CA1072073A

CA1072073A - Extreme-pressure mixed metal borate lubricant

Info

Publication number: CA1072073A
Application number: CA230,813A
Authority: CA
Inventors: John M. King; Nicolaas Bakker
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1974-07-15
Filing date: 1975-07-04
Publication date: 1980-02-19
Also published as: GB1514993A; JPS5139702A; FR2278756B1; IT1039859B; JPS5422201B2; US3907691A; GB1514994A; FR2278756A1; DE2531002C2; DE2531002A1

Abstract

ABSTRACT OF THE DISCLOSURE
EXTREME-PRESSURE AGENT AND ITS PREPARATION
A lubricating composition comprising a major portion of a lubricating oil and a minor amount of a partic-ulate dispersion of a mixed alkaline earth metal and alkali metal borate.

Description

t~Z~3 DESCP~IPTION O~_THE_NVENTION 38 "
~ lu~erous aaditives are incorporated into lubricating 40 oils and greas~s to enhance their lubricating properties. A 42 wide variety of materials have been employed to increase the load-carrYing capacity of lubricants employed under boundary or 44 extreme-pressure ~Pl conditions. When moving suraces are 45 separated by oil or a grease, as the load is increased and the 46 clearance is reduced between the sur~aces, the condition of 47 bounaary, or thin~ilm, lubrication is reached. Metal-to-metal 48 contact occurs and ~ear or seiZure results. Under these 49 conditions, the effectiveness of lu~ricants in reducing ~ear or 50 friction varies ~iaely. At still higher loads, the condition 51 commonly ~no~n as extreme-pressure lubrication is reached. ~2 Scuffing, galling, and rapid ~ear or seizure may occur. S3 '~elding of two contacting surfaces occurs, follo~ed by metal 54 transfer (galling) or cleavage and proauction o~ metal 55 `~
fragments. 56 In order to aYoid the undesirahle effects which 57 ' result ~hen using an uncompounaed lubricant under high load 59 conditionsr extreme-pressure agents are adaed. For the most 60 part, the extreme~pressure agents have been oil-solu~le agents 61 containing a chemically reactive element, e.g.~ chlorine, sulfur, or phosphorus, which react with the metal surface at 62 the high temperatures produced onder load conditions. This 64 chemical bond to the EP agent then provides relatîvely good~
boundary protection. 65 Recently, a new type of additive has been de~eloped 66 ~hich, unlike the chemically reactive chlorine~, sulfur- or 67 phosphorus-containing EP agent, does no~ react with the metal 68 surfaces to become chemically honded thereto. Instead, this~ 70 extreme-pressure additive is a dispersion of microparticulate 71 alkali meta1 ~orates which is belieYed to deposit on the metal

- 2 ~

~ ~ V~ 3 surf2ce of ~ viscous lubric~ting ~ln. Ihese borates and the~r Preparation are disclo~ed in United States~Patènt 3,313,727.
~he microparticulate metal borates are typlcally prep~red by ~ ~
dissolving an alkali metal borate, or its precursors, in water and emulsi~y- -ing the aqueous solution in oil to form a micro-emulsion. The emulsion is then dohydrated, leaving amorphous or glassy particles of the hydrated alkali metal borate dispersed within the lubricating oil.
~e have now found that a mixed alkali and alkaline earth metal borate dispersion exhibits excellent extreme pressure properties in lubricat~
ing oils. These dispersions may be prepared by contacting boric acid with -`
an aIkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate to prepare an alkaline earth metal borate, which is then contacted with an alkali metal base to form the mixed metal borate. ~ s referred to herein, overbased materials are characterized by a metal content in excess of that stoichiometrically required by the reaction of the metal with the `
particular sulfonic acid. I~he base ratio is the ratio of the chemical equivalents of excess metal in the product to the chemical equivalents of ~-the metal required to neutralize the sulfonic acid.) By employing a mixed alkaline earth metal and alkali metal borate, it was found that the lubricant exhibited excellent extreme-pressure -properties. In addition, it was discovered that the mixed metal borate ~ ;
dispersions exhibited improved compatibility with other additives which are normally incorporated into lubricating oils.
Thus, in a first embodiment, this invention provides for a lubricating composition comprising a m~ or portion of an oil of lubricating viscosity and a minor portion of an improved extreme-pressure additive comprising a particulate mixed alkali and alkaline earth metal borate dis- ` i persion h~ving a mean particle size below about 1 micron. `
In a second embodiment~ this inYention provides for a lubricating composition comprising a portian of an oil of lubricating viscosity and from 0.1 to 60 weight percent of a particulate mixed aIkali and alkaline earth metal borate dispersion prepared by reacting within an inert, stable, oleo-~ - 3 -10~2~3 philic, reaction med~um~ horic acid, With (2~ an alkaline earth metal carb~nate overbased alkali or alkal~ne earth ~etal sulfonate dispersant, to form an intermiediate reaction product which is then reacted W~th an alkali metal base to form said mixed alkali and alkaline earth m~tal borate dispersion. ~
In a third embodiment, this invention provide~ for a particulate i`
dispersion of an aIkali and alkaline earth metal borate prepared by contact~
ing boric acid with an alkaline earth metal carbonate overbased alkali or ~ ~
alkaline earth metal sulfonate within a stable, inert, oleophilic, liquid ~ -reaction medium to formian intermiediate reaction product~ which is then react-ed with an alkali metal hydroxode to form a mixed alkali and alkal~ne earth -metal borate dispersionO i-~
In a fourth embodiment, this invention provides for a process for preparing a particulake alkali and alkaline earth metal borate dispersion which comprises contacting an alkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate with boric acid within a stable, inert, oleophilic, li~uid reaction medium to form an intermediate reaction product ~`
which is thereafter contacted with an alkali metal base to form said mixed alkali and alkaline earth metal borate.
In a fifth embodiment, this invention provides for a process for preparing a particulate alkali and alkaline earth metal metaborate dispersion which comprises contacting within an inert, stable, oleophilic reaction medium 2 to 6 molar parts of boric acid with each molar part of boric acid with each molar part of an alkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate to form an intermediate reaction product, there-after contacting said n~ermediate reaction product with 1 to 3 molar parts of an alkali metal ~droxide per molar part of said intermediate reaction .. .; .;.
product to prepare said alkali and alkaline earth metal borate dispersion.
Detailed Description of the Invention The borate dispersions of this invention are stable dispersions of -micronic size particles of a mixed alkaline earth metal and alkali metal borate. The borate particles are ~ 3a -~0'7XO~

almost entirely less than 1 micron, and more usually less than 114 0.1 micron, in si~e. The produc-t may be filtered to remove ~he 11 larger i~icroparticles.
The borate mixture may be a physical mixture of 117 alkaline earth metal borates and alkali metal borates; a 118 chemical mixture, such as alkaline earth and alkali metal borate; or a mixture thereof. 119 Exemplary types of mi~ed me~al borates which may be 121 einployed in the practice o~ this invention include calcium and 122 sodium borate, barium and sodium borate~ calcium and Fotassium 123 borate, barium and potassium borate, etc. Borates containing 125 magnesium or lithium may also be employed, but are less 126 pre~erre~. In additionr mixtures-of al~aline earth metals and 127 mixtures of alkali metals may be ernployed; for example, 129 calcium-barium and soaium borate, calcium and soaium-Fotassium 130 borate, etc.
The mixed metal borates may also have from 0 to 8 132 -~aters of hydration, although f~om 0 to 3 waters of hydration 133 are preferred, and ~ore pre~erably from 0 to 2 waters of 134 hydration~ ~ 135 In a preferred embodiment, the borate dispersion is 137 prepared by the ~ollowi~g steps: (1) contacting ~ithin an 138 inert, stable, oleophilic reaction medium from 2 to 6 molar 13g parts of boric acid per molar yart of an alkaline earth metal 141 carbonater which is present as an oYerbased oil-soluble alkali 142 or alkaline earth metal sulfonate, to for~ an alkaline earth metal borate; and ~2) contacting the alkaline earth metal 143 borate ~ith an alkali metal base to form the mixed alkaline 144 earth ~etal and alkali metal borate. This exemplary processing 146 scheme may be condu~ted in a continuous ~anner or in a batch 147 manner, or a combination of both. The opti~um reaction 149 conditions may vary, dependin~ on whether continuous or batch 1~0 ~ 4 ~

~ 3 processing is selected; howeYer, the broad conditions set forth 151 hereinafter are su~stantially inclusive of both types of 152 processing.
The alkaline earth metal car~onate overbased alkaline 153 earth or alkali metal sulfonate which is one of the reactants 154 herein is prepared by overbasing neutral alkali or al~aline 156 earth metal sulfonate.

