and 3,798,012.
Suitable carboxylic acids include aliphatic, cycloaliphatic and aromatic mono- and polybasic car~oxylic acids free from acetylenic unsaturation, including naph~henic acids, alkyl- or alkenyl substituted cyclopentanoic acids, alkyl- or alkenyl-substitutad cyclohexanoic acids, and alkyl- or alkenyl~ubstituted aromatic carboxylic acids. The aliphatic acid~ generally contain ~rom abou~ 8 to abou~
50, and preferably from about 12 to about 25 carbon ato~s. The cycloaliphatic and aliphatic carboxylic acids are preferred, and they can be sa~ura~ed or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer~substituted maleic acid, behenic acid, isostearic aGid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricino~eic acid, underyclic acid, dioctylcyclopentanecarboxylic acid, myristic ac~d, dilau~yldecahydronaphthalene-carboxylic acid, stearylocta~ydro$nden~carboxy1ic acid, pal~tic acid, alkyl- and alkenylsuccinic acids, acids formed ~y . . .. .

, ' ' , .

~:8~

oxidation o~ petrolatum or of hydrocarbon waxes, and commercially available mixtures of two or more carboxylic acids such as tall oil acids, rosin acids~
and the like.
The pentavalenk phosphorus acids use~ul in the preparation of component (B) may be represenked by the formula R (X )a ~ 11 3 R4(X2)b wherein each f R3 and R4 is hydrogen or a hydrocarbon or essentially hydrocarbon group preferably having from about ~ ~o about 25 carbon atoms, at least one of R3 and R4 being hydrocarbon or essentially hydrocarbon; each of Xl, X2, X3 and X4 is oxygen or sulfur; and each of a and b is o or 1. Thus, it will be appreciated that the phosphorus acid may be an organophosphoric, phosphonic or phosphinic acid, or a thio-analog o~ any of thesa.
The phosphorus acids may be those of the formula R30 \ 1 / P-OH

wherein R3 is a phenyl group or (preferably) an alkyl group having up to 18 carbon atoms, and R4 is hydrogen or a similar phenyl or alkyl group. Mix~ures of such phosphorus acids are often pre~erred because of their ease of preparation.

Component tB) may also be prepared from phenols; that is, compounds containing a hydroxy group bound directly to an aromatic ring. The term 'Iphenol'' as used herein includes compounds having more than one hydroxy group bound to an aromatic r~ng, such as catechol, resorcinol and hydroquinone. It also includes alkylphenols such as the cresols and ethylphenols, and alkenylphenols. Preferred are phenols containing at least one alkyl substituent containing about 3-100 and especially about 5-50 carbon atoms, such as heptylphenol, octylphenol, dodecyl-phenol, te~rapropene-alkylated phenol, octadecylphenol and polybutenylphenols. Phenols containing more than one a}kyl substituen~ may also be used, but ~he monoalkylphenols are pre~erred because of their availability and ease of production.
Also useful are condensation products of the above-described phenols with at least one lower aldehyde or ketone, the term "lower" denoting aldehydes and ketones containing no~ more than 7 carbon atoms.
Suitable aldehydes include for~aldehyde, acetaldehyde, propionaldehyde, the butyraldehydes, the valexaldehydes and benzaldehyde. Also suitable are aldehyde-yielding reagents such as para~ormaldehyde, trioxane, methylol, Nethyl Formcel and paraldehyde. Formaldehyde and the formaldehyde-yielding reagents are especially preferred.
The equivalent weight of the acidic organic compound is its molecular weight divided by th number of acidic groups (i.e., sul~onic acid, carboxy or acidic hydroxy groups) present per molecule.
In one preferred embodiment, the alkali metal salts (B) are basic alkali me~al salts having metal - . - :

- .

-~7-ratios of at least about 2 and more generally rom about 4 to about ~0, pre~erably from about 6 to about 30 and especially f rom about 8 to about 25.
In another and preferred embodiment, the ba~ic salts ~B) are oil-soluble dispersions prepared by contacting for a period of time sufficient to form a stable dispersion, at a temperature between the solidif ication temperature of the reaction mixture and its decomposition temperature:
(B-l) at least one acidic gaseous material selected from the group consisting of carbon dioxide, hydrogen sulfide and sulfur dioxide, with (B-2) a reaction mixture comprising tB-2-a) at least one oil-soluble sulfonic acid, or derivative thereof suscep~ible to overbasing;
(B-2-b) at least one alkali metal or basic alkali metal compound;
(B-2-c) at least one lower aliphatic alcohol, alkyl phenol~ or sulfurized alkyl phenol; and (B-2-d) at least one oil-soluble carboxylic acid or functional derivative thereof. When (B-2-c~ is an alkyl phenol or a sulfuri~ed alkyl phenol, component (B-2-d) is optional. A satisfactory basic sulfonic acid salt can be prepared with or without the carboxylic acid in the mixture (B~2)~
Reagent (B-l) is at least one acidic gaseous material which may be carbon dioxide~ hydrogen sulfide or sulfur dioxide; mixtures of these gases are also useful. Carbon dioxide is preferred.
As mentioned above, reagent ~B-2) generally is a mixture containing at least four components of which component (B-2-a) is at least one oil-soluble sulfonic -68~

acid as previously defined, or a derivative knereof susceptible to overbasing. Mixtures of sulfonic acids and/or their derivatives may also be used. Sulfonic acid derivatives susceptible to overbasing include their metal salts, especially ~he alkaline ear~h, zinc and lead salts; ammonium salts and amine salts ~e.g., the ethylamine, butylamine and ethylene polyamine salts); and esters such as the ethyl, butyl and glycerol esters.
Component (~-2 b) is at least one alkali metal or a basic compound thereof. Illustrative of basic alkali metal compounds are the hydroxides, alkoxides ~typically those in which the alkoxy group contains up to 10 and preferably up to 7 carbon atoms~, hydrides and amides. Thus, useful basic alkali metal compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium propoxide; lithium methoxide~
potassium ethoxide, sodium butoxide, lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide and potassium amide. Especially preferred are sodium hydroxide and the sodium lower alkoxides (i.e., those containing up to 7 carbon atoms). The equivalent weight of component (B-2-b) for the purpose of this invention is equal to its molecular weight, since the alkali metals are monovalent.
Component (R-2-c) may be at least one lower aliphatic alcohol, preferably a monohydric or dihydric alcohol. Illustrative alcohols are mekhanol, ethanol, l-propanol, l-hexanol, i~opropanol, isobu~anol, 2-pentanol, 2,2-dimethyl-1-propanol, ethylene glycol, 1-3-propanediol and 1,5-pentanediol. The alcohol also may be a glycol ether such as Methyl Cellosolve. Of these, the preferred alcohols are me~hanol, ethanol and propanol, with methanol being especially preferred.

.
.

.
, ~;28~4~i ~69-Component (B-2-c) also may be at least one alkyl phenol or sulfurized alkyl phenol. The sulfurized alkyl phenols are preferred, especially when (B-2-b) is potassium or one of its basic compounds such as potassium hydroxide. As used herein, the term "phenol" includes compounds having more than one hydroxy group bound to an aromatic ring, and the aromatic ring may be a benzyl or naphthyl ring. The term "alkyl phenol" includes mono- and di-alkyla~ed phenols in which each alkyl substituent contains from abou~ 6 to about 100 carbon atoms, preferably about 6 to about 50 carbon atoms.
Illustrative alkyl phenols include heptyl-phenols, octylphenols, decylphenols, dodecylphenols, polypropylene (M.W. of about 150)-substitutèd phenols, polyisobutene (M.W. of about 1200)-substituted phenol~, cyclohexyl phenols.
Also useful are condensation products of the above-described phenols with at least one lower aldehyde or ketone, the term "lower" denoting aldehydes and ketones containing not more than 7 carbon atomsO
Suitable aidehydes include formaldehyde, ace~aldehyde~
propionaldehyde~ the butyraldehydes, the valeraldehydes and benzaldehyde. Also suitable are aldehyde-yielding reagents such as paraformaldehyde, trioxane, methylol, Methyl Formcel and paraldehyde. Formaldehyde and the formaldehyde-yielding reagents are especially preferred.
The sulfurized alkylphenols include phenol sulfides, disulfides or polysulfides. The sulfurized phenols can be derived from any sui~able alkylphenol by technique known to those skilled in the artf and many sulfurized phenols are commercially availableO The 8 ~ ~ ~ S

sulfurized alkylphenols may be prepared by reacting an alkylphenol with elemental sulfur and/or a sulfur monohalide (eOg., sulfur monochloride). This reaction may be conducted in the presence o~ excess ba~e to result in the salts o the mixture of sulfides, disulfides or polysulfides that may be produced depending upon the reaction conditions. It is the resulting product of this reaction which is used in the preparation of component (B-2) in the present invention. U.S. Patents 2,971,9~0 and 4,309,293 disclose various sulfurized phenols which are illustrative of component (B-2-c).
The following non-limiting examples illustrate the preparation of alkylphenols and sulfurized alkylphenols useful as component (B-2-c).
Example 1 While maintaining a temp~rature of 55C, 100 parts phenol and ~8 parts sulfonated polystyrene catalyst (marketed as Amberlyst-15 by Rohm and Haas Company) are charged to a reactor equipped with a stirrer, condenser, thermometer and subsurface gas inlet tube. The reactor contents are then heated to 120 while nitrogen blowing for 2 hoursO Propylene tetramer (1232 parts) is charged, and the reaction mixture is stirred at 120C for 4 hours. Agitation is stopped, and the batch is allowed to settle for 0.5 hour. The crude supernatant reaction mixture is filtered and vacuum stripped until a maximum of 0.5%
residual propylene tetramer remains.
Example 2 Benzene (217 parts) is added to phenol (324 parts, 3.45 moles) at 38C and the mixture is heated to 47C~ Boron trifluoride (8.8 parts, 0.13 mole) is ~ , .

