CA2056340A1 - Lubricating oil compositions and concentrates and the use thereof - Google Patents

Abstract

Case EI-6218+
LUBRICATING OIL COMPOSITIONS
AND CONCENTRATES AND THE USE THEREOF

Abstract of the Disclosure Oleaginous compositions and additive concentrates therefor having enhanced performance characteristics comprise at least a) one or more oil-soluble metal dihydrocarbyl di-thiophosphates or dithiocarbamates; and b) one or more oil-soluble additive compositions formed by heating concurrently or in any sequence at least one ashless dispersant which contains basic nitrogen and/or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride, or at least one partial or total sulfur analog thereof, or any combination of the foregoing; or (ii) at least one water-hy-drolyzable organic phosphorus compound and water; and (iii) at least one boron compound; such that a phosphorus- and boron-containing liquid composition is formed, and from which ex-cessive water, if present, has been removed at least during or after heating with (ii), if used.

Description

Case EI-6218+ 2 LUBRICATING OIL COMPOSITIONS
AND CONCEN~RATES AND THE USE THEREOF

TECHNICAL FIELD
This invention relates to oleaginous compositions of enhanced p~rformanca characteri~tics, to additive concentrates for enhancing the performance characteristics of oleaginous base fluids (e.g., lubricants and functional fluids), and to methods of achieving such enhanced performance characteris-tiCs .
: BACKGROUND
Over the years the demand for performance improvements in lubricating oils and functional fluids has persisted and,if anything, progressively increased. For example, lubrica-ting oils for use in internal combustion engines, and in par-ticular, in spark-ignition and diesel engines, are constantly being modi~ied and improved to provide improved performance.
Various organizations including the SAE (Society of Automotive Engineers), the ASTM (formerly the American Society for Testing Materials) and the API (American Petroleum Institute) as well as the automotive manufacturers continually seek to improve the~performance of lubricating oils. Various stan-dards have been e~ablished and modified over the yearsthrough the efforts ~f these organizations. As engines have increased in power output and complexity, and in many cases decreased in size, the performance requirements have been increased to provide lubricating oils that will exhibit a reduced tendency to deteriorate under conditions of use and thereby to reduce wear and the formation of such undesirable deposits as varnish, sludge, carbonaceous materials and re-sinous materials which tend to adhere to various engine parts and reduce the operational efficiency of the engine.
Current objectives include the development of additive formulations and lubricant compositions, especially crankcase lubricants and crankcase lubricant additive packages, capable of achieving these stringent performance requirements without requiring use of increased amounts of metal-containing compo-Case EI-6218+ 2 nents, such as zinc dihydrocarbyl dithiophosphates. Indeed, if possible, it is desired to achieve these stringent perfor-mance requirements with reduced amounts of such metal-contain-ing components. Still another desirable objective is to pro-vide additive formulations and lubricant compositions whichexhibit good compatibility with elastomeric substances uti-lized in the manufacture of seals, gaskets, clutch plate facings, and like parts. Unfortunately, commonly used addi-tives containing basic nitrogen constituents tend to cause excessive degradation of such elastomers when oils containing such additives come in contact with such elastomers during actual service conditions.
There are literally hundreds, if not thousands, of patent disclosures describing attempts (some more successful than others) to improve the performance characteristics of oils of lubricating viscosity. A small selection from this vast body of literature comprises U.S. 3,087,936; 3,184,411;
3,185,6~5; 3,235,497; 3,254,025; 3,265,618; 3,281,428;
3,282,955; 3,284,410; 3,324,032; 3,325,567; 3,338,832;
3,344,069; 3,403,102; 3,502,677; 3,511,780; 3,513,093;
3,533,945; 3,623,985; 3,718,663; 3,865,740; 3,950,341;
3,991,056; 4,097,389; 4,234,435; 4,338,205; 4,428,849;
4,554,086; 4,615,826; 4,63~,543; 4,648,~80; 4,747,971;
4,857,214; and 4,873,004.
THE INVENTION
This invention provides additive systems capable of imparting enhanced performance characteristics to natural and synthetic oils of lubricating viscosity. In addition, this invention makes it possible to achieve such enhanced perfor-mance with additive systems containing reduced amounts ofmetal-containing performance enhancers such as metal dithio-phosphates and/or metal dithiocarbamates. In short, this invention makes it possible to achieve a high level of perfor-mance with a reduced level of conventional metal-containing performance enhancers such as zinc dialkyldithiophosphates.
In accordance with this invention there is provided in one of its embodiments a composition comprising a major pro-Case EI-6218+ 2 ~ ~ ~ 3 ~ ~

portion of at least orle oil of lubricating viscosity and a minor proportion of at least the following components:
a) one or more oil-soluble metal hydrocarbyl dithio-phosphates or dithiocarbamates; and b) one or more oil-soluble additive compositions formed by heating concurrently or in any se~uence at least one ashless dispersant which contains basic nitrogen and~or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride, or at lo least one partial or total sulfur analog thereof, or any combination of the foregoing; or (ii) at least one water-hydrolyzable organic phosphorus compound and water; and ~iii) at least one boron compound; such that a liquid composition is formed.
In the formation of such liquid composition from (ii) and (iii), water is removed at least during or after the heating with (ii) and (iii) (if conducted concurrently) or at least during or after the heating with (ii) (if conducted sequen-tially).
The cooperation between components a) and b) of such compositions makes it possible to achieve performance levels (reduction in sludge formation and/or deposition and reduction in wear in gears and/or other relatively move~^ble metal sur-faces in contact with each other) normally achieved, if at all, by higher concentrations of component a). Morevert these performance levels can be maintained for long periods of time despite the well-known relatively low thermal stability of compounds such as the zinc dihydrocarbyl dithiophosphates.
Another advantageous feature of this invention is that certain preferred combinations oE components a) and b) can ex-hibit good compatibility toward elastomers commonly employed in the manufacture of seals or gaskets, clutch plate facings, etc., such as nitrile rubbers, fluoroelastomers, and silicone-type elastomersO In other words, such elastomers are not sub-jected to excessive degradation when in contact under actual service conditions with a preferred lubricant or functional fluid composition of this invention containing particular com-3 '~ ~
Case EI-6218+

binations of components a) and b), which combinations are thus preferred becauss of this advantageous characteristic which they possess and exhibit in the base oil. To realize these advantageous characteristics, component b) should be formed from one or more sulfur-free phosphorus compounds and the overall sulfur content of the finished lubricant or functional fluid composition should be kept below about 1% and most pre-ferably below about 0.3% based on the total weight of the finished lubricant or functional fluid composition.
~nother embodiment of this invention involves the dis-covery, inter alia, that basic alkali metal-containing and/or basic alkaline earth metal-containing detergents of the types generally known to be useful in oleaginous fluids (e.g., overbased sulfonates, overbased phenates, overbased sulfurized phenates, overbased salicylates, overbased sulfurized salicy-lates, etc.) can serve a dual role in the compositions of this invention. sesides contributing detergency to the composi-tions, such metal compounds can serve to reduce corrosive at-tack on so-called "yellow metals" such as copper, bronze, and the like. Detergents of the foregoing types having a total base number (TBN) of at least about 50 are utilized in the practice of this embodiment of the invention In this connec-tion, TBN is determined in accordance with AST~ D-2896-88~
Accordingly, another embodiment of this in~ention is a composition comprising a major proportion of at least one oil of lubricating viscosity and a minor proportion of at least the following components:
a) one or more oil-soluble metal hydrocarbyl dithiophos-phates or dithiocarbamates;
30 b) one or more oil-soluble additive compositions formed by heating concurrently or in any se~uence at least one ashless dispersant which contains basic nitrogen and/or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride, or at least one partial or total sulfur analog thereof, or any combination of the foregoing; or (ii) at least one water-hydrolyzable organic phosphorus compound and Case EI-6218+ 2 ~ ~ ~ 3 ~ ~

water; and (iii) at least one boron compound; such that a liquid phosphorus- and boron-containing composition is formed; and c) one or more oil-soluble alkali or alkaline earth metal-containing detergents having a TBN of at least about 50.
When b) is formed from (ii) and (iii), water is removed at some stage during or after the heating with at least (ii).
Additive concentrates comprising at least components a) and b) above, and preferably additionally containing com-ponent c), i.e., one or more suitably basic, oil-soluble alka-li metal-containing and/or alkaline earth metal-containing detergents, constitute additional embodiments of this invention.
Among the preferred embodiments of this invention are oleaginous compositions and additive concentrates in which component a~ is at least one oil-soluble metal hydrocarbyl dithiophosphate (preferably a zinc hydrocarbyl dithiophosphate and most preferably a zinc dialkyl dithiophosphate), and in which the relative proportions of components a) and b) are such that the atom ratio of phosphorus in the form of com-ponent a) to phosphorus in the form of component b), respec-tively, falls in the range of about 10:1 to about 0.01:1 (and more preferably in the range of about 5:1 to about 0.1:1 and most preferably in the range of about 4:1 to about 1:1). Par-ticularly preferred are compositions of these types which additionally contain component c) in an amount such that the atom ratio of total metal in the form of component a3 to total metal in the form of component c), respectively, falls in the range of about 0.01:1 to about 10 1 (and more preferably in the range of about 0.1:1 to about 4:1). Especially preferred are lubricants and functional fluids containing components a)l b), and c~ proportioned as specified in this paragraph wherein the total content of metals in the form of components a) and c) is in the range of about 0.01 to about 3, preferably in the range of about 0.05 to about 1.8, and most preferably in the range of about 0.1 to about 1.0 weight percent of metals based Case ~I-6218+

2~ 3~

on the total weight of the lubricant composition or functional fluid composition. Despite t.heir low level of "ash" or metal-containing components, such lubricant and functional fluid compositio~s can provide a high level of performance.
In order to satisfy the stringent specification re-quirements to qualify for top-grade crankcase lubricating oils, it is necessary to include in the compositions of this invention a combination of antioxidant and corrosion inhibi-tor. In this way, the enhanced performance (e.g., effective control of sludge, deposit and varnish formation and of wear of contacting metal parts) made possible by this invention can be maintained while at the same time satisfying specification requirements associated with oxidation and corrosion inhibi-tion. Thus in another preferred embodiment of this invention, there is provided a crankcase lubricant composition which com-prises a major proportion of at least one oil of lubricating viscosity and a minor proportion of at least the following components:
a) one or more oil-soluble metal hydrocarbyl dithiophos-phates or dithiocarbamates;
b) one or more oil-soluble additive compositions formed by heating concurrently or in any sequence at least one a shless dispersant which contains basic nitrogen ; and/or at least one hydroxyl group with ~i) at least one inorganic phosphorus acid or anhydride, or at least one partial or total sulfur analog thereof, or any combination of the foregoing ~- preferably one or more sulfur-free inorganic phosphorus acids; most preferably phosphorous acid (H3PO3); or ~ii) at least one water-hydrolyzable organic phosphorus compound and water -- preferably one or more halogen-free boron compounds; most preferably boric acid and/or one or more boric acid esters; and (iii) at least one boro~
compound -- preferably one or more halogen-free boron compounds; most preferably boric acid and/or one or more boric acid esters; such that a liquid composition is formed;

-~ Case EI-6218~

c) one or more oil-soluble alkali or alkaline earth metal-containing detergents having a TBN of at least about 50, preferably above 100, more preferably above 200, and most preferably above 300;
d) one or more oil-soluble antioxidants; and e) one or more oil-soluble corrosion inhibitors;
such that said lubricant composition satisfies (1) the requi-rements of the Sequence IID, Sequence IIIE, and Sequence VE
procedures of the American Petroleum Institute; and/or (2) the requirements of the L-38 Test Procedure of the American Petro-leum Institute; and/or (3) the requirements of the Caterpil-lar~ lG(2) and/or the lH(2) Test Procedure.
Additional preferred embodiments of this invention involve providing oleaginous compositions and additive compo-sitions in which the amount of phosphorus present in the form of component b) is equal to or in excess of the amount of phosphorus present in the form of component a). Thus ~or example, in accordance with this embodiment, preferred are compositions in which the atom ratio of phosphorus in the form of component a) to phosphorus in the form of component b), respectively, falls in the range of about 0.001 1 to 1:1, more preferably in the range of about 0.01:1 to O.g9:1, and most preferably in the range ~e about 0.1:1 to about 0.95:1.
Among the most preferred embodiments of this invention are oleaginous fluids wherein component a) is composed of one or more oil-soluble zinc dihydrocarbyl dithiophosphates, wherein components a) and b) are proportioned such that the atom ratio of phosphorus in the form of component a) to phos-phorus in the form of component b), respectively, ~alls in the range of about 4:1 to about 1:1, and wherein the phosphorus content of such fluids is in the range of about 0.05 to about 0.15% by weight of the total composition, especially where such fluids additionally contain at least one oil-soluble al-kali or alkaline earth metal containing detergent having a TBN
of at least 50, preferably above 100, more preferably above 200, and most preferably above 300.

2 ~
Case EI-6218+

Other embodiments of this invention include the provi-sion of methods for inhibiting sludge formation and/or deposi-tion in oils normally tending to occur during actual service conditions, and methods for imparting antiwear and/or extreme pressure properties to oils of lubricating viscosity.
The above and other embodiments and features of this invention ~ill become further apparent from the ensuing des-cription and appended claims.

Component a) In essence, there are two general categories of addi-tives which may be used singly or in combination with each other as component a) in the practice of this invention. One type of such additives is comprised o~` oil-soluble metal hy-drocarbyl dithiophosphates. The other is comprised of oil-soluble metal hydrocarbyl dithiocarbamates.
Type 1 - Metal hydrocarbyl dithiophosphates. As is well known, metal hydrocarbyl dithiophosphates are usually prepared by reacting phosphorus pentasulfide with one or more alcohols or phenolic compounds or diols to produce a hydrocar-byl dithiophosphoric acid which is then neutralized with oneor more metal-containing bases. When a monohydric alcohol or phenol is used in this reaction, the ~inal product is a metal dihydrocarbyl dithiophosphate. On the other hand, when a suitable diol (e.g., 2,4-pentanediol) is used in this reac-tion, the final product is a metal salt of a cyclic hydrocar-byl dithiophosphoric acid. See, for example, U.S. Pat. No.

3,089,850. Thus typical oil-soluble metal hydrocarbyl dithio-phosphates used as component a) may be represented by the formula R ~ \1 1 ~ P--S ~ M

` Case EI-621g+ 2~63~

where R1 and Rz are, independently, hydrocarbyl groups or taken together are a single hydrocarbyl group forming a cyclic structure with the phosphorus and two oxygen atoms, preferably a hydrocarbyl-substituted trimethylene group of sufficient carbon content to render the compound oil soluble, M is a metal, and x is an integer corresponding to the valence of M.
The preferred compounds are those in which R1 and Rz are separate hydrocarbyl groups (i.e., the metal dihydrocarbyl dithiophosphates). Usually the hydrocarbyl groups of the metal dihydrocarbyl dithiophosphates will contain no more than about 50 carbon atoms each although even higher molecular weight hydrocarbyl groups can be present in the compound. The hydrocarbyl groups include cyclic and acyclic groups, both saturated and unsaturated, such as alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, cycloalkylalkyl, aralkyl, and the like.
It will be understood that the hydrocarbyl groups may contain elements other than carbon and hydrogen pro~ided such other elements do not detract from the predominantly hydrocarbona-ceous character of the hydrocarbyl group~ Thus the hydrocar-byl groups may contain ether oxygen atoms, thioether sulfuratoms, secondary or tertiary amino nitrogen atoms, and/or inert functional groups such as esterified carboxylic groups, keto groups, thioketo groups, and the like.
The metals present in the oil-soluble metal dihydrocar-byl dithiophosphates and oil-soluble metal cyclic hydrocarbyl dithiophosphates include such metals as lithium, sodium, po-tassium, copper, magnesium, calcium, zinc, strontium, cadmium, barium, mercury, aluminum, tin, lead, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, etc., as well as combinations of two or more such metals. Of the fore-going, the salts containing group II metals, aluminum, lead, tin, molybdenum, manganese, cobalt, and/or nickel, are pre-ferred. The dihydrocarbyl dithiophosphates of zinc and copper are particularly preferred, with the zinc salts being the most preferred type of compound for use as component a).
The phosphorodithioic acids from which the metal salts are formed can be prepared by the reaction of about 4 moles of Case EI-6218+
2 ~

one or more alcohols (cyclic or acyclic) or one or more phe-nols or mixture of one or more alcohols and one or more phe-nols (or about 2 moles of one or more diols) per mole of phos-phorus pentasulfide, and the reaction may be carried out with-in a temperature range of from about 50 to about 200C. Thereaction generally is completed in about 1 to 10 hours. Hy-drogen sulfide is liberated during the reaction.
~ nother method for the preparation of the phosphoro-dithioic acids involves reaction of one or more alcohols and/or one or more phenols with phosphorus sesquisulfide in the presence of sulfur such as is described in PCT Interna-tional Publication No. Wo 90/07512. This reaction is con-ducted at an elevated temperature, preferably in the range of 85-150C with an overall atomic P:S ratio of at least 2.5:1.
The alcohols used in forming the phosphorodithioic acids by either of the above methods are preferably primary alcohols, or secondary alcohols. Mixtures thereof are also suitable. The primary alcohols include propanol, butanol, isobutyl alcohol, pentanol, 2-ethyl-1-hexanol, isooctyl alcohol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, octadecanol, eicosanol, and the like. The primary alcohols may contain various substituent groups such as halogen atoms, nitro groups, etc., which do not interfere with the desired reaction. Among suitable secondary alcohols are included 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 5-methyl-2-hexanol, and the like. In some cases, it is prefer-able to utilize mixtures of various alcohols, such as mixtures of 2-propanol with one or more higher molecular weight primary alcohols, especially primary alcohols having from 4 to about 13 carbon atoms in the molecule. Such mixtures preferably contain at least 10 mole percent of 2-propanol, and usually will contain from about 20 to about 90 mole percent of 2-propanol. In one preferred embodiment, the alcohol comprises about 30 to 50 mole percent of 2-propanol, about 30 to 50 mole percent isobutyl alcohol and about 10 to 30 mole percent of 2-ethyl-1-hexanol.

-~ Case ~I-6218+

~ther suitable mixtures of alcohols include 2-propa-nol/butanol;2-propanol/2-butanol;2-propanol/2-ethyl-1-hexa-nol; butanol/2-ethyl-1-hexanol; isobutyl alcohol/2-ethyl-1-hexanol; and 2-propanol/tridecanol.
Cycloaliphatic alcohols suitable for use in the pro-duction of the phosphorodithioic acids include cyclopentanol, cyclohexanol, methylcyclohexanol, cyclooctanol, borneol and the like. Preferably, such alcohols are used in combination with one or more primary alkanols such as butanol, isobutyl alcohol, or the like.
Illustrative phenols which can be employed in forming the phosphorodithioic acids include phenol, o-cresol, m-cre-sol, p-cresol, 4-ethylphenol, 2,4-xylenol, and the like. ~t is desirable to employ phenolic compounds in combination with primary alkanols such propanol, butanol, hexanol, or the like.
Other alcohols which can be employed include benzyl alcohol, cyclohexenol, and their ring-alkylated analogs.
It will be appreciated that when mixtures of two or more alcohols and/or phenols are employed in forming the phos-phorodithioic acid, the resultant product will normally com-prise a mixture of three or more different dihydrocarbyl phos-phorodithioic acids, usually in the form of a statistical dis-~ribution in relation to the number and proportions of alco-hvls and/or phenols used.
Illustrative diols which can be used in forming the phosphorodithioic acids include 2,4-pentanediol, 2,4-hexane-diol, 3,5-heptanediol, 7-methyl-2,4-octanediol, neopentyl glycol, 2-butyl-1,3-propanediol, 2,2-diethyl-1,3 propanediol, and the like.
The preparation of the metal salts of the dihydrocarbyl dithiophosphoric acids or the cyclic hydrocarbyl dithiophos-phoric acids is usually effected by reacting the acid product with a suitable metal compound such as a metal carbonate, metal hydroxide, metal alkoxide, metal oxide, or other appro-priate metal salt. Simply mixing and heating such reactants is normally sufficient to cause the reaction to occur and the resulting product is usually of sufficient purity ~or use in Case EI-6218+ ~ 3 the practice of this invention. Typically, the salts are formed in the presence of a diluent such as an alcohol, water or a light mineral oil. Neutral salts are prepared by reac-ting one equivalent of metal oxide or hydro~ide with one equivalent of the acid. Basic metal salts are prepared by adding an excess (i.e., more than one equivalent) of the metal oxide or hydroxide with one equivalent of the dihydrocarbyl phosphorodithioic acid or cyclic hydrocarbyl phosphorodithioic acid.
Illustrative metal compounds which may be used in such reactions include calcium oxide, calcium hydroxide, silver oxide, silver carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium ethoxide, zinc oxide, zinc hy-droxide, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium carbonate, barium oxide, aluminum oxide, aluminum propoxide, iron carbonate, copper hydroxide, lead oxide, tin butoxide, cobalt o~ide, nickel hydroxide, manganese oxide, and the like.
In some cases, incorporation of certain ingredients such as small amounts of metal acetate or ~cetic acid in con-junction with the metal reactant will facilitate the reaction and provide an improved product. ~or example, use of up to about 5% of ~.-`nc acetate in combination with the required amount of zinc oxide tends to facilitate the formation of zinc dihydrocarhyl dithiophosphates.
Examples of useful metal salts of dihydrocarbyl dithio-phosphoric acids, and methods for preparing such salts are found in the prior art such as for example, U.S. Pat. Nos.

4,263,153; 4,28g,635; 4,30~,154; 4,322,479; 4,41~,990; and 4,466,895.
Generally speaking, the preferred types of metal salts of dihydrocarbyl dithiophosphoric acids are the oil-soluble metal salts of dialkyl dithiophosphoric acids. Such compounds generally contain alkyl groups having at least three carbon atoms, and preferably the alkyl groups contain up to 10 carbon atoms although as noted above, even higher molecular weight alkyl groups are entirely feasible. A few illustrative zinc Case EI-6218+

dialkyl dithiophosphates include zinc diisopropyl dithiophos-phate, zinc dibutyl dithiophosphate, zinc diisobutyl dithio-phosphate, zinc di-sec-butyl dithiophosphate, the zinc dipen-tyl dithiophosphates, the zinc dihexyl dithiophosphates, the zinc diheptyl dithiophosphates, the zinc dioctyl dithiophos-phates, the zinc dinonyl dithiophosphates, the zinc didecyl dithiophosphates, and the higher homologs thereof. Mixtures of two or more such metal compounds are often preferred for use such as metal salts of dithiophosphoric acids formed from mixtures of isopropyl alcohol and secondary butyl alcohol;
isopropyl alcohol, isobutyl alcohol, and 2-ethylhexyl alcohol;
isopropyl alcohol, butyl alcohol, and pentyl alcohol; isobutyl alcohol and octyl alcohol; and the like.
If desired, the metal dihydrocarbyl dithiophosphate additives of the type described above may be treated with an epoxide to form an adduct. In general, the most suitable metal dihydrocarbyl dithiophosphates useful in forming such adducts are the zinc dihydrocarbyl dithiophosphates. The epoxides comprise alkylene oxides and arylalkylene oxides.
Typical alkylene oxides which may be used include alkylene oxides having up to about 8 carbon atoms in the molecule, such as ethylene oxide, propylene oxide, 1,2-butene oxide, trime-thylene oxide, tetramethylei~ oxide, butadiene monoepoxide, 1,2-hexene oxide, epichlorohydrin, and the like. The arylal-kylene oxides are exemplified by styrene oxide. Other suit-able epoxides include, for example, butyl 9,10-epoxystearate, epoxidized soybean oil, epoxidized tung oil, and epoxidized styrene-butadiene copolymer. Procedures for preparing epoxide adducts are known and are reported, for example, in U. S. Pat.
No. 3,390,082.
The adduct may be obtained by simply mixing the metal phosphorodithioate and the epoxide. The reaction is usually exothermic and may be carried out within wide temperature limits from about 0C to about 300C. Because the reaction is exothermic, it is best carried out by adding one reactant, usually the epoxide, in small increments to the other reactant in order to obtain convenient control of the temperature of Case EI-6218+

the reaction. The reaction may be carried out in a solvent such as benzene, mineral oil, naphtha, or n-hexene.
The chemical structure of the adduct is not known. The adducts obtained by the reaction of one mole of the phosphoro-dithioate with from about 0.25 mole to 5 moles, usually up to about 0.75 mole or about 0.5 mole of a lower alkylene oxide, particularly ethylene oxide and propylene oxide, are the pre-ferred adducts.
Another type of metal dihydrocarbyl phosphorodithioate additives contemplated as useful as component a) in the compo-sitions of this invention comprises mixed-acid metal salts of a combination of (a3 at least one phosphorodithioic acid of the formula (RO)(R'O)PSSH, as exemplified above (R and R' be-ing, independently, hydrocarbyl groups (or taken together, a single hydrocarbyl group forming a cyclic moiety with the two oxygen atoms and the phosphorus atom) of sufficient carbon content to render the salt soluble in lubricating oil), and (b? at least one aliphatic or alicyclic carboxylic acid. The carboxylic acid may be a monocarboxylic or polycarboxylic acid, usually containing from 1 to about 3 carboxy groups and preferably only one. It may contain from about 2 to about ~0, preferably from about 2 to about 20 carbon atoms, and advanta-geously about 5 to about 20 carbon atoms. ~ e preferred car-boxylic acids are those having the formula R3CooH, wherein R3 is an aliphatic or alicyclic hydrocarbon-based radical prefer-ably free from acetylenic unsaturation. Suitable acids in-clude the butanoic, pentanoic, hexanoic, octanoic, nonanoic, decanoic, dodecanoic, octadecanoic and eicosanoic acids, as well as olefinic acids such as oleic, linoleic, and linolenic acids and linoleic acid dimer. For the most part, R3 is a saturated aliphatic group and especially a branched alkyl group such as the isopropyl or 3-heptyl group. Illustrati~e polycarboxylic acids are succinic, alkyl- and alXenylsuccinic, adipic, sebacic and citric acids.
The mixed-acid metal salts may be prepared by merely blending a metal salt of a phosphorodithioic acid with a metal salt of a carboxylic acid in the desired ratio. The ratio of `` Case EI-6218+ ~ 3 equivalents of phosphorodithioic to carboxylic acid salts is between about 0.501 and about 200:1. Advantageously, the ratio can be from about 0.5:1 to about 100:1, preferably from about 0.5:1 to about 50:1, and more preferably from about 0.5:1 to about 20:1. Further, the ratio can be from about 0.5:1 to about 4.5:1, preferably about 2.5:1 to about 4.25:1.
For this purpose, the e~uivalent weight of a phosphorodithioic acid is its molecular weight divided by the number of -PSSH
groups therein, and that of a carboxylic acid is its molecular weight divided by the number of carboxy groups therein.
A second and preferred method for preparing the mixed-acid metal salts useful in this invention is to prepare a mix-ture of the acids in the desired ratio and to react the acid mixture with a suitable metal base. When this method of pre-paration is used, it is frequently possible to prepare a salt containing an excess of metal with respect to the number of equivalents of acid present; thus, mixed-acid metal salts containing as many as two equivalents and especially up to about 1.5 equivalents of metal per equivalent of acid may be prepared. The equivalent of a metal for this purpose is its atomic weight divided by its valence.
Variants of the above-described methods may also be used to prepare the mixed-acid metal salts useful in th~:-invention. For example, a metal salt of either acid may be blended with an acid of the other, and the resulting blend reacted with additional metal hase.
Suitable metal bases for the preparation of the mixed-acid metal salts include the oxides, hydroxides, alkoxides and other basic salts of the metals previously enumerated, and in some cases the free metals themselves. Examples are sodium hydroxide, potassium hydroxide, magnesium oxide, calcium hy-droxide, zinc oxide, lead oxide, nickel oxide and the like.
The temperature at which the mixed-acid metal salts are prepared is generally between about 30C and about 150C, preferably up to about 125C. If the mixed-acid salts are prepared by neutralization of a mixture of acids with a metal base, it is preferred to employ temperatures above about 50C

Case EI-621$+ ~ n and especially above about 75C. It is frequently advanta-geous to conduct the reaction in the presence of a substan-tially inert, normally liquid organic diluent such as naphtha, benzene, xylene, mineral oil and the like. If the diluent is mineral oil, it frequently need not be removed before using the mixed-acid metal salt as an additive for lubricants or functional fluids.
U. S. Patents 4,308,15~ and 4,417,970 describe pro-cedures for preparing these mixed-acid metal salts and dis-close a number of examples of such mixed salts.
T~e 2 - Metal hydrocarbYl dithiocarbamates. The second type of oil-soluble metal salts used as component a) in the compositions of this invention are salts of one or more dithiocarbamic acids of the formula RR'N-CSSH wherein R and R' are each independently hydrocarbyl groups in which the total number of carbon atoms in R and R' is sufficient to render the metal salt oil-soluble. R and R' taken together may represent a polymethylene or alkyl substituted polymethylene group thereby forming a cyclic compound with the nitrogen atom (i.e., a monocyclic hydrocarbyl dithiocarbamate). Zenerally the hydrocarbyl groups will each contain at least two carbon atoms and may contain 50 or more carbon atoms. The metal com-.;ponent present in the dihydrocarbyl (or monocyclic hydrocar-byl) dithiocarbamate salts may be a monovalent metal or a polyvalent metal, although polyvalent metals are preferred as the salts of the polyvalent metals tend to possess better solubility in oils of lubricating viscosity. Thus althou~h the alkali metal monocyclic hydrocarbyl or dihydrocarbyl di thiocarbamates may be used if oil-soluble, the preferred salts include, for example, salts of one or more of the alkaline earth metals, zinc, cadmium, magnesium, tin, molybdenum, iron, copper, nickel, cobalt, chromium, lead, etc. ~he Group II
metal dihydrocarbyl dithiocarbamates are preferred.
In selecting a metal salt of a dithiocarbamic acid to be used in the compositions of this invention, R, R', and the metal may be varied so long as the metal salt is adequately oil~soluble. The nature and type of the mineral base stock, ~ Case EI-6218~

and the type of service contemplated for the treated lubrica-ting oil should he taken into consideration in the choice of metal salt.
The metal constituent of the metal dihydrocarbyl di-thiocarbamate is usually a simple metal cation. However inthe case of certain polyvalent metal derivatives such as the tin and lead compounds, the metal constituent itself may be hydrocarbyl substituted (e.g., (RR'N-CSS-)XMR1R2, where M is a polyvalent metal, R, R', R1 and R2 are, independently, hydro-carbyl groups (and, optionally R and R' taken together are asingle cyclic hydrocarbyl group) in which the total number of carbon atoms is sufficient to render the compound oil-soluble, and x is an integer sufficient to satisfy the remaining va-lence(s) of M. Techniques described for example in U.S. Pat.
No. 2,786,814, may be employed for preparing such hydrocarbyl-substituted metal dithiocarbamates.
Mixtures of metal salts of dithiocarbamic acids also are contemplated as being useful in the present invention.
Such mixtures can be prepared by first preparing mixtures of dithiocarbamic acids and thereafter converting said acid mixtures to metal salts, or alternatively, metal salts of various dithiocarbamic acids can be prepared and thereafter mixed to give t~he desired product. Thus, the mixtures which can be incorporated in the compositions of the invention may be merely the physical mixture of the different metallic dithiocarbamic compounds, or compounds having different dithiocarbamate groupings attached to the same polyvalent metal atoms.
Examples of alkyl groups are ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecyl, pen-tadecyl and hexadecyl groups including isomeric forms thereof.
Examples of cycloalkyl groups include cyclohexyl and cyclo-heptyl groups, and examples of aralkyl groups include benzyl and phenethyl. Examples of polymethylene groups include penta- and hexamethylene groups, and examples of alkyl-sub-stituted po~ymethylene groups include methyl pentamethylene, dimethyl pentamethylene, etc.