NEUTR~L META _S~11FON}lTE 159 The neutral alkall or al~alinç earth metal sulfonates 161 which may be overbasea in the practice o~ ~his invention can 162 comprise any oil-soluhle alkali or alkaline earth ~e~al 164 sulfonate. Pre-~erably, these sulfonates are aromatic and have 165 the follol~ing generalized chemical formula: 166 P . ~

wherei~: R is hydrogen or a~ alkyl ha~ing from 10 t~ 22 158 carbons (preferably from 15 to 21 carbons) and pre~era~ly 169 attached to the benzene ring through a secondary carbon atom; 171 Rl is selected from ~a~ an alkyl ha~ing from 3 to 10 carbons 172 ~;
when R is an alkyl, or (b) an alkyl having fro~l 8 to 22 carbons 1~3 when R is hydrogen; M is an alkali or alkaline earth metal; and 175 p is an integer ~rom 1 to 2 and sufficient to make M electro- 117 neutral.
In a particular embodiment~ the neut~al metal 178 sulfonate is a aialkylbenzene sul~onate of the above formula 179 wherein R is a straight~chain aliphatio h~arocarbon radical of 180 17 to 21 carhon atoms, usually having at least 2 ho~olcgs 18i present, and having secondary carbon attachment to the benzene 1~2 ring; and Rl ls a ~ranched-~hain alkyl group of 3 to 10 carbon 183 - 5 ~

lO~Z~3 ato~s, ~ore usually from 4 to 9 carbon ato~s,.having at least 1 184 ho~olog present, and preferably having at least 2 homologs 185 1 ~.
present, and there being at least 1 branch of 1 to 2 carbon 186 atoms, more usually of 1 carbon a~o~ i.e~, methyl, per 2 1S7 carbon atoms along the longest chain. The attachment af the 189 shorter alk~l group ~ill generally be secondar~ or te~-tiary~ 190 Particular compositions have Rl ~ith an average of 5 to 8 1g2 carbon atoms.
~sually, ~he differe~ce in average number of carbon 19l~ :
atoms ~et~een the short~ and long-chain alkyl groups will be dt 195 least 10 and more usually at least~12, and not more than 16~ 19 : The preferrea dialkylben~ene sul~onates which may be 197 ll employed in the practice of this invention will generally have 198 1.
small a~ounts of ~onoal~ylbenzene sulfonate~ wherein the alkyl 200 group is o-f from 17 to 21 carbon atoms,.p.resent ~ithin the 20l l~
admixture. Preferably the amount of the monoalkylben~ene 202 1 :
sulfonate ~ill not exceea 30~ and more preferably the 203 monoalkylbenzene s~l~onate ~ill not.exceea 20% by weight of the ~S l total sul~onate. Generally, it will be in the range of a~out 5 207 to 20 weight percent. l,.
The positions of the alkyl group and the sulfonate on . 209 the ~enzene ring in relation to each other are not critical to 210 , this inventionO Generally, most of the isomeric possi~ilities 211 ~j .
~ill be encountered -- with the particular isomers having the 212 I .
least steric hindrance being predominant Also, there ~ill be 214 ~ :
a broaa spectru~ of isomers based on the carbon of the alkyl 215 group bonded to the benzene ring, depending on the methGd o~ 216 11 preparation and the reactants used in the preparation~ 217 ~¦
Illustrativ~ short~chain alkyl groups are isopropyl, 21 tert.-butylr neopentyl, diisobutyl, dipropenyl, tripropenyl, 21 e~c. 220 ~

'~ . .
.

~ q3 Illustrati~e of the long-chain alkyl groups are 221 heptadecyl, octadecyl, nonadecyl, eicosyl and heneicosyl. 222 The monoalkyl ~eazenes can be prepared by simply 223 reacting benzene ~ith a ~ono-ole~in in a simple alXylation 224 process. Typical alkylation catal~sts incluae ~rieael-Crafts 226 catalysts such as hydrogen fluoride, aluminum chloride, 227 phosphoric acid, etc. The alkylation temperatures ~ill 22a ordinarily be in the range o~ about 4C. (40F~ to 38C. 229 ~100F.).
The particular dialkyl~enzenes can be prepared in Z31 substantially the same manner. A aescription of its 232 preparation is disclosed in ~.S. Patent 3,470,097. 233 The mono- or dîalkylbenzenes may then be readily 234 sulEonated, using conventional sulfonation procedures and 235 a~ents, including oleum, chlorosulfonic acid, sul~ur trioxiae 236 (complexed or thin-film ailution tech~igues) and the lika~ 237 Various methods may be used to neutralize the 238 sulPonic acla obtalned, these methods being extensively 239 described in the art. See for example ~.S. Patents 2~485,861, 241 2,402~325 and 2,732,344. The neutralization step is 243 conveniently conducted ~y contacting the sulfonatea al~yl~ or 244 dialkylbenzenes with an aqueous al~ali metal hydroxide 246 solution. The product is a neutral alkali metal sulfonate. 247 ~he neutral alkaline earth metal sulfonate is prepared by a 24~
simple metal-exchange process~ The alkali metal sul-fonate is 250 contacted ~ith an alkaline earth metal salt, typically the 251 halide salt, and the mixture heated~ The exchange process may 252 be accomplished at temperatures o~ 50 to 150C. and contact 253 times of 0.5 to 10 hours, usually from 1 to 3 hours. 254 Ordinarily, the neutralized product will be mildly 256 oYerbased~ having from about 0.02 to 0~7 mol percent excess of 257 ~asic l~etal oYer that required ~or neutralizing the acid.

, ~ 7 3 Alkalinity values of these neutral compositions will generally be in the range of about 1 to 30, more usually from about 1 to 10 mg KOH/g.
Specific examples of exemplary metal sulfonates which may be overbased for use in this inven~ion are disclosed in United States Patents

3,691,075, 3,629,209, 3,595,790, and 3,537,996.
Illustrative individual compositions are sodium isopropyl eicosylbenzene sulfonate~ potassium or barium tert.-butyl nonadecylbenzene sulfonate, calcium dipropenyl oc~adecylbenzene sulfonate, calcium diisobu~yl octadecylbenzene sulfonate, sodium ~propylene trimer) nonadecylbenzene sulfonate, barium isopropyl eicosylbenzene sulfonate, etc.
OVERBASING OF THE NEllTRAL ~ETAL SULFONAT13 `-Various methods of overbasing neutral metal sulfonates have been reported in the literature. See for example United States Pa~ents 2,695,910, 3,282,835, and 3~155,616~ as well as Canadian Patent 570,814. The preferTed method employs a method similar to that described in United States Patent 3,155,616.
The overbasing process can be conveniently conducted by charging to a suitable rsaction zone the neutral metal sulfonate and an inert hydro- -carbon solvent. An alkaline earth metal base ~usually the oxide or ;
hydroxide; and a Cl to C4 alkanol is added while ~he mixture is agitated and maintained at a temperature and pressure to retain most of the alkanol charged. Carbon dioxide is simultaneously contacted with the reaction medium, preferably sparged or bubbled through the liquid mixture~ The introduction of the carbon dioxide is continued until its absorption rate into the mixture ceases or substantially subsides. Generally, from 0.2 to 1.6 equivalents and m~re usually from 0.9 to 1.3 equivalen~s of carbon dioxide `.j ~0'~2~