. .

blown into the mixture over a one-half hour period at 38-52C. Polyisobutene (1000 parts, 1.0 mole) derived from the polymerization of C4 monomers predominating in isobutylene is added to the mixture at 52-58C over a 3.5 hour period. The mixtu~e i~ held at 52C for 1 additional hour. A 26% solution o~
aqueous ammonia (15 parts) is added and the mixture is heated to 70C over a 2-hour period. rhe mixture is then filtered and the filtrate is the desired crude polyisobutene-substituted phenol. This intermediate is stripped by heating 1465 parts to 167C and the pressure is reduced to 10 mm~ as the material is heated to 218C in a 6-hour period. A 64% yield of stripped polyisobutene substituted phenol ~Mn=885) is obtained as the residue.
- Example 3 A reactor equipped with a stirrer, condenser, thermometer and subsur~ace addition tube is charged with 1000 p~rts of the reaction product of Example 1.
The temperature is adjusted to 48-49 and 319 parts sulfur dichloride is added while the temperature is kept below 60. The batch is then heated to 88-93 while nitrogen blowing until the acid number ~using bromphenol blue indicator) is less than 4.0~ 400 par~s diluent oil is then added, and the mixture is mixed ~horoughly.
Example 4 Following the procedure of Example 3, 1000 parts of ~he reaction product of ~xamplP 1 is reacted with 175 parts of sulfur dichloride. The reaction product is diluted with 4~0 parts diluent oil.
Example 5 Following the procedure of ~xample 3, 1000 parts of the reaction product of Example 1 is reacted '"

.
.

with 319 parts of sulfur dichloride. Diluent oil (788 parts) is added to the reaction product, and the materials are mixed thoroughly.
Example 6 Following the procedure of Example 4, 1000 parts of the reaction product of Example 2 are reacted with 44 parts of sulfur dichloride to produce the sulfurized phenol.
Example 7 Following the procedure of Example 5, 10~0 parts of the reaction product of Example 2 are reacted with 80 parts of sulfur dichloride.
The equivalent weight of component (B-2-c) is its molecular weight divided by the number of hydroxy groups per molecule.
Component (B-2-d) is at least one oil-soluble carboxylic acid as previously described, or functional derivative thereof. Especially suitable carboxylic acids are those of the formula R5(COOH)~, wherein n is an integer from 1 to 6 and is preferably 1 or 2 and R5 is a saturated or substantially satura~ed aliphatic radical (preferably a hydrocarbon radical) having at least 8 aliphatic carbon atoms. Depending upon the value of n, R5 will be a monovalent to hexavalent radical.
R5 may contain non-hydrocarbon substituents provided they do not alter substantially its hydrocarbon character. Such substituents are preferably present in amounts of not more than about 20% by weight. Exemplary substituents include the non-hydrocarbon substituents enumerated hereinabove with reference to component (B-2-a)O R5 may also contain olefinic unsaturation up to a maximum of about 5% and '''. ' '' .
-~a~

preferably not more than 2% ole~inic linkages based upon the total number of carbon-to-carbon covalent linkages present. The number of carbon atoms in R5 is usually about 8-700 depending upon the source o~
R5. AS discussed below, a preferred series of carboxylic acids and derivatives is prepared by reacting an olefin polymer or halogenated ole~in polymer with an alpha,beta-unsaturated acid or its anhydride such as acrylicJ methacrylic, maleic or fumaric acid or maleic anhydride to form the corresponding substituted acid or derivative thereo.
The R5 groups in these products have a number average molecular we.ight from about 150 to about 10,000 and usually rom about 700 to about 5000, as determined, for example, by gel permeation chromatographyO
The monocarboxylic acids useful as component (B-2-d) have the formula R5CooH. Examples of such acids are caprylic, capric, palmitic, stearic, isostearic, linoleic and behenic acids. A particularly preferred group of monocarboxylic acids is prepared by the reaction of a halogenated olefin polymer, such as a chlorinated polybutene, with acrylic acid or methacrylic acid.
Suitable dicarboxylic acids include the substituted succinic acids having the formula wherein ~6 is the same as R5 as defined above.
R6 may be an olefin polymer-derived group formed by polymerization of such monomers as ethylene, propylene, l-butene, lsobutene, l-pentene, 2-pentene~ 1-he~ene and ~za4L~

3-hexene. R6 may also be derived from a high molecular weight substantially saturated petroleum fraction. The hydrocarbon~substituted succinic acids and their derivatives constitute the most pref0rred class of carboxy~ic acids for use as component tB-2-d)-The above-described classes of carboxylic acids derived from olefin polymers, and their deriva~ives, are well known in the art, and me~hods for their preparation as well as representative exam~les of the types use~ul in the present inventlon are also well known.
Functional derivatives of the above-discussed acids useful as component (B-2-d) include the anhydrides, esters, amides, imidesf amidines and metal or ammonium salts. The reaction products of olefin polymer-substituted succinic acids and mono~ or polyamines, particularly polyalkylene polyamines, having up to about 10 amino ni~rogens are especially suitable. These reaction produc~s generally comprise mixtures of one or more of amides, imides and amidines. The reaction products of polyethylene amines containing up to a~out 10 nitrogen a~oms and polybutene-substituted succinic anhydride wherein the polybutene radical comprises principally isobutene units are particularly useful. Included in this group of functional derivatives are the compositions prepared by post-treating the amine-anhydride reaction product with carbon disulfide, boron compounds, nitriles, urea, thiourea, guanidine, alkylene oxid~s or the like. The half-amide, half-metal salt and half-ester, half-metal salt derivatives of such substituted succinic acids are al~o useful.

.~ .

, ,~, . . ---~2 ~

Also useful are the esters prepared by the reaction of the substituted acids or anhydrides with a mono- or polyhydroxy compound, such as an aliphatic alcohol or a phenol. Preferred are the esters o olefin polymer-substituted succinic acids or anhydrides and polyhydric aliphatic alcohols containing 2-10 hydroxy groups and up to about 40 aliphatic carbon atoms. This class of alcohols includes ethylene glycol, glycerol, sorbitol, pentaerythritol, poly ethylene glycol/ diethanolamine, triethanolamine, N,N'-di(hydroxyethyl)ethylene diamine and the like~
When the alcohol contains reactive amino groups, the reaction product may comprise products resulting from the reaction of the acid group with both the hydroxy and amino functions. Thus, this reaction mixture can include half-esters, half-amides, esters, amides, and imides.
The ratios of equivalents of the constituents of reagent (E~-2) may vary widely. In general, the ratio of component (B-2-b) to (B-2~a) is at least about

4:1 and usually not more than about 40:1, preferably between 6:1 and 30:1 and most preferably between 8:1 and 25~ hile this ratio may sometimes exceed 40:1, such an excess normally will serve no useful purpose.
The ratio of equivalents of component (B-2-c) to component (B-2-a) is between about 1:20 and 80:1, and preferably between about 2:1 and sa: 1 . As mentioned above, when component (B-2-c) is an alkyl phenol or sulfurized alkyl phenol, tbe inclusion of the carboxylic acid (B-2-d) is optional. When present in the mixture, the ratio of equivalents of component (B-2-d) to component (B-2-a) g nerally is from about 1:1 to about 1:20 and preferably from about 1:2 to about l lOo .

.