--~ Case EI-6218+

Specific examples of the metal dithiocarbamates useful as component a) in the compositions of this invention include zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc di(2-ethylhexyl)dithiocarbamate, cadmium dibutyldithiocarba-mate, cadmium dioctyldithiocarbamate, cadmium octylbutyldi-thiocarbamate, magnesium dibutyldithiocarbamate, magnesium dioctyldithiocarbamate,cadmiumdicetyldithiocarbamate,copper diamyldithiocarbamate,sodiumdioctadecyldithiocarbamate,lead dioctyldithiocarbamate,nickeldiheptyldithiocarbamate,calci-um di-2-ethylhexyldithiocarbamate, etc.
The various metal salts of dithiocarbamic acids uti-lized in the compositions of this invention are well known in the art and can be prepared by known techniques. See for example Ullmann, Encyklopadie der technischen Chemie, Band 10, Verlag Chemie, Weinheim, copyright 1975, pages 167-170 (and references cited therein); Thorn and Ludwig, The Dithiocar-bamates and Related Compounds, Elsevier Publishing Company, 1962, pages 12 to 37 (and references cited therein); Delepine, compt. Rend., 144, 1125 (1907); Whitby et al, Proceedin s and Transactions of The Royal Societv of Canada, XVIII, 111-114 (1924) (and references cited therein), Chabrier et al, Bul-letin de la Societe Chimique De France, 1950, pages 43 et seq.
(and references cited therein)-~ and U. S. Pat. Nos. 1,622,534;
1,921,~91; 2,04~,875; 2,046,g76; 2,258,847; 2,406,960;
2,443,160; 2,450,633; 2,492,314; 2,580,274; 3,513,094;
3,630,897; 4,178,258; and 4,226,733.
While boron is not a metallic element, boron tris(di-hydrocarbyl dithiocarbamates) can be used as component a) of the compositions of this invention, either individually or in combination with one or more metal dihydrocarbyl dithiocarba-mates. Methods suitable for the production of such boron di-thiocarbamates are set forth in U.S. Pat. No. 4,879,071.
Derivatives of metal dihydrocarbyl dithiocarbamates may be used in addition to or in lieu of the metal dihydrocarbyl dithiocarbamates. Such derivatives include dithiocarbamate-derived phosphates such as are described in U.S. Pat. No.
4,919,830, reaction products of N,N-diorganodithiocarbamates ~ Case EI-6218~

with thionyl chloride such as are described in U.S. Pat. No.
4,867,~93, N,N-diorganodithiocarbamate-alkylthiosulfinyl ha-lide reaction products such as are described in U.S. Pat. No.
4,859,35~, reaction products of halogenated EPDM terpolymers and alkali metal dialkyldithiocarbamate such as are described in U.S. Pat. No. 4,502,972, and sulfurized metal dihydrocarbyl dithiocarbamates such as are described in U.S. Pat. No.
4,360,438, among others. In addition, the metal dihydrocarbyl dithiocarbamates may be used in combination with other carba-mate compounds such as for example, a 1,2-dicarbethoxyethyl dialkyldithiocarbamate such as is disclosed in U.S. Pat. No.
~,479,883; or a mercaptoalkanoic acid dithiocarbamate of the type described in U.S. Pat. No. 3,890,363.
Mixtures of different metal dihydrocarbyl dithiocarbam-ates as well as combinations of (1) one or more metal dihydro-carbyl dithiophosphates and (2) one or more metal dihydrocar-byl dithiocarbamates can be used as component a) in the prac-tice of this invention.

Component b) The other indispensable additive ingredient of the com-positions of this invention is comprised of one or more oil-soluble additive compositions formed by heati.~g concurrently or any sequence at least one ashless dispersant which contains basic nitrogen and/or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride or at least one partial or total sulfur analog thereof, or any combination of the foregoing; or (ii) at least one water-hydrolyzable or-ganic compound of phosphorus -- preferably a water hydrolyza-ble ester of an acid of phosphorus -- and water; and (iii) at least one boron compound, such that a li~uid phosphorus- and boron-containing composition is formed, and from which water has been removed when (ii) and (iii) are used. The ashless dispersant which is heated concurrently or in any sequence with components (i) or (ii) and (iii) is preferably a pre-formed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group. Thus, for example, any suitable --~ Case EI-6218+

ashless dispersant formed in the customary manner can be heated with one or more boron compounds to cause boronation to occur and the resultant product mixture can then be heated with (i) one or more inorganic phosphorus compounds or (ii) one or more water-hydrolyzable organic phosphorus compounds and water, such that a liquid phosphorus- and boron-contalning composition [component b)] is formed. Conversely, a preformed ashless dispersant can be heated with (i) one or more inorga-nic phosphorus compounds or (ii) one or more water-hydrolyza-ble organic phosphorus compounds and water, and thereafter the product mixture can be heated with one or more boron compounds so that a liquid phosphorus- and boron-containing composition is formed. The preferred way of forming component b) is to heat a preformed ashless dispersant with a combination of one or more inorganic phosphorus compounds and one or more boron compounds to form a li~uid phosphorus- and boron-containing composition. In other words, to form component b) in the preferred manner, the preformed ashless dispersant is concur-rently heated with one or more inorganic phosphorus compounds and one or more boron compounds. In all cases, the resulting liquid product composition when subjected to chemical analysis reveals the presence of both phosphorus and boron.
Rather than utilizing a preformed ashless dispe~sant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component b) by:
1) forming the ashless dispersant in the presence of oneor more suitable boron compounds (e.g., boron ester or boron oxide) and then heating the resultant composi-tion with (i) one or more inorganic phosphorus com-3~ pounds or (ii) one or more water-hydrolyzable organic phosphorus compounds and water; or 2) forming the ashless dispersant in the presence o~ (i) one or more suitable inorganic phosphorus compounds (e.g., a phosphorus oxide or sul~ide) and then heating the resultant composition with one or more boron com-pounds, or forming the ashless dispersant in the pre-sence of (ii) one or more water-hydrolyzable organic Case EI-621~ - 21 -phosphorus compounds and then heating the resultant composition with one or more boron cGmpounds in the presence o~ water; or 3) forming the ashless dispersant in the presence of one or more suitable boron compounds (see 1) above) and one or more suitable inorganic phosphorus compounds (see 2) above); or forming the ashless dispersant in the presence of one or more boron compounds and one or more water-hydrolyzable organic phosphorus compounds and heating the ashless dispersant in the presence of water either during or after the formation of the ash-less disp~rsant; or 4) heating one or more boron compounds with a basic ni-trogen-containing and/or hydroxyl group-containing reactant used in forming the ashless dispersant, using the resultant boronated reactant to form the ashless dispersant and then heating the resultant ashless dis-persant with (i) one or more inorganic phosphorus com-pounds or (ii) with one or more water-hydrolyzable 2Q organic phosphorus compounds in the presence of water;
or 5) heating (i) one or more inorganic phosphorus compounds or (ii) one or more water-hydrolyzable organic phos-phorus compounds in the presence of water, with a basic nitrogen containing and/or hydroxyl group-con-taining reactant used in forming the ashless disper-sant, using the resultant phosphorylated reactant to form the ashless dispersant and then heating the resultant ashless dispersant with one or more boron compounds; or 6) heating (i) one or more inorganic phosphorus compounds and one more boron compounds or (ii) in the presence o~ water one or more water-hydrolyzable organic phos~
phorus compounds and one more boron compounds, with a basic nitrogen-containing and/or hydroxyl group-con-taining reactant used in forming the ashless disper-Case EI-6218~ 2 ~ ~ ~ 3 ll ~

sant, and using the resultant phosphorylated and boronated reactant to form the ashless dispersant.
In all cases, the final product composition [component b)]
should be a liquid composition that on analysis reveals the presence of boron and phosphorus. Such product composition should also exhibit dispersant properties. In any case where-in an ashless dispersant usecl in forming component b) is not a liquid but rather is in whole or in part in the solid state of aggregation at room temperature (e.g., 25C), it is pre-ferable to dissolve such dispersant in a suitable solvent or diluent (polar or non-polar, as may be required to dissolve the dispersant) before the dispersant is subjected to phospho-rylation and/or boronation (as the case may be) in forming component b). In this connection, the phrase "such that a liquid composition is formed" as used herein in connection with such solid state dispersants means that component b), including such solvent or diluent, is in the liquid state of aggregation at room temperature (e.g., ~5C), even though at a lower temperature the dispersant may revert in whole or in part to the solid state. Of course in any case, component b) must be oil-soluble within the meaning of such term as set forth hereinafter.
Irlespective of the method used in forming component b), in any instance wherein macro (i.e., non-dispersible) solids are formed or remain in the liquid composition after it has been formed, such solids should be removed, and can be readily removed, by any of a variety of conventional separa-tion techniques such as filtration, centrifugation, decanta-tion, or the likeO
The actual chemical structures of the final product compositions used as component b) in the practice of this invention, however prepared, are not known with absolute cer-tainty. While it is believed that phosphorus-containing moie-ties and boron-containing moieties are chemically bonded to the ashless dispersant, it is possible that component b) is in whole or in part a micellar structure containing phosphorus-and/or boron-containing species or moieties. Thus, this in-Case EI-6218+ 2 vention is not limited to, and should not be construed as being limited to, any specific structural configurations with respect to component b). As noted above, all that is required is that component b) is a liquid that is oil soluble and that 5if subjected to analysis reveals the presence of both phospho-rus and boron. In addition, component b) should possess dis-persant properties.
Although any of a variety of standard methods can be used to analyze the phosphorylated and boronated dispersant 10for the presence of phosphorus and boron therein, it is de-sirable to use the analytical procedure set forth in ASTM
M 951. In this procedure it is convenient to use a Perkin-Elmer Plasma 40 Emission Spectrometer. The analyzing wave-lengths for acceptable measurements are 213.618 nm and 249.773 15nm for phosphorus and boron, respectively.
The phosphorylated and boronated dispersants utilized as component b) in the compositions of this invention when in their undiluted state should have on a weight basis a phospho-rus content of at least 100 parts per million (ppm) (prefera-20bly at least 500 ppm and more preferably at least 1000 ppm) and a boron content of at least 100 ppm (preferably at least 500 ppm and more preferably at least 1000 ppm).
It is to be understood and appreciated that component b) mav contain chemical species and/or moieties besides the 25phosphorus- and boron-containing species or moieties such as, for example, nitrogen- and/or oxygen- and/or sulîur-containing species or moieties over and above the basic nitrogen and/or -hydroxyl group(s) forming an essential part of the initial ashless dispersant itself. It is also to be understood and 30appreciated that organic phosphorus-containing compounds may be used along with inorganic phosphorus compounds in making component b). Further, the inorganic phosphorus compound or compounds can be formed in situ, as, for example, by heating a mixture of phosphorus and sulfur to form a phosphorus 5ul-35fide, or by treating one or more organic phosphorus compounds to convert the same in whole or in part into one or more inor-ganic phosphorus compounds. Also, inorganic phosphorus-con-Case EI-6218+
3 ~

taining compounds may be used along with water and one or more water-hydrolyzable organic phosphorus compounds in making com-ponent b). Further, the water-hydrolyzable organic phosphorus compound or compounds can be formed in situ, as, for example, by heating a mixture of one or more alcohols or phenols with one or more phosphorus halides (e.g., PCl3, POCl3, PSCl3, RPC12, ROPC12, RSPC12, RPOC12, ROPOC12, F'~SPOC12, RPSC12, ROPSC12, RSPSC12, R2PCl, (RO)2PCl, (RS)2PCl, (RO)(RS)PCl, R2POCl, (RO)2POcl~ (RS)2POcl~ (RO)(RS)POcl~ R2pscl~ (RO)2PSCl, (RS)2PSCl, etc., where each R is, independently, a hydrocarbyl group) and introducing water into the system in order to hydrolyze the water-hydrolyzable phosphorus ester so formed.
As used herein, the term "phosphorylated" means that the ashless dispersant has been heated with (i) one or more inorganic phosphorus compounds or with (ii) one or more water-hydrolyzable organic phosphorus compounds and water, such that the resultant product, on analysis, reveals the presence of phosphorus. Likewise, as used herein, the term "boronated"
means that the ashless dispersant has been heated with one or more boron compounds such that the resultant product, on analysis, reveals the presence of boron. As noted herein-above, the precise chemical ma~eup of the phosphorylated and boronated dispersant compositions is5 ot known with absolute certainty. Thus the terms "phosphorylated" and "boronated"
are not to be construed as requiring that the resultant com-position contain chemically bound phosphorus or boron. While it is believed that chemical reactions do occur to produce a composition containing at least some chemically bound phos-phorus moieties and at least some chemically bound boron moieties, moieties or species of either or both of such elements conceivably could be present, at least in part, in the form of micellar structures.
Any of a variety of ashless dispersants can be utilized in forming component b) of the compositions of this invention.
These include the following types:
Type A - Carboxylic Dispersants. These products are described in many patents, including British patent specifica-Case EI-6218+

tion No. 1,306,529 and the following U. S. Patents:
3,163,603; 3,184,474; 3,215,707; 3,219,666; 3,271,310;
3,272,746; 3,281,357; 3,306,908; 3,311,558; 3,316,177;
3,340,281; 3,341,542; 3,346,493; 3,381,022; 3,399,141;
3,415,750; 3,433,744; 3,444,170; 3,448,048; 3,448,049;
3,451,933; 3,454,607; 3,467,668; 3,522,179; 3,541,012;
3,542,678; 3,574,101; 3,576,743; 3,630,904; 3,632,510;
3,632,511; 3,697,428; 3,725,441; 3,868,330; 3,948,800;
~,234,435; and Re 26,433.
There are a number of sub-categories of carboxylic dispersants. One such sub-category which constitutes a preferred type for use in the formation of component b) is composed of the polyamine succinamides and more preferably the polyamine succinimides in which the succinic group contains a hydrocarbyl substituent containing at least 30 carbon atoms.
The polyamine used in forming such compounds contains at least one primary amino group capable of forming an imide group on reaction with a hydrocarbon-substituted succinic acid or acid derivative thereof such an anhydride, lower alkyl estPrl acid halide, or acid-ester. Representative e~amples of such dis-persants are given in U.S. Pat. Nos. 3,172,892; 3,202,67~;
3,216,936; 3,219,666; 3,254,025; 3,272,746; and 4,234,435.
The alkenyl succinimides may be formed by conventiona~ methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group. The alkenyl suc-cinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to about 180--220C. The olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1-butene, isohutene and the like.
The more preferred source of alkenyl group is from polyisobu-tene having a number average molecular weight of up to 100,000 or higher. In a still more preferred embodiment the alkenyl group is a polyisobutenyl group having a number average mo-lecular weight (determined using the method described in de-tail hereinafter) of about 500-5,000, and preferably about 700-2,500, more preferably about 700-1,400, and especially -Case EI-6218+

- 26 ~

800-1,200. The isobutene used in making the polyisobutene is usually (but not necessarily) a mixture of isobutene and other C4 isomers such as l-butene. Thus, strictly speaking, the acylating agent formed from maleic anhydride and "polyiso-butene" made from such mixtures of isobutene and other C4isomers such as l-butene, can be termed a "polybutenyl suc-cinic anhydride" and a succinimide made therewith can be termed a "polybutenyl succinimide". However, it is common to refer to such substances as "polyisobutenyl succinic anhy-dride" and "polyisobutenyl succinimide", respectively. Asused herein "polyisobutenyl" is used to denote the alkenyl moiety whether made from a highly pure isobutene or a more impure mixture of isobutene and other C4 isomers such as l-butene.
Polyamines which may be employed in forming the ashless dispersant include any that have a~ least one primary amino group which can react to form an imide group. A few represen-tative examples include branched-chain alkanes containing two or more primary amino groups such as tetraamino-neopentane, etc.; polyaminoalkanols such as 2-(2-aminoeth~lamino)-ethanol and 2-[2-(2-aminoethylamino)-ethylamino]-ethanol; heterocyclic compounds containing two or more amino groups at least one of which is a primary amino group such as 1-(B-aminoethyl)-2-imidazolidone, 2-(2-aminoethylamino)-5-nitropyridine, 3-amino-N-ethylpiperidine, 2-(2-aminoethyl)-pyridine, 5-aminoindole, 3-amino-5-mercapto-1,2,4-tria~ole, and 4-(aminomethyl)-piperi-dine; and the alkylene polyamines such as propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, N-(2-amino-ethyl)-1,3-propanediamine, hexamethylenediamine and tetra-(1,2-propylene)pentamine.
The most preferred amines are the ethylene polyamines which can be depicted by the formula H2N ( CH2CH2NH) nH
wherein n is an integer from one to about ten. These incll~de:
ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like, including mixtures thereof in which case n is the average va-Case EI-6218+
- 27 - 2 a ~

lue of the mixture. These ethylene polyamines have a primary amine group at each end so can form mono-alkenylsuccinimides and bis-alkenylsuccinimides. Commercially available ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, ~T,N'-bis(aminoethyl)piperazine, N,N'-bistpiperazinyl)ethane, and like compounds. The preferred commercial mixtures have approximate overall compositions falling in the range corre-sponding to diethylene triamine to pentaethylene hexamine, mixtures generally corresponding in overall makeup to tetra-ethylene pentamine being most preferred. Methods for the production of polyalkylene polyamines are known and reported in the literature. See for example U.S. Pat. No. 4,8~7,037 and references cited therein.
Thus especially preferred ashless dispersants for use in the present invention are the products of reaction of a polyethylene polyamine, e.g. triethylene tetramine or tetra-ethylene pentamine, with a hydrocarbon-substituted carboxylic acid or anhydride (or other suitable acid derivative) made by reaction of a polyolefin, preferably polyisobutene, having a number ave.rage molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400 and especially 800 to 1,200, with an unsaturated polycarboxylic acid or anhy-dride, e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures of two or more such substances.
As used herein the term "succinimide" is meant to encompass the completed reaction product from reaction between the amine reactant(s) and the hydrocarbon-substituted carboxy-lic acid or anhydride (or like acid derivative) reactant(s), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
Residual unsaturation in the alkenyl group of the alkenyl succinimide may be used as a reaction site, if de-sired. For example the alkenyl substituent may be hydrogena-ted to form an alkyl substituent. Similarly the olefinic --- Case EI-6218+

bond(s) in the alkenyl substituent may be sulfurized, halo-genated, hydrohalogenated or the like. Ordinarily, there is little to be gained by use of such techniques, and thus the use of alkenyl succinimides as the precursor of component b) is prefarred.
Another sub-category of carboxylic dispersants which can be used in ~orming component b) includes alkenyl succinic acid esters and diesters of alcohols containing 1-20 carbon atoms and 1-6 hydroxyl groups. Representative examples are described in U.S. Pat. Nos. 3,331,776; 3,381,022; and 3,522,179. The alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succini-mides described above including the same preferred and most preferred subgenus, e.g., alkenyl succinic acids and anhy-drides, etc., where the alkenyl group contains at least 30 carbon atoms and notably, polyisobutenyl succinic acids and anhydrides wherein the polyisobutenyl group has a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,~00, and especially 800 to 1,200. As in the case of the succinimides, the alkenyl group can be hydrogenated or subjected to other reactions involving olefinic double bonds.
Alcohols useful in ~reparing the esters include metha-nol, ethanol, 2-methylpropanol, octadecanol, eicosanol, ethy-lene glycol, diethylene glycol, tetraethylene glycol, diethy-lene glycol monoethylether, propylene glycol, tripropylene glycol, glycerol, sorbitol, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, l,1,1-trimethylol butane, pentaerythri-tol, dipentaerythritol, and the like.
The succinic esters are readily made by merely heating a mixture of alkenyl succinic acid, anhydrides or lower alkyl (e.g., C1-C4) ester with the alcohol while distilling out water or lower alkanol. In the case of acid-esters less alcohol is used. In fact, acid-esters made from alkenyl succinic anhy-drides do not evolve water. In another method the alkenyl succinic acid or anhydrides can be merely reacted with an - Case EI-6218+

appropriate alkylene oxide such as ethylene oxide, propylene oxide, and the like, including mixtures thereof.
Still another sub-category of carboxylic dispersants useful in forming component b) comprises an alkenyl succinic ester-amide mixture. These may be made by heating the above-described alkenyl succinic acids, anhydrides or lower alkyl esters or etc. with an alcohol and an amine either sequen-tially or in a mixture. The alcohols and amines described above are also useful in this embodiment. Alternatively, amino alcohols can be used alone or with the alcohol and/or amine to form the ester-amide mixtures. The amino alcohol can contain 1-20 carbon atoms, 1-6 hydroxy groups and 1-4 amine nitrogen atoms. Examples are ethanolamine, diethanolamine, N-ethanol-diethylene triamine, and trimethylol aminomethane.
Here again, the alkenyl group of the succinic ester-amide can be hydrogenated or subjected to other reactions involving olefinic double bonds.
Representative examples of suitable ester-amide mix-tures are described in U.S. Pat. Nos. 3,184,474; 3,576,743;
3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480;
3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098;
4,071,54~; and 4,173,540.
Yet another sub-category of carboxylic dispersants useful in forming component b) comprises the Mannich-based derivatives of hydroxyaryl succinimides. Such compounds can be made by reacting a polyalkenyl succinic anhydride with an aminophenol to produce an N-(hydroxyaryl) hydrocarbyl succini-mide which is then reacted with an alkylene diamine or polyal-kylene polyamine and an aldehyde (e.g., formaldehyde), in a Mannich-base reaction. ~etails of such synthesis are set forth in U.S. Pat. No. 4,354,950. As in the case of the other carboxylic dispersants discussed above, the alkenyl succinic anhydride or like acylating agent is derived from a polyole-fin, preferably a polyisobutene, having a number average mo-lecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400, and especially 800 to 1,200. Like-wise, residual unsaturation in the polyalkenyl substituent Case EI-6218+

- 30 ~

group can be used as a reaction site as for example, by hy-drogenation, sulfurization, or the like.
Ty~e B - H~ carbYl Polyamine Dispersants. This category of ashless dispersants which can be used in forming component b) is li~ewise well known to those skilled in the art and fully described in the literature. The hydrocarbyl polyamine dispersants are generally produced by reacting an aliphatic or alicyclic halide (or mixture thereof) containing an average of at least about 40 carbon atoms with one or more amines, preferably polyalkylene polyamines. Examples of such hydrocarbyl polyamine dispersants are described in U.S. Pat.
Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,671,511;
3,821,302; 3,394,576; and in European Patent Publication No.
382,405.
In general, the hydrocarbyl-substituted polyamines are high molecular weight hydrocarbyl-N-substituted polyamines containing basic nitrogen in the molecule. The hydrocarbyl group typically has a number average molecular weight in the range of about 750 lQ,000, more usually in the range of about 1,000-5,000.
The hydrocarbyl radical may be aliphatic or alicyclic and, except for adventitious amounts of aromatic components in petroleum mineral oils, will be free of aromatic unsat~lration.
The hydrocarbyl groups will normally be branched-chain alipha-tic, having 0-2 sites of unsaturation, and preferably from 0-1 site of ethylene unsaturation. The hydrocarbyl groups are preferably derived from petroleum mineral oil, or polyolefins, either homo-polymers or higher-order polymers, or l-olefins of from 2-6 carbon atoms. Ethylene is preferably copolymerized with a higher olefin to insure oil solubility.
Illustrative polymers include polypropylene, polyiso-butylene, poly-l-butene, etc. The polyolefin group ~ill nor-mally have at least one branch per six carbon atoms along the chain, preferably at least one branch per four carbon atoms along the chain. These branched-chain hydrocarbons are readi-ly prepared by the polymerization of olefins of from 3-6 car-Case EI 6218+
2~3~

bon atoms and preferably from olefins of from 3-4 carbon atoms.
In preparing the hydrocarbyl polyamine dispersants, rarely will a single compound having a defined structure be employed. ~ith both polymers and petroleum-derived hydrocar-bon groups, the composition is a mixture of materials having various structures and molecular weights. Therefore, in re-ferring to molecular weight, number average molecular weights are intended. Furthermore, when speaking of a particular hydrocarbon group, it is intended that the group include the mixture that is normally contained within materials which are commercially available. For example, polyisobutylene is known to have a range of molecular weights and may include small amounts of very high molecular weight materials.
Particularly preferred hydrocarbyl-substituted amines or polyamines are prepared from polyisobutenyl chloride.
The polyamine employed to prepare the hydrocarbyl-sub-stituted polyamine is preferably a polyamine having from 2 to about 12 amine nitrogen atoms and from 2 to about 40 carbon atoms. The polyamine is r~acted with a hydrocarbyl halide (e.g., chloride) to produce the hydrocarbyl-substituted poly-amine. The polyamine pre~erably has a carbon-to-nitrogen ratio of from about 1:1 to about 10:1.
The amine portion of the hvdrocarbyl-substituted amine may be substituted with substituents selected from (A) hydro-gen, and (B) hydrocarbyl groups of from about 1 to about 10 carbon atoms.
The polyamine portion of the hydrocarbyl-substituted polyamine may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to about 10 carbon atoms, (C) acyl groups of from 2 to about 10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivati~es of (B) and (C).
"Lower" as used in terms like lower alkyl or lower alkoxy, means a group containing from 1 to about 6 carbon atoms.