~ill be absor~ed by the mixture for every egulvalent of 299 alkaline earth metal base present.
The crude reaction proauct is then heated to strip 300 out the residual alkanol and water of reaction. The stripping 302 ~ill generally be conducted at temEeratures below 150C. a~d usually below 125C. After stripping the alkanol and ~ater, 304 the product may be filtered. 305 In a diEferent embodiment~ the hydrocarbon ailuen~ is 306 ~irst stripped and then the product is -Eiltered. Alsoy urther 308 addition of oil may be maae to obtain a product having a 309 some~hat lower viscosity~ The choice of the particular route 310 will depend on the equipment, -the materials used~ their 311 physical properties, and the product desired. 312 The alkanol used, preferably methanolt will generall~Y 314 have from about 0.01 to 1 ~eight percent water, more usually 315 .
from about 0.1 to 0~7% water. The alkanol will generally be 317 prese~t from about 0.1 to 20~ more usually from a~out 1 to 10 318 weight parts per part of alkaline earth metal base~ 3i9 The hydrocarbon diluent will be one having a boiling 320 point h~gher than alkanol to permit its retention ~hen the 321 alcohol is removed during processing. The boiling point should 323 generally be less ~han a~out 280C. and preferably less than 324 about 250~C. Usually the hydrocarbon diluent will form an 32 azeotrope with ~ater. The usual diluents contain aromatic 327 hydrocarbons o~ 7 to 10 carbon atoms, havinq boiling Foints in 328 the rallge of about 100 to 180C~ These include toluene, 330 xylene, cumene and cymene. The hydrocarbonaceous diluent can 331 ~e present in an amount to form about a 5- to 20-~eight-percent 332 dispersion of alkaline earth metal base in the initial 333 composition~ usually an 8 to 15 weight percent dispersion. 334 The amount of overbasing varies greatlyt depending 33 upon the amount of borate dispersion ultimately wanted. 336 9 _ l~Z~3 Typically, from 1 to 20 equivalents o~ alkaline earth metal 337 base will be used per equivalent of neutral metal sul~onate, 338 more usually from about ~ to 15 equivalents of alkaline ear~h 340 metal base per equivalent o~ neutral metal sul~onate. Thus, 341 alkalinity values range from 50 to 460 ~g KO~I/g, and preferably 342 from about 150 to 300 mg KOH~g. 343 It should be recognizea that mixtures of alkaline 3q4 earth metal carbonates may be employed as well as mixtures o~ 345 alkali and alkali~e earth metal sulfonates. Thus, a calcium 347 ~ -and barlum carbonate overbased sodium and calcium sulEonate may 348 be present in the same mixture, which may be further reactea ~49 with the boric acid to form the intermeaiate borate particulate 350 dispersion.
OLLQP~IILIC R13ACTION MEDIUM 353 The overbasoa metal sulfonate is contacted with boric 356 acid within a suitable oleophilic reaction medium. as re~errea 358 ~
to herein, "oleophilic'1 is defined as a property of a su~stance 359 having a stro~g affinity to oils. The liquid oleophilic ~edium 36 is generally present in the preparation o~ the overbased 361 sul~onate, ana hence e~traneous addition of the medium is 362 normally not necessary. T~e oleophilic reaction medium can 363 comprise any stablet inert, organic oil having a viscosity 364 ranging from 50 to 10~0 SUS at 38 ~C. (100F.) and preferably 366 from 50 to 350 SUS at 38C. Examples of stable organic oils 367 which ~ay be employed include a wide Yariety of hydrocarhon 369 lubricating oils (preferred~, such as naphthenic-base, -~
paraffin-base and mixed-base lubricating oils~ Other 371 oleophilic oils include oils derived fro~ coal pro2ucts and synthetic oils, e.g., alkylene polymers (such as polymers of 372 propvlene, butylene, etc., and mixtures thereof~, alkylene 373 oxide-type p~lymers (e.~., alkylene oxide polymers p~epared by 374 polymerizing alkylene o~ide~ e.g~, propylene oxide poly1ners, 375 lO'~Z~q3 etc., in the presence of ~ater or alcohols, e.g., ethyl 376 ~ ;
alcohol), liquid esters of acids of phosphorus) alkylben~enes, 378 polyphenols ~e.g., biphenols and terphenols), alkyl biphenol 379 ethers, polymers oE silicon, e~g., hexyl~4-~ethyl-2-pentoxy)- 380 disilicone, poly~ethyl)siloxane, and poly~methyl- 382 phenyl)siloxane, etc~ The oleophilic lubricating oils may be 3~4 used individually or in co~binations, ~hene~er: isci~le or 385 whenever made so by use of mutual sol~ents~ 386 When concentrates are desired, the viscosity of ~he 388 o~erbased sulfonate in the oleophilic reaction medium is generally too high ~or normaI processing. In these ins~ances, 389 it is preferred that a light hydrocarbon diluent be employed to 390 reduce the viscosity of the reaction medium. The diluen~ may 392 be aliphatic or aromatic and boiling b lo~ 250C. and 393 preEerably belou 200C. Exemplary aromatic diluents include 394 ~-benzene, toluene, xylene, etc~; exemplary alipha~ic ailuents - 395 .
include cyclohe~ane~ the heptanes, octanes, etc. The diluent 396 should not boil belo~ 70C. and preferably not below 100C. 397 At the end of the processing steps~ the diluent may 399 .i..~
~e strippea from the s~stem. Any of the conventional stripping techniques may be employed. 400 PREPARATION_OF MIXED ~METAL BOR~TES 403 'rhe mixea metal borate 2ispersion may be prepared, in 406 a preferred e~bo~i~ent, by the follo~inq steps: a sui~able 408 reaction vessel is charged with the alkaline earth metal 409 carbonate o~erbased metal sulfonate uithin the oleophilic 410 ;~
reactioD medium (typically the hydrocarbon medium e~loyed to 411 prepare the overbased ~etal sulfonate) and, preferably, a light 412 hydrocarbon diluent. The bo~ic acid is then charged to the 413 reactian ~essel and the contents heated, while vigorously - 415 agitated. Th~ reaction proauct is an alkaline earth metal 416 borate aispersed ~ithin the oleophilic reaction medium 417 ... : . . . : , . . : :

~ ZO~3 - ~
-Th~ reaction may be conducted for a period o~ 0.5 to 419 7 hours, usually from l to 3 hours, at a reaction temperature of 20 to 200C., preferably from 20 to 150C., and ~ore 421 preferably ~rom 40 to 125C~ ~t the end of the reaction - 422 period, tha temperature May be raised to 100 to 200C., 423 preferably from 100 to 150C~, to strip the ~edium of any water 425 and a portion up to the whole thereo of the reaction diluent.
The stripping may be done at atmospheric press~re or und~r 426 reducea pressure of 700 mm to 10 mm 8g absolute~ 428 The amount of boric acid charged to the reaction 430 mediu~ may ~ary from 2 to 6 molar parts and preferably from 3 431 to S molar parts per Dlolar part of alkaline earth metal carbonate~ Preferred composltions are prepared ~hen apFroxi- 432 mately 4 molar parts of boric acid are contacted ~ith each 434 molar part of alkaline earth metal carbonate~
The alkaline earth metal borate ~ithin the oleophilic 435 reaction medium and diluent is then contacted ~ith an alcoholic 437 solution o~ an alkali metal base to form the mixed metal borate 438 -dispersion. Exe~plary alkali metal bases include sodium 439 hydroxide, potassium hydroxide, lithium hydroxide, sodium 441 alcoholate (Cl-C3), potassium alcoholate (Cl-C3), etç7 Preferred alkali metal bases are the hydroxides~ An alcoholic 4~3 solution is preferred, and can comprise any o the lo~er 444 alcohols, e.g. C1-C5 alkanols. Methanol is pre~erred. The use 445 o-f an alcoholic medium only represents a preferred embodiment 447 of the practice of the present invention. Any person skilled 449 in the art could easily select other media which may be 450 successfully employea. 451 This reaction i5 conducted at a te~perature of 90 to 452 140C. and preferably from 110 to 120C. for a period varying 453 from 0~1 to 3 hours~ The resulting product may be ~iltered to 455 remove any large particulate matter~ 456 ~Z~3 ~