~34~

Reagents (B-l) and (B-2) are generally contacted until there is no further reaction between the two or until the reaction substantially ceases.
While it is usually preferred that the reaction be continued until no urther overbased product is Eormed, useful dispersions can be prepared when contact between reagents (B-l) and (B-2) is maintained for a period of time sufficient for about 70% of reagent (B-l), relative to the amount required if the reaction were permitted to proceed to its completion or "end point", to react.
The point at which the reaction is completed or substantially ceases may be ascertained by any of a number of conventional methods. One such method is measurement of the amount of gas (reagent tB-l)) entering and leaving the mixture the reaction may be considered substantially complete when the amount leaving is about 90-100% of the amount entering. These amounts are readily determined by the use of metered inlet and outllet valves.
When (B-2-c) is an alcohol, the reaction temperature is not ~ritical. Generally~ it will be between the solidification temperature of the reaction mixture and its decomposition temperature ~i.e., the lowest decomposition temperature of any component thereof). Usually, the ~em~erature will be from about 25 to about 200C and preerably from about 50 to about 150C. Reagents (B-l) and (B-2) are conveniently contacted at the reflux temperature of ~he mixture. This ~emperature will obviously depend upon the boiling points of the various components; thus, when methanol is used as component (B-2-c), the contact temperature will be ~t or below the reflux temperature of methanol.

- : .
.

. ' ' 4~

When reagent ~B-2-c) is an alkyl phenol or a sulfuri~ed alkyl phenol, the temperature of the reaction must be at or above the water-diluent azeotrope tempera~ure so that the water ~ormed in the reaction ca~ be removed. Thus the diluent in such cases generally will be a volatile organlc liquid such as aliphatic and aromatic hydrocarbons. E~amples of such diluents include heptane, decane, toluene, xylene, etc.
The reaction is ordinarily conducted at atmospheric pressure, although superatmospheric pressure often expedites the reaction and promotes optimum utilization of reagent (B-l). The process can also be carried out at reduced pressure but, for obvious practical reasons, this is rarely done.
The reaction is usually conducted in the presence of a substantially inert, normally liquid organic diluent, which functions as both the dispersing and reaction medium. This diluent will comprise at least about 10% of the total weight of the reaction mixture. Ordinarily it will not exceed about 80% by weight, and it is preferably about 30-70~ thereof~
Although a wide variet:y of diluents are useful, it is preferred to use a diluent which is soluble in lubricating oil~ The diluen~ usually itself comprises a low viscosity lubricating oil.
Other organic diluents can be employed ei~her alone or in combination with lubricating oil Preferred diluents for this purpose include the aromatic hydrocarbons such as benzene, toluene and xylene; halogenated derivatives thereof such as chlorobenzene; lower boiling petroleum distillates such as petroleum ether and various naphthas; normally , ~

liquid aliphatic and cycloaliphatic hydrocarbons such as hexane, heptane, hexene, cyclohexene, cyclopentane, cyclohexane and ethylcyclohexane, and their halogenated derivatives. Dialkyl ketones such as dipropyl ketone and ethyl butyl ketone, and the alkyl aryl ketones such as acetophenone, are likeuise useul, as are ethers such as n-propyl ether, n-butyl ether, n-butyl methyl ether and isoamyl ether.
~ hen a combination of oil and other diluent is used, the weight ratio of oil to the other diluent is generally from about 1:20 to about 20:1. It is usually desirable for a mineral lubricating oil to com~rise at least about 5~% by weight of the diluent, especially if the product is to be used as a lubricant additive. The total amount of diluent present is not particularly critical since it is inactive. However, the diluent will ordinarily comprise about 10-80% and preferably about 30-70~ by weight of the reaction mixture.
Upon completion of the reaction, any solids in the mixture are preferably removed by filtration or other conventional means. Optionally, readily removable diluents, the alcoholic promoters, and water formed during ~he reaction can be removed by conventional techniques such as distillation~ It is usually desirable to remove substantially all water from the reaction mixture since the presence of water may lead to difficulties in filtration and to the formation of undesirable emulsions in fuels and lubrican~s Any such water present is readily removed by heating at atmospheric or reduced pressure or by azeotropic distillation. In one preerred embodiment, when basic potassium sulfonates are desired as component (B), the potassium salt is prepared using carbon dioxide and the sulfurized alkylphenols as component (B-2-c). The usc of the su}furiæed phenols results in basic salts of higher metal ratios and the formation of more uniform and stable salts. Also, the reaction generally is conducted in an aromatic diluent such as xylene, and water is removed as a xylene-water azeotrope during the reaction.
The chemical structure of component ~B) is not known with certainty. The basic salts or complexes may be solutions or, more likely, stable dispersisns~
Al ernatively, they may be regarded as "polymeric salts" formed by the reaction of the acidic material, the oil-soluble acid being overbased, and the metal compound. In view of the above, these compositions ar0 most conveniently defined by reference to the method by which they are formed.
The above-described procedure for preparing alkali metal salt-~ of sulfonic acids having a m~al ratio of at least about 2 and preferably a metal ratio between about 4 to 40 using alcohols as component (B-2-c) is ~escribed in more detail in Canadian Patent 1,055,700 which corresponds to British Patent 1,481,553. The preparation of oil-soluble dispersions of alkali metal sulfonates useful as component (B) in the diesel lubricants of this invention is illustrated in the following examples.
Example B-l To a solution of 790 parts (1 equivalen~ of an alkylated benzenesul~onic acid and 71 parts of polybutenyl succinic anhydride (equivalent weight about 560) containing predominantly isobutene units in 176 .

parts of mineral oil is added 320 parts (8 e~uivalents) of sodium hydroxide and 640 parts ~2Q equivalents) of methanol. The temperature of the mixture increases to 89C (reflux) over 10 minutes due to exotherming.
During this period, the mixture is blown with carbon dioxide at 4 cfh. (cubic feet/hr.). Carbonation is continued for about 30 minutes as the ~emperature gradually decreases to 74C. The methanol and other volatile materials are stripped from the carbonated mixture by blowing nitrogen through it at 2 cfh. while the temperature is slowly increased to 150C over 90 minutes. After stripping is completed, the remaining mixture is held at 155-165C for about 30 minutes and filtered to yield an oil solution of the desired basic sodium sulfona~e having a metal ratio o about 7.75.
This solution contains 12.5% oil.
Example B-2 Following the procedure of Example B-l, a solution of 780 parts (1 equivalent) of an alkyla~ed benzenesulfonic acid and 119 parts of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed with 800 parts (20 equivalents) of sodium hydroxide and 704 parts (22 equivalents) of methanol. The mixture is blown with carbon dioxide at 7 ch. for 11 minutes as the temperature slowly increases to 97C. The rate of carbon dioxide flow is reduced to 6 cfh. and the temperature decreases slowly to 88C over about 40 mlnutes. The ra~e of carbon dioxide flow is reduced to cfh. for about 35 minutes and the temperature slowly decreases to 73C. The volatile materials are stripped by blowing nitrogen through the carbonated mixture at 2 cfh. for 105 minutes as the temperature is slowly increased to 160C~ After stripping i5 .

~L2~ 5 completed, the mixture is held at 160C for an additional 45 minutes and then filtered to yield an oil solution of the desired basic sodium sulonate having a metal ratio of about 19.75. This solution contains 18.7% oil.
Example B 3 Following the procedure of Example B-l, a solution of 3120 parts (4 equivalents) of an alkylated benzenesulfonic acid and 284 parts of the polybutenyl succinic anhydride in 704 parts of mineral oil is mixed with 1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 equivalents~ of methanol. The mixture is blown with carbon dioxide at 10 cfh~ for 65 minutes as the temperature increases to 90C and then slowly decreases to 70C. The volatile material is stripped by blowing nitrogen at 2 cfh~ for 2 hours as the temperature is slowly increased to 160C. After stripping is completed, the mixture is held a~ 160C
for 0.5 hourl, and then filtered to yield an oil solution of the desired basic sodium sulfonate having a metal ratio of about 7.75. This solution contains 12.35% oil content.
Example B-4 Following the procedure of Example B-l, a solution of 3200 parts (4 equivalents) of an alkylated benzenesulfonic acid and 284 parts of the polybutenyl succinic anhydride in 623 parts of mineral oil is mixed with 1280 parts (32 equivalents) of sodium hydroxide and 2560 parts (80 equivalents) of methanol~ The mixture is blown with carbon dioxide at 10 cfh. for about 77 minutes. During this time the temperature increases to 9~C and then gradually drops to 73C. The volatile materials are stripped by blowing ~284~

with nitrogen gas at 2 cfh. for about 2 hours as the temperature of the reaction mixture is slowly increased to 160C. The final traces of volatile material are vacuum stripped and the residue is held at 170C and then filtered to yield a clear oil solu~ion o~ the desired sodium salt, having a metal ratio o~ about 7.72. This solution has an oil content of 11%.
Example B-5 - Following the procedure of Example B-l, a solution of 780 parts (1 equivalent) of an alkylated benzenesulfonic acid and 8S parts of the polybutenyl succinic anhydride in 254 parts of mineral oil is mixed with 480 parts (12 equivalents) of sodium hydroxide and 640 parts (20 equivalents) of methanol. The reaction mixture is blown with carbon dioxide at 6 cfh. for about 45 minutes. During this time the temperature in~reases to 95C and then gradually decreases to 74C. The volatile material is stripped by blowing with nitrogen gas at 2 cfh. for about one hour as the temperature is increased to 160C. After stripping is complete the mixture is held at 160C for 0.5 hour and then filtered to yield an oil solution of the desired sodium salt, having a metal ratio of 11.8. The oil content of this solution is 14.7%.
Example B-6 Following the procedure of Example B-l, a solution of 3120 parts (4 equivalents) of an alkylated benzenesulfonic acid and 344 parts of the polybutenyl succinic anhydride in 1016 parts of mineral oil is mixed with 1920 parts (48 equivalents) of sodium hydroxide and 2560 parts (80 equivalents) of methanol~
The mixt~re is blown with carbon dioxide at 10 cfh. for about 2 hours. During this time t~e temperature ' .