- Case EI-6218+ 2 ~ ~ ~ 31~ ~

At least one of the nitrogens in the hydrocarbyl-substituted amine or polyamine is a basic nitrGgen atom, i.e., one titratable by a strong acid.
Hydrocarbyl, as used in describing the substituents in the amine or polyamine used in forming the dispersants, de-notes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl. Preferably, the hydrocarbyl group will be re-latively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation. The hydro-carbyl substituted polyamines used in forming the dispersants are generally, but not necessarily, N-substituted polyamines.
Exemp]ary hydrocarbyl groups and substituted hydrocarbyl groups which may be present in the amine portion of the dis-persant include alkyls such as methyl, ethyl, propyl, butyl,isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as pro-penyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2 hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 4-hy-droxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 6-keto-octyl, etc., alkoxy and lower alkenoxy alkyls, such as eth-oxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl, 3,6 C3,12-tetraoxytetradecyl, 2-(2-ethoxyethoxy)hexyl, etc.
Typical amines useful in preparing the hydrocarbyl-substituted amines include methylamine, dimethylamine, ethyl-amine, diethylamine, n-propylamine, di-n-propylamine, etc.
Such amines are either commercially available or are prepared by art recognized procedures.
The polyamine component may also contain heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocyclic comprises one or more 5-6 membered rings containing oxygen and/or nitrogen.
Such heterocyclics may be saturated or unsaturated and substi-tuted with groups selected from the aforementioned (A), (B), tC), and (D). The heterocyclics are exemplified by pipera-zines, such as 2-methylpiperaæine, 1,2-bis(N-piperazinyl-eth-ane), and N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazo-Case EI~6218+ 2 line, 3-aminopiperidine, 2-aminopyridine, 2-(B-aminoe-thyl)-3-pyrroline, 3-aminopyrrolidine, N-(3-aminopropyl)morpholine, etc. Among the heterocyclic compounds, the piperazines are preferred.
Typical polyamines that can be used to form the hydro-carbyl polyamine dispersants include the following: ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethy-lene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, methylaminopropylene diamine, N-(B-aminoethyl)piperazine, N,N'-di(B-aminoethyl)piperazine, N,N'-di(B-aminoethyl)imidazolidone-2, N-(B-cyanoethyl)ethane-1,2-diamine, 1,3,6,9-tetraaminooctadecane, 1,3,6-triamino-9~oxa-decane, N-methyl-1,2-propanediamine, 2-(2-aminoethylamino)-ethanol, and the like.
Another group of suitable polyamines are the polyal-kylene amines in which the alkylene groups differ in carbon content, such as for example bis(aminopropyl)ethylenediamine.
Such compounds are prepared by the reaction of acrylonitrile with an ethyleneamine, for example, an ethyleneamine having the formula H2H(CH2CH2NH)nH wherein n is an integer from 1 to 5, followed by hydrogenation of the resultant intermediate.
Thus, the product prepared from ethylene diamine and acrylo-nitrile has the fol~ula H2N(C~2)3NH(CH2)2NH(CH2)3NH2-In many instances the polyamine used as a reactant in 2~ the production of the hydrocarbyl-substituted polyamine is not a single compound but a mixture in which one or several com-pounds predominate with the average composition indicated.
For example, tetraethylene pentamine prepared by the poly-merization o~ aziridine or the reaction of 1,2-dichloroethane and ammonia will have both lower and higher amine members, eOg., triethylene tetramine/ suhstituted piperazines and pentaethylene hexamine, but the composition will be largely tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethy-lene pentamine. Finally, in preparing the hydrocarbyl substi-tuted polyamines for use in this invention, where the various nitrogen atoms of the polyamine are not geometrically equiva-Case EI-6218~ 2 lent, several substitutional isomers are possible and are encompassed with the final product. Methods of preparation of polyamines and their reactions are detailed in Sidgewick, The Orqanic Chemistry of Nitroqen, Clarendon Press, Oxford, 1966;
Nollier, Chemistry of Orqanic Compounds, Saunders, Philadel-phia, 2nd Ed., 1957; and Kirk-Othmer, EncycloPedia of ~hemical Technolo~y, 2nd Edition, especially volume 2, pp. 99-116.
The preferred hydrocarbyl-substituted polyalkylene polyamines for use in this invention may be represented by the formula R1NH-(-R2-NH-)~-H
wherein R1 is hydrocarb~l having an average molecular weight of from about 750 to about 10,000; ~2 is alkylene of from 2 to 6 carbon atoms; and a is an integer of from 0 to about 10.
Preferably, R1 is hydrocarbyl having an average molecu-lar weight of from about 1,000 to about 10,000. Preferably, R2 is alkylene of from 2 to 3 carbon atoms and ~ is preferably an integer of from 1 to 6.
Type C - Mannich pol~amine disPersants. This category of ashless dispersant which can be utilized in the formation of component b) is comprised of reaction products of an alkyl phenol, with one or more aliphatic aldehydes containing from 1 to about 7 carbon atoms (especial ~ formaldehyde and deriva-tives thereof), and polyamines (especially polyalkylene poly-amines of the type described hereinabove). Examples of theseMannich polyamine dispersants are described in the following U.S. Patents: 2,459,112; 2,962,442; 2,984,550; 3,036,003;
3,166,516; 3,236,770; 3,368,972; 3,413,347; 3,442,808;
3,448,047; 3,454,~97; 3,459,661; 3,493,520; 3,539,633;
3,558,743; 3,586,629; 3,591,598; 3,600,372; 3,634,515;
3,649,229; 3,697,574; 3,703,536; 3,70~,308; 3,725,277;
3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953;
3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,872,019;
3,980,569: and 4,011,380.
The polyamine group of the Mannich polyamine disper-sants is deri~ed from polyamine compounds characterized by containing a group of the structure -NH- wherein the two Case ~I-6218+ 2 ~ ~ ~ 3 ~ ~

remaining valances of the nitrogen are satisfied by hydrogen, amino, or organic radicals bonded to said nitrogen atom.
These compounds include aliphatic, aromatic, heterocyclic and carbocyclic polyamines. The source of the oil-soluble hydro-carbyl group in the Mannich polyamine dispersant is a hydro-carbyl-substituted hydroxy aromatic compound comprising the reaction product of a hydroxy aromatic compound, according to well known procedures, with a hydrocarbyl donating agent or hydrocarbon source. The hydrocarbyl substituent provides substantial oil solubility to the hydroxy aromatic compound and, preferably, is substantially aliphatic in character.
Commonly, the hydrocarbyl substituent is derived from a polyolefin having at least about 40 carbon atoms. The hydro-carbon source should be substantially free from pendant groups which render the hydrocarbyl group oil insoluble. Examples of acceptable substituent groups are halide, hydroxy, ether, car-boxy, ester, amide, nitro and cyano. However, these substi-tuent groups preferably comprise no more than about 10 weight percent of the hydrocarbon source.
The preferred hydrocarbon sources for preparation of the Mannich polyamine dispersants are those derived from sub-stantially saturated petroleum fractions and olefin polymers, preferably polymers of mono-olefins having from ~ to about 30 carbon atoms. The hydrocarbon course can be derived, for ex-ample, from polymers of olefins such as ethylene, propene, 1-butene, isobutene, l~octene, 1-methylcyclohexene, 2-butene and 3-pentene. Also useful are copolymers of such olefins with other polymerizable olefinic substances such as styrene. In general, these copolymers should contain at least 80 percent and preferably about 95 percent, on a weight basis, of units derived from the aliphatic mono olefins to preserve oil solu-bility. The hydrocarbon source generally contains at least about 40 and preferably at least about 50 carbon atoms to provide substantial oil solubility to the dispersant. The olefin polymers having a number average molecular weight between about 600 and 5,000 are preferred for reasons of easy reactivity and low cost. However, polymers of higher mole-Case EI-6218+ 2 cular weight can also be used. ~specially suitable hydrocar-bon sources are isobutylene polymers.
The Mannich polyamine dispersants are generally pre-pared by reacting a hydrocarbyl-substituted hydroxy aromatic compound with an aldehyde and a polyamine. Typically, the substituted hydroxy aromatic compound is contacted with from about 0.1 to about 10 moles of polyamine and about 0.1 to about 10 moles of aldehyde per mole of substituted hydroxy aromatic compound. The reactants are mixed and heated to a temperature above about 80C. to initiate the reaction. Pre-ferably, the reaction is carried out at a temperature from about 100 to about 250C. The resulting Mannich product has a predominantly benzylamine linkage between the aromatic com-pound and the polyamine. The react.ion can be carried out in an inert diluent such as mineral oil, benzene, toluene, naph-tha, ligroin, or other inert solvents to facilitate control of viscosity, temperature and reaction rate.
Polyamines are preferred for use in preparing the Mannich polyamine dispersants, and suitable polyamines in-clude, but are not limited to, alkylene diamines and polyal~-lene polyamines (and mixtures thereof) of the formula:
A-N-(-R-l-)n-H
A A
wherein n is an integer from 1 to about 10, R is a divalent hydrocarbyl group of from l to about 18 carbon atoms~ and each A is independently selected from the group consisting of hy-drogen and monovalent aliphatic groups containing up to 10 carbon atoms which can be substituted with one or two hydroxyl groups. Most preferably, R is a lower alkylene group of from 2 to 6 carbon atoms and A is hydrogen.
Suitable polyamines for use in preparation of the Mannich polyamine dispersants include, but are not limited to, methylene polyamines, ethylene polyamines, butylene polya-mines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologs of - Case EI~6218~

such amines and related aminoalkyl-substituted piperazines are also included. Specific examples of such polyamines include ethylene diamine, triethylene tetramine, tris(2-aminoethyl)-amine, propylene diamine, pentamethylene diamine, hexamethy-lene diamine, heptamethylene diamine, octamethylene diamine,decamethylene diamine, di(heptamethylene) triamine, penta-ethylene he~amine, di(trimethylene) triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs, ob-tained by condensing two or more of the above mentioned amines, are also useful, as are the polyoxyalkylene polya-mines.
The polyalkylene polyamines, examples of which are set forth above, are especially useful in preparing the Mannich polyamine dispersants for reasons of cost and effectiveness.
Such polyamines are described in detail under the heading "Diamines and Higher Amines" in Kirk-Othmer, EncycloPedia of Chemical TechnoloqY, Second Edition, Vol. 7, pp. 22-39. They are prepared most conveniently by the reaction of an ethylene imine with a ring-opening reagent such as ammonia. These reactions result in the production of somewhat complex mix-~u es of polyalkylene polyamines which include cyclic conden sation products such as piperazines. Because of their avail-ability, these mixtures are particularly useful in preparing the Mannich polyamine dispersants. ~owever, it will be appre-ciated that satisfactory dispersants can also be obtained by use of pure polyalkylene polyamines.
Alkylene diamines and polyalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atom are also useful in preparing the ~annlch polyamine dispersants.
These materials are typically obtained by reaction of the cor-responding polyamine with an epoxide such as ethylene oxide or propylene oxide. Preferred hydroxyalkyl-substituted diamines and polyamines are those in which the hydroxyalkyl groups have less than about lO carbon atoms. Examples of suitable hy-droxyalkyl-substituted diamines and polyamines include, but Case EI-6218+ 2 are not limited to, N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, mono(hydroxypropyl)diethy-lenetriamine, (di(hydroxypropyl)tetraethylenepentamine and N-(3-hydroxybutyl)tetramethylenediamine. ~igher homologs ob-tained by condensation of the above mentioned hydroxyalkyl-substituted diamines and polyamines through amine groups or through ether groups are also usefui.
Any conventional formaldehyde yielding reagent is use-ful for the preparation of the Mannich polyamine dispersants.
Examples of such formaldehyde yielding reagents are trioxane, paraformaldehyde, trioxymethylene, aqueous formalin and gase-ous formaldehyde.
Type D - PolYmeric polYamine dispersants. Also suit-able for preparing component b) of the compositions of this invention are polymers containing basic amine groups and oil solubilizing groups (for example, pendant alkyl groups having at least about 8 carbon atoms). Such polymeric dispersants are herein referred to as polymeric polyamine dispersants.
Such materials include, but are not limited to, interpolymers of decyl methacrylate, vinyl decyl ether or a relatively high molecular weight olefin with aminoalkyl acrylates and amino-alkyl acrylamides. Examples of polymeric polyamine disper-sants are set l~ th in the following patents: U.S. Pat. Nos.
3,329,658; 3,4~9,250; 3,~93,520; 3,519,565; 3,666,730;
3,687,849; 3,702,300.
Type E - Post-treated basic nitroqen-containinq and/or hvdroxyl-containinq ashless dis~rsants. As is well known in the art, any of the ashless dispersants referred to above as types A-D can be subjecked to post-treatment with one or more suitable reagents such as urea, thiourea, caxbon disulfide, aldehydes, ketones, carboxylic acids, anhydrides of low mole-cular weight dibasic acids, nitriles, epoxides, and the like.
Such post-treated ashless dispersants can be used in forming component b) of the compositions of this invention provided that the post-treated dispersant contains residual basic ni-trogen and/or one or more residual hydroxyl groups. Alter-natively, the phosphorylated and boronated dispersant can be Case EI 6218~ 2 ~ 3 ~ ~

subjected to post-treatment with such reagents. Likewise, the post-treatment can be conducted in between the phosphorylation and boronation or conversely, between the boronation and the phosphorylation. Examples of post-treatment procedures and 5 post-treated ashless dispersants are set forth in the fol-lowing U.S. Patents: 3,036,003; 3,087,936; 3,200,107;
3,216,936; 3,254,025; 3,256,185; 3,278,550; 3,218,428;
3,280,234; 3,281,428; 3,282,955; 3,~12,619; 3,366,569;
3,367,943; 3,373,111; 3,403,102; 3,442,808; 3,455,831;
3,455,832; 3,493,520; 3,502,677; 3,513,093; 3,533,945;
3,539,633; 3,573,010; 3,579,450; 3,591,59~; 3,600,372;
3,639,242; 3,649,229; 3,649,659; 3,658,836; 3,697,574;
3,702,757; 3,703,536; 3,704,308; 3,708,422; 4,025,445; and 4,857,214~
Mannich-based derivatives of hydroxyaryl succinimides that have been post-treated with C5-C9 lactones such as ~-ca-prolactone and optionally with other post-treating agents as described for example in U.S. Pat. No. 4,971,711 can also be utilized in forming component b) for use in the practice of this invention, provided that such post-treated Mannich-based derivatives of hydroxyaryl succinimides contain basic nitro-gen, and/or at least one hydroxyl group. The disclosures of U.S. Pat. No. 4,971,711, ~.~ well as related U.S. Pat. Nos.
4,8209432; 4,828,742; 4,866,135; 4,866,139; 4,866,140;
4,~66,141; 4,866,142; 4l906,39~; and 4,gl3,830 are referred to as regards additional suitable basic nitrogen-containing and/or hydroxyl group-containing ashless dispersants which may be utilized in forming component b).
One preferred category of post-treated ashless disper-sants is comprised o~ basic nitrogen-containing and/or hydrox-yl group-containing ashless dispersants which have been heated with (1) a phosphorus compound such that they contain phospho-rus, or (2) a boron compound such that they contain boron, all with the proviso that such post-treated products contain resi-dual basic nitrogen and/or one or more residual hydroxyl groups. Numerous examples of such dispersants and methods for their production are described in the U.S. Patents re~erred to Case EI-6213+ 2 ~ l O

at the outset of this disclosure under the caption "Back-ground". The boron-containing post-treated ashless disper-sants of the prior art type can be converted into a material suitable for use as component b) simply by conducting a phos-phorylation in the manner described herein. If desired, addi-tional boron can also be incorporated into a prior art type post-treated boron-containing ashless dispersant by conducting a boronation in the manner described herein either before, during or after the phosphorylation. Likewise, the phos-phorus-containing post-treated ashless dispersants of the prior art type can be converted into a material suitable for use as component b) simply by conducting a boronation in the manner described herein. If desired, additional phosphorus can also be incorporated into a prior art type post-treated phosphorus-containing ashless dispersant by conducting a phosphorylation in the manner described herein either before, during or after the boronation. It is a~so possible by using the phosphorylation and/or boronation procedures described herein to phosphorylate and/or boronate a post-treated ashless dispersant that already contains both phosphorus and boron, again provided that such initial post-treated ashless disper-sant contains at least some residual basic nitrogen and/or at least some residual hydroxyl substitul~n.
The ashless dispersant(s) used in forming component b) can be any mixture containing any two or more ashless disper-sants containing basic nitrogen and/or at least one hydroxyl group. Thus, for example, with reference to dispersants of the above types A, B, C, D and E, use can be made of such mixtures as:
(1) Two or more different type A dispersants, (2) Two or more different type B dispersants;
(3) Two or more different type C dispersants;
(4) Two or more different type D dispersants;
(5) Two or more different type E dispersants;
(6) One or more type A dispersants with one or more type B
dispersants;

Case EI-6218+ - 41 - 2 0 ~ l O

( 7 ) One or more type A dispersants with one or more type C
dispersants;
(~) One or more type A dispersants with one or more type D
dispersants;
( 9 ) One or more type A dispersants with one or more type E
dispersants;
(10) One or more type B dispersants with one or more type C
dispersants;
(11) One or more type B dispersants with one or more type D
dispersants;
( 12 ) One or more type B dispersants with one or more type E
dispersants;
( 13 ) One or more type C dispersants with one or more type D
dispersants;
( 14 ) One or more type C dispersants with one or more type E
dispersants;
(15) One or more type D dispersants with one or more type E
dispersants;
(16) One or more type A dispersants with one or more type B
2 0 dispersants and with one or more type C dispersants;
( 17 ) One or more type A dispersants with one or mo:re type B
dispersants and with one or more type D dispersants;
(18) One or more type A dispersants with one or m~ e type B
dispersants and with one or more type E dispersants, ( 19 ) One or more type A dispersants with one or more type C
dispersants and with one or more type D dispersants;
(20) One or more type A dispersants with one or more type C
dispersants and with one or more type E dispersants;
(21) One or more type A dispersants with one or more type D
3 0 dispersants and with one or more type E dispersants;
(22) One or more type B dispersants with one or more type C
dispersants and with one or more type D dispersants;
(23) One or more type B dispersants with one or more type C
dispersants and with one or more type E dispersants;
(24) One or more type B dispersants with one or more type D
dispersants and with one or more type E dispersants;

`` Case EI-6218+

(25) One or more type C dispersants with on~ or more type D
dispersants and with one or more type E dispersants;
(26) One or more type A dispersants with one or more type B
dispersants, with one or more type C dispersants, and with one or more type D dispersants;
(27) One or more type A dispersants with one or more type B
dispersants, ~ith one or more type C dispersants, and with one or more type E dispersants;
(28) One or more type A dispersants with one or more type C
dispersants, with one or more type D dispersants, and with one or more type E dispersants;
(29) One or more type B dispersants with one or more type C
dispersants, with one or more type D dispersants, and with one or more type E dispersants; and (30j One or more type A dispersants with one or more type B
dispersants, with one or more type C dispersants, with one or more type D dispersants, and with one or more type E disper-sants.
It will also be understood that any given type of dis-persant whether used with one or more other dispersant types or without any other dispersant type can comprise:
(I) A mixture in which at least one component contains ~a-`~ sic nitrogen but no hydroxyl group and another component of the mixture contains at least one hydroxyl group but no basic nitrogen;
(II) A mixture in which at least one component contains ba-sic nitrogen but no hydroxyl group and another component of the mixture contains basic nitrogen and at least one hydroxyl group;
(III) A mixture in which at least one component contains at least one hydroxyl group but no basic nitrogen and another component of the mixture contains basic nitrogen and at least one hydroxyl group; and (IV) A-mixture in which at least one component contains ba-sic nitrogen but no hydroxyl group, another component of themixture contains at least one hydroxyl group but no basic ni-Case EI-6218~ 2 trogen, and still another component of the mixture contains basic nitrogen and at least one hydroxyl group.
Because of environmental and conservational concerns it is desirable to employ ashless dispersants which contain little, if any, halogen atoms such as chlorine atoms. Thus, in order to satisfy such concerns, it is desirable (althouyh not necessary from a performance standpoint) to select ashless dispersants (as well as the other components used in the com-positions of this invention) such that the total halogen con-tent, if any, of the overall lubricant or functional fluidcomposition does not exceed 100 ppm. Indeed, the lower the better. Likewise, it is preferable in accordance with this invention, to provide additive concentrates which, when dissolved in a halogen-free base oil, at a concentration of 10% by weight, yield an oleaginous composition in which the total halogen content, if any, is 100 ppm or less.
Suitable compounds of boron useful in forming the phosphorylated and boronated ashless dispersants for use as component b) include, for example, boron acids, boron oxides, boron esters, and amine or ammonium salts of boron acids.
Illustrative compounds include boric acid (sometimes referred to as orthoboxic acid), boronic acid, tetraboric acid, meta-boric ~cid, pyroboric acid, esters of such acids, such as mono-, di-, and tri-organic esters with alcohols or polyols having up to 20 or more carbon atoms (e.g., methanol, ethanol, 2-propanol, propanol, butanols, pentanols, hexanols, ethylene glycol, propylene glycol, trimethylol propane, diethanol amine, etc.), boron oxides such as boric oxide and boron oxide hydrate, and ammonium salts such as ammonium borate, ammonium pyroborate, etc. While usable, boron halides such as boron trifluoride, boron trichloride, and the like, are undesirable as they tend to introduce halogen atoms into the boronated dispersant, a feature which is detrimental from the environ-mental, toxicological and conservational standpoints. Amine borane addition compounds and hydrocarbyl boranes can also be used, although they tend to be relatively expensive. The pre-ferred boron rea~ent is boric acid, H3B03.

~~ Case EI-6218+ 2 ~ 44 -For further details concerning procedures for conduc-ting the boronation operation apart from the phosphorylation operation, reference may be had, for example; to the disclo-sures of U.S. Pat. Nos. 3,087,936; 3,254,025; 3,281,428;
3,282,955; 3,284,410; 3,338,832; 3,3~4,069; 3,533,945;
3,718,663; 4,097,389; 4,554,0~6; and 4,634,543.

Producing Phosphorylated and Boronated Ashless Dispersants from at least one Inorganic Phosphorus Compound and at least one Boron Compound Typical procedures for producing the phosphorylated and boronated ashless dispersants from (i) and (iii) above involve concurrently or sequentially heating one or more ashless dis-persants of the types described above with at least one inor-ganic phosphorus compound and at least one boron compound un-der conditions yielding a liquid phosphorus- and boron-con-taining composition. Examples of inorganic phosphorus com-pounds which are useful in forming such products include phosphorous acid (H3Po3 , sometimes depicted as H2(HPO3), and sometimes called ortho-phosphorous acid or phosphonic acid), phosphoric acid (H3PO4, sometimes called orthophosphoric acid), hypophosphoric acid (H4P206), metaphosphoric acid (HP03), pyro-phosphoric acid (~ P2O7), hypophosphorous acid (H3PO2, sometimes called phosphinlc acid), pyrophosphorous acid (H4P2O5, some-times called pyrophosphonic acid), phosphinous acid (~3PO), tripolyphosphoric acid (H5P30~0), tetrapolyphosphoric acid (H6P4O13), trimetaphosphoric acid (H3P309), phosphorus trioxide, phosphorus tetraoxide, phosphorus pentoxide, and the like.
Partial or total sulfur analogs such as phosphorotetrathioic acid (H3PS4), phosphoromonothioic acid (H3P03S ), phosphorodi-thioic acid (H3PO2S2), phosphorotrithioic acid (H3POS3), phos-phorus sesquisulfide, phosphorus heptasulfide, and phosphorus pentasulfide (P2S5, sometimes referred to as P4Slo) can also be used in forming products suitable for use as component b) in the practice of this invention. Also usable, though less pre-ferred, are the inorganic phosphorus halide compounds such as 2 ~
Case EI 6218~

PC13, PBr3, POC13, PSC13, etc. The preferred phosphorus rea-gent is phosphorous acid, (H3PO3).
It will be understood and appreciated by those skilled in the art that the form or composition of the inorganic com-pound(s) as charged into the mixture to be heated or beingheated may be altered in situ. For example, the action of heat and/or water can transform certain inorganlc phosphorus compounds into other inorganic phosphorus compounds or spe-cies. Any such in situ transformations that may occur are within the puxview of this invention provided that the liquid phosphorylated ashless dispersant reveals on analysis the presence therein of phosphorus (as well as boron).
Optionally, additional sources of basic nitrogen can be included in the inorganic phosphorus compound-ashless dispersant-boron compound mixture so as to provide a molar amount (atomic proportion) of basic nitrogen up to that equal to the molar amount of basic nitrogen contributed by the ashless dispersant. Preferred auxiliary nitrogen compounds are long chain primary, secondary and tertiary alkyl amines containing from about 12 to 24 carbon atoms, including their hydroxyalkyl and aminoalkyl derivatives. The long chain alkyl group may optionally contain one or more ether groups.
Examples of suitable compoun~s are oleyl amine, N-oleyltrimethylene diamine, N-tallow diethanolamine, N,N~
dimethyl oleylamine, and myristyloxapropyl amine.
Other materials normally used in lubricant additives which do not interfere with the process may also be added, for example, a benzotriazole, including lower (C1-C4) alkyl-substi-tuted benzotriazoles, which function to protect copper surfaces.
The concurrent heating step or the combination of sequential heating steps is conducted at temperatures suffi-cient to produce a final liquid composition which contains both phosphorus and boron. The heating can be carried out in the absence of a solvent by heating a mixture of the ashless dispersant and one or more suitable inorganic phosphorus com-pounds, or one or more suitable boron compounds, or, prefer-Case EI-6218~
2 ~

ably, a combination of one or more suitable inorganic phos-phorus compounds and one or more suitable boron compounds.
The temperatures used will vary somewhat depending upon the nature of the ashless dispersant and the inorganic phosphorus and/or boron reagent being utilized. Generally speaking how-ever, the temperature will usually fall within the range of about ~0 to about 200C. The duration of the heating is likewise susceptible to variation, but ordinarily will fall in the range of about 1 to about 3 hours. When conducting the lo heating in bulk, it is important to thoroughly agitate the components to insure intimate contact therebetween. When utilizing the preferred phosphorus and boron reagents (phos-phorous acid and boric acid), it is preferable to add water to facilitate initial dissolution of the boric acid. Alterna-tively, the phosphorous acid may be utilized in the form of an aqueous solution thereby introducing water into the system to facilitate dissolution of the boric acid. Water (and when using boron esters, alcohol) formed in the process and any added water is preferably removed from the heated mixture by vacuum distillation at temperatures of from about: 100 to about 140C. Preferably the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, and the like. ~
The amount of phosphorus compound employed in the heat-ing process ranges from about 0.001 mole to 0.999 mole per mole of basic nitrogen and free hydroxyl in the mixture being heated, up to one half of which may be contributed by an auxi-liary nitrogen compound. The amount o-E boron compound em-ployed ranges from about 0.001 mole to about 1 mole per mole of basic nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount of inorganic phosphorus compound.
When conducting the phosphorylation and boronation on a se-quential basis (or when conducting one of these operations on a dispersant which has previously been subjected to the other such operation), the last-to-be-used reagent(s) -- inorganic phosphorus compound(s) or boron compound(s), as the case may be -- can be used in an amount equivalent to (or even in ex-Case EI-6218+ ~ 3 cess of) the amount of basic nitrogen and/or hydroxyl groups in the dispersant being heated with such last-to-be-used rea-gent(s).
When used, the amount of added water is not particu-larly critical as it is removed by distillation during thecourse of, or at the end of, the heating step. Amounts of up to 1% by weight of the mixture being heated are preferred.
When used, the amount of diluent usually ranges from about 10 to about 50% by weight of the mixture being subjected to heating.
When conducting the preferred concurrent heating step for production of component b), it is desirable to employ pro-cedures such as descxibed in U.S. Pat. No. 4,857,214.
When forming component b) in part by use of one or more organic phosphorus compounds such as one or more organic phos-phates (e.g., trihydrocarbyl phosphates, dihydrocarbyl mono-acid phosphates, monohydrocarbyl diacid phosphates, or mix-tures thereof), phosphites (e.g., trihydrocarbyl phosphites, dihydrocarbyl hydrogen phosphites, hydrocarbyl diacid phos-phites, or mixtures thereof), phosphonates (e.g., hydrocarbylphosphonic acids, mono- and/or dihydrocarbyl esters of phos-phonic acids, or mixtures thereof), phosphonites (e.g., hydro-carbyl phosphinic acids, mono- and/or dihydrocarbyl esters of phosphinic acids, or mixtures thereof), etc., or the partial or total sulfur analogs thereof, and in part by use of one or more inorganic phosphorus compounds, the latter should be used in an amount sufficient to provide at least 10~ (preferably at least 50% and more preferably at least 75%) of the total con-tent of phosphorus in the phosphorylated and boronated disper-sant. For crankcase lubricant usage, component b) when in theundiluted state preferably contains at least 3,000 ppm (more preferably at least 5,000 ppm and most preferably at least 7,000 ppm) of phosphorus and at least 1,500 ppm (more prefer-ably at least 2,500 ppm and most preferably at least 3,500 ppm) of boron.
The preparation from (i) and (iii) of phosphorylated and boronated ashless dispersants suitable for use as compo-- Case EI-6218+
- 48 - ~ 3~

nent b) in the compositions of this invention is illustrated by the following examples in which all parts and percentages are by weight unless otherwise clearly specified.