The a~ount of alkali metal base which may be charged 458 to the reaction medium may vary over a ~ide range Generally 459 from 1 to 3 molar partsr'preferably frorn 1.5 to 2.~ molar parts 460 oE alkali metal base is contacted ~ith each molar part o~
alkaline earth metal borate. 461 The preferred borate dispersion is a mixed calcium 462 sodium borate having fro~ 0 to 8 ~aters of h~dration ~pref- 463 erably 0 to 3 and prepared ~y reacting a calciu~ carbonate 465 overbased soaium, calcium or barium petroleum sulfonate ~lth 466 boric acid followed ~y the r~action with sodium hydroxide. 467 LUBRIC~NT 470 The amount of'mi~ed metal borate which may be present 473 in the lubricating oil to form the lubricant'may vary ~rom 0.1 475 to 60 weiyht percent~ depending on whether a concentrata or 476 inal lubricant is desire~. Generally, for c~ncentrates, the 4~8 mixed metal borate content ~aries from 20 to 50 weight percent, 479 and preferably from 35 to 45 ~eight percent. For lubricants, 481 'the amount of ~ixed ~etal borate generally varies from 0.1 to 482 20 weight percent and yreferably from 4 to 15 weight percent, 4~3 based on the total composltion.- The lubricating oil~which may 484 be employed herein can comprise any stable oil of lubricating 485 viscosity, i.e., viscosity ranging from 50 to 1000 SUS at 38C~ 486 (100F_) and preferably from 50 to 350 SUS at 38C~ Exemplary 488 lubricating oils are illustrated under the discussion of' 489 exemplary oleophilic reaction media. 490 OTHER P.DDITIVES 493 The water-tolerance properties of tbe ~ixed ~etal 49S
borate dispersion ~ay be i~proved by the addition of a 49~
lipophilic, nonionic, surface-active agent to the lubricant. 498 The lipophilic, nonionic, surface-active agents include those 500 generally referred to as "ashless detergents~ Preferably the 501 nonionic surfactants will have an ~I~B ~alue (hydrophilic-, ~7~
, ~
l1pophilic balance) below about 7 and pre~erably belo~ about 5. 502 These ashless detergents are ~ell known in the art and include 503 hydrocarbyl-substituted amines, a~ides and cyclo-imides. The 505 h~ydrocarbyl group or groups act as the oil-solu~ iny group, 506 and the a~ine~ a~ide or imide groups act as the polar-liqui~
solubilizing group. 507 A principal class of lipophilic, nonionic, sur~ace- 50a acti~e agents is the N-substituted al~enyl succinimides, S09 derived from alkenyl succinic acid or anhydride ana alkylene 510 polyamines. These compounds are generally considered ~o have ~ 511 the f or ;nula: ~ ~

O O ' . : :
R-C~I-C A A ,,C-C~I-R~
I ~-Alk~(N-Alk)n-N- -Alk-N
C~I2-C' ' C-C112 ~.
O 0 m uherein R is a hydrocarbon radical having a molecular weight 513 from about 400 to about 3000 ~that is, R is a-hydrocarbon 514 radical containing about 30 to about 200 carbon atoms) r ~lk is 515 :~
an al~ylene radical~of ~ to 10, preferably 2 to 6~ carbon 516 atoms, ~ is hydrogen or an alkyl having from 1 to 6 car~ons; n 517 is an integer from 0 to 6, preferably 0 to 3, and m is an 5l8 integer from 0 to 1, preferahly 0~ ~The actual reaction 520 product of alkenyl succinic acid or anhydride and alkylene 521 polya~ine will comprise~a mixture of compounas, including 522 succinamic acids and succinimides. However, it is customary to S2~ ~;
designate this reaction product as "succinimide" of the 524 described formula, since that ~ill be a principal com~onent of 525 the dispersant mixture~ See U.S~ Patents 3,202,678; ~,~24,237; 526 and 3,172,891.

These ~I-substituted alkenyl succinimides can be 527 prepared by reacting maleic anhydride ~ith an oIefi~nic hydro- 528 carbon, followed by reacting the resulting alkenyl succinic 529 ~ 14 -2~73 ~ ~
' -anhydride ~ith the alkylene polyamine. ~he ~Rl' radical o~ the ab~ve formula, that is, the alkenyl r~dical, is preferably deri~ed from an olefin Contain~ng from 2 to 5 carbon atQms.
Thus, the alkenyl radical may be obtained by polymerizing an ;;
;, :
~lèfin containing from 2 to 5 carbon atoms to form a ~-hydrocarboh having a molecular weight ranging from about 400 to 3000. Such ole~ins are exemplified by ethylene, propylene, 1~
: -~
butene, 2-butene, isobutene, and mixtureS thereof. Sir.ce the `
: ~ .
methods of polymerizing the olefins to form polymers thereof lQ are not the invention described herein~ any of the numerous processes a~ailable in the art can be used.
, . .. .
m e alkylene amines used to prepare the succinimides are of the formula , ~.-' .
H-N ~Alkl _ ~ Rl ;.
A L
Y ~ :
~herein y is an integer from 1 to 10, preferably from 1 to 6, A -~ `~
and Rl are each a substantially hydrocarbon radical having from 1 to 6 carbons or hydrogen, and the alkylene radical Alkl is preferably a lower alkylene radical having less than about 8 carbon atoms. The alkylene amines include ethylene amines, propylene amineS, butylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines, and also the cyclic and the higher homologs of such amines as piperazines and amino-alkyl-substituted piperazines. -They are exemplified specifically by: propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, trimethylene diamine, di(trimethylene~ triamine, 2-heptyl 3-(2 . . . . .
aminopropyl~ imidazoline, 1,3 bis~2-aminoethyl) imidazoline, 1-~2-aminopropyI)piperazine, 1,4-bis(2-aminoethyl)piperazine, and , 2-methy1-1-(2-aminobutyl) piperazine. Highér homolo~s Such as ~-2~
,~.

are obtained by condensing two or more of the above~ strated 565 alkylene amines likewise are useful. 566 A second group of i~portant nonionic dispersants 568 -~comprises certain pentaerythritol derivatives. Particular 570 derivatives ~hich ~ind use in this invention are those in ~hich 571 pentaerythritol is co~bined with a polyolefin and maleic anhydride or ~ith a polyole~in and a phosphorus sulfiae. The 573 polyole~ins are the poly~ers oE monon~eric ole~ins having 2 to 6 574 carbon atoms, such as polyet~hylene, polypropylene, polybutene, 575 i~
polyisobutylene, an a the like. Such olefins generally contain 577 a total of 20 to 250 carbon atoms and preferably 30 to 150 578 carbon atoms. The phosphorus sulfides include P2S3, P2S5, 579 P4S7, P4S3 and related materials. Of theser P2SS (phosphorus 581 pentasulfide) is pre~erred principally because of its ready 582 availability.