increases to 96C and then gradually drops to 74C. The volatile materials are stripped by blowing with nitrogen gas at 2 cfh. for about 2 hours as the temperature is increased from 74 to 160C by external heating. The stripped mixture is heated for an additional hour at 160C and filtered. The filtrate is vacuum stripped to remove a small amount of water, and again filtered to give a solution of the desired sodium salt, having a metal ratio of about 11.8. The oil content of this solution is 14.7%.
Example B-7 Following the procedure of Example B-l, a solution of 2800 parts ~3.5 equivalents~ of an alkylated benzenesulfonic acid and 302 parts of the polybutenyl succinic anhydride in 818 parts of mineral oil is mixed with 1680 parts (42 equivalents) of sodium hydroxide and 2240 parts (70 equivalents) of methanol.
The mixture is blown with carbQn dioxide for about 30 minutes at 10 cfh During this period, the temperature increases to 96C and then slowly drops to 76C.
The volatile materials are stripped by blowing with nitrogen at 2 cfh. as the temperature is slowly increased from 76C to 165C by external heating.
Water is removed by vacuum stripping. Upon filtration, an oil solution of the desired basic sodi~m salt is obtained. It has a metal ratio of abou~ 10.8 and the oil content is 13.6~.
Example B-8 Following the procedure of Example B 1~ a solution of 780 parts ~1 equivalent) of an alkylated benzenesulfonic acid and 103 parts of the polybutenyl succinic anhydride in 350 parts of mineral oil is mixed with 640 parts (16 equivalents) of sodium hydroxide and .. ,. ~ ~,. -~z~ s 640 parts ~20 equivalents) of methanol. This mixture is blown with carbon dioxide for about one hou,r at 6 cfh. During this period, the temperature increases to 95C and then gradually decreases to 75C. The volatile material is stripped by blowing with nitrogen. During stripping, the temperature initially drops to 70C over 30 minutes and then slowly rises to 78C over 15 minutes. The mixture is then heated to 155C over 80 minutes. The stripped mixture is heated for an additional 30 minutes at 155-160C and filtered. The filtrate is an oil solution of the desired basic sodium sulfonate~ having a metal ratio of about 15.2. It, has an oil content of 17.1%.
Example B-9 Following the procedure of Example B-l, a solution of 2400 parts (3 equivalents) of an alkylated benzenesulfonic acid and 308 parts of the polybutenyl succinic anhydride in 991 parts of mineral oil is mixed with 1920 parts (48 equivalents) of sodium hydroxide and 1920 parts (60 equivalents) of methanol. This mixture is blown with carbon dioxide at lO cfh. for 110 minutes, during which time the temperature rises to 98C and then slowly decreases to 76C over about minu~es. The methanol and water are stripped by blowing with nitrogen at 2 ch. as the temperature of the mixture slowly increases to 165C. The last traces of volatile material are vacuum stripped and the residue is filtered to yield an oil solution of the desired sodium salt having a metal ratio of 15.1. The solution has an oil content of 16.1~.
Example B-10 Following the procedure of Example B-l, a solution of 7~0 parts (1 equivalent) of an alkylated . -- ;, .
- ~

~28~14~;i benzenesulfonic acid and 119 parts of the polybutenyl succinic anhydride in 442 parts of mineral oil is mixed well with 800 parts (20 equivalents) of sodium hydroxide and 640 parts (20 equivalents) o~ methanol, This mixture is blown with carbon dioxide for about 55 minutes at 8 cfh. During this periodt the temperature of the mixture increases to 95C and then slowly decreases to 67C. The methanol and water are stripped by blowing with nitrogen at 2 cfh. for about minutes while the temperature is slowly increased to 160C. After stripping, the temperature of the mixture is maintained at 160-165C for about 30 minutes. The product is then filtered to give a solution of the corresponding sodium sulfonate having a metal ratio of about 16.8. This solution contains 18.7% oil.
Example B-ll Following the procedure of Example B-l, 836 parts (1 equivalent) of a sodium petroleum sulfona~e (sodium ~Petronaten) in an oil solution containing 48~
oil and 63 parts of the polybutenyl succinic anhydride is heated to 60C and treated with 280 parts (7 equivalents) of sodium hydroxide and 320 parts (10 e~uivalents) of methanol. The reaction mixture is blown with carbon dioxide at 4 cfh. for about 45 minutes. During this time, the temperature increases to 85C and then slowly decreases to 74C. The volatile material is stripped by blowing with nitrogen at 2 cfh. while the temperature is gradually increased to 160C. After stripping is completedr the mi~ture is heated an additional 30 minutes at 160C and tben is filtered to yield the sodium salt in solution. The product has a metal ratio of 8~0 and an oil content of 22.2%.

.

- .. ~ ' ':' ' .

Example B-12 Following the procedure of Example B-ll, 1256 parts (1.5 equivalents) o~ the sodium petroleum sulfonate in an oil solution contalning 4~ oil and 95 parts of polybutenyl succinic anhydride is heated to 60C and treated with ~20 parts ~10.5 equivalents) of ssdium hydroxide and 960 parts (30 equivalents) of methanol. The mixture is blown with carbon dioxide at 4 cfho for 60 minutes. During this ~ime, the temperature is increased to 90C and then slowly decreases to 70C. The volatile materials are stripped by blowing with nitrogen and slowly increasing the temperature to 160C. After stripping, the reaction mixture is allowed to stand at 160C for 30 minutes and then is filtered to yield an oil solution of sodium sulfonate having a metal ratio of about 8Ø
The oil content of the solution is 22.2%.
Example B-13 A mixture of 584 parts (0.75 mole) of a commercial dialkyl aromatic sulfonic acid, 144 parts (0O37 mole) of a sulfurized tetrapropenyl phenol prepared as in Example 3, 93 parts of a polybutenyl succinic anhydride as used in Example B~l, 500 parts o xylene and 549 parts of oil is prepared and heated with stirring to 70C whereupon 97 parts of potassium hydroxide are added. The mixture is heated to 145C
while azeotroping water and xylene. Additional potassium hydroxide (368 parts) is added over 10 minutes and heating is continued at about 145-150C
whereupon the mixture is blown with carbon dioxide at 1.5 cfh. for about 110 minutes. The volatile materials are stripped by blowing with nitrogen and slowly increasing the temperature to about 160C. After - .

~L2~

stripping, the reaction mixture is filtered to yield an oil solution of the desired potassium sulfonate having a metal ratio of about 10. Additional oil is added to the reaction product to provide an oil content of the final solution o~ 39%.
Example B-14 A mixture of 705 parts (0.75 mole) of a commercially available mixture of straight and branched chain alkyl aromatic sulfonic acid, 98 parts (0.37 mole~ of a tetrapropenyl phenol prepared as in Example 1, 97 parts of a polybutenyl succinic anhydride as used in Example B-l, 7S0 parts of xylene, and 133 parts of oil is prepared and heated with stirring to about 50C whereupon 65 parts of sodium hydroxide dissolved in 100 parts of water are added. The mixture is heated to about 145C while removing an azeotrope of water and xylene. After cooling the reaction mixture overnight, 279 parts of sodium hydroxide are added.
The mixture is heated to 145C and blown with carbon dioxide at about 2 cfh. for 1.5 hours. An azeotrope of water and xylene is removed. ~ second increment of 179 parts of sodium hydroxide is added as the mixture is stirred and hea~ed to 145C whereupon the mixture is blown with carbon dioxide at a rate of 2 cfh~ for about 2 hours. Additional oil (133 parts) is added to the mixture after 20 minutes. A xylene:wa~er azeotrope is removed and the residue is stripped to 170C at 50 mm. Hg. The reaction mixture is filtered through a filter aid and the filtrate is the desired product containing 17.01% sodium and 1.27~ sulfur.
Example B-15 A mixture of 386 parts (0~75 mole~ of a commercially available primary branched chain monoalkyl .