EXAMPLE A-l 5A mixture is formed from 260 parts of a commercial succinimide ashless dispersant (HiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.), 100 parts of a 100 Solvent Neutral refined mineral oil dilu-ent, 8 parts of phosphorous acid, 3.5 parts of tolutriazole, 108 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained 15which is soluble in oil and suitable for use as component b).

The procedure of Example A-l is repeated except that the succinimide ashless dispersant used is derived from poly-butene having a number average molecular weight of 1,100. The 20average number of succinic groups per alkenyl group in the succinimide is approxim~tely 1.2.

The procedure of Example A-l is repeated except that the succinimide ashless dispersant used is derived from poly-25butene having a number average molecular weight of 2,100.

The procedure of Example A-l is repeated except that the succinimide ashless dispersant i5 replaced by an equal amount of a Mannich polyamine dispersant (A~CO~ 9250 disper-30sant; Amoco Corporation). The Amoco 9250 dispersant as sup-plied by the manufacturer is believed to be a boronated dis-persant and in such case, another material suitable ~or use as component b) can be fo~med by eliminating the boric acid and Case EI-5218+
- 49 - 2~3~

water from the procedure used in this example and thereby conducting phosphorylation on an already boronated dispersant.

The procedure of Example A-l is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a commercial ashless dispersant of the pentaerythri-tol succinic ester type (Lubrizol~ 936 dispersant; The Lubri-zol Corporation). As in the case of Example A-4, the initial dispersant as supplied by the manufacturer is believed to be a boronated dispersant. In such cases, the dispersant can, if desired, be subjected just to phosphorylation to thereby form still another product suitable for use as component b).

~he procedure of Example A-l is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2Ss is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100C to provide a clear, oil-soluble composition suitable for use as component b).

The procedure of Example A-6 is repeated except that the PzS5 is replaced by 7 parts of phosphorus pentoxide (P2Os).

The procedures of Examples A-1 through A-7 are repeated except that the tolutriazole is omitted from the initial mix-tures subjected to the thermal processes~

A mixture of 11,904 parts of a commercial boronated succinimide (HiTEC~ 648 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.) and 96 parts of phos-phorous acid is heated to 100-110C for 2 hours to form a homogeneous liquid composition suitable for use as component Case EI 621~+ 2 b) in the practice of this invention. For convenience in handling, lO0 Solvent Neutral mineral oil can be added to form an 80% solution of the additive in the oil.

A mixture of 260 parts of a commercial succinimide tHiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.), and 8 parts of phosphorous acid is heated to 100C for 2 hours. To this product is added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110C. The resultant homogeneous liquid composition is suitàble for use as component b) in the practice of this invention.

EXAMPLE A-ll A mixture of 260 parts of a commercial succinimide (HiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum A~ditives, Ltd.), 8 parts of orthoboric acid and 4 parts of water is heated to 100C for 2 hours. Then 8 parts of phosphorous acid is added to the reaction mixture and the temperature of the mixture is held at 100C for an~ther 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110C. The resultant homogeneous liquid com-position is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial succinic penta-erythritol ester ashless dispersant (Lubrizol3 936 dispersant;
The Lubrizol Corporation), and 8 parts of phosphorous acid is heated to 100C for 2 hours. To this product is added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 Case EI-6218~
2 ~
~ 51 -mm of Hg and gradually raising the temperature to 110C. The resultant homogeneous liquid composition is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial succinic penta-erythritol ester ashless dispersant (Lubrizol~ 936 dispersant;
The Lubrizol Corporation), 8 parts of orthoboric acid and 4 parts of water is heated to 100C for 2 hoursO Then 8 parts of phosphorous acid is added to the reaction mixture and the temperature of the mixture is held at 100C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110C. The resultant homogeneous liquid compo-sition is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial Mannich poly-amine dispersant (AMOCO~ ~250 dispersant; Amoco Corporation), and 8 parts of phosphorous acid is heated to 100C for 2 hours. To this product is added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100C for another 2 hours. Water present in the reaction mixture is removed by applying a vacuum of 40 mm of Hg and gradually raising the temperature to 110C. The ~esultant homogeneous liquid composition is suitable for use as com-ponent b) in the practice of this invention.

_ A mixture of 260 parts of a commercial Mannich poly-amine dispersant (AMOC0~ 9250 dispersant; Amoco Corporation), 8 parts of orthoboric acid and 4 parts of water is heated to 100C for 2 hoursu Then 8 parts of phosphorous acid is added to the reaction mixture and the temperature of the mixture is held at 100C for another 2 hours. Water present in the reac-tion mixture is removed by applying a vacuum of 40 mm of Hg Case EI-6218+ 2 and gradually raising the temperature to 110C. The resultant homogeneous liquid composition is suitable for use as compo-nent b) in the practice of this invention.

(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C. This mixture is heated to 184C in 6 hours during which 85 parts (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 with nitrogen purged for 26 hours. The residue is predominantly polyiso-butenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene poly-amines having the approximate overall composition of tetra-ethylene pentamine to 1,067 parts of mineral oil and 893 parts (1.38 equivalents) of substituted succinic acylating agent prepared as in (a) while maintaining the temperature at 140-145C. The reaction mixture is then heated to 155C over a three hour period and s~ripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product composed predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts o~ the poly-isobutenyl succinimide product solution formed as in (b), 8 parts of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to- 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

`` Case EI-6218+ 2 The procedure of Example A-16 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c) .

EXA~PLE A-18 The procedure of Example A-16 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100C to provide a clear, oil-soluble composition suitable for use as component b).

EXAMPLE A-l9 The procedure of Example ~-18 is repeated except that the P2Ss is replaced by 7 parts of phosphorus pentoxide (P2Os).

(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) of maleic anhydride i5 heated to 110C. This mixture is heated to 184C in 5 hours during which 85 parts (~.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 with nitrogen purged for 26 hours. The residue is predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 1~3.2 parts (0.433 equivalents) of a commercial mixture of ethylene polyamines having the approximate o~erall composition of tetraethylene pentamine to 392 parts of mineral oil and 348 parts (0.52 e~uivalent) of substituted succinic acylating agent prepared as in (a) while maintaining the temperature at 140C. The reaction mixture is then heated to 150C in 1.8 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution Case EI-6218+ 2 ~ 3 ~ ~

of the desired product composed predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyiso-butenyl succinimide product solution formed as in (b), 8 parts 5of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dis-solved. A vacuum of 40 mm Hg is gradually drawn on the pro-duct to remove the water while the temperature is slowly 10raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example A-20 is repeated except that the tolutriazole is eliminated from the reaction mixture of 15(c).

The procedure of E~ample A-20 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the PzS5 is added to the mixture after water 20distillation, and the mixture is then heated for an additional hour at 100C to provide a clea~, oil-soluble composition suitable for use as component b).

The procedure of Example A-22 is repeated except that 25the P2Ss is replaced by 7 parts of phosphorus pentoxide (P2O5).

(a) A mixture of 1,000 parts (0.495 mole) of pol~-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles3 of maleic anhydride is 30heated to 110C. This mixture is heated to 18~C in 6 hours during which 85 parts (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 Case EI-6218+

mixture is stripped by heating at 186-190C with nitrogen purged for 26 hours. The residue is predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture of 334 parts (0.52 equivalents) of the polyisobutene substituted succinic acylating agent prepared as in (a), 548 parts of mineral oil, 30 parts (0.88 e~uivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Poly-glycol 112-2 demulsifier (Dow Chemical Company) is heated at 150C for 2.5 hours. The reaction mixture is then heated to 210~ over a period of 5 hours and then held at 210C for an additional 3.2 hours. The reaction mixture is cooled to 190C
and 8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines having an overall composition approxima-ting that of tetraethylene pentamine is added. The reaction mixture is stripped by heating at 205C with nitrogen blowing for 3 hours, and then filtered to yield the filtrate as an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 300 parts of the ashless dispersant product solution formed as in (b), 8 parts of phos-phorous acid, 3.5 parts of tolutriazole, 8 parts of boricacid, and 3.0 parts of water. The mixture is heated at 100C
for two hours until all of the solid materials are dissolved.
A vacuum of 40 mm Hg is gradually drawn on `~e product to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b~.

The procedure of Example A-24 i5 repeated except that the tolutriazole is eliminated from the reaction mixture of (c) .

The procedure of Example A-~4 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional Case EI-6218+ ~ 3 hour at 100C to provide a clear, oil-soluble composition suitable for use as component b).

EXAMPLE A~27 The procedure of Example A-26 is repeated except that the P2Ss is replaced by 7 parts of phosphorus pentoxide ( P205 ) -(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) of maleic anhydride is heatsd to 110C. This mixture is heated to 184C in 6 hours during which 85 parts (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 with nitrogen purged for 26 hours. The residue is predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture of 3225 parts (5.0 equivalents) of the polyisobutene-substituted succinic acylating agent prepared as in ~a), 289 parts (8.5 equivalents) of pentaer~thritol and 5204 parts of mineral oil is heated at 225-235C for 5.~
hours. The reaction mixture is filtered at 130C to yield an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 300 parts of the ashless dispersant product solution formed as in (b), 8 parts of phos-phorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C
for two hours until all of the solid materials are dissolved.
A vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

Case EI-6218+ 2 EXAMP~E A-29 The procedure of Example A-28 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c) .

The procedure of Example A-28 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at lOO C to provide a clear, oil-soluble composition suitable for use as component b~.

The procedure of Example A-30 is repeated except that the P2S5 is replaced by 7 parts of phosphorus pentoxide (P2Os)-(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C. This mixture is heated to 184C in 6 hours during which 85 parts (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 with nitrogen purged for 26 hours. The residue is predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture of 322 parts (0.5 equivalent) of the polyisobutene-substituted succinic acylatin~ agent prepared as in (a), 68 parts (2.0 equivalents) of pentaerythritol and 508 parts of mineral oil is heated at 204-227C for 5 hours. The reaction mixture is cooled to 162C and 5.3 parts (0.13 equi-valent) of a commercial ethylene polyamine mixture having an overall composition approximating that of tetraethylene pen-tamine is added. The reaction mixture is heated at 162-163C

2 ~3 ~
Case EI-6218+

for 1 hour, then cooled to 130C and filtered. The filtrate is an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 350 parts of the ashless dispersant product solution forlned as in (b), 8 parts of phos-5phorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C
for two hours until all of the solid materials are dissolved.
A vacuum of ~0 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 10100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example A-32 is repeated except that 15the tolutriazole is eliminated from the reaction mixture of (c) .

The procedure of Example A-32 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the 20phosphorous acid, the P2S5 is added to the mixture after water distillation, and the mixture is then heated for an additional hour at lO~JC to provide a clear, oil-soluble composition suitable for use as component b).

25The procedure of Example A-34 is repeated except that the P2Ss is replaced by 7 parts of phosphorus pentoxide (P2Os).

(a) A mixture of 510 parts (0.28 mole) of polyiso~
butene (Mn = 1845; Mw = 5325, both as per U. S. Pat. No.
304,234,435) and 59 parts (0.59 mole) of maleic anhydride is heated to 110C. This mixture is heated to l90~C 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 Case EI-6218+

mixture is stripped by heating at 190-193~C with nitrogen blowing for 10 hours. The residue is predominantly polyisobu-tenyl succini~ anhydride acylating agent.
(b) A mixture of 334 parts (0.52 equivalents) of the polyisobutene substituted succinic acylating agent prepared as in (a), 548 parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Poly-glycol 112-2 demulsifier (Dow Chemical Company) is heated at 150~C for 2.5 hours. The reaction mixture is then heated to 210C over a period of 5 hours and then held at 210C for an additional 3.2 hours. The reaction mixture is cooled to l90 C
and 8.5 parts (0.~ equivalent) of a commercial mixture of ethylene polyamines having an overall composition approxima-ting that of tetraethylene pentamine is added. The reaction mixture is stripped by heating at 205C with nitrogen ~lowing for 3 hours, and then filtered to yield the filtrate as an oil solution of the desired ashless dispersant productO
(c) A mixture is formed from 260 parts of the ashless dispersant product solution formed as in (b), 8 parts of phos-phorous acid, 3.5 parts of tolutriazole, 8 parts of boricacid, and 3.0 parts of water. The mixture is heated at 100C
for two hours until all of the solid materials are dissolved.
vacuum of 40 mm Hg l~ gradually drawn on the product to remove the water while the temperature is slowly ra sed to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example A-36 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c) .

The procedure of Example A-36 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2Ss is added to the mixture after water distillation, and the mixture is then heated for an additional 2~
Case EI-6218+

hour at 100C to provide a clear, oil-soluble composition suitable for use as component b).

E~AMPLE A-39 The procedure of Example A-38 is repeated except that the P2Ss is replaced by 7 parts of phosphorus pentoxide ( P20s ) -(a) A mixture of 510 parts (0.28 mole) of polyiso-butene (Mn = 1845; Mw = 5325, both as per U. S. Pat. No.
4,234,435) and 59 parts (0.59 mole) of maleic anhydride is heated to llO~C. 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 predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 10.2 parts (0.25 equivalent) of a commercial mixture of ethylene polyamines having the approximate overall composition of tetraethylene pentamine to 113 par~ of mineral oil and 161 parts (0.25 equivalent) of the substituted succinic acylating agent prepared as in (a) while maintaining the temperature at 138C. The reaction mixture is heated to 150~ over a 2 hour period and stripped by blowing with nitrogen. The reaction mixture i5 filtered to yield the filtrate as an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 125 parts of the poly-isobutenyl succinimide product solution formed as in (b), 8 parts of phosphorous acid, 3.~ parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of 40 mm ~g is gradually drawn on the product to remove the water while the temperature is slowly Case EI-621~+ 2 raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example A-40 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c) .

_XAMPLE A-42 The procedure of Example A-40 is repeated except that 11 parts of phosphorus pentasulfide is used in place of the phosphorous acid, the P2Ss is added to the mixture after water distillation, and the mixture is then heated for an additional hour at 100C to provide a clear, oil-soluble composition suitable for use as component b).

The procedure of Example A-42 is repeated except that the P2Ss is replaced by 7 parts of phosphGrus pentoxide (P205) -To a reactor are charged under a nitrogen .î~mosphere 67.98 parts of a commercially-available polyisobutenyl suc-cinimide of a mixture of polyethylene polyamines ha~ing the approximate overall composition of tetraethylene pentamine (the polyisobutenyl group derived from polyisobutene having a number average molecular weight of about 900; the succinimide product having a ratio of about 1.15 succinic groups per al-kenyl group) and 26.14 parts of a 100 Solvent neutral refined mineral oil. After raising the temperature of the resulting solution to 100-105 C, 2.09 parts of boric acid and 2.09 parts of phosphorous acid are introduced into the reactor, followed by 0.92 part of tolutriazole (Cobratec TT-100; PMC Specialties Group, Cincinnati, Ohio) and then 0.78 part of water. The resultant mixture is heated at 100-105C for two hours and then the temperature is gradually raised to 115C with the Case EI-6218+ ~ a application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 12dC/40 mm Hg has been reached. A
flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mixture is suitable for use as component b) in the compositions of this invention.

E~AMPLE _-45 The procedure of Example A-44 is repeated except that the tolutriazole is omit~ed from the reaction mixture.

~ a~ A mixture of 322 parts of the polyisobutene-substituted succinic acylating agent prepared as in Example A-40(a), 68 parts of pentaerythritol and 508 parts of mineral oil is heated at ~04-227C for 5 hours. The reaction mixture is cooled to 162~C and 5.3 parts of a commercial ethylene polyamine mixture having the apprcximate overall composition corresponding to tetraethylene pentamine is added. The reac-tion mixture is heated at 162-163C for 1 hour, then cooled to 130C and filtered. The filtrate is an oil solution of the desired product.
(b) A mixture is formed from 275 parts of the product --solution formed as in (a), 8 parts of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of ~0 mm Hg is gradually drawn on the product to remove the water while the tempe~ature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedures of Examples A-1 through A-8 are repeated except that in each case a chemically equivalent amount of trimethyl borate is substituted for the boric acid, and the water used with the boric acid is omitted.

Case EI-6218+

The procedures of Examples A-1 through A-5, and A-10 through A-15 are repeated except that in each case the boro-nating agent consists of a chemically equivalent amount of trimethyl borate in lieu of boric acid, the water used with the boric acid is omitted, and the phosphorylating agent consists of a chemically equivalent amount of a mixture consisting of an equimolar mixture of phosphorous acid and dibutyl hydrogen phosphite.

(a) To 120 parts of chlorinated polyisobutylene having a number average molecular weight of about 1,300 and contain-ing about 2.8 weight percent chlorine are added 21.7 parts of pentaethylene hexamine and 5.6 parts of sodium carbonate. The reaction mixture is heated to about 205C and maintained at this temperature for about 5 hours. A stream of nitrogen is passed through the reaction mixture to remove the water of reaction. The reaction mixture is diluted with 60 parts of light mineral oil and hexane, filtered and extracted with methanol to remove excess pentaethylene hexamine. The hexane is stripped from the product by heating the mixture to 120C
un~r a suitable vacuum. The product should have a nitrogen content of approximately l.o to 1.5 weight percent.
(b) A mixture is formed from 80 parts of a diluted reaction product formed as in (a), 20 parts of a 100 Solvent Neutral refined mineral oil diluent, 2.1 parts of phosphorous acid, 4.6 parts of boric acid, and 1.5 parts of water. The resultant mixture is heated at 100-105C for 2 hours and then the temperature is gradually raised to 115C with the applica-tion of a vacuum to 40 mm ~g. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mixture is suitable for use as component b) in the compositions of this invention.
(c) 2 Parts of powdered anhydrous boric acid is added with stirring to 80 parts of a 50 weight percent mineral oil Case EI-6218~

solution of a reaction product formed as in ~a) heated to 90C. The temperature of the mixture is then increased ~o 150C and maintained at this temperature for 4 hours while collecting the water of reaction overhead. The mixture is then filtered and mixed with 10 parts of a 100 Solvent Neutral refined mineral oil diluent, and 1.5 parts of phosphorous acid. The resultant mixture is heated at 100-105C for 2 hours and then the temperature is gradually raised to 115C
with the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mix-ture is suitable for use as component b) in the compositions of this invention.

EX~MPLE A-50 (a) Into a reactor are placed 220 parts of p-nonyl-phenol and 465 parts of diethylenetriamine. The mixture is heated to 80C and 152 parts of 37% formalin is added dropwise over a period of about 30 minutes. The mixture is then heated to 125C for several hours until the evolution of water has ceased. The resultant product should contain approximately 16-20% nitrogen (b) Into a reactor are placed 202 parts of styrene-maleic anhydride resin (having a number average molecular weight in the range of 600-700 and a mole ratio of styrene to maleic anhydride of 1:1), 202~5 parts of octadecyl amine and 472 parts of a 95 VI lubricating oil having a viscosity at 100~ of 150 SUS. The mixture is heated to 225'C for several hours. To this mixture is added dropwise over a period of about 30 minutes, 85 parts ol the product formed as in (a).
The resulting mixture is heated ~or 6 hours at 210-230C while collecting the water formed during reaction. The polymeric product so formed should have a nitrogen content of about 2.1 weight percent.
(c) To a reactor are charged 200 parts of the basic nitrogen polymer produced as in (b) and 50 parts of a 100 Case EI-6218+
2 ~

Solvent Neutral refined mineral oil. After raising the tem-perature of the resulting mixture to 100-105C, 5.7 parts of boric acid, 4.0 parts of phosphorous acid, and 2.0 parts of water are added. The resultant mixture is heated at 100-105C
for two hours and then the temperature is gradually raised to 115C with the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mix-ture is suitable for use as component b) in the compositionsof this invention.

Producing Phosphorylated and Boronated Ashless Dispersants from Water and at least one Water-Hydrolyzable Organic Phosphorus Compound and at least one Boron Compound Typical procedures for producing the phosphorylated and boronated ashless dispersants from (ii) and (iii) above in-volve concurrently cr sequentially heating one or more ashless dispersants of the types described above with (ii) water and at least one water-hydrolyzable organic phosphorus compound and (iii) at least one boron compound under conditions yield-ing a liquid phosphorus- and boron-containing composition.
Examples of organic phosphorus ~ompounds which are useful in forming such products include mono-, di-, and triesters of phosphoric acid (e.g., trihydrocarbyl phosphates, dihydro-carbyl monoacid phosphates, monohydrocarbyl diacid phosphates,and mixtures thereof), mono-, di-, and triesters of phospho-rous acid (e~g., trihydrocarbyl phosphites, dihydrocarbyl hy-drogen phosphites, hydrocarbyl diacid phosphites, and mixtures thereof), esters of phosphonic acids (both "primary", RP(O)(OR)2, and "secondary", R2P(O)(OR)), esters of phosphinic acids, phosphonyl halides (e.g., RP(O)Cl2 and R2P(O)Cl), halophosphites (e.g., (RO)PCl2 and (RO)2PCl), halophosphates (e.g., ROP(O)Cl2 and (RO)2P(O)Cl), tertiary pyrophosphate esters (e.g., (RO)2P(O)-O-P(O)(OR)2), and the total or partial sulfur analogs of any of the foregoing organic phosphorus com-pounds, and the like. Also usable, although less preferred, Case EI-6218+ ~ 3 '10 are the halophosphine halides (e.g., hydrocarbyl phosphorus tetrahalides, dihydrocarbyl phosphorus trihalides, and trihy-drocarbyl phosphorus dihalides), and the halophosphines (mono-halophosphines and dihalophosphines). By "water-hydrolyza-ble" is meant that the organic phosphorus compound when boiledat atmospheric pressure for a period of 5 hours with either (a) distilled water, or (b) water adjusted to at least one pH
between 1 and 7 by use of H2SO4, or (c) water adjusted to at least one pH between 7 and 13 with KOH, is hydrolyzed to the extent of at least 50 mole ~. In some cases, hydrolysis of certain types of organophosphorus compounds results in con-comitant oxidation, and compounds which undergo both hydroly-sis and oxidation under the foregoing conditions are usable in forming the phosphorylated dispersants for use in this inven-tion. Likewise, certain sulfur-containing organophosphorus compounds undergo loss of sulfur under hydrolysis conditions.
Here again, compounds of this type are suitable for use in forming the phosphorylated dispersants used in the practice of this invention. Considerable information exists in the literature concerning hydrolysis of organophosphorus compounds -- see for example Kosolapoff, Orqanophosphorus Compounds, John ~iley & Sons, Inc., 1950 (and pertinent references cited therein), Van Wazer, Phosphorus and its Com-~~unds, Intersci-ence Publishers, Inc., Vol. I: Chemistry, 1958 (and pertinent references cited therein), and Vojvodic, et al, Arch. Belg.
Med. Soc. Hyg. Med. Trav. Med. Leq. ~uP~l~ (Proc.-World Congr. "New Compd. Biol. Chem. Warf.- Tox ~val.", 1st, lg84), pp. 49-52. The preferred water-hydrolyzable organic phospho-rus compounds are the water-hydrolyzahle phosphate esters, and the water-hydrolyzable phosphite esters, especially the dihy-drocarbyl hydrogen phosphites.
Optionally, additional sources of basic nitrogen can be included in the organic phosphorus compound-ashless disper-sant-boron compound-water mixture so as to provide a molar amount (atomic proportion) of basic nitrogen up to that equal to the molar amount of basic nitrogen contributed by the ashless dispersant. Preferred auxiliary nitrogen compounds Case EI-6218+ 2~ 3 - 67 ~

are long chain primary, secondary and tertiary alkyl amines containing from about 12 to 24 carbon atoms, including their hydroxyalkyl and aminoalkyl derivatives. The long chain alkyl group may optionally contain one or more ether groups. Exam-ples of suitable compounds are oleyl amine, N-oleyltrimethy-lene diamine, N-tallow diethanolamine, N,N-dimethyl oleyla-mine, and myristyloxapropyl amine.
Other materials normally used in lubricant additives which do not interfere with the process may also be added, for example, a benzotriazole, including lower (C~-C4) alkyl-substi-tuted benzotriazoles, which function to protect copper surfaces.
The concurrent heating step or the combination of sequential heating steps is conducted at temperatures suf-ficient to produce a final liquid composition which contains both phosphorus and boron. The heating can be carried out in the absence of a solvent by heating a mixture of the ashless dispersant, water and one or more suitable organic phosphorus compounds, or one or more suitable boron compounds, or, pre-ferably, a combination of water, one or more suitable organic phosphorus compounds and one or more suitable boron compound;.
The temperatures used will vary somewhat depending upon t;he nature of the ashless dispersant and the organic phosphc~ s and/or boron reagent being utilized. Generally speaking how-ever, the temperature will usually fall within the range of about 40 to about 200C. The duration of the heating is like-wise susceptible to variation, but ordinarily will fall in the range of about 1 to about 3 hours. ~hen conducting the heat-ing in bulk, it is important to thoroughly agitate the compo-nents to insure intimate contact therebetween. When utilizing the preferred boron reagent (boric acid) in a boronation con-ducted separately from the phosphorylation, it is preferable to add water with the boric acid to facilitate initial disso-lution of the boric acid.
Various methods can be used for removing water from component b) during or after its formation. The preferred method involves applying a sultable vacuum to the reaction Case EI-6218+

system while heating the water-containing mixture to a suita-bly elevated temperature. In this way the water is readily stripped off. When conducting the phosphorylation (separately or concurxently with boronation) using a phosphorus ester made from a lower alcohol such as methanol, ethanol, propanol, 2-propanol, butanol, isobutyl alcohol, etc., both lower alcohol liberated in the process and water can be stripped off from the product mixture during or on completion of the heating operation. For example, water and relatively volatile alco-hols formed in the hydrolysis process and the added water arepreferably removed from the heated mixture by vacuum distilla-tion at temperatures of from about 100 to about 140C. Pre-ferably the heating step or steps will be conducted in a dilu-ent oil or other inert liquid medium such as light mineral oils, and the like.
The amount of phosphorus compound employed in the heating process ranges from about 0.001 mole to 0.999 mole per mole of basic nitrogen and free hydroxyl in the mixture being heated, up to one half of which may be contributed by an aux-iliary nitrogen compound. The amount of boron compound em-ployed ranges from about 0.001 mole to about 1 mole per mole of basic nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount of inorganic phosphorus compound.
When conducting the phosphorylation and boronation on a se-quential basis (or when conducting one of these operations ona dispersant which has previously been subjected to the other such operation), the last-to-be-used reagent(s) -- water and organic phosphorus compound(s) or boron compound(s~, as the case may be -- can be used in an amount equivalent to (or even in excess of) the amount of basic nitrogen a~d/or hydroxyl groups in the dispersant being heated with such last-to-be-used reagent(s).
As noted above, insofar as the phosphorylation is concerned, it is preferable to heat the ashless dispersant with one or more water-hydroly2able organic phosphorus com-pounds in the presence of water. In this case the water can be added before and/or during the heating step, and before, Case EI-6218+ ~ ~3 after, or at the same time one or more phosphorus compounds are introduced into the vessel in which the heating is taking place or is to take place. It is also possible to heat the ashless dispersant with the organic phosphorus compound and then subsequently heat the resultant composition with water, although this procedure is less preferred.
The amount of added water is not particularly critical as long as a sufficient amount is present to effect hydrolysis of the water-hydrolyzable organic phosphorus compound. Water present in the system can be removed by distillation (prefera-bly at reduced pressure) during the course of, and preferably is removed at the end of, the heating step. Amounts of water up to 15% by weight of the mixture being heated are preferred, and amounts of water of up to 5% by weight are particularly preferred. When used, the amount of diluent usually ranges from about 10 to about 50% by weight of the mixture being subjected to heating.
The hydrolysis of the water-hydrolyzable organic phos-phorus compound(s) employed in the phosphorylation operation can be effected in any of a variety of ways. For example, the dispersant to be phosphorylated, one or more water-hydrolyza-ble organic phosphorus compounds, and water may be mixed toge-ther andi ~eated either in an open system at atmospheric pres-sure or in a closed system at superatmospheric pressure. If conducted with an open system, the temperature may be kept below the boiling point of water and the mixture subjected to stirring of sufficient intensity to cause and maintain inti-mate contact among the components within the hydrolysis reac-tion mixture. It is also feasible to raise the temperature of the mixture in an open system to the boiling point of water and allow the water vapor either to escape from the system or to be condensed in a suitable condensing system and returned to the refluxing hydrolysis reaction mixture. If the water is allowed to escape, sufficiently large amounts of water should be used to insure that a substantial amount of hydrolysis occurs before the supply of water in the hydrolysis mixture has been depleted. In all such cases, water can be fed to the Case EI-6218+ ~ 9 system as an initial complete charge or it can be fed inter-mittently or continuously into the hydrolysis mixture.
When conducting the hydrolysis in a closed system, the system may be kept at one or more selected autogenous pres-sures by suitable adjustment and regulation of the tempera-ture. And, still higher pressures may be imposed upon the system, as for example by injecting high pressure steam into a sealed autoclave containing the hydrolysis reaction mixture.
The water itself may be charged to the system in any suitable form, such as in the form of liquid water, steam, or even ice. Similarly, the water may be introduced in the form of hydrated solids so that the water is released by the appli-cation of heat during the course o~ the hydrolysis operation.
Injection of wet steam into a well-agitated hydrolysis system is one preferred way of conducting the operation.
The hydrolysis operation should be conducted under any given set or sequence of hydrolysis conditions for a period of time long enough that at least 10%, preferably at least 50%, and most preferably at least 75%, of the organic phosphorus compound(s) present in the hydrolysis mixture have been hydro-lyzed. The nature of the hydrolysis products can be expected to vary in relation to the type of phosphorus compound(s) used and the severity of th~;lydrolysis conditions imposed upon the hydrolysis system. Thus inorganic and organic hydrolysis pro-ducts can be formed in the system, and these in turn can beexpected to be taken up by the ashless dispersant~s) present in the system substantially as they are formed. Accordingly, although the chemical structure(s) of the phosphorylated dis-persant(s) are not known with absolute certainty, it is rea-sonable to conclude that at least some interaction occurs be-tween the dispersant(s) and organic and/or inorganic phospho-rus-containing species formed in the hydrolysis reactions taking place in the system. It is also conceivable that such interacted components may undergo displacements and/or other forms of interactions with components present in the hydroly-sis system as the hydrolysis operation proceeds.