Other nonionic emulsifiers ~hich may be used include 583 ~ .
polymethacrylates ana copolymers of poly~ethacrylate or poly- 584 acrylate ~ith vinyl pyrrolidone, acryla~ide or methacrylamide. 585 ..
If a lipophilic, nonionict sur-face-active agent is 586 employed, it will generally be present in about 0 01 to S 588-~eight percent, more usually from ahout 0.~ to 3 weight percent, of the final composition. The actual amount of 590 dispersant requirea ~ ary with the particular dispersant 591 used and the total a~ount of borate in the oil. Generally, 593 about 0.001 to 1, more usually about 0.01 to 0.5, par~ by 594 weight of nonionic surface-active agent will be used per part 595 by ~eight of the borateO In the concèntrates, the mixture 596 ;~.
concentration ~ill be based on the relationship to borate 597 rather than on the fixed percentage li~its of the lubricant; 598 noted above. Generally, the upper ranges of the nonionic 599 ~ surface-active agent concentration ~ e used ~ith the upper 600 ; ranges of the alkali metal borate concentration~ 601 ~ - 16 '" ` . : . ~`:
l~Z1~3 Other materials may also he present as additiYes in 603 the composition of this invention. Such materials may be added 604 for enhancing some of the properties ~hich are imparted to the 605 lubricatillg medi~m by ~he alkall ~etal borate or providing 606 other desirable properties to the lubricat.ing medium. These 607 inclu~e additives such as rust inhihitors, antioxidants~
oiliness agents, viscosity inaex improvers, etc ~sually, - 609 these will be ln the range Erom about 0.1 to 5 ~eigh~ pe~cent, preferably in the range from about 0 1 to 2 weight percen~, of 610 the total composition. An antifoaming agent may also be added 611 wi~h aaYantage. The amount required uill generally be about 612 0.5 to 50 ppm~ based on the total composition. 613 The borate dispersions are pre-Eera~ly elnployed Ln 614 lubricating oils, such as gear and bearing oils~ cut~ing oils, 615 etc. ~
The borate dispersion may also be employed in greases 616 ~ -to impart e~treme-pr2ssure properties. The grease ccl~position 618 :
may be prepared by adding a thickening agent to the borate 619 dispersion in the oleophilic lubricating oil. The thickening 620 agent may be adaea directly to the borate dispersion or 621 produced l'in situ" uithin the oleophilic oil. Typical 62 thickening agents which may be employed include organic or metal orqanic thickeners such as polyurea, alkali metal 623 ~ ;
.
terephthalamate, lithium hyaroxy stearate~ ca~cium complex 624 soap, aluminum complex soap, polymeric thickeners, or 6~5 combinations thereof. 626 Exemplary polyurea greàses which nay be emFloyed are 628 disclosed in ~S. Patent 3,243,372. These greases are prepared 629 by reacting, ~ithin the lubricat;ng oil to be thickened, a 63Q

polyamine having from 2 to 20 carbons, a diisocyanate ha~lng ~31 from 6 to 16 carbons and a monoalnine or monoisocyanate, each 632 having from 10 to 3Q carbons~ Typically, these greases contain 633 io~ 3 from 5 to 15 ~eight psrcent of the pol~ure~ thi~kenar, although 634 lesser amounts may be used i~ other thickelling agents are 635 p~esent. ~ par~icularly preferred polyurea is a tetraure~ 636 p~epared by reacting one molar part of ethylene diamine ~ith 637 two molar parts of tolylene diisocyanate and two molar parts of 638 a monoamine having from 16 to 20 carbons. 639 ~ xemplary alkali meta~ terephthalamate greases are 640 disclosed in U~S. Patents 2~820,012 and 2,892~778~ These 642 greases may be prepared by~reacting a monoester of terephthalic acid ~ith an alkali metal base in the presence of a solYen~. ~ 644 particularly preferred grease contains from 8-15 weight percent of a sodium M-(hydrocarbyl~ terephthalamate having ~rom 5 to 24 645 carbons in the hydrocarbyl group, such as sodium N-octadeCyl 646 terephthalamate. 647 ~ `
The lithium hydroxy-stearate greases are the most 6~s8 L
widely employed Multi-purpose greases. These greases ha~e the ~50 properties ~hich~ render them particularly suita~le for use in 651 the practice of this inventionO The lithium thickening agent 652 - ~
is typically prepared by reacting lithium hydroxide ~ith 653 hydrogenated castor oil ana is present within a lubricating oil 654 at a concentration o~ 10 to 20%.
~ nother class of high-temperature greases which may 655 be employed is the calcium complex greases. These greases are 657 'composed of 5-20~o of a calcium soap, e.g., calcium hydroxy- 658 stearate, 4-20% of calcium acetate and 1-10~ of calcium 663 carbonate. A s~all amount of calcium hydroxide may also be 661 eMployed. Exemplary greases of this type are described in U~S~ 662 Patents 3,186t944 and 3,15g,575. 663 Exemplary aluminum complex greases are described in 665 U.S. Patents 3,476,684 and 3~514,400. Thése greases are 666 - prepared by incorporating into a lubricating oll from S-20~ oE 667 ! `:

Z~3 .

the reaction product of a long-chain fatty acid, an aromatic ~8 acid and aluminum isopropoxide.
The amount of thickener e~ployed in making the 66g greases of this invention ~aries, depending upon the type 670 thickener, type of lubricatin~ oil, hardness of the grease 671 desired and the presence of other additives~ When greases 673 having the preferred hardness of ~o. 2-4 NLGI t~STM work 674 penetration varying from 340 to 175) are employed, ~he amount 6~5 o~ thick-ener generally ~aries ~rom S to 25 weight percent and 676 more usually from 8 to 15 weight percent of the grease composition. 677 E~AMPLE 1 630 This example is presentea to illustrate the 682 preparation of a dial~ylbenzene sul~onate ~hich may be used to 68 prepare the overbasea met2l sul~onates.
Benzene is alkylated using a tetra~er polypropylene 686 fraction aDd H~ alkylation catalystr a reaction tempera-ture o~ 6~7 .. . .
~ about 18C. ~65Fr~ t and efficient mixing~ The hydrocarbon 689 .

phase is separated, washed and fractionated. The lower 690 al~ylbenzene fraction (boiling range 159C~ ~318F ] to 248C.
~478F.], asT~ D-447 distillation) is collected as feed for the 691 ;~
secona-stage alky~ation with a mixture o~ straight-chain i- 693 olefins. The average ~olecular ~eight of the above branched- 694 chain alkyIbenzene is 164. This corresponds to an average of 6 696 carbon atoms per alkyl group in the mixture~ The o~er-all 698 alk~l carbon ato~ content corresponding to the above boiling 699 range is the C4-C9 range.
Using the above branched-chain monoalkylbenzene and a 701 substantially straight-chain C17-C21 1-alkene fraction obtained from cracked wax~ and hydrogen fluoride catalyst, the desired 702 dialkyl~enzene is produced in a stirred~ continuous reactor~ 703 The 1-alkene feea has the follo~îng characteristics: 70~
; 19. - ~.

10'~7~
' ~verage mol ~eiyht 268 708 ~verage No. of carbon atoms per molecule 19 709 Ole-fin distribution, weight percent: 710 C19 ~ 39 7~3 C21 5 7l5 Reaction conditions: 717 .
LHSV 2 ; 718 Temperature 3~C. ~100F.j 719 Monoalkylbenzene to àlpha-olefin, 720 mol ratio 2-1 721 ~ydrocarbon to ~F ratio, volume 2.3-1 722 After reaction, the settled product is separa~ed into 726 an organlc phase and a lower HF-acid phase. The crude -727 dialkylbenzene organic phase is washed and then fractionated by 728 ~"~
distillat1on. ~ mlnor amount of forecut, mainly mono- 729 alkylbenzene, is collecte~ up to all~overhead temperature of 731 ..
about 232C. (450F.) at a pressure of 10 mm Hg absolute. The 733 balance oE the distillate is the desirea product7 and has an 734 .
average molecular weight of ahout 405~ l'he d1fference between 735 the average carhon atom content of the alkyl chain types is 736 about 13.
The dial~ylbenzene is charged to a stirred reaction 738 ~`
vessel fitted for temperature control, along ~ith 130 neutral ~39 oil ~hich is substantially free of sulfvnatable material. The 741 volu~e ratio of the t~o materials is 3-1/2 to 4, respecti~ely, and to this mixture is added~ over a period of several hours, 2 743 volumes of 25% oleum. The reaction temperature is maintained 744 at about 38C. (100F~)~ T~o phases develop in the settled 745 .