.. .. ~ . ~ . -aromatic sulfonic acid, 58 parts (0.15 mole) of a sulurized tetrapropenyl phenol prepared as in Example 3, 926 grams of oil and 700 grams of xylene is prepared, heated to a temperature o 70~ whereupon 97 parts of potassium hydroxide are added over a period of 15 minutes. The mixture is heated to 145C while removing water. An additional 368 parts of potassium hydroxide are added over 10 minutes, and the stirred mixture is heated to 145C whereupon the mixture is blown with carbon dioxide at 1.5 cfh. for about 2 hours. The mixture is stripped to 150C and finally at 150C at 50 mm. Hg. The residue is filtered, and the fil~rate is the desired product.
The diesel lubricants of the present invention containing components (A) and (B) as described above may be further characterized as containing at least about 0.8 sulfate ash and more generally at least about 1% sulfate ash. The amounts of components tA) and tB) included in the diesel lubricants o~ the present invention may vary over a wide range as can be determined by one skilled in the art. Generally, however, the diesel lubricants of the present invention will contain from about 1.0 to about 10% by weight of component tA) and from about 0.05 to about 5% and more generally up to about 1% by weight of component tB).
In another preferred embodiment, the diesel lubricants o~ the present invention also contain tC) at least one oil-soluble neutral or basic alkaline earth metal salt of at least one acidic organic compound.
Such salt compounds genera1ly are referred to as ash-containing detergents. The acidic organic compound may be at least one sulfur acid, carboxylic acid, phosphorus acid, or phenol, or mixtures thereof.

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Calcium, magnesium and barium are the preferred alkaline earth metals. Salts containing a mixture of ions of two or more of these alkaline earth metals can be used.
The salts which are useful as component (C) can be neutral or basic. The neutral salts contain an amount of alkaline earth metal which is just sufficient to neutralize the acidic groups present in the salt anion, and the basic salts contain an excess of the alkaline earth metal cation.
The commonly employed methods for preparing the basic salts comprises heating a mineral oil solution of ~he acid with a stoichiometric excess of a metal neutralizing agent, e~g., a metal oxide, hydroxide, carbona~e, bicarbonate, sulfide, etc., at temperatures above about 50C. In addition, various promo~ers may be used in the neutralizing process to aid in the incorporation of the large excess of metal.
These promoters are presently known and include such compounds as the phenolic substances, e.g., phenol, naphthol, alkylphenol, thiophenol, sulfurized alkyl phenol and the various conderlsation products of formaldehyde with a phenolic substance, e.g., alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve carbitol, ethylene, glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylene-diamine, phenothiazine, phenyl-beta~naphthylamine, and dodecyl amine, etc. A particularly effective process for preparing the basic salts comprises mixing the acid with an excess of the basic alkaline earth metal in the presence of the phenolic promo~er and a smal} amount o water and carbonating the mixtu~e at an elevated temperature, e.g., 60C to about 200C.

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.
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As mentioned above, the acidic organic compound from which the salt of component (C) is derived may be at least one sulfur acid, carboxylic acid, phosphorus acid, or phenol or mixtures thereo~.
Such acidic organic compounds previously have been described above with respect to the preparation of the alkali metal salts 5component (B)), and all o the acidic organic compounds described above can be utilized in the preparation of the alkaline earth metal salts useful as component (C~ by techniques known in the art. The amount of component (C) included in the diesel lubricants of the present invention also may be varied over a wide range, and useful amounts can be readily determined by one skilled in the art.
Component ~C) functions as an auxiliary or supplemental detergent. The amount of component (C) contained in a diesel lubricant of the invention may vary from about 0~ to about 5% or more.
The following examples illustrate the preparation of neutral and basic alkaline earth metal salts useful as component (C).
Example C-l A mixture of 906 parts of an oil solution of an alkyl phenyl sulfonic acid (having an average molecular weight of 450, vapor phase osmometry), 56~
parts mineral oil, 600 parts toluene, 9807 parts magnesium oxide and 120 parts water is blown with carbon dioxide at a temperature of 78-85~C for 7 hours at a rate of about 3 cubic feet of carbon dioxide per hour. The reaction mixture is constantly agitated throughout the carbonation. After carbonationl the reaction mixture is stripped to 165/20 tor and the residue filteredO The filtrate is an oil solution of , .

3L;2~4~5 the desired overbased magnesium sulfonate having a metal ratio of about 3.
Example C-2 A polyisobutenyl succinic anhydride is prepared by reacting a chlorinated polytisobutene) (having an average chlorine content of 4.3% and an average of 8~ carbon atoms) with maleic anhydride at about 200C. The resulting polyisobutenyl succinic anhydride has a saponification number of 90~ To a mixture of 1246 parts of this succinic anhydride and 1000 parts of toluene there is added at 25C, 76 6 parts of barium oxide. ~he mixture is heated to 115C and 125 parts of water i5 added drop-wise over a period of one hour. The mix~ure is then allowed to reflux at 150C until all the barium oxide is reacted. Stripping and filtration provides a filtrate having a barium content of 4.71%.
Example C-3 A basic calcium sulfonate having a metal ratio of about 15 is prepared by carbonation, in increments~
of a mixture of calcium hydroxide, a neutral sodium petroleum sulfonate, calcium chloride, methanol and an alkyl phenol.
Example C-4 A mixture of 3~3 parts of mineral oil, 4.8 parts of water, 0.74 parts of calcium chloride, 79 parts of lime, and 128 parts o methyl alcohol is prepared, and warmed to a tempera~ure of about 50C.
To this mixture there is added 1000 parts of an alkyl phenyl sulfonic acid having an average molecular weight (vapor phase osmometry) of 500 with mixing. The mixture then is blown with carbon dioxide at a temperature of about 50C at the rate of about 5 D 4 ~za~

pounds per hour for ahout 2.5 hours. A~ter carbonation, 102 additional parts of oil are added and the mixture is stripped of volatile materials at a temperature o~ about 150-155C at 55 mm. pressure.
The residue is f iltered and the filtrate is the desired oil solution of the overbased calcium sulfonate having calcium content of about 3.7% and a metal ratio of about 1.70 The present invention also contemplates the use of other additives in the diesel lubricant compositions of the present invention. These other additives include such conventional additive types as anti-oxidants, extreme pressure agents, corrosion-inhibiting agents, pour point depressants, color stabilizing agents, anti-foam agents, and other such additive materials known generally to ~hose skilled in the art of formulating diesel lubricants.
Extreme pressure agents and corrosion- and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wa~; organic sulf ides and polysulfides such as benzyl disulfide, bis~chlorobenzyl)disulfide, dibutyl tetra-sulfide, sulfurized methyl estPr of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpcne; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulf ide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphi~e, pen~yl phenyl phosphite, dipentyl phenyl phosphite, tridecyl phosphite, distearyl phosphi~e, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite~ polypro 34~

pylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite;
metal thiocarbamates, such as zinc dioctyldithiocarba-mate, and barium heptylphenyl dithiocarbamate; Group II
metal phosphorodithioates such as zinc dicyclohexyl-phosphorodithioate, zinc dioctylphosphorodithioate;
barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by ~he reaction of phosphorus pen~asulfide with an equimolàr mixture of isopropyl alcohol and n-hexyl alcohol.
Many of the above-mentioned auxiliary extreme pressure agents and corrosion-oxidation inhibitors also serve as antiwear agents. Zinc dialkylphosphoro-dithioates are a well known example~
Pour point depressants ar~ a particularly useful type of additive often included in the lubricating oils described herein. The use of such pour point depressants in oil-based compositions to improve low temperature properties of oil-based compositions is well known in the art. See, for example, page 8 of "Lubricant Additives" by C.V.
Smalheer and R. Kennedy Smith (Lezius-Hiles Co~
publishers, Cleveland, Ohio, 1967).
Examples of useful pour point depressants are polymetha~rylates; polyacrylates; polyacrylamides;
condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants useful for the purposes o this inven~ion, techniques for their preparation and their uses are described in U.S. Patents 2,387,501, 2,015,748, 2,655,479, - , , ' ,' :`

' ,," ~;

~LZ8~

1,815,022; 2,191,498; 2,666,746; ~,721,877; 2,721,878; and 3,250,715.
Anti-~oam agents are used to reduce or prevert the formation of stable Eoam. Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents", by H~nry T. Kerner (Noy~s Data Corporation, 1976), pages 125-162.
The present invention will be further understood by a consideration of the following examples which are intended to be purely exemplary of the invention. Other embodiments of the invention will be apparent to those skilled in the art from a consideration of the following examples.
Parts by Product of Example A-ll 2 Product of Example B-2 0.5 Lubricating Oil 97.5 ~h~ .
Product of Example A-12 l.O
Product of Example B-2 0~4 Product of Example C-3 0.25 Lubricating Oil 98.35 - ' ,. . . ., . . ' , . - , . . .~
. :
.