Case EI-6218+ 2 ~ 3 As pointed out above, the phosphorylation may be con-ducted apart from the boronation, or it may be conducted con-currently with the boronation. When performing the phosphory-lation and boronation operations concurrently, any of the fore~oing hydrolysis procedures can be utilized, the principal difference being that one or more boron compounds are used in combination with one or more water-hydrolyzable organic phos-phorus compounds.
If desired, small amounts of one or more acids (e.g., sulfuric acid, phosphoric acid, phosphorous acid, etc.) or bases (e.g., NaOH, XOH, ammonium hydroxide, etc.) may be added to the hydrolysis mixture to facilitate hydrolysis of the or-ganic phosphorus compound(s) being used.
When forming component b) in part by use of one or more inorganic phosphorus compounds such as phosphorous acid (H3PO3, sometimes depicted as H2(HPO3), and sometimes called ortho-phosphorous acid or phosphonic acid), phosphoric acid (H3PO4, sometimes called orthophosphoric acid), hypophosphorous acid (H3POz~ sometimes called phosphinic acid), hypophosphoric acid (H4P206), metaphosphoric acid (HPO3j, pyrophosphoric acid (H4P207), pyrophosphorous acid (H4P20s, sometimes called pyro-phosphonic acid), phosphinous acid (H3PO), tripolyphosphoric acid (HsP301o), tetrapolyphosphoric a ~ 6P40l3), trimetaphos-phoric acid (H3P309), phosphorus trioxide, phosphorus tetra-oxide, phosphorus pentoxide, and/or partial or total sulfur analogs of the foregoing such as phosphorotetrathioic acid (H3PS43, phosphoromonothioic acid (H3PO3S), phosphorodithioic acid (H3PO2S2), phosphorotrithioic acid (X3POS3), phosphorus sesquisul~ide, phosphorus heptasulfide, and phosphorus penta sulfide (P2Ss, sometimes referred to as P4S10), or the like, and in part by use of one or more water-hydrolyzable organic phos-phorus compounds, the latter should be used in an amount suf-ficient to provide at least 10% (preferably at least 50% and more preferably at least 75%) of the total phosphorus content of the phosphorylated and boronated dispersant. For crankcase lubricant usage, component b) when in the undiluted state pre-ferably contains at least 3000 ppm (more preferably at least Case EI-6218+ 2 5000 ppm and most preferably at least 7000 ppm) of phosphorus and at least 1500 ppm (more preferably at least 2500 ppm and most preferably at least 3500 ppm) of boron.
The preparation of phosphorylated and boronated ashless dispersants suitable for use as component b) in the composi tions of this invention from (ii) and (iii) above is illustra-ted by the following examples in which all parts and percen-tages are by weight unless otherwise clearly specified.

XAMPLE B-l A mixture is formed from 260 parts of a commercial succinimide ashless dispersant (HiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.), 100 parts of a 100 Solvent Neutral refined mineral oil dilu-ent, 26 parts of dibutyl hydrogen phosphite, 3.5 parts of tolutriazole, 10 parts of boric acid, and 8 parts of water.
The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradu-ally drawn on the product to remove the water and butanol while the temperature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example B-l is repeated except that the succinimide ashless dispersant used is derive~ from poly-butene having a number average molecular weight of 1,100. Theaverage number of succinic groups per alkenyl group in the succinimide is approximately 1.2.

The procedure of Example B-l is repaated except that the succinimide ashless dispersant used is derived from poly-butene having a number average molecular weight of 2,100.

Case EI-6218+ 2 The procedure of Example B-1 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a Mannich polyamine dispersant (~MOC0~ 9250 disper-sant; Amoco Corporation). The Amoco 9250 dispersant as sup-plied by the manufacturer is believed to be a boronated dis-persant and in such case, another material suitable for use as component b) can be formed by elimina-ting the boric acid from the procedure used in this example and thereby conducting phosphorylation on an already boronated dispersant.

The procedure of Example B-1 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a commercial ashless dispersant of tha pentaery-thritol succinic ester type (Lubrizol~ 936 dispersant; TheLubrizol Corporation). As in the case of Example B-~, the initial dispersant as supplied by the manufacturer is believed to be a boronated dispersant. In such cases, the dispersant can, if desired, be subjected just to phosphorylation to thereby form still another product suitable for use as com-ponent b).

The procedure of Example B-l is repeated exGept that 16 parts of trimethyl phosphite is used in place of the dibutyl hydrogen phosphite, to provide a clear, oil-soluble composition suitable for use as component b).

The procedure of Example B-l is repeated except that the dibutyl hydrogen phosphite is replaced by 16.3 parts of 0-ethyl-0,0-1,2-ethanediyl phosphite.

` ~ase EI-6218~ 2 ~ ~ ~

The procedures of Examples B-l through B-7 are repeated except that the tolutriazole i5 omitted from the initial mix-tures subjected to the thermal processes.

A mixture of 12,000 parts of a commercial boronated succinimide (HiTEC~ 648 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.), 90 parts of water, and 584 parts of triphenylmethane phosphonyl dichloride is heated to 100-110C for 6 hours while sweeping the reaction mixture with nitrogen. A vacuum of 40 mm Hg is then gradually applied to remove water and thereby form a homogeneous liquid composi-tion suitable for use as component b) in the practice of this invention. For convenience in handling, 100 Solvent Neutral mineral oil can be added to form an 80% solution of the addi-tive in the oil.

EXA~PLE B-10 A mixture of 260 parts of a commercial succinimide (HiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.), 3 parts of water, 13 parts of tri-bu~l phosphate, and 4 parts of phosphorous acid is heated to lOO~C for 2 hours. To this product is added 8 parts of ortho-boric acid and 4 parts of ~ater, and the resultant mixture is heated at 100C for another 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110C. The resultant homogeneous liquid composition is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial succinimide (HiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.), 8 parts of orthoboric acid and 4 parts of water is heated to 100C for 2 hours. Then 16 parts of diethyl hydrogen phosphite and 6 parts of aqueous ammonium Case EI-6218+

hydroxide ~3N~ are added to the reaction mixture and the tem-perature of the mixture is held at 100C for another 2 hours.
A vacuum of 40 mm of Hg is applied to the system and the tem-perature is gradually raised to 110C. The resultant homoge-neous liquid composition is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial succinic penta-erythritol ester ashless dispersant (Lubrizol0 936 dispersant;
The Lubrizol Corporation), 6 parts of water, and 16 parts of methyl dichlorophosphate is heated to 100C for 2 hours. To this product are added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100C for another 2 hours. The mixture is then swept with nitrogen for one hour at 100C. A vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110C. The resultant homogeneous li~uid composition is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial succinic penta-erythritol ester af:lless dispersant (Lubrizol~ 936 dispersant;
The Lubrizol Corporation), 8 parts of orthoboric acid and 6 parts of water is heated to 100C for 2 hours. Then 19 parts of methyl bis(phenyl) phosphate, 5 parts of phosphoric acid, and 0.4 part of additional water are added to the reaction mixture and the temperature of the mixture is held at 100C
for another 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is ~radually raised to 130C.
The resultant homogeneous liquid composition is suitable for use as component b) in the practice of this invention.

A mixture of 260 parts of a commercial Mannich poly-amine dispersant (AMOC00 9250 dispersant; Amoco Corporation), 8 parts of water, and 35 parts of dibenzyl methyl phosphate is Case EI-6218+

heated to 100C for 2 hours. To this product is added 8 parts of orthoboric acid and 4 parts of water, and the resultant mixture is heated at 100C for another 2 hours. A vacuum of ~0 mm of Hg is applied to the system and the temperature is gradually raised to 130C. The resultant homogeneous liquid composition is suitable for use as component b) in the prac-tice of this invention.

A mixture of 260 parts of a commercial Mannich poly-amine dispersant (AMOC0~ 9250 dispersant; Amoco Corporation), parts of orthoboric acid and 4 parts of water is heated to 100C for 2 hours. Then 9 parts of monophenyl phosphate, 4 parts of phosphorous acid, and an additional 3 parts of water are added to the reaction mixture and the temperature of the mixture is held at 100C for another 2 hours. A vacuum of 40 mm of Hg is applied to the system and the temperature is gra-dually raised to 130C. The resultant homogeneous liquid com-position is suitable for use as component b) in the practice of this invention.

(a) A mixture of l,OC0 parts (0.495 mole~ of poly-isobutene ~Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C. This mixture is heated to 184C in 6 hours during which 85 parts (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 with nitrogen purged for 26 hours. The residue i5 predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 57 parts (1.38 equivalents) of a commercial mixture of ethylene polya-mines having the approximate overall composition of tetraethy-lene pentamine to 1,067 parts of mineral oil and 893 parts (1.38 equivalents) of substituted succinic acylating agent Case EI-6218-~
- 77 - 2~

prepared as in (a) while maintaining the temperature at 140-145C. The reaction mixture is then heated to 155C over a three hour period and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product composed predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyiso-butenyl succinimide product solution formed as in (b), 11 parts of dibutyl chlorophosphate, 5 parts of phosphoric acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is heated at 100C for four hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the tempera~ure is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suit-able for use as component b).

The procedure of Example B-16 is repeated except that the tolutriazole is eliminated from the reacl:ion mixture of (c).

The procedure of Example B-16 is repeated except that 9 parts of an equimolar mixture of dibutyl hydrogen phosphite and monobutyl dihydrogen phosphite is used in place o~ the dibutyl chlorophosphate to provide a clear, oil-soluble compo-sition suitable for use as component b).

The procedure of Example B-16 is repeated except that the dibutyl chlorophosphate is replaced by 11 parts of mono-2-naphthyl orthophosphate.

Case EI-6218~

(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
~,234,435) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C. This mixture is heated to 184C in 6 hours during which 85 parts (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 with nitrogen purged for 26 hours. The residue is predominantly polyisobutenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 18.2 parts (0.433 equivalents) of a commercial mixture of ethylene polyamines having the approximate overall composition of tetraethylene pentamine to 392 parts of mineral oil and 348 parts (0.52 equivalent) of substituted succinic acylating agent prepared as in (a) while maintaining the temperature at 140C. The reaction mixture is then heated to 150C in 1.8 hours and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired product composed predominantly of polyisobu-tenyl succinimides.
(c) A mixture is formed from 250 parts of the ~oly-isobutenyl succinimide product solution formed as in (b), 18 parts of phenyl dimethyl phosphate, 3.5 parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is heated at 100C for three hours. A vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 130C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example B-20 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).

Case EI-6218+ 2 ~ ~ ~ 3 ~ ~

EX~MPLE B-22 The procedure of Example B-20 is repeated except that 15 parts of trimethyl phosphite is used in place of the phenyl dimethyl phosphate to provide a clear, oil-soluble composition suitable for use as component b).

The procedure of Example B-20 is repeated except that the phenyl dimethyl phosphate is replaced by 36 parts of 4-di-methyl-aminophenyl phosphorus tetrachloride and the heated mixture in (c) is swept with nitrogen duriny the three-hour period.

(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; MW = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) of maleic anhydride is heated to 110C. This mixture is heated to 184 C in 6 hours during which 85 parts (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 with nitrogen purged for 26 hours. The residue is predominantl~ polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture of 334 parts (0. 52 e~uivalents) of the polyisobutene substituted succinic acylating agent prepared as in (a), 548 parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0. 0057 equivalent) of Poly-glycol 112-2 demulsifier (Dow Chemical Company) is heated at 150C for 2.5 hours. The reaction mixture is then heated to 210C over a period of 5 hours and then held at 210C for an additional 3.2 hours. The reaction mixture is cooled to 190C
and 8.5 parts (0. 2 e~uivalent) of a commercial mixture of ethylene polyamines having an overall composition approxima-ting that of tetraethylene pentamine is added. The reaction mixture is stripped by heating at 205C with nitrogen blowing Case EI-6218+ 2 for 3 hours, and then filtered to yield the filtrate as an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 300 parts of the ashless dispersant product solution formed as in (b), 37 parts of bis-(2-ethylhexyl) hydrogen phosphite, 3.5 parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 130C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example B-24 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).

The procedure of Example B-24 is repeated except that 26 parts of dibutyl hydrogen phosphite is used in place of the bis(2-ethylhexyl) hydrogen phosphite to provide a clear, oil-soluble composition suitable for use as component b).

The procedure of Example B-24 is repeated except that the bis(2-ethylhexyl) hydrogen phosphite is replaced by 15 parts of trimethyl phosphite.

(a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw = 6049, both as per U. S. Pat. No.
4,234,435) and 115 parts (1.17 moles) o~ maleic anhydride is heated to 110C. This mixture is heated to 184C in 6 hours during which 85 parts (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 ~ith nitrogen Case EI-6218+ 2 purged for 26 hours. The residue is predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture of 3225 parts (5.0 equivalents) of the polyisobutene-substituted succinic acylating agent prepared as in (a), 289 parts (8.5 equivalents) of pentaerythritol and 5204 parts of mineral oil is heated at 225-235C for 5.5 hours. The reaction mixture is filtered at 130C to yield an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 300 parts of the ashless dispersant product solution formed as in (b), 27 parts of di-butyl chlorophosphate, 3.5 parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dis-solved. A vacuum of 40 mm Hg is gradually drawn on the pro-duct to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example B-28 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c) .

The procedure of Example B-28 is repeated except that 8 parts of ethyl dichlorophosphate and 4 parts of phosphorous acid are used in place of the dibutyl chlorophosphate to pro-Yide a clear, oil-soluble composition suitable for use as com-ponent b).

The procedure of Example B-28 is repeated except that the dibutyl chlorophosphate is replaced by 10 parts of dibutyl hydrogen phosphite and 5 parts of phosphoric acid.

~~ Case EI-6218~ 2 EXA~PLE B-32 (a) A mixture of 1,000 parts (0.495 mole) of poly-isobutene (Mn = 2020; Mw - 6049, both as per U. S. Pat. No.
4,234,~35) and 115 parts (1.17 moles) of maleic anhydride is 5heated to 110C. This mixture is heated to 184C in ~ hours during which 85 parts (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 with nitrogen 10purged for 26 hours. The residue is predominantly polyisobu-tenyl succinic anhydride acylating agent.
(b) A mixture of 322 parts (0.5 equivalent) of the polyisobutene-substituted succinic acylating agent prepared as in (a), 58 parts (2.0 equivalents) of pentaerythri'ol and 508 15parts of mineral oil is heated at 204-227C for 5 hours. The reaction mixture is cooled to 162C and 5.3 parts (0.13 equi-valent) of a commercial ethylene polyamine mixture having an overall composition approximating that of tetraethylene pen-tamine is added. The reaction mixture is heated at 162-163C
20for 1 hour, then cooled to 130C and filtered. The filtrate is an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 350 parts of the ashless dispersant pr~duct solution formed as in (b), 16 parts of di-ethyl hydrogen phosphite, 3.5 parts of tolutriazole, 8 parts 25of boric acid, and 6 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dis-solved. A vacuum of 40 mm Hg is gradually drawn on the pro-duct to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained 30which is soluble in oil and suitable for use as component b).

The procedure of Example B-32 is repeated except that the tolutriazole is eliminated from the reaction mixture of 35(c).

Case EI-6218+

EXAMPLE B-3~
The procedure of Example B-32 is repeated except that 20 parts of diethyl chlorophosphate is used in place of the diethyl hydrogen phosphite to provide a clear, oil-solu~le composition suitable for use as component b).

The procedure of Example B-32 is repeated except that the diethyl hydrogen phosphite is replaced by 12 parts of eth-yl dibutyl phosphate and 4 parts of phosphorous acid.

lo EXAMPLE B-36 (a) A mixture of 510 parts (0.28 mole) of poly-isobutene (Mn = 1845; Mw = 5325, both as per U. S. Pat. No.
4,23~,435) and 59 parts (0.59 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 predominantly polyisobu-tenyl succinic anhydride acy]ating agent.
(b) A mixture o~ 33~ parts (0.52 equivalents) of thepolyisobutene substituted succinic acylating agent prepared as in (a), 54~ parts of mineral oil, 30 parts (0.88 equivalent) of pentaerythritol and 8.6 parts ~0.0057 equivalent) of Poly-glycol 112-2 demulsifier (Dow Chemical Company) is heated at 150C for 2.5 hours. The reaction mixture is then heated to 210C over a period of 5 hours and then held at 210C for an additional 3.2 hours. The reaction mixture is cooled to 190C
and 8.5 parts (0.2 equivalent) of a commercial mixture of eth-ylene polyamines having an overall composition approximatingthat of tetraethylene pentamine is added. The reaction mix-ture is stripped by heating at 205C with nitrogen blowing for 3 hours, and then filtered to yield the filtrate as an oil so-lution of the desired ashless dispersant product.

Case EI-6218+ 2 (c) A mixture is formed from 260 parts of the ashless dispersant product solution formed as in (b), 20 parts of eth-yl dichloro phosphate, 3.5 parts of tolutriazole, 8 parts oE
boric acid, and 8 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dis-solved. A vacuum of 40 mm Hg is gradually drawn on the pro-duct to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedure of Example B-36 is repeated except that the tolutria~ole is eliminated from the reaction mixture of (c) .

The procedure of Example B-36 is repeated except that 23 parts of butyl dichloro phosphate is used in place of the ethyl dichloro phosphate to provide a clear, oil-soluble com-position suitable for use as component b).

The procedure of Example ~-36 is r~peated except that the ethyl dichloro phosphate is replaced by 30 parts of mono-butyl-mono-2-ethylhexyl hydrogen phosphite.

(a) A mixture of 510 parts (0.28 mole) of poly-isobutene (Mn = 1845; Mw = 5325, both as per U. S. Pat. No.
4,234,435) and 59 parts (0.59 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 predominantly polyisobu-tenyl succinic anhydride acylating agent.

Case EI-6218+

~ 85 -(b) A mixture is prepared by the addition of 10.2parts (0.25 equivalent) of a commercial mixture of ethylene polyamines having the approximate overall composition of te-traethylene pentamine to 113 parts of mineral oil and 161 parts (0.25 equivalent) of the substituted succinic acylating agent prepared as in (a) while maintaining the temperature at 138C. The reaction mixture is heated to 150C over a 2 hour period and stripped by blowing with nitrogen. The reaction mixture is filtered to yield the filtrate as an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 125 parts of the poly-isobutenyl succinimide product solution formed as in (b), 9 parts of monobenzyl phosphate and 4 parts of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 6 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacuum of ~0 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 100C. A clear solution or composition is obtained which is soluble in oil and suit-able for use as component b).

The procedure of Example B-40 is repeated except that the tolutriazole is eliminated from the reaction mixture of (c).

The procedure of Example B-40 is repeated except that 14 parts of dibenzyl phosphate is used in place of the mono-benzyl phosphate to provide a clear, oil-soluble composition suitable for use as component b).

The procedure of Example B-40 is repeated except that the monobenzyl phosphate is replaced by 17 parts of monophenyl dibenzyl phosphate.

Case EI-6218+

To a reactor are charged under a nitrogen atmosphere 67.98 parts of a commercially-available polyisobutenyl suc-cinimide of a mixture of polyethylene polyamines having the approximate overall composition of tetraethylene pentamine (the polyisobutenyl group derived from polyisobutene having a number average molecular weight of about 900; the succinimide product having a ratio of about 1.15 succinic groups per al-ken~l group) and 26.14 parts of a 100 Solvent neutral refined mineral oil. After raising the temperature of the resulting solution to 100-105C, 2.09 parts of boric acid and 4.6 parts of dibutyl hydrogen phosphite are introduced into the reactor, followed by 0.92 part of tolutriazole tCobratec TT-100; PMC
Specialties Group, Cincinnati, Ohio~ and then 3 parts of water. The resultant mixture is heated at 100-105C ~or two hours and then the temperature is gradually raised to 115C
with the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mix-ture is suitable for use as component b) in the compositions of this invention.
.

The procedure of Example B-44 is repeated exc~pt that the tolutriazole is omitted from the reaction mixture.

(a) A mixture of 322 parts of the polyisobutene-sub-stituted succinic acylating agent made as in ~xample B-40(a), 68 parts of pentaerythritol and 508 parts of mineral oil is heated at 204-227C for 5 hours. The reaction mixture is cooled to 162C and 5.3 parts of a commercial ethylene pol~-amine mixture having the approximate overall composition cor-responding to tetraethylene pentamine is added. The reaction mixture is heated at 162-163C for 1 hour, then cooled to Case EI-6218+ 2 - 87 ~

130C and filtered. The filtrate is an oil solution of the desired product.
(b) A mixture is formed from 275 parts of the product solution formed as in (a), 20 parts of diisopropyl hydrogen phosphite, 3.5 parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is heated at 100C for two hours until all of the solid materials are dissolved. A vacu-um of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 100C. A
clear solution or composition is obtained which is soluble in oil and suitable for use as component b).

The procedures of Examples B-l through B-8 are repeated except that in each case a chemically equivalent amount of trimethyl borate is substituted for the boric acid.

The procedures of Examples B-1 through B-5, and B-10 through B-15 are repeated except that in each case the boro-nating agent consists of a chemically equivalent amount oftrimethyl borate in lieu of boric acid, and the phosphoryla-ting ~gent consists of a chemically equivalent amount of a mixture consisting of an equimolar mixture of phosphorous acid and dibutyl hydrogen phosphite.

(a) To 120 parts of chlorinated polyisobutylene having a number average molecular weight of about 1,300 and contain-ing about 2.8 weight percent chlorine are added 21.7 parts of pentaethylene hexamine and 5.6 parts of sodium carbonate. The reaction mixture is heated to about 205C and maintained at this temperature for about 5 hours. A stream of nitrogen is passed through the reaction mixture to remove the water of reaction. The reaction mixture is diluted with 60 parts of light mineral oil and hexane~ filtered and extracted with methanol to remove excess pentaethylene hexamine. The hexane Case EI-6218+

is stripped from the product by heating the mixture to 120C
under a suitable vacuum. The product should have a nitrogen content of approximately 1.0 to 1.5 weight percent.
tb) A mixture is formed from 80 parts of a diluted reaction product formed as in (a), 20 parts of a 100 Solvent Neutral refined mineral oil diluent, 5.0 parts of dibutyl hy-drogen phosphite, 4.6 parts of boric acid, and 3.0 parts of water. The resultant mixture is heated at 100-105C for 2 hours and then the temperature is gradually raised to 115C
with the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mix-ture is suitable for use as component b) in the compositions of this invention.
(c) 2 Parts of powdered anhydrous boric acid is added with stirring to 80 parts of a 50 weight percent mineral oil solution of a reaction product formed as in (a) heated to 90C. The temperature of the mixture is then increased to 150C and maintained at this temperature for 4 hours while collecting the water of reaction overhead. The mixture is then filtered and mixed with 10 parts of a 100 Solvent Neutral refined mineral o i diluent, 3.6 parts of dibutyl hydrogen phosphite and 3.0 parts of water. The resultant mixture is heated at 100-105C for 2 hours and then the temperature is ~radually raised to 115C with the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mixture is suitable for use as component b) in the compositions of this invention.

(a) Into a reactor are placed 220 parts of p-nonyl-phenol and 465 parts of diethylenetriamine. The mixture is heated to 80C and 152 parts of 37% formalin is added dropwise over a period of about 30 minutes. The mixture is t.hen heated Case EI-6218+ ~ 3 ~ 3 to 125C for several hours until the evolution of water has ceased. The resultant product should contain approximately 16-20% nitrogen.
(b) Into a reactor are placed 202 parts of styrene-maleic anhydride resin (having a number average molecular weight in the range of 600-700 and a mole ratio of styrene to maleic anhydride of 1:1), 202.5 parts of octadecyl amine and 472 parts of a 95 VI lubricating oil having a viscosity at 100F of 150 SUS. The mixture is heated to 225DC for several hours. To this mixture is added dropwise over a period of about 30 minutes, 85 parts of the product formed as in (a).
The resulting mixture is heated for 6 hours at 210-230C ~hile collecting the water formed during reaction. The polymeric product so formed should have a nitrogen content of about 2.1 weight percent.
(c) To a reactor are charged 250 parts of the basic nitrogen polymer produced as in (b) and 50 parts of a 100 Sol-vent Neutral refined mineral oil. After raising the tempera-ture of the resulting mixture to 100-105C, 5.7 parts of boric acid, 35 parts of dibutyl hydrogen phosphite, and 8 parts of water are added. The resultant mixture is heated at 100-105C
for two hours and then the temperature is gradually raised to 115C with the application of a ~ cuum to 40 mm Hg. Stripping is continued for 90 minutes and until 120C/40 mm Hg has been reached. A flow of dry nitrogen is then applied to the system and the product mixture is allowed to cool. The product mix-ture is suitable for use as component b) in the compositions of this invention.

The procedure of Example B-32 is repeated except that the dibutyl hydrogen phosphite is replaced by 10 parts of di-methyl hydrogen phosphite.

Case EI-6218+

The procedure of Example B-32 is repeated except that the diethyl hydrogen phosphite is replaced by 5 parts of di-methyl hydrogen phosphite and 4 parts of phosphorous acid.