-:
- ?0 -~' , . ~, , ~ ., ,-; ., .,, ,, . . . . . : . , iO~20~3 mixture, the lower being a spent mineral aci~ phase and the 746 upper being the desired sulfonic acid phase. 747 The separated sulfonic acid-oil mixture ;s then 748 neutralized ~ith one Yolume of 50~ aqueous caustic dilutea with 750 15 volu~es of 2-butanol. During the neutrali~ation the 751 temperature is maintained below about 43~C~ (110~.~, and af~er 752 completion thereof the neutral solution is heated and 7S3 maintained at 60C. ~140F.) during a second phase separation. 754 Two phases develop~ a lower brina-alcohol solution ana an upper 7~6 neutral alcohol~sodium sulfonate solution~ -FXAMPLE_2 759The preparation of a neutral calcium sulfonate is 761 illustrated in this example. A 3-liter glass f~ask is charged 764 ~ith 80 g of calcium chlori~e and ~00 ml of ~rater~ Th~reafter, 766 1500 g of the sodium sulfonate solution of the typ~ prepared by 767 the ~ethod of Example 1 is charged to the flask. The contents 769 are heated to 30C. (85F.) under agitation and maintained at 770 these conditions ~or one hour. The conten-ts are allowed to 771 phase-separate and the ~ater layer arawn off. 800 ml o~ 773 dlstilled ~ater~ i6 admixed ~ith the suIfonate and heated for 774 one hour. The phases are allowed to separate and the aqueous 775 phase dra~n off. ~he sulfonate is washed three additional 7~7 ti~es with uater and one time ~ith an agueous isobutyl alcohol 778 solution. The mixture is heated to 112C. to remove an~ 779 residual ~ater ana isobutyl alcohol~ 500 IQl of tol~ene is 781 added to the sulEonate and the admixture filtered through 782 Celite 512. The product is stripped to 185C at 3 mm Hg 783 pressure to yield 740 grams of neutral calGium sulonate. 784 analysis of the proauct reveals 785 Wt.% sulfated ash 60 09 788 ~t~% metal 1.92 calcium 789 , lO~Z~)~3 EXAMFI.E 3 792 ~ calcium carbonate overbased calcium sulEonate which 794 may be employea to prepare the mixea borate dispersion of ~he 795 present in~ention ~ay be prepared by the method of Example 5 of 797 U.S. Patent 3,155,616..Follo~ing that procedure, a calcium 799 carbonate overbase~ calcium petroleum sulfonate is prepared 800 ha~ing a base ratio oE 9.3 and containing ll~4 weight percent 801 calcium EX~MPLE 4 . 804 ~ calcium tetraborate is prepared by charging to a 2- 807 liter glass flask 308 g of the calcium carbonate overbased calcium sulfonate prepared by the method of Example 3 and 700 809 ml of a~ aliphatic hydrocarbon diluent having a boiling range 810 from 158~. to 202C. ana containing 17% aromatics~ The812 contents are heated to 50C. and 200 g oE boric ac.id are addedO
The temperature is slowly increased to 150C. over a 75-minute 813 period. The contents are cooled and filtered; the filtrate îs 814 strippea to 165C. at 5 mm Hg pressure absolute to reco~er 403 810 g o~ product. The product had an alkalinity value of 211 mg 817 KOR/g~ . 818 EXAMELE_5 . 821 a mixed calcium and sodiu~ borate dispersion is pre~ 823 pared by the method of this example. ~ 2-liter glass ~la.sk is 826 charged with 308 g of a calcium carbonate overbased calcium 827 sulfonate prepared by the method of Exawple 3 and 750 ml of an 828 aliphatic hydrocarbon diluent of the type described in Example 829

4. The contents are then heated to 50C. and 200 g of boric 830 acid added. The temperature is raised to 150Co over a 95- 832 minute period. The contents are cooled and filterea. A 2- 834 liter flask is charged ~ith 978 g of the above-described filtrate (alkalinity value of 85.5 m~ KOH~g) ana heated to 835 110C. A solution of 30 g of sodium hydroxide in 150 ml of 836 - 22 ~

107Zl~ '3 -~ ~;
methanol is. ada~d to the Elask oYer a 65-~inute period at 837 110C. The tempera-ture is raised to 140C. and then cooled 838 under vacuum. The product is filtered and then stripped to 839 165C. at 5 mm Hg pressure absolu~e. a to~al of 406 g of 841 product is reco~ered. The product has an alXalinity ~alue,of ' 842 284 mg KO~T/g. , 843 EXaMFI.E 6 846 ~ his examp3e is presented to demonstrate the 848 preparation of a representative mixed metal borate aispersion. 849 A 2-liter ~las~ is charged wi~h 308 grams of the calcium 851 carbonate overbased calcium sulfonate of the type prepared by 853 the method of Example 3 along ~ith 700 ml of an alipha~ic :
hydrocarbon diluent having a boiling range from 158C to 2~2C 855 and conta,ining 17~ aromatics. 200 grams of boric acid are adaea to the flask ana contents raised to. a temperature of 85~
160C. in a period of 1-3/4 hours. The contents of the flask ~58 are coolea under a pressure of 150 mm ~g absolute. T~e calcium 800 ~ . .
borate intermediate product is then f.iltered and reheatea to a 861 t~mperature of 110C. Thereafter, a solution of 56 g of sodium 863 hydroxide in 300 ~l methanol is added over a 2-1j2 hour period 864 at 110C. Upon completion of the addition of the sodium 865 hydroxide/methanol solution to the flask, the temperature is 866 raised to 150C., then cooled and filtered. The Eiltrate is 868 strippea by heating'to 160~C. at a pressure of 5 mm Hg .869 absolute. A total oE 343 g of ~roduct is reco~ered. Product 871 is analyzed and col~tains 5~86 weight percent calcium and 7.07 872 weight percent boron. The product has an alkalinity value of 873 346 mg KO~T/g. 874 ~X~MFLE 7 878 mixed calcium and sodium metaborate dispersion is 880 prepared by the me.hod of this example. The procedure of 883 Example 6 is dup3icated, except that ~7 g of a polyisobutenyl 885 2~3 ~ ;~
succini~ide dispersant are present during the.reaction steps .886.
and 60 g of sodium hydroxide and 300 ml of methanol are 887 ~ .
employed. A total of 351 g of product is recovered, having an .888 :~
alkalinity value of 345 mg KOEI/g. 889 ~ :~
EXAMPLE ~ 892 ~ 2-lite~ sk is charged with 100 g of a 38~ sodium 895 sulfonate solution prepared by neutralizing a sul~onated 480 897 neutral oil with sodium hydroxide as described in Exa~le 1~ 898 ; .
The contents are thereafter heated ~o 165C~ under a pressure 899 ,, of lS0 mm ~g absolute to strip 60 g of solvent Erom the 900 : sol.ution. ~fter cooling, 750 ml of an aliphatic hydrocarbon 902 :~.-thinner of the type descri~ed in Example 4 are added along with 903 270 g of a calcium carbonate o~erbased calciu~ sulfonate of the 904 .~.
type described in Example 3. The combinea co~tents of the. 905 ~lask are heated to 50C. and thereafter 176 g of boric acid 907 are charged. The temperature o- the flask is then raised to 90a 145C. o~er a 120-minute period. A 150-mm ~g ahsolute pressure 910 is applied to ~.he flask to cool the contants Thereafter, a 912 solution of 54 g of sodium hydroxi~e in 250 ml methanol is 913 ; , ~
added over a period of 150 minutes at 110-115C. After all of 916 the solution has b~en chargea, the contents of the flask are. 917 heated to a temperature of 150C. The contents are theD cooled 91 and filtered. The filtrate is then stripped to 165C~ at a 919 pressure of 5 mm Elg abs~lute. ~ total of 390 g oE product is 921 recoverea and analyzed to contain 5.64~ calcium and 6.57~ 923 boron. The alkalinity value oE the product.is 330 mg ~OH/g 924 EX~PLE_9 927 ~ 2-liter flask is charged Nith 100 g of a 3ax sodiu~ 929 sulfonate solution of the type described in Example 8 and 932 thereafter heated to 165C. under a pressure of 150 Inm of Hg 933 absolute to strip 60 g of solvent from the solution. After . 935 cooling, 750 ml of an aliphatic hydrocar~on thinner of t~le ~ype 936 -- 2 4 _ ' `~ :
1 ~ ~ 2 ~ ~ 3 described in Example 4 are added along with 270 g of a calcium carbonate overbased calcium sulfate of the ~pe described in -~
Example 3. me combined contents of the flask are heated to 50C and thereafter 176 g of borlc acid are charged. The ;
temperature of the flask is then raised to 150C over a 127-minute period. Thereafter, a pressure of 150 mm H~ absolute ~s applied to cool the contents to a temperature below 110C A
solution of 86 g of potassium hydroxide in 250 ml methanol is added to the solution over a period of 145 minutes at 115-120C. After all of the solution has been charged, the ~
contents of the flask are raised to a temperature of 150C. ` ;;
The contents are then cooled and 300 ml of an aliphatic hydro-carbon solvent are added. The combined contents are then filtered. The filtrate is stripped to 165C at a pressure of

5 mm Hg absolute. A total of LD5 g of product is recovered and analyzed to contain 5.33% calcium and 6.02% boron. me alkalinity value of the product is measured to be 299 mg KDH/g.