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Parts by Weigh~
Lubrican~s III-V III 1~ V Control Product of Example A-ll .47 ~47 .47 .47 Product of Example B-~, .45 .33 Product of Example C-3 - .12 Product of Example B-13 - - .25 Hydrogenated copolymer of isoprene-styrene .60 .60 .60 .60 Reaction product of maleic anhydride-st~rene copolymer with alcohol and amine .08 ,08 .08 .08 Polybutenyl succinic anhy-dride-ethylene polyamine 1 97 reaction product 1.97 1.97 1.97 Basic calcium salt of a sulfurized tetrapropenyl phenol 1.18 1.118 1.121.11 Zinc salt of m:ixed isobutyl-and primary amyl-phosphoro dithioic acid .39 .39 .3~ .39 Zinc salt of mixed isooctyl phosphorodithioic acid1.04 1.04 1.04 1.04 Alkylated aryl amine .08 .08 .06 .06 Bas c magnesium petroleu50 .50 ~4~ .49 sulfonate .27 .27 .25 .25 Silicone anti-foam agent lOppm lOppm lOppm lOppm Mineral oil balance ~

. .

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-~ ' - ~ ` " ' ~ ' .

. . .

The diesel lubricants of the present invention are useful in the operation of diesel engines, and when the diesel lubricants of the present invention are so utilized, the diesel engines can be operated ~or longer periods of time without undergoing undesirable viscosi~y increases. Furthermore, the diesel lubricants of the present invention are capable of passing the Caterpillar l-G-2 and the Caterpillar 1-H-2 test procedures.
The advantages of the diesel lubricants of the present invention is demonstrated by subjecting the diesel lubricants o~ lubricant Examples III~V to the Mack Truck ~echnical Services Standard Test Procedure No. 5GT 57 entitled "Mack T-7: Diesel Engine Oil Viscosity Evaluation", dated August 31, 1984. This test has been designed to correlate with field experience. In this test, a Mack EM6-285 engine is operated under low speed, high torque, steady-state conditions. l'he engine is a direct injection, in-line, six-cylinder, four-stroke, turbo-charged series charge air-cooled compression ignition engine containing keystone rings. The rated power iC 283 bhp at 2300 rpm governed speed.
The test operation consists of an initial break-in-period (after major rebuild only) a test oil flush, and 150 hours of steady sta~e operation at 1200 rpm and 1080 ft/lb. of torque. No oil changes or additions are made, although eight 4 oz. oil samples are taken periodically from the oil pan drain valve during the test for analysis. Sixteen ounces of oil are taken at the oil pan drain valve before each 4 oz.
sample is taken to purge the drain line. This purge sample is then returned to the engine after sampling.
No make-up oil is added to the engine to replace the 4 oz. samples.
.

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.~ .

The kinematic viscosity at 210F is measured at 100 and 150 hours into the test, and the "viscosity slope" is calculated. The "viscosity slope" is defined as the difference between the 100 and 150~hour viscosity divided by 50. It is desirable that the viscosity slope should be as small a number as possible, reflecting a minimum viscosity increase as the test progresses.
The kinematic viscosity at 210F can be measured by two procedures. In both procedures, the sample is passed through a No. ~00 sieve before it is loaded into the Cannon reverse flow viscometer. In the ASTM D-445 method, the viscometer is chosen to result in flow times equal to or greater than 200 seconds. In the method described in the Mack T-7 specification, a Cannon 300 viscometer is used for all viscosity determinations. Flow times for the latter procedure are typically 50-100 seconds or fully formulated 15~-40 diesel lubricants.
The results of the Mack T 7 test using three of the diesel lubricants of the invention are summarized in the following table.

- . . ~
, '~. . .

~ck T-7 Resul~
- Sulfated Ash Lubricant of DetergentSupplement ~iscosiky Exam~le ~s~1~m~n~ (Wt.~ lo~e*
Control - 0.16 III Sodium 0.33 0.01 IV Sodium ~ 0.33 0.02 Calcium Potassium 0.09 0.11 -* cst @ 210F per hour.

Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.

- . - . . . . -' . "' ' `, ,' '- , ' ~ . .
. . ~ ., :

: -

Claims

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

1. A diesel lubricant comprising a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising (A) at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -NH- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of at least about 1200 and an Mw/Mn ratio of at least about 1.5, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each equivalent weight of substituent groups, and (B) at least one basic alkali metal salt of at least one acidic organic compound having a metal ratio of at least about 2.

2. The lubricant of claim 1 containing at least about 0.8% sulfate ash.

3. The lubricant of claim 1 containing at least about 1% sulfate ash.

4. The lubricant of claim 1 wherein the substituent group in (A) is characterized by an Mn value of about 1300 to about 5000.

5. The lubricant of claim 1 wherein the substituent group in (A) is characterized by an Mw/Mn value of from about 1.5 to about 6.

6. The lubricant of claim 1 wherein the succinic groups correspond to the formula wherein R and R' are each independently selected from the group consisting of -OH, -Cl, -O-lower alkyl and, when taken together, R and R' are -O-, with the proviso that all the succinic groups need not be the same.

7. The lubricant of claim 1 wherein the substituent groups are derived from one or more polyalkene selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 40% of polymer units derived from internal olefins of up to about 16 carbon atoms.

8. The lubricant of claim 7 wherein said value of Mn is at least about 1500.

9. The lubricant of claim 7 wherein said value of Mw/Mn is at least about 1.8.

10. The lubricant of claim 1 wherein the substituent groups are derived from one or more polyalkene selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 25% of polymer units derived from internal olefins of up to about 16 carbon atoms.

11. The lubricant of claim 1 wherein the substituent groups are derived from a member selected from the group consisting of polybutene, ethylene-propylene copolymer, polypropylene, and mixtures of two or more of any of these.

12. The lubricant of claim 1 wherein said acylating agents are characterized by the presence within their structure of an average of at least 1.4 succinic groups for each equivalent weight of the substituent groups.

13. The lubricant of claim 1 wherein said value of Mn is about 1500 to about 2800.

14. The lubricant of claim 1 wherein said value of Mw/Mn is about 2.0 to about 3.4.

15. The lubricant of claim 1 wherein the acylating agents are characterized by the presence within their structure of at least 1.5 up to about 2.5 succinic groups for each equivalent weight of the substituent groups.

16. The lubricant of claim 11 wherein the substituent groups are derived from polybutene in which at least about 50% of the total units derived from butenes is derived from isobutene.

17. The lubricant of claim 1 wherein the succinic groups correspond to the formulae and mixtures of these.

18. The lubricant of claim 1 wherein the basic alkali metal salt (B) is a salt of at least one sulfur acid, phosphorus acid, carboxylic acid or phenol or mixtures thereof.

19. The lubricant of claim 1 wherein the alkali metal salt is a salt of an organic sulfonic acid.

20. The lubricant of claim 19 wherein the sulfonic acid (i) is represented by the formulae R'(SO3H)r or (R2)xT(SO3H)y in which R' and R2 are each independently an aliphatic group free from acetylenic unsaturation and containing up to 60 carbon atoms, T is an aromatic hydrocarbon nucleus, and x is a number of 1 to 3, and r and y are numbers of 1 to 4.

21. The lubricant of claim 20 wherein said sulfonic acid is an alkylated benzenesulfonic acid.

22. The lubricant of claim 19 wherein the basic sulfonate salt (B) is an oil-soluble dispersion prepared by the method which comprises contacting at a temperature between the solidification temperature of the reaction mixture and its decomposition temperature, (B-1) at least one acidic gaseous material selected from the group consisting of carbon dioxide, hydrogen sulfide, sulfur dioxide, and mixtures thereof, with (B-2) a mixture comprising (B-2-a) at least one oil-soluble sulfonic acid, or derivative thereof susceptible to overbasing;
(B-2-b) at least one alkali metal selected from the group consisting of lithium, sodium or potassium, or one or more basic compounds thereof selected from the group consisting of hydroxides, alkoxides, hydrides, or amides;
(B-2-c) at least one lower aliphatic alcohol selected from monohydric alcohols or dihydric alcohols, or at least one alkyl phenol or sulfurized alkyl phenol; and (B-2-d) at least one oil-soluble caxboxylic acid or functional derivative thereof.

23. The lubricant of claim 22 wherein the acidic gaseous material (B-1) is carbon dioxide.

24. The lubricant of claim 22 wherein the sulfonic acid (B-2-a) is represented by the formulae R'(SO3H)r or (R2)xT(SO3H)y in which R' and R2 are each independently an aliphatic group free from acetylenic unsaturation and containing up to 60 carbon atoms, T is an aromatic hydrocarbon nucleus, and x is a number of 1 to 3, and r and y are numbers of 1 to 4.