A particularly preferred embodiment of this invention involves using as component b) a phosphorylated and boronated alkenyl succinimide of a polyethylene polyamine or mixture of polyethylene polyamines, wherein the succinimide is formed from (i) an alkenyl succinic acylating agent having a succination xatio (i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acylating agent) in the range of 1 to about 1.3, the alkenyl group being derived from a polyolefin (most preferably a polyisobutene) having a number average molecular weight in the range of about 600 to about 1,300 (more preferably in the range of 700 to 1,250 and most preferably in the range of 800 to 1,200).
Unless otherwise expressly indicated, the following procedures are used to determine the succination ratio of the alkenyl succinic acylating agents utilized in forming such particularly preferred phosphorylated and boronated ashless dispersants:
A. The number average molecular weight (Mn) of the polyalkene from which the substituent is derived is determined by use of either of two methods, namely, vapor pressure osmo-metry (VPOj or gel permeation chromatography (GPC). The VPo determination should be conducted in accordance with ASTM
D2503-82 using high purity toluene as the measuring solvent.
Alternatively, a GPC procedure can ~e employed. As is well known, the GPC technique involves separating molecules according to their size in solution. For this purpose liquid chromatographic columns are packed with a styrene-divinyl benzene copolymer of controlled particle and pore sizes. When the polyalkene molecules from which the substituent is derived are transported through the GPC columns by a solvent (tetrahy-drofuran), the polyalkene molecules small enough to penetrate Case EI-62~8-~ 2 ~

into the pores of the column packing are retarded in their progress through the columns. On the other hand, the poly-alkene molecules which are larger either penetrate the pores only slighly or are totally excluded from the pores. As a conse~uence, these larger polyalkene molecules are retarded in their progress through the columns to a lesser extent. Thus a velocity separation occurs according to the size of the respective polyalkene molecules. In order to define the re-lationship between polyalkene molecular weight and elution time, the GPC system to be used is calibrated using known molecular weight polyalkene standards and an internal standard method. Details concerning such GPC procedures and methods for column calibration are extensively reported in the litera-ture. See for example, W. W. Yau, J. J. Kirkland, and D. D.
Bly, Modern Size-Exclusion Liquid Chromatography, John Wiley & Sons, 1979, Chapter 9 (pages 285-341), and references cited therein.
In general, the Mn determined by the VPO and ~PC
methods should agree within the precision of the respective methods.
B. The total weight of the substituent groups present in the substituted succinic acylating agent is determined by conventional methods for determination of the number of car~,o-nyl functions. The preferred procedure for use involves non-aqueous titration of the substituted acylating agent with standardized sodium isopropoxide. In this procedure the titration is conducted in a 1:1 mineral spirits:1-butanol solvent system. An alternative, albeit less preferred, pro-cedure is the ~STM D-94 procedure.
The results from procedures A and B above are used in calculating the weight of substituent groups per unit weight of total sample.
C. In determining the succination ratio of the alkenyl succinic acylating agents used in forming the particularly preferred phosphorylated and boronated ashless dispersants employed as component b) pursuant to this invention, the determination is to be based on the active portion of the Case EI-6218+ ~ ~ ~ 6 3 ~ ~

sample. That is to say, alkenyl succinic acylating ayents are often produced as a mixture with an inactive diluent. Thus for the purpose of succination ratio determination, such dilu-ent should not be considered a part of the succinic acylating agent, and accordingly a separation as between the diluent and the alkenyl succinic acylating agent should be accomplished.
Such separation can be effected before determination of total weight of the subtituent groups present in the substituted succinic acylating agent. However, it is preferable to effect such separation after such determination usiny a mathematical correction of the result. The separation itself can be achieved using a silica gel column separation technique. A
low molecular weight non-polar hydrocarbon solvent, such as hexane and more preferably pentane, is used as the solvent whereby the unreactive diluent is readily eluted from the co-lumn. The substituted succinic acylating agent entrained in the column can then be recovered by use of a more polar elu-tion solvent, preferably methanol/methylene dichloride.

Component c) The metal-containing detergents which preferably are employed in conjunction with components a) and b) of the com-positions of this invention are exemplified by oil-soluble basic salts of alkali or alkaline earth metals with one or more of the following acidic substances (or mixtures thereof):
(1) sulfonic acids, (2) carboxylic acids, (3) salicylic acids, (4) alkylphenols, (5) sulfurized alkylphenols, (6) organic phosphorus acids characterized by at least one direct car-bon-to-phosphorus linkage. Such organic phosphorus acids include those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phos-phorus heptasulfide, phosphorus pentasulfide, phosphorus tri-chloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium. The salts for use as com-Case EI-6218+ 2 ~ ~ ~ 3 ~ ~

ponent c) should be basic salts having a TBN of at least 50, preferably above 100, and most preferably above 200.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involve heating a mine-ral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature of about 50C, and filtering the resulting mass. The use of a "pro-moter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of com-pounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized al-kylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, oc-tyl alcohol, Cellosolve alcohol, Carbitol alcohol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and ~t least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60O-200C.
Examples of suitable metal-containing detergents in-clude, but are not limited to, the basic or overbased salts of such substances as lithium phenates, sodium phenates, potas-sium phenates, calcium phenates, magnesium phenates, sulfur-ized lithium phenates, sulfurized sodium phenates, sulfurized potassium phenates, sulfurized calcium phenates, and sulfur-ized ma~nesium phenates wherein each aromatic group has one or more aliphatic groups to impart hydrocarbon solubility; lith-ium sulfonates, sodium sulfonates, potassium sulfonates, cal-cium sulfonates, and magnesium sulfonates wherein each sul-fonic acid moiety is attached to an aromatic nucleus which in turn usually contains one or more aliphatic substituents to impart hydrocarbon solu~ility; lithium salicylates, sodium Case EI-6218-~

salicylates, potassium salicylates, calcium salicylates, and magnesium salicylates wherein the aromatic moiety is usually substituted by one or more aliphatic substituents to impart hydrocarbon solubility; the lithium, sodium, potassium, cal-cium and magnesium salts of hydrolysed phosphosulfurized ole-fins having 10 to 2000 carbon atoms or of hydrolyzed phospho-sulfurized alcohols and/or aliphatic-substituted phenolic com-pounds having 10 to 2000 carbon atoms; lithium, sodium, potas-sium, calcium and magnesium salts of aliphatic carboxylic acids and aliphatic-substituted cycloaliphatic carboxylic acids; and many other similar alkali and alkaline earth metal salts of oil-soluble organic acids. Mixtures of basic or overbased salts of two or more different alkali and/or alka-line earth metals can be used. Likewise, basic or overbased salts of mixtures of two or more different acids or two or more different types of acids (e.g., one or more calcium phe-nates with one or more calcium sulfonates) can also be used.
While rubidium, cesium and strontium salts are feasible, their expense renders them impractical for most uses. Likewise, while barium salts are effective, the status of barium as a heavy metal under a toxicological cloud renders barium salts less preferred for present-day usage.
As is well known, o~-~rbased metal detergents are gene-rally regarded as containing overbasing quantities of inorgan-ic bases, probably in the form of micro dispersions or col-loidal suspensions. ~hus the term "oil-soluble" as applied to component c) materials is intended to include metal detergents wherein inorganic bases are present that are not necessarily completely or truly oil-soluble in the strict sense of the term, inasmuch as such detergents when mixed into base oils behave in much the same way as if they were fully and totally dissolved in the oil.
Collectively, the various basic or overbased detergents referred to hereinabove, have sometimes been called, quite simply, basic alkali metal or alkaline earth metal-containing organic acid salts.

Case EI-6218+
- 95 - 2~

Methods for the production of oil-soluble basic and overbased alkali and alkaline earth metal-containing deter-gents are well known to those skilled in the art and are ex-tensively reported in the patent literature. See for example, the disclosures of U. S. Pat. Nos. 2,~51,345; 2,451,346;
2,485,861; 2,501,731; 2,501,732; 2,585,520; 2,671,758;
2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924;
2,616,925; 2,617,049; 2,695,910; 3,178,368; 3,367,867;
3,496,105, 3,629,109; 3,865,737; 3,907~691; 4,100,0~5;
4~129,589; 4,137,184; 4,148,740; 4,212,752; 4,617,135;
4,647,387; 4,880,550; GB Published Patent Application 2,082,619 A, and European Patent Application Publication Nos.
121,024 B1 and 259,974 A2.
The basic or overbased metal detergents utilized as component c) can, if desired, be oil-soluble boronated alkali or alkaline earth metal-containing detergents. Methods for preparing boronated, overbased metal detergents are described, for example, in U. S. Pat. Nos. 3,480,548; 3,679,584;
3,829,381; 3,909,691; 4,965,003; and 4,965,004.
Particularly pre~erred metal detergents for use as component c) are one or more calcium sulfonates, one or more magnesium sulfonates, or combinations of one or more calcium sulfonates and one or more magnesium ;ulfonates. Most pre-ferred are one or more overbased calcium sulfonates, one or more overbased magnesium sulfonates, and combinations of one or more overbased calcium sulfonates and one or more overbased magnesium sulfonates.

Other Additive Com~onents The lubricant and lubricant concentrates of this inven-tion can and preferably will contain additional components in order to partake of the properties which can be conferred to the overall composition by such additional components. The nature of such components will, to a large extent, be governed by the particular use to which the ultimate oleaginous compo-sition (lubricant or functional fluid) is to be subjected.

Case EI-6218~
~g3fl~

Antioxidants. Most oleaginous compositions will con-tain a conventional quantity of one or more antioxidants in order to protect the composition from premature degradation in the presence of air, especially at elevated temperatures. Ty-pical antioxidants include hindered phenolic antioxidants, se-condary aromatic amine antioxidants, sulfurized phenolic anti-oxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and the like.
Illustrative sterically hindered phenolic antioxidants include ortho-alkylated phenolic compounds such as 2,6~di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butylphenol, 2,6-diisopropylphenol, 2-methyl-6-tert-butylphenol,2,4-dimethyl-6-tert-butylphenol, 4-(N,N-dimethylaminomethyl)-2,6-di-tert-butylphenol,4-ethyl-2,6-di-tert-butylphenol,2-methyl-6-styrylphenol, 2,6-di-sty-ryl-4-nonylphenol, and their analogs and homologs. Mixtures of two or more such mononuclear phenolic compounds are also suitable.
The preferred antioxidants for use in the compGsitions of this invention are methylene-bridged alkylpheno:ls, and these can be used singly or in combinations with each other, or in combinations with sterically-hindered unbridgèd phenolic compoundsO Illustrative methylene bridged compoundsrinclude 4,4'-methylenebis(6-tert-butyl-o-cresol), 4,4'-methylenebis-(2-tert-amyl-o-cresol),2,2'-methylenebis(4-methyl-6-tert-bu-tylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), and similar compounds. Particularly preferred are mixtures of methylene-bridged alkylphenols such as are described in U.S.
Pat. ~70. 3,211,652.
~mine antioxidants, especially oil-soluble aromatic secondary amines can also be used in the compositions of this invention. Whilst aromatic secondary monoamines are prefer-red, aromatic secondary polyamines are also suitable. Illus-trative aromatic secondary monoamines include diphenylamine, alkyl diphenylamines containing 1 or 2 alkyl substituents each having up to about 16 carbon atoms, phenyl-~-naphthylamine, phenyl-~-naphthylamine, alkyl- or aralkyl-substituted phenyl-Case EI-6218+

~-naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkyl- or aralkyl-substituted phenyl-~-naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, and similar compounds.
A preferred type of aromatic amine antioxidant is an alkylated diphenylamine of the general formula R,- ~ ~H ~ R2 wherein R1 is an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms) and R2 is a hydrogen atom or an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms). Most prefer-ably, R1 and R2 are the same. One such preferred compound is available commercially as Naugalube 438L, a material which is understood to be predominantly a 4,4'-dinonyldiphenylamine (i.e., bis(4-nonylphenyl)amine) wherein the nonyl groups are branched.
Another useful type of antioxidant for inclusion in the compositions of this invention is comprised to one or more liquid, partially sulfurized phenolic compounds such as are prepared by reacting sulfur monochloride with a liquid mixture of phenols -- at least about 50 weight percent of which mix-ture of phenols is composed of one or more reactive, hindered phenols -- in proportions to provide from about 0.3 to about 0.7 gram atoms of sulfur monochloride per mole of reactive, hindered phenol so as to produce a liquid product. Typical phenol mixtures useful in making such liquid product compo-sitions include a mixture containing by weight about 75% of 2,6-di-tert-butylphenol, about 10% of 2-tert-butylphenol, about 13% of 2,4,6-tri-tert-butylphenol, and about 2% of 2,4-di-tert-butylphenolO The reaction is exothermic and thus is Case EI-6218-~ 2 preferably kept within the range of about 15C to about 70~C, most preferably between about 40C to about 60C.
Mixtures of different antioxidants can also be used.
One suitable mixture is comprised of a combination of (i) an oil-soluble mixture of at least three different sterically-hindered tertiary butylated monohydric phenols which is in the liquid state at 25C, (ii) an oil-soluble mixture of at least three different sterically-hindered tertiary butylated methy-lene-brid~ed polyphenols, and (iii) at least one bis(4-alkyl-phenyl)amine wherein the alkyl group is a branched alkyl group having 8 to 12 carbon atoms, the proportions of (i), (ii) and (iii) on a weight basis falling in the range of 3.5 to 5.0 parts of component (i) and 0.9 to 1.2 parts of component (ii) per part by weight of component (iii).
The lubricating compositions of this invention prefer-ably contain 0.01 to 1.0% by weight, more preferably 0.05 to 0.7~ by weight, of one or more sterically-hindered phenolic antioxidants of the types described above. Alternatively or additionally the lubricants of this invention may contain 0.01 to 1.0% by weight, more preferably 0.05 to 0.7% by weight of one or more aromatic amine antioxidants of the types described above.
Corrosion Inhibitors. rt is also preferred pursuant to this invention to employ in the lubricant compositions and additive concentrates a suitable quantity of a corrosion inhi-bitor. This may be a single compound or a mixture of compounds having the property of inhibiting corrosion of metallic surfaces.
One type of such additives are inhibitors of copper corrosion. Such compounds include thiazoles, triazoles and thiadiazoles. Examples of such compounds include benzotria-zole, tolyltriazole, octyltriazole, decyltriazole, dodecyl-triazole, 2-mercaptobenzothiazole,2,5-dimercapto-1,3,4-thia-diazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles, 2,5-bis(hy-drocarbylthio)-1,3,4-thiadiazoles, and 2,5-(bis)hydrocarbyldi-thio)-1,3,4-thiadiazoles. The preferred compounds are the Case EI-621g+
2 ~

1,3,4-thiadiazoles, a number of which are available as arti-cles of commerce. Such compounds are generally synthesized from hydrazine and carbon disulfide by known procedures. See for example U.S. Pat. Nos. 2,765,289; 2,749,311; 2,760,933;
2,850,453; 2,910,439; 3,663,561; 3,862,798; and 3,840,549.
Other types of corrosion inhibitors suitable for use in the compositions of this invention include dimer and trimer acids, such as are produced from tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humco Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Emery Chemicals. Another useful type of corrosion inhibitor for use in the practice of this invention are the alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuc-cinicanhydride, tetradecenylsuccinic acid, tetradecenylsucci-nic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like. Also useful are the half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. Other suitable corrosion inhibitors include ether amines; acid phos-phates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; imid-azolines; and the like. Materials of these types are well known to those skilled in the art and a number of such mate-rials are available as articles of commerce.
Other useful corrosion inhibitors are aminosuccinic acids or derivatives thereof represent~d by the formula:
R6 o R7-- C -- C -- oR5 ~N -- C -- C -- O R
R l 11 R2 o Case EI-6218+
2 ~

wherein each of R1, R2, Rs, R6 and R7 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, and wherein each of R3 and R4 is, independently, a hy-drogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon atoms.
The groups R1, R2, R3, R~, Rs, R6 and R7, when in the form of hydrocarbyl groups, can be, for example, alkyl, cycloal~yl or aromatic containing groups. Preferably Rl and Rs are the same or different straight-chain or branched-chain hydrocarbon ra-dicals containing 1-20 carbon atoms. Most preferably, R1 and Rs are saturated hydrocarbon radicals containing 3-6 carbon atoms. R2, either R3 or :E~4, R6 and R7, when in the form of hydrocarbyl groups, are preferably the same or different straight-chain or branched-chain saturated hydrocarbon radi-cals. Preferably a dialkyl ester of an aminosuccinic acid is used in which R1 and Rs are the same or different alkyl groups containing 3-6 carbon atoms, R2 is a hydrogen atom, and either R3 or R4 is an alkyl group containing 15-20 carbon atoms or an acyl group which is derived from a saturated or unsaturated carboxylic acid containing 2-10 carbon atoms.
Most preferred of the aminosuccinic acid derivatives is a dialkylester of an aminosuccinic acid of the above formula wherein R1 and Rs are isobutyl, R2 is a hydrc~n atom, R3 is octadecyl and/or octadecenyl and R4 is 3-carboxy-1-oxo-2-propenyl. In such ester R6 and R7 are most preferably hydrogen atoms.
The lubricant compositions of this invention most pre-ferably contain from 0.005 to 0.5% by weight, and especially from 0.01 to 0.2% by ~eight, of one or more corrosion inhibi-tors and/or metal deactivators of the type described above.
Antifoam Aqents. Suitable antifoam agents include si-licones and organic polymers such as acrylate polymers. Vari-ous antifoam agents are described in Foam Control A~ents by H.
T. Kerner ~Noyes Data Corporation, 1976, pages 125-176).
Mixtures of silicone-type antifoam agents such as the liquid dialkyl silicone polymers ~ith various other substances are also effective. Typical of such mixtures are silicones mixed ` Case EI-6218+
- 101 - 2 ~ a with an acrylate polymer, silicones mixed with one or more amines, and silicones mixed with one or more amine carboxy-lates.
Neutral Metal-Containinq Detergents. For some appli-cations such as crankcase lubricants for diesel engines, it isdesirable to include an oil-soluble neutral metal-containing detergent in which the metal is an alkali metal or an alkaline earth metal. Combinations of such detergents can also be em-ployed. The neutral detergents of this type are those which contain an essentially stoichiometric equivalent quantity of metal in relation to the amount of acidic moieties present in the detergent. Thus in general, the neutral detergents will have a TBN of up to about 50.
The acidic materials utilized in forming such deter-gents include carboxylic acids, salicylic acids, alkylphenols,sulfonic acids, sulfurized alkylphenols, and the like. Typi-cal detergents of this type and/or methods for their prepara-tion are known and reported in the literature. See for e.xam-ple U.S. Pat. Nos. 2,001,108; 2,081,075; 2,095,538; 2,144,078;
2,163,622; 2,180,697; 2,180,698; 2,180,699; 2,211,972;
2,223,127; 2,228,654; 2,228,661; 2,249,626; 2,252,793;
2,270,183; 2,281,824; 2,289,795; 2,292,205; 2,294,145;
2,321,463; 2,322,307; 2,335,017; 2,336,074; 2,339,692;
2,356,043; 2,360~302; 2,362,291; 2,399,877; 2,399,878;
2,409,687; and 2,416,281. A number of such compounds are available as articles of commerce, such as for example, HiTEC~
614 additive (Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
Supplemental Antiwear and/or Extreme Pressure Addi-tives. For certain applications such as use as gear oils, the compositions of this invention will preferably contain one or more oil-soluble supplemental antiwear and/or extreme pressure additives. These comprise a number of well known classes of materials including, for example, sulfur-containing additives, esters of boron acids, esters of phosphorus acids, amine salts of phosphorus acids and acid esters, higher carboxylic acids Case EI-6218+
2 ~

and deri~atives thereof, chlorine-containing additives, and the like.
Typical sulfur-containing antiwear and/or extreme pres-sure additives include dihydrocarbyl polysulfides; sulfurized olefins; sulfurized fatty acid esters of both natural (e.g.
sperm oil) and synthetic origins; trithiones; thienyl deriva-tives; sulfurized terpenes; sulfurized oligomers of C2-C8mono-olefins; xanthates of alkanols and other organo hydroxy com-pounds such as phenols; thiocarbamates made from alkyl amines and other organo amines; and sulfurized Diels-Alder adducts such as those disclosed in U. S. reissue patent Re 27,331.
Specific examples include sulfurized polyisobutene of Mn 1,100, sulfurized isobutylene, sulfurized triisobutene, dicy-clohexyl disulfide, diphenyl and dibenzyl disulfide, di-tert-butyl trisulfide, and dinonyl trisul~ide, among others.
Esters of boron acids which may be used include borate, metaborate, pyroborate and biborate esters of monohydric and/or polyhydric alcohols and/or phenols, such as trioctyl borate, tridecyl borate, 2-ethylhexyl pyroborate, isoamyl metaborate, txixylyl borate, (butyl)(2,4-hexanediyl)borate, and the like.
Typical esters of phosphorus acids which may be used as antiwear and/or extreme pressure additives include trihydrocarbyl phosphites, phosphonates and phosphates, and dihydrocarbyl phosphites; such as tricresyl phosphate, tributyl phosphite, tris(2-chloroethyl)phosphate and phosphite, dibutyl trichloromethyl phosphonates, di(n-butyl)phosphite, triphenyl phosphite, and tolyl phosphinic acid dipropyl ester.
Among the amine salts of phosphorus acids and phospho-rus acid-esters which can be employed are amine salts of par-tially esterified phosphoric, phosphorous, phosphonic, and phosphinic acids and their partial or total thio analogs such as partially esterified monothiophosphoric, dithiophosphoric, trithiophosphoric and tetrathiophosphoric acids; amine salts of phosphonic acids and their thio analogs; and the like.
Specific examples include the dihexylammonium salt of dodecyl-` Case EI-6218+ ~ 3 ~ ~

phosphoric acid, the diethyl hexyl ammonium salt o~ dioctyl dithiophosphoric acid, the octadecylammonium salt of dibutyl thiophosphoric acid, the dilaurylammonium salt of 2-ethylhex-ylphosphoric acid, the dioleyl ammonium salt of butane phos-phonic acid, and analogous compounds~
Higher carboxylic acids and derivatives which can be used as antiwear and/or extreme pressure additives are illu-strated by fatty acids, dimerized and trimerized unsaturated natural acids (e.g., linoleic) and esters, amine, ammonia, and metal (particularly lead) salts thereof, and amides and imida-zoline salt and condensation products thereof, oxazolines, and esters of fatty acids, such as ammonium di-(linoleic) acid, lard oil, oleic acid, animal glycerides, lead stearate, etc.
Suitable chlorine-containing additives include chlori-nated waxes of both the paraffinic and microcrystalline type,polyhaloaromatics such as di- and trichlorobenzene, trifluoro-methyl naphthalenes, perchlorobenzene, pentachlorophenol and dichloro diphenyl trichloroethane. Also useful are chlorosul-furized olefins and olefinic waxes and sulfuri~ed chlorophenyl methyl chlorides and chloroxanthates. Specific examples in-cludechlorodibenzyl disulfide, chlorosulfurizedpolyisobutene of Mn 600, chlorosulfurized pinene and chlorosulfurlzed lard oil.
Sup~lemental ~shless DisPersants. If desired, the compositions of this invention can include one or more supple-mental ashless dispersants in order to supplement the disper-sancy contributed by component b). The supplemental ashless dispersant(s) differ from component b) in that the supplemen-tal ashless dispersant(s) are not phosphorylated and boronated in the manner of component b). The supplemental ashless dis-persant(s) can, nevertheless, be a phosphorylated or boronated ashless dispersant formed by using procedures of the types described herein for use in forming component b) or by using procedures of the types conventionally employed for producing by conventional technology ashless dispersants containing phosphorus or boron. For example, the supplemental ashless dispersant can be a basic nitrogen-containing and/or hydroxyl-Case E~-6218+
2~3~

containing ashless dispersant which has been heated with either one or more inorganic or one or more organic phosphorus compounds, or a combination of on~ or more inorganic and one or more organic phosphorus compounds.
Thus, the supplemental ashless dispersant(s) which may be used in the compositions of this invention can be any of the basic nitrogen-containing and/or hydroxyl group-containing ashless dispersants of the type referred to hereinabove in connection with the preparation of component b). Use can therefore be made of any of the carboxylic dispersants and/or any of the hydrocarbyl polyamine dispersants and/or any of the Mannich polyamine dispersants and/or any of the polymeric polyamine dispersants referred to hereinabove. Other ashless dispersants which can be included in the compositions of this invention are imidazoline dispersants which can be represented by the formula:

N~

wherein R1 represents a hydrocarbon group having 1 to 30 car-bon atoms, e.g. an alkyl or alkenyl group having 7 to 22 car-bon atoms, and R2 represents a hydrogen atoms or a hydrocarbon radical of 1 to 22 carbon atoms, or an aminoalkyl, acylamino-alkyl or hydroxyalkyl radical having 2 to 50 carbon atoms.
Such long-chain alkyl (or long-chain alkenyl) imidazoline compounds may be made by reaction of a corresponding long-chain fatty acid (of formula R1-COOH), for example oleic acid, with an appropriate polyamine. The imidazoline formed is then ordinarily called, for example, oleylimidazoline where the radical R1 represents the oleyl residue of oleic acid. Other suitable alkyl substituents in the 2- position of these imida-zolines include undecyl, heptadecyl, lauryl and erucyl. Suit-Case EI-6218+ 2 ~ ~ ~ 3 -~ ~

able N-substituents of the imidazolines (i.e. radicals R2) include hydrocarbyl groups, hydroxyalkyl groups, aminoalkyl groups~ and acylaminoalkyl groups. Examples of these various groups include methyl, butyl, decyl, cyclohexyl, phenyl, ben-zyl, tolyl, hydroxyethyl, aminoethyl, oleylaminoethyl and stearylaminoethyl.
Another class of ashless dispersant which can bP incor-porated in the compositions of this invention are the products of reaction of an ethoxylated amine made by reaction of ammo-nia with ethylene oxide with a carboxylic acid of ~3 to 30 car-bon atoms. The ethoxylated amine may be, for example, mono-, di- or tri-ethanolamine or a polyethoxylated derivative there-of, and the carboxylic acid may be, for example, a straight or branched chain fatty acid of 10 to 22 carbon atoms, a naphthe-nic acid, a resinic acid or an alkyl aryl carboxylic acid.
Still another type of ashless dispersants which can ~e used in the practice of this invention are the ~-olefin-male-imide copolymers such as are described in U. S. Pat. No.
3,909,215. Such copolymers are alternating copolymers of N-substituted maleimides and aliphatic ~-olefins of from 8 to 30 carbon atoms. The copolymers may have an average of 4 to 20 maleimide groups per molecule. The substituents on the nitrogen of the maleimide may b~ he same or different and are organic radicals composed essentially of carbon, hydrogen and nitrogen having a total of 3 to 60 carbon atoms. A commer-cially available material which is highly suitable for use in this invention is Chevron OFA 425B, and this material is be-lieved to be or comprise an ~-olefin maleimide copolymer of the type described in U. S. Pat. No. 3,909,215.
The above and many other types of ashless dispersants can be utilized either sin~ly or in combination in the compo-sitions of this invention, provided of course that they are compatible with the other additive components being employed and are suitably soluble in the base oil selected for use.
Pour Point De~ressants. Another useful type of addi-tive included in compositions of this invention is one or more pour point depressants. The use of pour point depressants in Case EI-6218+ 2 ~ ~ ~ 3 ~ ~

oil-base compositions to improve the low temperature proper-ties of the compositions is well known to the art. See, for example, the books Lubricant Additives by C. V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. Publishers, Cleveland, Ohio, 1967); Gear and Transmission Lubricants by C. T. Boner (Reinhold Publishing Corp., New York, 1964); and Lubricant Additives by M. W. Ranney (Noyes Data Corporation, New Jersey, 1973). Among the types of compounds which function satisfac-torily as pour point depressants in the compositions of this invention are polymethacrylates, polyacrylates, condensation products of haloparaffin waxes and aromatic compounds, and vinyl carboxylate polymers. Also useful as pour point depres-sants are terpolymers made by polymerizing a dialkyl fumarate, vinyl ester of a fatty acid and a vinyl alkyl ether. Tech-niques for preparing such polymers and their uses are dis-closed in U. S. Pat. No. 3,250,715. Generally, when they are present in the compositions of this invention, the pour point depressants (on an active content basis) are present in amounts within the range of 0.01 to 5, and more often within the range of 0.01 to 1, weight percent of the total composi-tion.
Viscosity Index Improvers. Depending upon the viscosi-ty grade required, the lubricant compos!tions can contain up to 15 weight percent of one or more viscosity index improvers (excluding the weight of solvent or carrier fluid with which viscosity index improvers are often associated as supplied).
Among the numerous types of materials known for such use are hydrocarbon polymers grafted with, for example, nitrogen-containing polymers, olefin polymers such as polybutene, ethylene-propylene copolymers, hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene, polymers of alkyl acrylates or alkyl methacrylates, copolymers of alkyl methacrylates with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate; post-grafted polymers of ethylene-propylene with an active monomer such as maleic anhydride which may be further reacted with an alcohol or an Case EI-6218+ 2 alkylene polyamine; styrene/maleic anhydride polymers post-treated with alcohols and/or amines, and the like.
Dispersant viscosity index improvers, which combine the activity of dispersants and viscosity index improvers, suit-able for use in the compositions of this invention are de-scribed, for example, in U. S. Pat. Nos. 3,702,300; 4,068,056;
4,068,058; 4,089,794; 4,137,185; 4,146,489; 4,149,984;
4,160,739; and 4,519,929.
Friction Modifiers. These materials, sometimes known as fuel economy additives, include such substances as the al-kyl phosphonates as disclosed in U. S. Pat. No. 4,356,097, aliphatic hydrocarbyl-substituted succinimides derived from ammonia or alkyl monoamines as disclosed in European Patent Publication No. 20037, dimer acid esters as disclosed in U. S.
Pat. No. 4,105,571, oleamide, and the like. Such additives, when used are generally present in amounts of 0.1 to 5 weight percent. Glycerol oleates are another example of fuel economy additives and these are usually present in very small amounts, such as 0.05 to 0.2 weight percent based on the weight of the formulated oil.
Other suitable friction modifiers include aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic ca~oxylic es-ters, aliphatic carboxylic ester-amides, aliphatic phos~hates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil solu-ble.
A desirable friction modifier additive combination which may be used in the practice of this invention is de-scribed in European Patent Publication No. 389,237. This combination involves use of a long chain succinimide deri-vative and a long chain amide.
Seal S~ell Aqents. Additives may be introduced into the compositions of this invention in order to improve the seal performance (elastomer compatibility) of the composi-tions. Known materials of this type include dialkyl diesters Case EI-6218+ 2 ~ ~ ~ 3 ~ ~

such as dioctyl sebacate, aromatic hydrocarbons of suitable viscosity such as Panasol AN-3N, products such as Lubrizol 730, polyol esters such as Emery 2935, 2936, and 2939 esters from the Emery Group of Henkel Corporation and Hatcol 2352, 2962, 2325, 2938, 2939, 2970, 3178, and 4322 polyol esters from Hatco Corporation. Genera].ly speaking the most suitable diesters include the adipates, azelates, and sebacates of C8-Cl3 alkanols (or mixtures thereof), and the phthalates of C4-C13 alkanols (or mixtures thereof). Mixtures of two or more dif-ferent types of diesters (e.g., dialkyl adipates and dialkyl azelates, etc.) can also be used. Examples of such materials include the n-octyl, 2-ethylhexyl, isodecyl, and tridecyl di-esters of adipic acid, azelaic acid, and sebacic acid, and the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl diesters of phthalic acid.
Base Oils.
The additive combinations of this invention can be in-corporated in a wide variety of lubricants and functional flu-ids in effective amounts to provide suitable active ingredient concentrations. The base oils not only can be hydrocarbon oils of lubricating viscosity derived from petroleum (or tar sands, coal, shale, etc.), but also can be natural oils of suitahle viscosities such as rapeseed oil, etc., and synthet'c oils such as hydrogenated polyolefin oils; poly-~-olefins (e.g., hydrogenated or unhydrogenated ~-olefin oligomers such as hydrogenated poly-1-decene); alkyl esters of dicarboxylic acids; complex esters of dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic or phosphoric acids; poly-silicones; fluorohydrocarbon oils; and mixtures of mineral, natural and/or synthetic oils in any proportion, etc. The term "base oil" ~or this disclosure includes all the fore-going .
The additive combinations of this invention can thus be used in lubricating oil and functional fluid compositions, such as automotive crankcase luhricating oils, automatic transmission fluids, gear oils, hydraulic oils, cutting oils, etc., in which the base oil of lubricating viscosity is a Case EI-6218+