Example 10 ; A mixed calcium, sodium and potassium metaborate dis-. .
persion is prepared by the method of this example. A 2-liter glass flask is charged with (1) 38 g of sodium sulfonate prepared by neutralizing a sulfonated 480 nuetral hydrocarbon ;
oil with sodium hydroxide, (2) 100 ml of aliphatic hydrocarbon diluent, (3) 270 g of calcium carbonate overbased calcium sulfonate of the type prepared by the method of Example 3, and (4) 650 ml of aliphatic hydrocarbon diluent. The contents are -heated to 50C and 176 g of boric acid are added. me temperature is slowly increased to 150C over a 127-minute .~,;
period. rme contents are cooled to 116C and a filtered ~-~

solution of: (1) 43 g of potassium hydroxide; (2) 27 g of sodium hydroxide; and (3) 250 ml of methanol is added. The addition temperature is 115C and the addition time is 131 -'' ' ; .

,. ~

1~2~3 ~inutes. The temperature is raised to 150C~ and 477 ml of 982 methanol and diluent taken off overhead~ An additional 250 ml 984 o-E aliphatic hydrocarbon dilu`ent are added. The contents are 985 ~iltered and stripped to 165C. at a pressure of 5 mm Hg 986 a~solute. A total of 399 ~ o~ product is recovered having an 987 al~alinity value of 301 mg KO~g~ The proc~uct contains 5.63 989 - ~eight Dercen~ calcium and 6.30 ~eight percent boron. 990 ~ ;
EXA~IPLE 11 993 ~ 2-liter glass flas~ is char~ed with 242 grams o~ a - 996 38~ sodium sulfona~e soIu~ion of the type described in the preceding examples. This solution is stripped to 16~C. under ssa a pressure of 150 mm Hg absolute to strip out 148 grams 1000 solvent. The re~aining produc~ is then cool~a and 750 ml of an 1001 aliphatic thinner oE the type descrihea in Example 4 are added 1002 along with 216 grams of a calcium carbona-te overbased calcium 1003 ;`;~
sulfonate o, the type described in Example 3. The combi~ed 1005 contents are heated to 50C and th~reafter 176 g o~ boric acid 1006 are added. The temperature is then raised to 150C. over a 1007 110-minute period. The contents are then cooled to 116~C~ and 1008 a solution of 66 g of sodium hydroxide in 300 ml ~ethanol are 1009 slo~ly added to the flask. The addition time is 147 minutes 1010 and the adaition te~perature is maintained at 115~120C. ~fter 1012 all of the sodium hydroxide/methanol solutioD has been added, ~he temperature of the flask is raised to 150C. Thereafter, 101LI
vacuum is applied to the flask and 610 ml of soIYent taken o~f 1015 , overhead. Then, 200 ml of an aliphatic hydrocarbon thînner are 1016 ,~
added and the product filtered~ The filtrate is stripped to 1018 165C. at 5 mm ~g pressure absolute. A total of 362 grams of 1020 1 produc-t is recovered and is analyzed to have an alkalinity 102t l `

Yalue of ~18 mg K0~/g~ ¦ ~
~ 1 -'1 26 ~

~0~20~3 - ', "
EX~MPLE 12 tQ24 A mixed calcium-potassium tetraborate dispersion is 1026 preparea by the method of this example. A 2-liter glass flask 1029 is charged ~ith: ~l) 278 g of a calcium carbonate over~ased 1030 calcium sulfonate prepared by the methoa of Example 3; (2) 3~ g 1031 o~ sodium sulfonate as described in Example 10 and dissolved in 1032 100 ml of aliphatic hydrocarbon diluent; and ~3~- 6~0 nl of an 1033 aliphatic hydrocarbon diluent of the type described in Example ` 1034 4. The contents are heated to S0~C. and 176 g o ~o~ic acid1035 are added. The temperatuxe is slowly rai~ed to l45C. over a1036 140-minute period. The con-tents are cooled under vacuum to103~
116C~ and a solution of 86 g of potassium hydroxide in 250 ml 1039 of methanol are slowly added over a 154-minute period at 115-1040 120Co The temperature i5 increased to 150C. ana then cooled104t by applying vacuum to the flask. ~ total of 480 ml o~ methanol 1043 . . .
ana diluent is taken off overhead. 300 ml of aliphatic 1044 hydrocarbon ailuent are then added and the product filterea and 1045 stipped to 165C. at 5 mm of Hg pressure absolute. ~ total of1046 391 g o~ calcium-potassiu~ metaborate product is recoveredO1047 The calcium-potassium metaborate described a~ove is1048 converted into the tetraborate counterpart by charging to the 1049 flask 700 ~I of aliphatic hydrocarbon diluent and an additional 1051 130 g o boric acid. The contents are slo~tly heated to 150C.1052 over a 2-hour period. The contents are cooled, filtered and1053 s-~ripped to a temperature of 170C. at a pressure o 5--10 mm of105 Hg absolute. A total of 469 g of calcium-potassium tetraborate 1055 is recovered~ ~he product has an alkalinity value of 242 mg1056 KOH/g and contains 4.01 ~eight percent calcium and 10~25 weight 1057 percent boron. 1058 EX~llP~ 13 1061 ~ This example illustrates -the preparation of a mixed 1063 magnesium-soaium metaborate dispersion. ~ 2-liter glass flask 1~66 - 27 ~

~2 is charge2 ~ith 176 g of boric acid and 500 ml of aliphatic 1061 hydrocarbon diluent of the type described in Example 4. The 1069 contents are heated to 110C~ and the following soluti~n slowly added: 1070 256 g of Mg-overbased petroleum sul~onate having an alka- 1071 linity value of 303 mg KOH/g; 1072 52 g o~ sodium sulfonate of the type described in ~x~iple l074 10; and 2~0 ml of an aliphatic hydrocarbon diluen~ of the type 1075 descri~ed in Example 4. 1076 The solution is added to the flask over a 30~minute 1077 period at an aadition temperature of 105-110GC. ~he 1079 temperature of ~he flask is maintained at 110-120C. for an 1080 additional 30-minute period and then raised to l50C over a 1081 30-minute period. The flask contents are cooled to 110C. by 1082 applying a slight vacuum and 200 ml of diluent are remoqed 1083 overhead. A solution of 54 g of sodium hydroxiae in 250 ml 1084 methanol is slowly added to the flask o~er a 158-minute period 1085 at 110-115C. Th~ flask contents are heatea to 150~C~ and 1087 therea~ter cooled by applying a vacuum. 480 ml of ailuent are 108g ta~en off overheaa. 200 ml of an aliphatic hydrocar~on diluent 1090 are added, the contents filterea and the filtrate stripped to 1091 16~C. at 5 mm Flg pressure absolute. ~ total of 256 g of 1093 product is recovered having an alkalinity value of 304 mg 1094 ~OH/g~ The product contained 3.88 ~e;ght percent ~agnesium and 1095