25. The lubricant of claim 22 wherein the functional derivatives of component (B-2-d) are selected from the group consisting of anhydrides, esters, amides, imides, amidenes and metal salts.

26. The lubricant of claim 22 wherein the ratios of equivalents of the components of B-2 are:
(B-2-b)/(B-2-a) - at least 4:1;
(B-2-c)/(B-2-a) - between about 1:1 and about 80:1;
(B-2-d)/(B-2-a) - between about 1:1 and about 1:20.

27. The lubricant of claim 22 wherein the basic salt (B) has a metal ratio of from about 6 to about 30.

28. A lubricant according to claim 22 wherein component (B-2-d) is at least one hydrocarbon-substituted succinic acid or functional derivative thereof and the reaction temperature is in the range of about 25-200°C.

29. A lubricant according to claim 22 wherein component (B-2-a) is an alkylated benzenesulfonic acid.

30. A lubricant according to claim 22 wherein component (B-2-b) is sodium or a sodium compound.

31. A lubricant according to claim 22 wherein component (B-2-c) is at least one of methanol, ethanol, propanol, butanol and pentanol and component (B-2-d) is at least one of polybutenyl succinic acid and polybutenyl succinic anhydride wherein the polybutenyl group comprises principally isobutene units and has a number average molecular weight between about 700 and about 10,000.

32. The lubricant of claim 1 also containing (C) at least one oil-soluble neutral or basic alkaline earth metal salt of at least one acidic organic compound.

33. The lubricant of claim 32 wherein the alkaline earth metal salt is a salt of at least one sulfur acid carboxylic acid, phosphorus acid or phenol, or mixtures thereof.

34. The lubricant of claim 1 wherein the amino compound in (A) is an alkylene polyamine of the formula wherein V is an alkylene group of 2 to about 10 carbon atoms, each R3 is independently a hydrogen atom, a lower alkyl group or a lower hydroxy alkyl group, with the proviso that at least one R3 is a hydrogen atom, and n is 1 to about 10.

35. The lubricant of claim 1 wherein component (A) is at least one post-treated carboxylic derivative composition having been prepared by reacting said carboxylic derivative composition with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disulfide, H2S sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyanates, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols.

36. A diesel lubricant comprising a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising (A) at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -NH- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of at least about 1200 and an Mw/Mn ratio of at least about 1.5, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each equivalent weight of substituent groups, and (B) at least one basic sodium or potassium salt of at least one acidic organic compound having a metal ratio of at least about 2.

37. The lubricant of claim 36 containing at least about 0.8% sulfate ash.

38, The lubricant of claim 36 containing at least about 1% sulfate ash.

39. The lubricant of claim 36 wherein the substituent group in (A) is characterized by an Mn value of about 1300 to about 5000.

40. The lubricant of claim 36 wherein the substituent group in (A) is characterized by an Mw/Mn value of from about 1.5 to about 6.

41. The lubricant of claim 36 wherein the succinic groups correspond to the formula wherein R and R' are each independently selected from the group consisting of -OH, -Cl, -O-lower alkyl and, when taken together, R and R' are -O-, with the proviso that all the succinic groups need not be the same.

42. The lubricant of claim 36 wherein the substituent groups are derived from one or more polyalkene selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 40% of polymer units derived from internal olefins of up to about 16 carbon atoms.

43. The lubricant of claim 42 wherein said value of Mn is at least about 1500.

44. The lubricant of claim 42 wherein said value of Mw/Mn is at least about 1.8.

45. The lubricant of claim 36 wherein the substituent groups are derived from one or more polyalkene selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 25% of polymer units derived from internal olefins of up to about 16 carbon atoms.

460 The lubricant of claim 36 wherein the substituent groups are derived from a member selected from the group consisting of polybutene, ethylene-propylene copolymer, polypropylene, and mixtures of two or more of any of these.

47. The lubricant of claim 36 wherein said acylating agents are characterized by the presence within their structure of an average of at least 1.4 succinic groups for each equivalent weight of the substituent groups.

48. The lubricant of claim 36 wherein said value of Mn is about 1500 to about 2800.

49. The lubricant of claim 36 wherein said value of Mw/Mn is about 2.0 to about 3.4.

50. The lubricant of claim 36 wherein the acylating agents are characterized by the presence within their structure of at least 1.5 up to about 2.5 succinic groups for each equivalent weight of the substituent groups.

51. The lubricant of claim 46 wherein the substituent groups are derived from polybutene in which at least about 50% of the total units derived from butenes is derived from isobutene.

52. The lubricant of claim 36 wherein the succinic groups correspond to the formulae and mixtures of these.

53. The lubricant of claim 36 wherein the basic sodium salt (B) is a salt of at least one sulfur acid, phosphorus acid, carboxylic acid or phenol, or mixtures thereof.

54. The lubricant of claim 36 wherein the basic salt (B) is a sodium or potassium salt of at least one organic sulfonic acid.

55. The lubricant of claim 54 wherein the sulfonic acid is represented by the formulae R'(SO3H)r or (R2)XT(SO3H)y in which R' and R2 are each independently an aliphatic group free from acetylenic unsaturation and containing up to 60 carbon atoms, T is an aromatic hydrocarbon nucleus, and x is a number of 1 to 3, and r and y are numbers of 1 to 4.

56. The lubricant of claim 54 wherein the sulfonic acid is an alkyl-substituted benzene sulfonic acid wherein the alkyl group contains at least about 8 carbon atoms.

57. The lubricant of claim 36 wherein the basic salt (B) is an oil-soluble dispersion of a basic sodium or potassium sulfonate prepared by the method which comprises reacting at about 25-200°C and for a time sufficient to form the dispersion:
(B-1) at least one acidic gaseous material selected from the group consisting of carbon dioxide, hydrogen sulfide/ sulfur dioxide, and mixtures thereof, with (B-2) a mixture comprising (B-2-a) at least one oil-soluble sulfonic acid, or derivative thereof susceptible to overbasing;
(B-2-b) sodium or potassium, or one or more basic compounds thereof selected from the group consisting of hydroxides, alkoxides, hydrides, or amides;
(B-2-c) at least one lower aliphatic alcohol selected from monohydric alcohols or dihydric alcohols, or an alkyl phenol or sulfurized alkyl phenol; and (B-2-d) at least one oil-soluble carboxylic acid or functional derivative thereof selected from the group consisting of anhydrides, esters, amides, imides, amidines and metal salts.

58. The lubricant of claim 57 wherein the ratios of equivalents of the components of B-2 are (B-2-b)/(B-2-a) - at least 4:1;
(B-2-c)/(B-2-a) - between about 1:1 and about 80:1;
(B-2-d)/(B-2-a) - between about 1:1 and about 1.20.

59. The lubricant of claim 57 wherein the s material (B-1) is carbon dioxide.

60. The lubricant of claim 57 wherein the sulfonic acid (B-2-a) is represented by the formulae R'(SO3H)r or (R2)XT(SO3H)y in which R' and R2 are each independently an aliphatic group free from acetylenic unsaturation and containing up to 60 carbon atoms, T is an aromatic hydrocarbon nucleus, and x is a number of 1 to 3, and r and y are numbers of 1 to 4.

61. The lubricant of claim 60 wherein said sulfonic acid is an alkylated benzenesulfonic acid.

62. The lubricant of claim 57 wherein the alcohol (B-2-b) is a monohydric alcohol.

63. The lubricant of claim 62 wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol and mixtures thereof.

64. The lubricant of claim 63 wherein the alcohol is methanol.

65. The lubricant of claim 64 wherein (B-2-c) is an alkyl phenol.

66. The lubricant of claim 64 wherein (B-2-c) is a sulfurized alkyl phenol wherein the alkyl group contains froma bout 6 to about 100 carbon atoms.

67. The lubricant of claim 66 wherein (B-2-b) is potassium or a basic compound of potassium.

68. The lubricant of claim 57 wherein the carboxylic acid (B-2-d) is a dicarboxylic acid or its anhydride.

69. The lubricant of claim 68 wherein the dicarboxylic acid or its anhydride is selected from the hydrocarbon-substituted succinic acid, hydrocarbon-substituted succinic anhydride or a mixture thereof.

70. The lubricant of claim 69 wherein the hydrocarbon substituent on the succinic acid or its anhydride is derived from the polymerization of monomers selected from ethylene, propylene, butene or isobutene.

71. The lubricant of claim 70 wherein the hydrocarbon substituent on the succinic acid or anhydride is a polybutenyl-group comprising principally of isobutene units and has an an value in the range of about 700 to about 10,000.

72. The lubricant of claim 57 wherein the basic sodium or potassium sulfonate (B) has a metal ratio of from about 6 to about 30.

73. The lubricant of claim 36 containing from about 1 to about 10% by weight of (A).

74. The lubricant of claim 57 containing from about 0.05 to about 1% by weight of the dispersion (B).

75. The lubricant of claim 36 also containing (C) at least one oil-soluble neutral or basic alkaline earth metal salt of at least one acidic organic compound.