- 109 ~

mineral oil, a syn~hetic oil, a natural oil such as a vege-table oil, or a mixture thereof, e.g. a mixture of a mineral oil and a synthetic oil.
Suitable mineral oils include those of appropriate viscosity refined from crude oil of any source including Gulf Coast, Midcontinent, Pennsylvania, California, Alaska, Middle East, North Sea and the like. Standard refinery operations may be used in processing the mineral oil. Among the general types of petroleum oils useful in the compositions of this invention are solvent neutrals, bright stocks, cylinder stocks, residual oils, hydrocracked base stocks, paraffin oils including pale oils, and solvent extracted naphthenic oils.
Such oils and blends of them are produced by a number of conventional techniques which are widely known by those skilled in the art.
As is noted above, the base oil can consist essentially of or comprise a portion of one or more synthetic oils. Among the suitable synthetic oils are homo- and inter-polymers of C2-C12 olefins, carboxylic acid esters of both monoalcohols and polyols, polyethers, silicones, polyglycols, silicates, alky-lated aromatics, carbonates, thiocarbonates, ortho~ormates, phosphates and phosphites, borates and halogenated hydro-~-lrbons. Representative of such oils are homo- and inter-polymers of C2-C12 monoolefinic hydrocarbons, alkylated ben-zenes (e.g., dodecyl benzenes, didodecyl benzenes, tetradecylbenzenes, dinonyl benzenes, di-(2-ethylhexyl)benzenes, wax-alkylated naphthalenes); and polyphenyls (e.g., biphenyls, terphenyls).
Alkylene oxide polymers and interpolymers and deriva-tives thereof where the terminal hydroxyl groups have beenmodified by esterification, etherification, etc., constitute another class of synthetic oils. These are exemplified by the oils prepared through polymerization of alkylene oxides such as ethylene oxide or propylene oxide, and the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl poly-isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a mo-Case EI-6213+
2 ~

lecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500) or mono- and poly-carboxylic esters thereof, for example, the acetic acid ester, mixed C3-C6 fatty acid esters, or the C~3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alco-hol, 2-ethylhexyl alcohol, ethylene glycol). Specific exam-ples of these esters include dibutyl adipate, di(2-ethylhex-yl)adipate, didodecyl adipate, di(2-ethylhexyl)sebacate, di-lauryl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diiso-octyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, di(eicosyl)sebacate, the 2 ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene gly-col and two moles of 2-ethylhexanoic acid.
Esters which may be used as synthetic oils also include those made from ~3-C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaeryth~ ol and dipentaerythritol. Trimethylol propane tripelargonate and pentaerythritol tetracaproate serve as examples.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another class of synthetic lubricants (e.g., tetra-ethyl silicat~, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate,tetra-(p-tert-butylphenyl)silicate,poly(methyl~si-loxanes, and poly(methylphenyl)siloxanes. Other synthetic lu-bricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, triphen-yl phosphite, and diethyl ester of decane phosphonic acid.
Also useful as base oils or as components of base oils are hydrogenated or unhydrogenated liquid oligomers of C6-C16 alpha olefins, such as hydrogenated or unhydrogenated oligo-Case EI-6218~
2 ~

mers formed from 1-decene. Methods for the production of such liquid oligomeric 1-alkene hydrocarbons are known and reported in the literature. See for example U. S. Pat. Nos. 3,749,560;
3,763,244; 3,780,128; 4,172,855; 4,218,330; and 4,950,822.
Additionally, hydrogenated 1-alkene oligomers of this type are available as articles of commerce, for example, under the trade designations ETHYLFLO 162, ETHYLFLO 164, ETHYLFLO 166, ETHYLFLO 168, ETHYLFLO 170, ETHYLFLO 174, and ETHYLFLO 180 poly-~-olefin oils (Ethyl Corporation; Ethyl S.A.; Ethyl Canada Limited). Blends of such materials can also be used in order to adjust the viscometrics of the given base oil.
Suitable 1-alkene oligomers are also available from other suppliers. As is well known, hydrogenated oligomers of this type contain little, if any, residual ethylenic unsaturation.
Preferred oligomers are formed by use o~ a Friedel-Crafts catalyst (especially boron trifluoride promoted with water or a C120 alkanol) followed by catalytic hydrogenation of the oligomer so formed using procedures such as are de-scribed in the foregoing U. S. patents.
Other catalyst systems which can be used to form oligo-mers of l-alkene hydrocarbons, which, on hydrogenation, pro-vide suitable oleaginous liquids include Ziegler catalysts such as ethyl aluminum cc~:~quichloride with titanium tetrachlo-ride, aluminum alkyl catalysts, chromium oxide catalysts on silica or alumina supports and a system in which a boron tri-fluoride catalyst oligomerization is followed by treatment with an organic peroxide.
It is also possible in accordance with this invention to utilize blends of one or more liquid hydrogenated 1-alkene oligomers in combination with other oleaginous materials hav-ing suitable viscosities, provided that the resultant blend has suitable compatibility and possesses the physical proper-ties desired.
Typical natural oils that may be used as base oils or as components of the base oils include castor oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp oil, Case EI-6218+
2~3~

linseed oil, tung oil, oiticica oil, jojoba oil, and the like.
Such oils may be partially or fully hydrogenated, if desired.
The fact that the base oils used in the compositions of this invention may be composed of (i) one or more mineral oils, (ii) one or more synthetic oils, (iii) one or more natural oils, or (iv) a blend of (i) and (ii), or (i) and (iii), or (ii) and (iii), or (i), (ii) and (iii) does not mean that these various types of oils are necessarily equivalents of each other. Certain types of base oils may be used in cer-tain compositions for the specific properties they possess such as high temperature stability, non-flammability or lack of corrosivity towards specific metals (e.g. silver or cad-mium). In other compositions, other types of base oils may be preferred for reasons of availability or low cost. Thus, the skilled artisan will recognize that while the various types of base oils discussed above may be used in the compositions of this invention, they are not necessarily functional equiva-lents of each other in every instance.

Proportions and Concentrations In general, the components of the additive compositions of this invention are employed in the oleaginous liquids (e.g., lubricating oils and functi;nal fluids) in minor amounts sufficient to improve the performance characteristics and proper~ies of the base oil or fluid. The amounts will thus vary in accordance with such factors as the viscosity characteristics of the base oil or fluid employed, the vis-cosity characteristics desired in the finished product, the service conditions for which the finished product is intended, and the performance characteristics desired in the finished product. However, generally speaking, the following concen-trations (weight percent) of the compcnents (active ingre-dients) in the base oils or fluids are illustrative:

Case EI-6218+
- 113 - ~ ~6~

More Particularly General Preferred Preferred Pre-ferred _ Ranqe Ranqe Ranqe Ranqe Component a) 0.1-5 0.2-2 0.3-1.4 0.35-1.35 Component b) 0.01-20 0.~-15 0.5-10 1-8 Component c) 0-20 0.01-10 0.1-6 0.5-3 The concentrations (weight percent of active ingredi-ent) of typical optional ingredients in-the oleaginous liquid compositions of this invention are generally as follows:
Typical Preferred Ranqe Ranae Antioxidant 0 - ~ 0.05 - 2 Corrosion inhibitor 0 - 3 0.02 - 1 Foam inhibitor 0 - 0.3 0.0002 - 0.1 Neutral metal detergent 0 - 3 0 - 2.5 Supplemental antiwear/EP agent 0 - 5 0 - 2 Supplemental ashless dispersant 0 - 10 0 - 5 Pour point depressant 0 - 5 0 - 2 Viscosity index improver 0 - 15 0 - 5 Friction modifier 0 - 3 0 - 1 Seal swell agent 0 - 20 0 - 10 Dye 0 - 0.1 0 - 0.05 It will be appreciated that the individual components a) and b), preferably component c) as well, and also any and all auxiliary components employed, can be separately blended into the base oil or fluid or can be blended therein in vari-ous subcombinations, if desired. Moreover, such components can be blended in the form of separate solutions in a diluent.
Except for viscosity index improvers and/or pour point depres-sants (which are usually blended apart from other components), it is preferable to blend the components used in the form of an additive concentrate of this inventionr as this simplifies the blending operations, reduces the likelihood of blending Case EI-6218-~

114 - 2 ~ 6 errors, and takes advantage of the compatibility and solu-bility characteristics afforded by the overall concentrate.
The additive concentrates of this invention will con-tain components a) and b), and preferably component c), in amounts proportioned to yield finished oil or fluid blends consistent with the concentrations tabulated above. In most cases, the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate. Thus concentrates containing up to 50% by weight of one or more diluents or solvents can be used.
The oleaginous liquids provided by this invention can be used in a variety of applications. For example, they can be employed as crankcase lubricants, gear oils, hydraulic fluids, manual transmission fluids, automatic transmission fluids, cutting and machining fluids, brake fluids, shock absorber fluids, heat transfer fluids, quenching oils, trans-former oils, and the like. The compositions are particularly suitable for use as crankcase lubricants for spark ignition (gasoline) engines, and compression ignition tdiesel) engines.

Blendinq The formulation or blending operations are relatively simple and involve mixing together in a suitabl~ container or vessel, using a dry, inert atmosphere where necessary or de-sirable, appropriate proportions of the selected ingredients.Those skilled in the art are cognizant of and familiar with the procedures suitable for formulating and blending additive concentrates and lubricant compositions. Usually the order of addition of components to the blending tank or vessel is not critical provided of course, that the components being b~ended at any given time are not incompatible with each other. Agi-tation such as with mechanical stirring equipment is desirable to facilitate the blending operation. Frequently it is help-ful to apply sufficient heat to the blending vessel during or after the introduction of the ingredients thereto, so as to maintain the temperature at, say, 40-60C. Similarly, it is Case EI-6218~
2~3~

sometimes helpful to preheat highly viscous components to a suitable temperature even before they are introduced into the blending vessel in order to render them more fluid and thereby facilitate their introduction into the blending vessel and render the resultant mixture easier to stir or blend. Natu-rally the temperatures used during the blending operations should be controlled so as not to cause any significant amount of thermal degradation or unwanted chemical interactions.
When forming the lubricant compositions of this inven-tion, it is usually desirable to introduce the additive ingre-dients into the base oil with stirring and application of mildly elevated temperatures, as this facilitates the disso-lution of the components in the oil and achievement of product uniformity.
The practice and advantages of this invention are still further illustrated by the following examples in which all parts and percentages are by weight unless otherwise specifi-cally indicated. In these examples, the weights of the vari-ous ingredients are on an "as received" basis ~- i.e., the weights include solvents or diluents which are in the products as supplied.

A crankcase lubricating oil of this invention contain-ing 0.11% phosphorus and 0.02% boron is formed by blending to-gether the following components:
Component a)1 0.580%
Component b)2 7.544%
Component c) 3 1.440%
Nonylphenol sulfide4 0.280%
Bistp-nonylphenyl)amine5 0.050%
Antifoam agent6 0.005%
Process oil diluent 0.080%
Viscosity index improver7 7.000%
Base oil8 83.021%
100.000%

Case EI-6218+
2 ~ 0 (1) Zinc dialkyl dithiophosphate tHiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.).
(2) A product formed as in Example A-44.
(3) Overbased calcium sulfonate (HiTEC~ 611 additive;
Ethyl Petroleum Additives, Inc., a product having a nominal TBN of 300).
~4) ~iTEC~ 619 additive; Ethyl Petroleum Additives, Inc.
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company, Inc.
(6) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl silicone solution from Dow Corning Company.
(7) Polymethylmethacrylate (Acryloid ~53 polymer, Rohm Haas Chemical Company).
(8) A blend of 62.050% 100 Solvent Neutral refined mineral oil (Turbine 5 oil) and 20.971% 150 Solvent Neutral refined mineral oil (Esso Canada MCT-10 oil).

Using the same ingredients as in Example 1 except where otherwise indicatec~ a crankcase lubricating oil of this in-vention containing 0.13% phosphorus and 0.01% boron is formed by blending together the following components:
Component a) 1.200%
Component b) 3.000%
Component c)1 1.630%
Nonylphenol sulfide 0.260%
Bis(p-nonylphenyl)amine 0.050%
Antifoam agent 0.007 Pour point depressantZ 0.450%
Process oil diluent 0.347~
; Viscosity index improver3 10.200%
Base oil4 82.856%

100 . 000%

Case EI-6218+
- 117 - 2~3~

(1) A combination of 1.31% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 0.32% of neutral calcium sul~onate (HiTEC~
614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd., a product having a nominal TBN sf 30).
(2) HiTEC~ 672 additive; Ethyl Petroleum Additives, Inc.
(3~ Texaco TLA 555 additive, (Texaco Inc., a dispersant-VII olefin copolymer).
(4) Exxon 100 neutral, low pour oil; Exxon Chemical Company.

The procedure of Example 2 is repeated except that com-ponent b) is prepared as in Example A-~5 and is employed at a concentration of 2.970%. The amount of the base oil is thus 82.886%.

Using the same ingredients as in Example 1 except where otherwise indicated, a crankcase lubricating oil of this in-vention is formed by blending ~ogether the following compo-nents:
Component a) 0.640%
Component b) 5.300%
Component c)1 1.530%
Bis(p-nonylphenyl)amine 0.0~0%
Partially sulfurized tert-butyl phenols2 0.300%
Antifoam agent 0.007%
Sulfurized fatty ester3 0.300%
Viscosity index improver 7.000%
Process oil diluent 0.333%
Base oil4 ~4.500%
100.000%

Case EI-6218+

- 118 - ~3~

(1) A combination of 1.23% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 0.30% of neutral calcium sulfonate (HiTEC~
614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
(2) A product formed by reacting ETHYL~ Antioxidant 733 with sulfur monochloride, for example as in U.S. Pat.
No. 4,946,610.
~3) SUL-PERM 60-93 (Keil Chemical Division of Ferro Corporation).
(4) A blend of 55.94% of Esso Canada LXT oil and 28.56%
Esso Canada MCT-10 oil.

Using the same ingredients as in Example 4 except where otherwise indicated, a crankcase lubricating oil o~ this invention is formed by blending together the ~ollowing components:
Component a) 0.630%
Component b) 6.000%
Component c)l 3.150%
Bis(p-nonylphenyl)amine 0.050%
Partially sulfurized tert-butyl phen~.s 0.500%
Antifoam agent 0.007%
Sulfurized fatty ester 0.300%
~iscosity index improver2 7.500%
Process oil diluent 1.363%
Base oil3 80.500%
100.000%
- - - - _ _ _ (l) A combination of 1.90% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 1.25% of neutral calcium sulfonate (HiTEC~
614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).

(2) Polymethylmethacrylate (Acryloid 954 polymer; Xohm &
Haas Chemical Company).

` Case EI-6218+
2 ~

: (3) A blend of 64.40% Petro Canada 160 neutral oil and 16.10% Petro Canada 650 neutral oil.

The procedures o~ Examples 4 and 5 are repeated except that in each case the sulfurized fatty ester is eliminated and replaced by a corresponding amount of process oil.

The procedure o~ Example 4 is repeated using the same ingredients as therein specified except where otherwise indicated below:
Component a) 0.820~
Component b) 4.000%
Component c) 1.530%
Partially sulfurized tert-butyl phenols 0.300%
Antifoam agent 0.007%
Sulfurized fatty ester 0.300%
Viscosity index improver 7.500%
Process oil diluent 0.383%
Base oil1 85.160~
100.000%
_ (1) A blend of 56.38% of Esso Canada LXT oil and 28.78%
Esso Canada MCT-10 oil.

: EXAMPLE 8 The procedure of Example 5 is repeated using the same ingredients as therein specified except where otherwise indi-cated below:
Component a) 0.680%
Component b) 5.500%

Component c) 3.150%
Partially sulfurized tert-butyl phenols 0.500%
Antifoam agent 0.007%
Sulfurized fatty ester 0.300%

Case EI-6218+ ~ 3 Viscosity index improver8.000%
Process oil diluent 1.363%
Base oil1 80.500%
100. ooo%
- - _ _ _ _ (1) A blend of 64.40% Petro Canada 160 neutral oil and 16.10% Petro Canada 650 neutral oil.

The procedures of Examples 7 and 8 are repeated except that in each case the sulfurized ~atty ester is eliminated and replaced by a corresponding amount of process oil.

A synthe~ic lubricant of this invention is formed by blending together the following components in the amounts specified:
Component a)l 0.500%
Component b)2 6.000%
Component c)3 2.000%
Partially sulfurized tert-butyl phenols4 0.500%
Antifoam agentS 0.010%
Antirust additive6 0.150%
Pour point depressant7 0.300%
Process oil diluent 1.000%
Viscosity index improver84.200%
Base oil9 85.340%

10~. 000%

(1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive Ethyl Petroleum Additives, Inc.~.
(2) A product formed as in Example A-44.

(3) A combination of 1.5% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 0.5% of neutral calcium sulfonate (HiTEC~
614 additive; Eth~vl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).

` Case EI-6218~
~63~

(4) A product formed by reacting ETHYL~ Antioxidant 733 with sulfur monochloride, for example as in U.S. Pat.
No. 4,946,610.
(5) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl silicone solution from Dow Corning Company.
(6) Sterox ND (Monsanto Company), believed to be ~-(nonylphenyl)-~-hydroxy~poly(oxy-1,2-ethanediyl).
(7) Santolube C (Monsanto Company).
(8) Texaco TLA 347A additive, (Texaco Inc.).
(9) A blend of 77.001% 8 cSt poly-~-olefin oil (ETHYLFLO
168 oil; Ethyl Corporation) and 8.339% 4 cSt poly-~-olefin oil (Emery 2921 oil; Emery Group of Henkel Corporation).

The procedure of Example 10 is repeated except that component b) is prapared as in Example A-45 and is employed at a concentration of 5.940%, and the amount of process oil used is 1.560%.

The procedure of Example 10 is repeated usîng the same ingredients except as otherwise specified:
Component a) 0.500%
Component bj 6.000%
Component c)l 3.150%
Partially sulfurized tert-butyl phenols 0.750%
Bis(p-nonylphenyl)amine2 0.050%
Antifoam agent 0.010%
Antirust additive 0.150%
Process oil diluent 0.110%
Base oil3 89.280%
1~0.000%

Case EI-6218+
2 ~

(1) A combination of 1.90% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petrol~um Additives, Inc.;
Ethyl Petroleum Additive~, Ltd.); and 1.~5% of neutral calcium sulfonate (HiTEC~ 614 additive; Ethyl Petrole-um Additives, Inc.; Eth~l Petroleum Additives, Ltd.).
(2) ~augalube 438L antioxidant; Uniroyal Chemical Company, Inc.
(3) A blend of 82.14% 8 cSt poly-~-olefin oil (ETHYLFLO
168 oil; Ethyl Corporation) and 7.14% 40 cSt poly-~-olefin oil (ETHYLFLO 174 oil; Ethyl Corporation).

The procedure of Example 12 is repeated using the same ingredients except where otherwise specified:
Component a~ 0.500%
Component b) 6.000%
Component c) 3.150%
Partially sulfurized tert-butyl phenols 0.750%
Bis(p-nonylphenyl)amine 0.050%
Antifoam agent 0.010%
Viscosity index improver1 7.200%
Process oil diluent 0.260~
Base oil2 82.080%
100.000%
- - - _ _ _ _ (1) Paratone 715 (Exxon Chemical Company).
(2) A blend of 69.77% 8 cSt poly-~-olefin oil (ETHYLFLO
168 oil; Ethyl Corporation) and 12.31% 40 cSt poly-~-olefin oil (ETHYLFLO 174 oil; Ethyl Corporation).

An additive concentrate of this invention is formed by blending together the ~ollowing components as identified in Example 1:

Case EI-621~+
2~63~0 Component a) 5.81%
Component b) 75.60%
Component c) 14.43%
Nonylphenol sulfide 2.81%
Bis(p-nonylphenyl)amine 0.50%
Antifoam agent 0.05%
Process oil diluent 0.80%
100. 00%

An additive concentrate of this invention is formed by blending together the following components as identified in Example 3:
Component a) 18.48%
Component b) 45.73%
Component c) 25.10%
Nonylphenol sulfide 4.00%
Bis(p-nonylphenyl)amine 0.77%
Antifoam agent 0.11%
Process oil diluent 5.81%
100.00%

An additive concentrate of this invention is formed by blending together the following components as identified in Example 4:
Component a) 7.53%
Component b) 62.35%
Component c) 18.00%
Bis(p-nonylphenyl)amine 0.47%
Partially sulfurized tert-hutyl phenols 3.53%

Antifoam agent 0.08%
Sulfurized fatty ester 3.53%
Process oil diluent 4.51%
100.00%

Case EI-6218-~ 2 ~ ~ 6 3 4 ~

An additive concentrate of this invention is formed by blending together the following components as identified in Example 5:
Component a) 5.25~
Component b) 50.00%
Component c) 26.25%
Bis(p-nonylphenyl)amine 0.42%
Partially sulfurized tert-butyl phenols 4.17%
Antifoam agent 0.06%
Sulfurized fatty ester 2.50%
Process oil diluent 11.35%
100.00%

An additive concentrate of this invention is formed by blending together the following components as identified in Example 4: .
Component a) 7.80%
Component b) 64.63%
Component c) 18.66%
Bis(p-nonylphenyl)amine 0.49%
P.r1.ially sulfurized tert-butyl phenols 3.66%
Antifoam agent o.og%
Process oil diluent 4.67%
100.00%

An ad.ditive concentrate of this invention is formed by blending together the following components as identified in Example 7:
Component a) 11.17%
Component b) 54.50%
Component c) 20.83%
Partially sulfurized tert-butyl phenols 4.09%
Antifoam agent 0.10%

Case EI-6218+ ~ 3 Sulfurized fatty ester 4.09%
Process oil diluent 5.22%
100.00%

5 An additive concentrate of this invention is formed by blending together the followiny components as identified in Example 8:
Component a) 6.07%
Component b) 49.10%
Component c) 28.13%
Partially sulfurized tert-butyl phenols 4.46%
Antifoam agent 0.06%
Process oil diluent 12.18%
100 . 00%

EXAMPI.E 21 An additive concentrate of this invention is formed by blending together the ~ollowing components:
Component a)l 5.23%
Component b)2 46.15%
Component c)3 24.23%
Partially su~ rized tert-butyl phenols4 7.69%
Bis(p-nonylphenyl)amine5 2.31%
Antifoam agent6 0.11%
Sulfurized fatty ester7 2.31%
Seal Swell Agent8 3.85%
Antirust Additive9 1.54%
Process oil diluent 6.58%
100. 00%

0 (1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.).
(2) A product formed as in Example A-45.

Case EI-6218+
2 ~

(3) A combination of 1.90% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 1.25% of neutral calcium sulfonate (HiTEC~
614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
(4) A product formed by reacting ETHYL~ Antioxidant 733 with sulfur monochloride, for example as in U.S. Pat.
No. 4,946,610.
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company, Inc.
(6~ Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl silicone solution from Dow Corning Company.
(7) SUL-PERM 60-93 (Keil Chemical Division of Ferro Corporation).
(8) Santicizer 160; Monsanto C'ompany; believed to be butyl benzyl phthalate.
(9) Sterox ND (Monsanto Company), believed to be ~-(nonylphenyl)-~-hydroxy-poly(oxy-1,2-ethanediyl).

A lubricant composition of this invention is formed by 20 blending the above concentrate and a viscosity index improver in a base oil as follows:
Above additive concentrate13.0%
Viscosity index improver'7.5%
Base oil2 79.5%
100.0%

(1) Polymethylmethacrylate (Acryloid 954 polymer; Rohm &
Haas Chemical Company).
(2) A blend of 63.6% Petro Canada 160 neutral oil and 15.9% Petro Canada 650 neutral oil.

An additive concentrate of this invention is formed by blending together the components as identified in ~xample 21 in the following proportions:

Case EI-6218+
2~3l~0 Component a) 4.22%
Component b) 51.85%
Component c) 23.33%
Partially sulfurized tert-butyl phenols 7.41%
Bis(p-nonylphenyl)amine 2.22%
Antifoam agent 0.10%
Sulfurized fatty ester 2.22%
Seal Swell Agent 3.70%
Antirust Additive 1.48%
Process oil diluent 3.47%
100.00%
A lubricant composition of this invention is formed by blend-ing the above concentrate and the viscosity index improver of Example XXI in a base oil composed of 63.2% Petro Canada 160 neutral oil and 15.8% Petro Canada 650 neutral oil as follows:
Above additive concentrate 13.5%
Viscosity index improver 7.5%
Base oil 79.0%
100.0%

A crankcase lubricating oil of this invention is formed by blending together the following componen:c:
Component a)1 . 0.580%
Component b) 2 7.544%
Component c)3 1.440%
Nonylphenol sulfide~ 0.280%
Bis(p-nonylphenyl)amine5 0.050%
Antifoam agent6 0.005%
Process oil diluent 0.080%

Viscosity index improver7 7.900%
Base oil8 83.021%
10~. 000%

(1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.)O

Case EI-6218+ 2 ~ Q

(2) A product formed as in Example B-1.
(3) Overbased calcium sulfonate (~IiTEC~ 611 additive;
Ethyl Petroleum Additives, Inc.).
(4) HiTEC~ 619 additive; Ethyl Petroleum Additives, Inc.
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company, Inc.
(6) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl silicone solution from Dow Corning Company.
(7) Polymethylmethacrylate (Acryloid 953 polymer; Rohm &
Haas Chemical Company).
(8) A blend of 62.050% 100 Solvent Neutral refined mineral oil (Turbine 5 oil) and 20.971% 150 Solvent Neutral refined mineral oil (Esso Canada MCT-10 oil).