6.41 wei~ht percent boron. 109~
EXAMYLE_14 1099 This example is presented to illustrate a fe~ o~ the 1101 performance propertieis of the mlxed me-tal borate dispersions o~ 1104 this invention. A series of tests is perfor~ed uith each 1105 ~ borate dispersion prepared by the methods of the preceding 1106 i examples to measure the extre~e-presisure proper-ties (Tim~en 1107 ~ - 2~ -~ 3 E.P. ~est), the anti-wear properties ~4-Ball Wear Test) and -the compatibility properties (Compatability Test~. The Timken E.P. Test is described in ASTM D-2782-69T. The 4-Ball Wear Test is described in ASTMi D-2873-695. (The Conditions are 50-kg force, l/2-hour period at 1750 RPM, room temperatur~
The Compatibility Test is conducted by admixing with each weight part of a lube oil containing 5~ by weight of the mixed metal borate l weight part of a lube oil con~aining 3 to 5 weight percent of a conventional sulfurized ester additive. The . . .
admixture is placed in an oven at 300F for 24 hours. After this period, if a stable gel of 5% to l00~ of the mixture has formed, the compatability is noted as IlFail''. If a light gel or sediment representing less than 5~ of the mixtu~e has formed, the compatability is rated as l'Pass".
A group of 9 test samples is employed in these experiments. The samples consist of a lubricating oil contain ing l0 weight percent of the borate dispersions made in the preceding examples. One test is conducted without any additive -and one test ~s conducted ~ith a calcium carbonate dispersion.
2Q m e data from these tests are reported in the following Table I. ;
As can be seen from Table I, the use of a mixed metal borate exhibits good EP and anti-wear properties.

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

~3 '~
,.'''''' ~.

T~BLF' I
PERPOR~fA2~lCE pRopER~rIEs OF BORA'rE DISPERSIO~S `~
- 4-Ball Test Test-Scar Test Compatabillty -~-~ r~one tl~s, ~ (Pass/~ai 2 CaC0 3 D i s pe rsi;on ( Ex . 3 ) 3 Calcium Borate (E~c 4 ) 4 Ca/~a Borate (Ex, 5) 0~ 8 30 .~ -Ca~2~1a ~letaborate (Ex. 6) 0~59 30 --6 Ca/.~a ~etaborate (Ex.~:3 ~ O

7 Ca/E~ ~letaborate~ (Ex 9~ ~ .52 90 Pass .. !.

8 ~ Ca/K/N~a ~letaborate (Ex. lO) o . 5~ lO0 Pass Ca~Na ~letaborate ~Ex. 11) 0,54 lr Pass Ca/~ Tetraborate~(Ex. 12) 0 55 ll .Mg/Na 2~fetaborate (Ex. 13) 0 62 90 --: . . :
. . .
'~

- . ~
:: .

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

, '. . , ' ' ,` :' ` `:
:
- .:
:.
- 30 ~

.- . .. . .... - . . . .. ... . .. . ...... .~ .. .. .... ... . . . . . .. .. . . . .... .

Claims

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

1. A lubricating composition comprising a major portion of an oil of lubricating viscosity and a minor portion of an improved extreme-pressure additive comprising a particulate mixed alkali and alkaline earth metal borate dispersion having a mean particle size below about 1 micron.

2. A lubricating composition comprising a portion of an oil of lubricating viscosity and from 0.1 to 60 weight percent of a particulate mixed alkali and alkaline earth metal borate dispersion prepared by reacting within an inert, stable, oleophilic, reaction medium: (1) boric acid, with (2) an alkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate dispersant, to form an intermediate reaction product which is then reacted with an alkali metal base to form said mixed alkali and alkaline earth metal borate dispersion.

3. The lubricating composition defined in claim 2 wherein said particulate mixed alkali and alkaline earth metal borate has a mean particle size below about 1 micron.

4. The lubricating composition defined in claim 3 wherein said oil of lubricating viscosity is a hydrocarbon petroleum oil having a viscosity of 50 to 1000 SUS at 38°C.

5. The lubricating composition defined in claim 4 wherein a lipophilic, nonionic, surface-active agent having a hydro-philic-lipophilic balance value below 7 is also present at a concentration of 0.01 to 5 weight percent.

6. The lubricating composition defined in Claim 3 wherein said particulate mixed alkali and alkaline earth metal borate is present at a con-centration of 4 to 15 weight percent.

7. The lubricating composition defined in Claim 6 wherein a thickener selected from the group consisting of polyurea, alkali metal terephthalamate, lithium hydroxy stearate, calcium complex soap and aluminum complex soap is also present in an amount to thicken said lubricating oil to the consistency of a grease.

8. The lubricating composition defined in Claim 6 wherein said mixed alkali and alkaline earth metal borate is sodium and calcium borate.

9. The lubricating composition defined in Claim 6 wherein said mixed alkali and alkaline earth metal borate is potassium and calcium borate.

10. The lubricating composition defined in Claim 6 wherein said alkaline earth metal carbonate is calcium carbonate and wherein said alkali or alkaline earth metal sulfonate is sodium, calcium or barium sulfonate.

11. The lubricating composition defined in Claim 10 wherein said particulate alkali and alkaline earth metal borate has from 0 to 8 waters of hydration.

12. A particulate dispersion of an alkali and alkaline earth metal borate prepared by contacting boric acid with an alkaline earth metal carbonate over-based alkali or alkaline earth metal sulfonate within a stable, inert, oleophilic, liquid reaction medium to form an intermediate reaction product, which is then reacted with an alkali metal hydroxide to form a mixed alkali and alkaline earth metal borate dispersion.

13. The composition defined in Claim 12 wherein said alkaline earth metal carbonate is calcium carbonate and wherein said alkali or alkaline earth metal sulfonate is sodium, calcium or barium sulfonate.

14. A process for preparing a particulate alkali and alkaline earth metal borate dispersion which comprises contacting an alkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate with boric acid within a stable, inert, oleophilic, liquid reaction medium to form an inter-mediate reaction product which is thereafter contacted with an alkali metal base to form said mixed alkali and alkaline earth metal borate.

15. The process defined in Claim 14 wherein said reaction of boric acid with alkaline earth metal carbonate is conducted at a temperature of 20 to 200°C. for a period of 0.5 to 7 hours and the reaction of said intermediate reaction product and said alkali metal base is conducted at a temperature of 90 to 140°C. for a period of 0.1 to 3 hours.

16. The process defined in Claim 14 wherein from 2 to 6 molar parts of boric acid are contacted for each molar part of alkaline earth metal carbonate.

17. The process defined in claim 16 wherein said alkaline earth metal carbonate is calcium carbonate and said alkali or alkaline earth metal sulfonate is sodium, calcium or barium sulfonate.

18. The process defined in claim 17 wherein said particu-late mixed alkali and alkaline earth metal borate has from 0 to 8 waters of hydration.

19. The process defined in claim 18 wherein said mixed alkali and alkaline earth metal borate is a sodium and calcium borate or a potassium and calcium borate, wherein said alkaline earth metal carbonate is calcium carbonate, and said alkali or alkaline earth metal sulfonate is calcium sulfonate.

20. A process for preparing a particulate alkali and alkaline earth metal metaborate dispersion which comprises contacting within an inert, stable, oleophilic reaction medium 2 to 6 molar parts of boric acid with each molar part of an alkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate to form an intermediate reaction product, thereafter contacting said intermediate reaction product with 1 to 3 molar parts of an alkali metal hydroxide per molar part of said intermediate reaction product to prepare said alkali and alkaline earth metal borate dispersion.

21. The process defined in claim 20 wherein said contact-ing of boric acid with said overbased metal sulfonate is conducted at a temperature of 20 to 200°C. for a period of 0.5 to 7 hours.

22. The process defined in claim 20 wherein said alkaline earth metal carbonate is calcium carbonate and said alkali or alkaline earth metal sulfonate is sodium, calcium or barium sulfonate.

23. The process defined in Claim 22 wherein a lipophilic, nonionic, surface-active agent is also present during the contacting of said intermediate reaction product and said alkali metal hydroxide.

24. The composition defined in Claim 12 prepared by contacting two molar parts of boric acid with each molar equivalent of an alkaline earth metal carbonate overbased alkali or alkaline earth metal sulfonate to form an intermediate reaction product which is then reacted with two molar parts of an alkali metal hydroxide per molar part of said intermediate reaction product.