76. The lubricant of claim 75 wherein the acidic organic compound is at least one sulfur acid, carboxylic acid, phosphorus acid, or phenol or mixtures thereof.

77. The lubricant of claim 76 wherein the sulfur acid is an alkyl-substituted benzene sulfonic acid wherein the alkyl group contains at least about 8 carbon atoms.

78. The lubricant of claim 36 wherein the amino compound is an alkylene polyamine of the formula wherein U is an alkylene group of 2 to about 10 carbon atoms, each R3 is independently a hydrogen atom, a lower alkyl group is a lower hydroxy alkyl group, with the proviso that at least one R3 is a hydrogen atom, and n is 1 to about 10.

79. A diesel lubricant comprising a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising (A) at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -NH- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of from about 1300 to about 5000, and an Mw/Mn ratio of from about 1.5 to about 4, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each equivalent weight of substituent groups, and (B) at least one basic sodium sulfonate dispersion having a metal ratio of at least about 4 and prepared by reacting at about 25-200°C for a time sufficient to form the dispersion, (B-1) carbon dioxide with (B-2) a mixture of (B-2-a) at least one oil-soluble alkylated benzenesulfonic acid or a derivative thereof susceptible to overbasing, (B 2-b) sodium hydroxide, (B-2-c) a monohydric alcohol, an alkyl phenol, or a sulfurized alkyl phenol, (B-2-d) at least one oil-soluble polybutenyl-substituted succinic acid or its anhydride wherein the polybutenyl substituent has a number average molecular weight of 700-5000, the ratios of equivalents of components (B-2) being:
(B-2-b)/(B-2-a) between about 6:1 and 30:1 (B-2-c)/(B-2-a) between about 2:1 and 50:1 (B-2-d)/(B-2-a) between about 1:2 and 1:10.

80. The lubricant of claim 79 containing at least about 0.8% sulfate ash.

81. The lubricant of claim 79 containing at least about 1.0% sulfate ash.

82. The lubricant of claim 79 wherein the amino compound in (A) is at least one alkylene polyamine of the general formula wherein U is an alkylene group of 2 to about 10 carbon atoms, each R3 is independently a hydrogen atom, a lower alkyl group is a lower hydroxy alkyl group, with the proviso that at least one R3 is a hydrogen atom, and n is 1 to about 10,

83. The lubricant of claim 79 wherein the amino compound in (A) is an ethylene, propylene or trimethylene polyamine of at least about 2 to about 8 amino groups or mixtures of such polyamines.

84. The lubricant of claim 79 wherein the Mn value of the polyalkene in (A) is about 1500 to about 2800.

85. The lubricant of claim 79 wherein the Mw/Mn value of the polyalkene in (A) is from about 2.0 to about 3.4.

86. The lubricant of claim 79 wherein the acylating agents in (A) are characterized by the presence within their structure of at least about 1.5 up to about 2.5 succinic groups for each equivalent weight of the substituent group.

87. The lubricant of claim 79 wherein the substituent groups in (A) are derived from one or more polyalkenes selected from the group consisting of homopolymers and interpolymers of terminal olefins of 2 to about 16 carbon atoms, with the proviso that said interpolymers can optionally contain up to about 40% of polymer units derived from internal olefins of up to about 16 carbon atoms.

88. The lubricant of claim 87 wherein the polyalkene substituents in (A) are derived from polybutene in which at least about 50% of the total units derived from butenes is derived from isobutene.

89. The lubricant of claim 87 also containing (C) at least one neutral or basic alkaline earth metal salt of at least one acidic organic material.

90. The lubricant of claim 89 wherein the acidic organic material is at least one sulfur acid, carboxylic acid, phosphorus acid or phenol, or mixtures thereof.

91. The lubricant of claim 89 wherein the acidic material is at least one alkyl-substituted benzene sulfonic acid wherein the alkyl group contains at least about 8 carbon atoms.

92. The lubricant of claim 79 wherein the metal ratio of the sulfonate (B) is from about 6 to about 30.

93. A diesel lubricant comprising a major amount of an oil of lubricating viscosity and a minor amount, sufficient to minimize undesirable viscosity increases of the lubricant when used in diesel engines, of a composition comprising (A) at least one carboxylic derivative composition produced by reacting at least one substituted succinic acylating agent with at least one amino compound containing at least one -NH- group wherein said acylating agent consists of substituent groups and succinic groups wherein the substituent groups are derived from polyalkene characterized by an Mn value of from about 1300 to about 5000, and an Mw/Mn ratio of from about 1.5 to about 4, and wherein said acylating agents are characterized by the presence within their structure of an average of at least about 1.3 succinic groups for each equivalent weight of substituent groups, and (B) at least one basic potassium sulfonate dispersion having a metal ratio of at least about 4 and prepared by reacting at about 25-200°C
for a time sufficient to form the dispersion, (B-1) carbon dioxide with (B-2) a mixture of (B-2 a) at least one oil-soluble alkylated benzenesulfonic acid or a derivative thereof susceptible to overbasing, (B-2-b) potassium hydroxide, (B-2-c) an alkyl phenol, or a sulfurized alkyl phenol, (B-2-d) at least one oil-soluble polybutenyl-substituted succinic acid or its anhydride wherein the polybutenyl substituent has a number average molecular weight of 700-5000, the ratios of equivalents of components (B-2) being:
(B-2-b)/(B-2-a) between about 6:1 and 30:1 (B-2-c)/(B -2-a) between about 2 1 and 50:1, and (B-2-d)/(B-2-a) between about 1:2 and 1:10.

94. The lubricant of claim 93 wherein (B-2-c) is a sulfurized alkyl phenol.

95. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 1.

96. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 22.

97. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 32.

98. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 36.

99. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 57.

100. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 75.

101. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant o claim 79.

102. A method of operating diesel engines which comprises lubricating said engines during operation with the diesel lubricant of claim 89.

103. A method of operating diesel engines which comprises lubricanting said engines during operation with the diesel lubricant of claim 93.

104. A method of preparing an oil-soluble, basic alkali metal salt of a sulfonic acid having a metal ratio of at least about 2 comprising contacting at a temperature between the solidification temperature of the reaction mixture and its decomposition temperature, (B-1) at least one acidic gaseous material selected from the group consisting of carbon dioxide, hydrogen sulfide, sulfur dioxide, and mixtures thereof, with (B-2) a mixture comprising (B-2-a) at least one oil-soluble sulfonic acid, or derivative thereof susceptible to overbasing;
(B-2-b) at least one alkali, or one or more basic compounds thereof selected from the group consisting of hydroxides, alkoxides, hydrides, or amides;
(B-2-c) at least one alkyl phenol or sulfurized alkyl phenol; and optionally (B-2-d) at least one oil-soluble carboxylic acid or functional derivative thereof.

105. The method of claim 104 wherein the acidic gaseous material (B-1) is carbon dioxide.

106. The method of claim 104 wherein the mixture (B-2) contains at least some carboxylic acid (B-2-d).

107. The method of claim 104 wherein the sulfonic acid (B-2-a) is represented by the formulae R'(SO3H)r or (R2)XT(SO3H)y in which R' and R2 are each independently an aliphatic group free from acetylenic unsaturation and containing up to 60 carbon atoms, T is an aromatic hydrocarbon nucleus, and x is a number of 1 to 3, and r and y are numbers of 1 to 4.

108. The method of claim 104 wherein the functional derivatives of component (B-2-d) are selected from the group consisting of anhydrides, esters, amides, imides, amidenes and metal salts.

109. The method of claim 106 wherein the ratios of equivalents of the components of (B-2) are:
(B-2-b)/(B-2-a) - at least 4:1;
(B-2-c)/(B-2-a) - between about 1:20 and about 80:1;
(B-2-d)/(B-2-a) - between about 1:1 and about 1:20.

110. The method of claim 104 wherein (B-2-c) is an alkyl phenol or a sulfurized alkyl phenol.

111. The method of claim 104 wherein the basic salt (B) has a metal ratio of from about 6 to about 30.

112. The method of claim 109 wherein (B-2-b) is potassium or one or more basic compounds thereof.

113. A method according to claim 104 wherein component (B-2-d) is at least one hydrocarbon-substituted succinic acid or functional derivative thereof and the reaction temperature is in the range of about 25-200°C.

114. A method according to claim 104 wherein component (B-2-a) is an alkylated benzenesulfonic acid.

115. The method of claim 104 wherein the mixture (B-2) also contains at least one hydrocarbon diluent.

116. The method of claim 115 wherein the diluent is a volatile organic solvent.

117. The method of claim 116 wherein component (B-2-c) is an alkyl phenol or sulfurized alkyl phenol and the temperature is at or above the water:solvent azeotrope temperature.