Using the same ingredients as in Example 23 except where otherwise indicated, a crankcase lubricating oil of this invention is formed by blending together the following components:
Component a) 1.200%
Component b) 3.000%
Component c) 1.310%
No~lphenol sulfide 0.260%
Bis(p-nonylphenyl)amine 0.050%
Antifoam a~ent 0 007%
Neutral calcium sulfonate1 0.320%
Pour point depressant2 0.450%
Process oil diluent 0.347%
Viscosity index improver3 10.200%
Base oil4 82.856%
100.000%

(1) HiTEC~ 614 additive; (Ethyl Petroleum Additives, Inc.).

(2) HiTEC9 672 additive; Ethyl Petroleum Additives, Inc.

Case EI-6218+ 2 ~ ~ 6 ~ ~ ~

(3) Texaco TLA 555 additive, (Texaco Inc., a dispersant-VII olefin copolymer).
(4) Exxon 100 neutral, low pour oil; Exxon Chemical Company.

The procedure of Example 24 is repeated except thatcomponent b) is prepared as in Example B-45 and is employed at a concentration of 2.970%. The amount of the base oil is thus 82.886%.

Using the same ingredients as in Example 23 except where otherwise indicated, a crankcase lubricating oil of this invention is formed by blending together the following compo-nents:
Component a) 0.640%
Component b) 5.300%
Component c)l 1.530%
Bistp-nonylphenyl)amine 0.040%
Partially sulfurized tert-butyl phenols2 0.300%
Antifoam agent 0.007%
Sulfurized fatty e;ter3 0.300%
Viscosity index improver 7.000%
Process oil diluent 0.383%
Base oil4 84.500%
100.000%

(1) A combination of 1 23% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 0.30% of neutral calcium sulfonate (HiTEC~
614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
(2) A product formed by reacting ETHYL~ Antioxidant 733 with sulfur monochloride, for example as in U.S. Pat.
No. 4,946,610.

Case EI-6218~ 2 (3) SUL PERM 60-93 (Keil Chemical Division o~ Ferro Corporation).
(4) A blend of 55.94% of Esso Canada LXT oil and 28.56%
Esso Canada MCT-10 oil.

Using the same ingredients as in Example 26 except where otherwise indicated, a crankcase lubricating oil of this invention is formed by blending together the following components:
Component a) 0.630%
Component b) 6.000%
Component c)1 3.150%
Bis(p-nonylphenyl)amine 0.050%
Partially sulfurized tert-butyl phenols 0.500%
Antifoam agent 0.007%
Sulfurized fatty ester 0.300%
Viscosity index improver2 7.500%
Process oil diluent 1.363%
Base oil3 80.500%
100.000%

(1) A combination of 1.90% of overbased calcium sulfonate (HiTECD 611 additive; Ethyl Petroleum Additives, Inc.); and 1.25% of neutral calcium sulfonate (HiTEC~
614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
(2)Polymethylmethacrylate (Acryloid 954 polymer, Rohm &
Haas Chemical Company).
(3)A blend of 64~40% Petro Canada 160 neutral oil and 16.10% Petro Canada 650 neutral oil.

The procedures of Examples 26 and 27 are repeated except that in each case the sulfurized fatty ester is eliminated and replaced by a corresponding amount of process oil.

Case EI-6218+

The procedure of Example 26 is repeated using the same ingredients as therein specified except where otherwise indicated below:
Component a) 0.820%
Component b) 4.000%
Component c) 1.530%
Partially sulfurized tert-butyl phenols 0.300%
Antifoam agent 0.007%
Sulfurized fatty ester 0.300%
Viscosity index improver 7.500%
Process oil diluent 0.383%
Base oil1 85.160%
100. ooo%
- - - ~ _ _ _ (1) A blend of 56.38% of Esso Canada LXT oil and 28.78%
Esso Canada MCT-10 oil.

The procedure of Example 27 is repeated using the same ingredients as therein specified except where otherwise indi-cated below:
Component a) 0.680%
Component b) 5.500%
Component c) 3.150%
Partially sulfurized tert-butyl phenols 0.500%
Antifoam agent 0.007%
Sulfurized fatty ester 0.300%
Viscosity index improver 8.000%
Process oil diluent 1.363%

Base oil1 80.500%
100. ~00%
_ (1) A blend of 64.40% Petro Canada 160 neutral oil and 16.10% Petro Canada 650 neutral oil.

Case EI-6218+ ~ ~ 5 ~ ~ ~

The procedures of Examples 29 and 30 are repeated except that in each case the sulfurized fatty ester is eliminated and replaced by a corresponding amount of process oil.

A synthetic lubricant of this invention is formed by blending together the following components in the amounts specified:
Component a)1 0.500%
Component b)2 6.000~
Component c) 3 2.000%
Partially sulfurized tert-butyl phenols4 0.500%
Antifoam agent5 0.010%
Antirust additive6 0.150%
Pour point depressant7 0.300 Process oil diluent 1.000%
Viscosity index improver8 4.200%
Base oil9 85.340%
100.000%
_ (1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.).
(2) A product formed as in Example B-44.
(3) A combination of 1.5% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.); and 0.5% of neutral calcium sulfonate (HiTEC~
- 614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
(4) A product formed by reacting ETHYL~ Antioxidant 733 with sulfur monochloride, for example as in U.S. Pat.
NG. 4,946,610.
(5) Dow Corning Fluid 200; 60,000 cSt, an 8~ dimethyl silicone solution from Dow Corning Company.
(6) Sterox ND (Monsanto Company), believed to be ~-(nonylphenyl)-~-hydroxy-poly(oxy-1,2-ethanediyl).

` Case EI-6218+ 2~3~

(7) Santolube C (Monsanto Company).
(8) Te~aco TLA 347A additive, (Texaco Inc.).
(9) A blend of 77.001% 8 cSt poly-~-olefin oil (ETHYLFL0 168 oil; Ethyl Corporation) and 8.339% 4 cSt poly-~-olefin oil (Emery 2921 oil; Emery Group of Henkel Corporation).

The procedure of Example 32 is repeated except that component b) is prepared as in Example B-45 and is employed at a concentration of 5.940%, and the amount of process oil used is 1.560%.

~XAMPLE 34 The procedure of Example 32 is repeated using the same ingredients except as otherwise specified:
Component a) 0.500%
Component b) 6.000%
Component c)1 3.150%
Partially sulfurized tert-butyl phenols 0.750%
~is(p-nonylphenyl)amine2 0.050%
Antifoam agent 0.010%
~ntirust additive 0.150%
Process oil diluent 0.110%
Base oil3 89.280%
100.000%
- ~
(1)A combination of 1.90% of overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.); and 1.25% of neutral calcium sulfonate (HiTEC~ 614 additive; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.).
(2)Naugalube 438L antioxidant; Uniroyal Chemical Company, Inc.

(3)A blend of 82.14% 8 cSt poly-~-olefin oil (ETHYLFL0 168 oil; Ethyl Corporation) and 7.14% 40 cSt poly-~-olefin oil (ETHYLFL0 174 oil; Ethyl Corporation).

Case EI-6218+ 2 ~ 6 ~ 4 0 - 13~ -The procedure of Example 34 is repeated using the same ingredients except where otherwise specified:
Component a) 0.500%
Component b) 6.000%
Component c) 3.150%
Partially sulfurized tert-butyl phenols 0.750%
Bis(p-nonylphenyl)amine 0.050%
Antifoam agent 0.010%
Viscosity index improver17.200%
Process oil diluent 0.260%
Base oil2 82.080%
100.000%

(1) Paratone 715 (Exxon Chemical Company).
(2) A blend of 69.77% 8 cSt poly-~-olefin oil (ETHYLFLO
168 oil; Ethyl Corporation) and 12.31% 40 cSt poly-~-olefin oil (ETHYLFLO 174 oil; Ethyl Corporation).

An additive c:oncentrate of this invention is formèd by blending together ~ e following components as identified in Example 23:
Component a) 5.81%
Component b) 75.60%
Component c) 14.43%
Nonylphenol sulfide 2.81%
Bis(p-nonylphenyl)amine 0.50%
Antifoam agent 0.05%
Process oil diluent 0.80%
100.00%

EX~MPLE 37 An additive concentrate of this invention is formed by blending together the following components as identifisd in Example 25:

Case EI-6218+
2 ~

Component a) 18.48%
Component b) 45.73%
Component c) 25.10%
Nonylphenol sulfide 4.00%
Bis(p-nonylphenyl)amine 0.77%
Antifoam agent 0.11%
Process oil diluent 5.81%
100. 00%

An additive concentrate of this .invention is formed by blending together the following components as identified in Example IV:
Component a) 7.53%
Component b) 62.35%
Component c) 18.00%
Bis(p-nonylphenyl)amine 0.47%
Partially sulfurized tert-butyl phenols 3.53%
Antifoam agent 0.08%
Sulfurized fatty ester 3.53%
Process oil diluent 4 51%
~00. 00%

An additive concentrate of this invention is formed by blending together the following components as identified in Example 27:
Component a) 5.25%
Component b) 50.00%
Component c) 26.25%
Bis(p-nonylphenyl)amine 0.42%

Partially sulfurized tert-butyl phenols 4.17%
Antifoam agent 0.06%
Sulfurized fatty ester 2.50%
Process oil diluent 11.35%
100. 00%

Case EI-6218+ 2 An additive concentrate of this invention is formed by blending together the following components as identified in Example 26:
Component a) 7.80%
Component b) 64.63%
Component c) 18.66%
Bistp-nonylphenyl)amine 0.49%
Partially sulfurized tert-butyl phenols 3.66%
Antlfoam agent 0.09%
Process oil diluent 4.67%
100.00%

An additive concentrate of this invention is formed by 15 blending together the following components as identified in Example 29:
Component a) 11.17%
Component b) 54.50%
Component c) 20.83%
Partially sulfurized tert-butyl phenols 4.09%
Antifoam agent 0.10%
Sulfurized fatty ester 4.09%
Process oil diluent 5.22%
100. ~0%

An additive concentrate of this invention is formed by blending together the following components as identified in : E~ample 30:
Component a) 6.07%
Component b) 49.10%
Component c) 28.13%
Partially sulfurized tert-butyl phenols 4.~6%
Antifoam agent 0.06%
Process oil diluent 12.18%
100.00%

Case EI-6218~ 2a~3~

An additive concentrate of this invention is formed by blending together the following components:
Component a)1 5.23%
Component b) 2 46.15%
Component c)3 24.23%
Partially sulfurized tert-butyl phenols4 7.69%
Bis(p-nonylphenyl)amine5 2.31%
Antifoam agent6 0.11%
Sulfurized fatty ester7 2.31%
Seal Swell Agent8 3.85%
Antirust Additive9 1.54%
Process oil diluent 6.58%
100. 00%
15 - - - _ _ _ _ (1) Zinc dialkyl dithiophosphate having a mixture of alkyl groups formed from 40 mole % 2-propanol, 40 mole %
isobutyl alcohol, and 20 mole % 2-ethyl~1-hexanol~.
(2) A product formed as in Example B-45.
(3) A combination of 1.90% of overbased calcium sulfonat:e (HiTEC~ 611 additive; Ethyl Petroleum Additives, Inc., a product having a nominal TBN of 300); and 1.25% of neutral calcium sulfonate (HiT~C~ 614 additive; Et~
Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd., a product having a nominal TBN of 30).
(4) A product formed by reacting ETHYL~ Antioxidant 733 with sulfur monochloride, for example as in U.S. Pat.
No. 4,946,610.
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company, Inc.
(6) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl silicone solution from Dow Corning Company.
(7) SUL-PERM 60-93 (Keil Chemical Division of Ferro Corporation).
(8) Santicizer 160; Monsanto Company; believed to be butyl benzyl phthalate.

(9) Sterox ND (Monsanto Company), believed to be ~-(nonyl~
phenyl)-~-hydroxy-poly(oxy-1,2 ethanediyl).

Case EI-6218+ 2~3~

A lubricant composition of this invention is formed by blend-ing the above concentrate and a viscosity index improver in a base oil as follows:
Above additive concentrate 13.0%
Viscosity index improver1 7.5%
Base oil2 79.5%
100. 0%

: (1) Polymethylmethacrylate (Acryloid 954 polymer; Rohm &
Haas Chemical Company).
~2) A blend of 63.6% Petro Canada 160 neutral oil and 15.9% Petro Canada 650 neutral oil.

An additive concentrate of this invention is formed by 15 blending together the components as identified in Example 43 in the following proportions:
Component a) 4.22%
Component b) 51.85%
Component c);~ 23.33%
Partially sulfurized tert-butyl phenols 7.41%
Bis(p-nonylphenyl)amine 2.22~
Antifoam agent 0.10%
Sulfurized fatty ester 2.22 Seal Swell Agent 3.70 Antirust Additive 1.48 Process oil diluent 3.47%
100. oo%

A lubricant composition of this invention is ~ormed by blending the above concentrate and the viscosity index improver of Example XXI in a base oil composed of 63.2% Petro Canada 160 neutral oil and 15.8% Petro Canada 650 neutral oil as follows:

` Case EI-6218+
2~3~

Above additive concentrate13.5%
Viscosity index improver 7.5%
Base oil 79.0~
100.0%

The lubricating oil composition of Example I was subjected to the standard Sequence VE engine test procedure.
The results of this evaluation are summarized in the follo~ing table, which also shows the American Petroleum Institute SG
passing limits ~or the various parameters.

Table - Sequence VE Test Results Passing API SG
Ratin~ This Invention Limits Bnqine Cleanliness Average Sludge 9.38 9.0 min.
Average Varnish 7.44 5.0 min.
Oil Pump Relief Valve Varnish 9.65 --Rocker Arm Cover Sludge 8.81 7.0 min.
Piston Skirt Varnish6.64 6.5 min.

Enqine Wear Average Cam Lobe Wear, mils 0.78 5.0 max.
Maximum Cam Lobe Wear, mils 1.0 15.0 max.
Average Rocker Arm Wear, mg 8.7 --Maximum Rocker Arm Wear, mg 12.3 --Average Top Ring Gap, mils 8.8 --Maximum Top Ring Gap, mils 10.0 --Average Rod Bearing Loss, mg 145.3 --Maximum Rod Bearing Loss, mg 165.5 --Case EI-6218+
2 ~
-- 1~0 --The antiwear advantages that can be achieved by the practice of this invention were further illustrated by a series of standard 4-Ball wear tests (40 kg load, 1800 rpm, 130F, 30 minute test length) on three lubricating oil com-positions having the same total concentration of phosphorus therein. The compositions were identical to each other except that one such composition (Oil A) contained only zinc dialkyl-dithiophosphate as the phosphorus-containing component whereas another such composition (Oil B) contained a phosphorylated and boronated succinimide of this invention as the sole source of phosphorus. Oil C, a representative composition of this invention, contained the combination of both the same zinc di-alkyldithiophosphate and the same phosphorylated and boronated succinimide dispersant. All compositions also contained the lS same concentration of overbased calcium sulfonate having a nominal TBN of 300. The makeup of these compositions was as follows:
Oil A
0.98 grams of zinc dialkyldithiophosphate1 1.85 grams of overbased calcium sulfonate2 147.19 grams of mineral oil3 Oil B
10.02 grams of phosphorylated and borona~ succinimide4 1.85 grams of overbased calcium sulfonate2 138.13 grams of mineral oil3 Oil C
0.48 grams of zinc dialkyldithiophosphatel 5.01 grams of phosphorylated and boronated succinimide4 1.85 grams of overbased calcium sulfonate2 142.66 grams of mineral oil3 (1) HiTEC~ 685 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.) (2) HiTEC~ 611 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.) (3) Turbine 5 oil, a 100 Solvent Neutral refined min~ral oil Case EI-6218+

(4) Prepared as in Example A-44.

The results of these 4-Ball tests were as follows:

Composition Scar Diameter, mm Oil A 0.479 Oil B 0.475 Oil C 0.431 The ability of overbased alkali or alkaline earth metal-containing detergents to suppress copper corrosion was demonstrated by a series of tests employing varied proportions of components a), b), and c) in a base oil (Turbine 5 oil).
These tests were conducted according to ASTM D-130 but under more severe conditions, viz., operation at 121C rather than at the standard temperature of 100C. In these tests compo-nent a) was HiTEC~ 685 additive (a zinc dialkyl dithiophos-phate described above), component b) was formed as in Example A-44, and compnent c) was HiTEC~ 611 additive (an overbased calcium sulfonate). The compositions tested (weight percen-tages) and the results obtained therewith are tabulated ~elow:

Compositions Run 1 Run_2 Run 3 Run 4 h~l 5 Component a) 0.58 0.58 0.58 0.58 0.58 Component b) 7.50 6.50 5.50 4.50 3.50 Component c) 1.44 1.44 1.44 1.44 1.44 Base oil90.4891.48 92.48 93.48 94.48 Results-3a/3b 3a 3a la la ~S (Brownish (Brownish coating) coating) Another feature of this invention is that the particu-larly preferred phosphorylated and boronated alkenyl succini-mides of polyethylene polyamines made from alkenyl succinic anhydrides (or like succinic acyla~ing agents, such as the Case EI-6218~ 2 ~ ~ ~ 3 ~ ~

acid, acid halide, lower alkyl ester, lower alkyl-acid ester) in which the succination ratio (i.e., ratio of the average number of succinic groups per alkenyl group chemically bound in the acylating agent) is in the range of 1:1 to about 1.3:1 and in which the alkenyl group is derived from a polyolefin having a number average molecular weight in the range of about 600 to about 1,300 (preferably about 700 to about 1,200, and most preferably about 800 to about 1,100) when utilized in accoxdance with this invention can provide greater dispersancy than the same concentration or an even higher concentration of an analogous succinimide not containing boron or phosphorus or an analogous boronated succinimide made from a polyolefin of even higher molecular weight.
For example, a group of lubricant compositions made from different succinimide dispersants were subjected to a bench test simulating sludge performance in the Sequence VE
engine tests. This test involves subjecting each lubricant to standard Hot Oil Oxidation Test (HOOT) conditions and deter-mining the change in dielectric constant of the lubricants before and after the oxidation. On completion of the oxida-tion, the oxidized oil is mixed with a known amount of stan~
dard oxidized oil (a laboratory preparation) and diluted with a hydrotreated base stock. Turbidity measurements are then taken and then dielectric constant measurement, HOOT time and turbidity data, are combined into a single number for report-ing and comparison purposes. A lower number indicates better anti-sludge properties.
The lubricant compositions subjected to this test each contained zinc dialkyl dithiophosphate and a succinimide dis-persant, together with the remainder of the additive comple-ment described in Example II above. The oils each contained 1.20% of the zinc dialkyl dithiophosphate (~iT~C~ 685 addi-~ive). The concentrations of the respective succinimides were adjusted such that the respective oils each cont~ined 6.0% by weight of the active succinimide dispersant disregarding the amount of any boron-containing or phosphorus- and boron-con-Case EI-~218+
2~5~3~

taining species introduced into the succinimide by boronation or by phosphorylation and boronation.
The results of these tests were as follows:
Bench Test Succinimide Dispersant Used Sludqe Factor Phosphorylated & boronated (Mn = 900)1 76.0 Phosphorylated & boronated (Mn = 900)2 86.7 Neither phosphorylated nor boronated (Mn = 900) 277.0 Neither phosphorylated nor boronated (Mn = 1300) 175.0 Boronated only (Mn = 1300) 187.0 _ (1) Produced as in Example A-44.
(2) Produced as in Example A-45.

Rendering these results all the more remarkable is the fact that in U.S. Pat. No. 4,873,004 it is pointed out that to achieve improved dispersancy properties it is necessary to have a molar ratio of succinic groups to alkenyl groups (some-times referred to as the "succination ratio") of at least 1.4 when using succinimides made from polyamines such as tetraeth-ylene pental~ine and polyisobutenyl succinic anhydrides having number average molecular weights in the range of 600 to l,300.
For example the patent shows in its Tables 3 and 4 that with succinimide derived from polyisobutylene of number average molecular weight of 950, maleic anhydride and tetraethylene pentamine, products having a succination ratio of 1.0 gave inferior results on dispersancy and varnish formation than corresponding succinimides in which the succination ratio was 1.8. Yet as shown hereinabove, a boronated and phosphorylated polyisobutenyl succinimide with a succination ratio of about 1.18 made from polyisobutene of number average molecular weight of about 900, gave excellent results both on disper-sancy and on wear prevention.
As used in the foregoing description, the term "oil-soluble" is used in the sense that the component in question Case EI-6218~

has sufficient solubility in the selected base oil in order to dissolve therein at ordinary temperatures to a concentration at least equivalent to the minimum concentration specified herein for use of such component. Preferably, however, the solubility of such component in the selected base oil will be in excess of such minimum concentration, although there is no requirement that the component be soluble in the base oil in all proportions. As is well known to those skilled in the art, certain useful additives do not completely dissolve in base oils but rather are used in the form of stable suspen-sions or dispersions. Additives of this type can be employed in the compositions of this invention, provided they do not significantly interfere with the performance or usefulness of the composition in which they are employed.

Claims (19)

1. A lubricant or functional fluid composition or additive concentrate which comprises at least one oil of lu-bricating viscosity and at least the following components:
a) one or more oil-soluble metal hydrocarbyl dithiophosphates or dithiocarbamates; and b) one or more oil-soluble additive compositions formed by a process which comprises heating concurrently or in any se-quence at least one ashless dispersant which contains basic nitrogen and/or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride, or at least one partial or total sulfur analog there-of, or any combination of the foregoing; or (ii) at least one water-hydrolyzable organic phosphorus compound and water; and (iii) at least one boron compound;
such that a phosphorus- and boron-containing liquid composi-tion is formed, and from which excessive water, if present, has been removed at least during or after heating with (ii), if used.

2. A composition as claimed in Claim 1 wherein com-ponent a) consists essentially of one or more oil-soluble zinc dihydrocarbyl dithiophosphates.

3. A composition as claimed in Claim 1 wherein com-ponent a) consists essentially of a combination of at least two oil-soluble zinc dialkyl dithiophosphates.

4. A composition as claimed in any of Claims 1 through 3 wherein component b) is further characterized in that said at least one ashless dispersant used in forming said phosphorus- and boron-containing liquid composition consists essentially of (1) at least one hydrocarbyl succinamide, or (2) at least one hydrocarbyl-substituted succinic ester-amide, or (3) at least one hydroxyester of hydrocarbyl succinic acid, Case EI-6218+

or (4) at least one Mannich condensation product of hydrocar-byl-substituted phenol, formaldehyde and polyamine, or (5) at least one hydrocarbyl succinimide, or any combination of any two, or any three, or any four, or all five (1), (2), (3), (4) and (5).

5. A composition as claimed in any of Claims 1 through 3 wherein component b) is further characterized in that said at least one ashless dispersant used in forming said phosphorus- and boron-containing liquid composition consists essentially of at least one acyclic hydrocarbyl-substituted succinimide of a mixture of ethylene polyamines having an approximate overall composition falling in the range corre-sponding to diethylene triamine to pentaethylene hexamine.

6. A composition in accordance with any of Claims 1 through 5 wherein component b) is further characterized in that said at least one ashless dispersant used in forming said phosphorus- and boron-containing liquid composition consists essentially of at least one acyclic hydrocarbyl-substituted succinimide ashless dispersant having a succination ratio of 1:1 to about 1.3:1.

7. A composition in accordance with any of Claims 1 through 6 wherein component b) is further characterized in that said at least one ashless dispersant used in forming said phosphorus- and boron-containing liquid composition is com-prised of at least one substituted succinimide in which the substituent is derived from a polyolefin having a number average molecular weight in the range of 500 to 5,000.

8. A composition as claimed in Claim 8 wherein said substituent is derived from polyisobutene having a number ave-rage molecular weight in the range of 700 to 2,500.

9. A composition as claimed in any of Claims 1 through 8 further comprising a minor proportion of at least Case EI-6218+

one oil-soluble alkali or alkaline earth metal-containing detergent.

10. A composition as claimed in any of Claims 1 through 9 further comprising a minor proportion of at least one oil-soluble overbased alkali or alkaline earth metal-con-taining sulfonate.

11. A composition in accordance with any of Claims 1 through 10 wherein component b) is formed by heating (i) and (iii) thereof with said ashless dispersant, concurrently or sequentially in any order.

12. A method of operating an internal combustion engine having a crankcase containing a lubricating oil formu-lation, which method comprises utilizing as the lubricating oil formulation in said crankcase a lubricant composition according to any of Claims 1 through 11 hereof.

13. A method of operating a mechanical mechanism in which an elastomeric material is in contact with a lubricant or functional fluid, which method comprises utilizing as said lubricant or functional fluid a composition according to any of Claims 1 through 11 hereof.

14. A method according to Claim 13 wherein the elas-tomeric material comprises a fluoroelastomer.

15. A method of formulating a lubricant or functional fluid wherein a plurality of additive components are blended into an oil of lubricating viscosity characterized in that at least one oil-soluble zinc dihydrocarbyl dithiophosphate and at least one oil-soluble phosphorus- and boron-containing li-quid composition are blended into said oil, said phosphorus-and boron-containing liquid composition having been prepared by a process which comprises heating at least one basic nitro-gen-containing and/or hydroxyl-containing ashless dispersant Case EI-6218+

concurrently or in any sequence with (i) at least one inor-ganic phosphorus acid or anhydride, or at least one partial or total sulfur analog thereof, or any combination of the fore-going; or (ii) at least one water-hydrolyzable organic phos-phorus compound and water; and (iii) at least one boron com-pound; such that a phosphorus- and boron-containing liquid composition is formed, and from which excessive water, if present, has been removed at least during or after heating with (ii), if used.

16. A method according to Claim 15 wherein the total concentration of said at least one zinc dihydrocarbyl dithio-phosphate and said phosphorus- and boron-containing liquid composition that is blended into said oil of lubricating vis-cosity is in the range of 0.11% to 25%, preferably 0.3% to

17%, more preferably 0.8% to 11.4%, and most preferably 1.35 to 9.35% by weight based on the total weight of the lubricant or functional fluid composition.

17. A method according to Claim 15 or 16 wherein a portion or substantially all of said phosphorus- and boron-containing liquid composition is blended into said oil of lu-bricating viscosity concurrently with a portion or substan-tially all of said at least one oil-soluble zinc dihydrocarbyl dithiophosphate.

18. A method of formulating a lubricant or functional fluid wherein a selected amount of phosphorus in the form of one or more oil-soluble phosphorus-containing components is blended into an oil of lubricating viscosity, wherein said amount of phosphorus is made up at least in part of at least one zinc dihydrocarbyl dithiophosphate, and wherein said se-lected amount includes phosphorus in the form of at least one liquid oil-soluble composition formed by heating concurrently or in any sequence at least one ashless dispersant which con-tains basic nitrogen and/or at least one hydroxyl group with (i) at least one inorganic phosphorus acid or anhydride, or at Case EI-6218+

least one partial or total sulfur analog thereof, or any com-bination of the foregoing; or (ii) at least one water-hydro-lyzable organic phosphorus compound and water; and (iii) at least one boron compound; such that a phosphorus- and boron-containing liquid composition is formed, and from which excessive water, if present, has been removed at least during or after heating with (ii), if used.

19. A method according to any of Claims 15 through 18 wherein said at least one ashless dispersant used in form-ing said phosphorus- and boron-containing liquid composition consists essentially of at least one acyclic hydrocarbyl-sub-stituted succinimide of a mixture of ethylene polyamines hav-ing an approximate overall composition falling in the range corresponding to diethylene triamine to pentaethylene hexa-mine; wherein said phosphorus- and boron-containing liquid composition is formed by heating (i) and (iii) thereof with said ashless dispersant, concurrently or sequentially in any order; and wherein there is also blended into said oil of lubricating viscosity a minor proportion of (1) at least one oil-soluble overbased alkali metal-containing detergent or (2) at least one oil-soluble overbased alkaline earth metal-con-taining detergent, or a combination of (1) and (2).