CA1041286A

CA1041286A - Homogeneous compositions prepared from dimercaptothiadiazoles

Info

Publication number: CA1041286A
Application number: CA204,625A
Authority: CA
Inventors: Kirk E. Davis
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1973-07-19
Filing date: 1974-07-11
Publication date: 1978-10-31
Also published as: FR2237957B1; JPS5219845B2; GB1462287A; IT1016450B; DE2434657C2; JPS5070407A; DE2434657A1; FR2237957A1; AU7097174A

Abstract

Abstract of the Disclosure:
Compositions which form homogeneous blends with lubricating oils and the like are produced by preparing a mixture of an oil-soluble dispersant (preferably a substan-tially neutral or acidic carboxylic dispersant) and a dimer-captothiadiazole, preferably 2,5-dimercapto-1,3,4-thiadia-zole, usually with a diluent, especially a lubricant base liquid, and heating said mixture above about 100°C. The compositions often contain dimercaptothiadiazole moieties in amounts substantially grater than stoichiometric. They are useful for suppression of copper activity and "lead paint" deposition in lubricants.

Description

; This invention relates to new compositions ofmatter useful as lubricant additives, especially for the inhibition of copper activity and "lead paint" deposition in lubrlcants, and to lubricants containing such additives.
More particularly, it relates to compositions obtained by ;~ :. preparing a mixture comprising at least one oil-soluble i~ . dispersant and at least one~dimercapkothiadiazole and . heating said mixture at a temperature above about 100C.
- until it is capable of form1ng a homogeneous blend with an 0 oleaginous liquid of iubricating viscosityO
. : Two phenomena sometimes encountered in internal .
combustion engine.].ubrication are copper.activity and . "lead paint" deposition. The first of these is a tendency ~ ~ of the lubricant to stain copper parts, and it frequently `: : 15 results from the use as additives of compounds containing ~ : ........... "active sulfur" - that is, sulfur which is highly labile .
and~ react1ve, The second phenomenon is the deposit1on on :engine surfaces of a .thin film of finely divided lead-c~ontain1ng~mat:erial from the lead additives in the fuel;
20:: ~this problem is not-alleviated by ordinary dispersants or detergents present in the lubricantO Both of these phenomena are~ undesirable and~lt lS of~interest to develop addltives for their suppressionO
. Ik has been known for some time that derivatives f dimercaptoth1adiazo1es, espec1al1y of 2,5-dimercapto-,4-thiadiazole, are effective additives for the . .inhibition of copper activity and many patents have issued on additives containing dimercaptothiadiazole nuclei. In the development of all of these additives, it has been necessary to find materials which react with the dimercapto-~a~
`~

.
_l _ ~04~Z~36 -thiadiazole to form oil-soluble products J since the dimer-captothiadiazoles themselves are not soluble in oil, An example of such an oil-soluble product, disclosed in ~.SO
Patent 3,519,564, is prepared from one mole of hydrazine, two moles of carbon disulfide and about 1-2 equivalents (based on the number of basic nitrogen atoms therein) of an acylated polyamine dispersant. Under the alkaline conditions thus prevailing, the hydrazine, carbon disul-~ . . - .
f`ide and dispersant react to form a salt of 2,5-dimercapto-1,3,4-thiadiazole.
A principal object of the present invention is to provide new compositions of matter useful as lubricant , additivesO
A further object is to provide-lubricant addi-tives which are effective at suppressing sulfur activity and "lead palnt" deposition.
A still further object is to provide new oil-soluble compositions containing the dimercaptothiadiazole : . .
nucleus 7 2Q A still ~urther object is to prepare new and useful lubricants for internal combustion engines and the like.
, Other objects will in part be obvious and will in ~ part appear hereinafter.
- 25 The present invention is based on the discovery that at temperatures above about 100C., usually about 100-250 and especially about 120-200, oil-soluble dis-persants interact with amounts of dimercaptothiadiazoles considerably in excess of those expected on the basis of ~alt formation of the type disclosed in the aforementioned .
~ U,S, Patent 3,519,56~o The compositions thus obtained are , ~ Og~LZ86 capable oi fo.rming substantially stable homogeneous blends with lubricati.ng li.qulds, which composi.tions contain higher proportions of dimercaptothiadiazole than those previously prepared and are effective for the purposes hereinbefore described~ . .
The flrst essential starting material for the preparation of the compositions of this invention is a dimercaptothiadiazoleO There are four such compounds possible, which are named and have structural formulas as . follows~

~: -?, 5-Dimercapto-1, 3, 4 -thiadiazole .
~ N N
:~ ' Il 11 .
HS-C C-SH
:; , S ' ' , . 3,5-Dimercapto-1,2,4-thiadiazole S N
. . 'I 11 . ~ , HS-~ : C-SH :

-Dimercapto-1~2,5-thiadiazole HS-C - C-SH

. N ~ N

4,5-Dimercapto-1~2,3-thiadiazole N~ C-SH

N C-SH
S ~
.~; . .
Of these the most readily available, and the one preferred .
for the purposes of this invention, is 2,5-dimercapto-1,3,4-thiadiazole, This compound will sometimes be referred to hereinafter as DMTDo However, it is to be understood that any of the other dimercaptothiadi.azoles may be substituted . ~ . .
,:

.
~L~4~
for all or a portion of the DMTD.
~ DMTD is conveniently prepared by the reaction of one mole of hydrazine, or a hydrazine salt, with two moles of carbon disulfide in an alkaline medium, followed by acidificationO For the preparation of the compositions of this invention, it lS possible to utilize already prepared DMTD or to prepare the DMTD in situ, subsequently adding the dispersant or adding the DMTD to the dispersant as described hereinafter.
10 ~ . The second essential starting material is an oil-~soluble dispersant, The materials chiefly contemplated are - often known as ~ashless.dispersants", although, depend'ing on . ' its constitutlon, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; howèver~ it does not ordinarily contain metal and . ' therefore does not yield a metal-containlng ash on combustion.
Oil-soluble dispersants of many types are known in :the art and'are described in various patents~ Any of them .: are sult:able f'or use in preparing the compositions of this ~'' 20 ~invention. The following are illustrative:
: . :
~ ~ : (1) Reaction products of carboxylic acids (or ; ~ derivatives thereof) containing ak least about 34 and prefer-: ably at least about 54 carbon atoms with~nitrogen-containing. compounds such as amines, organic hydroxy compounds such as : 25 phenols and alcohols, and/or basic inorganic materials.
Examples of these products, referred to herein as "carboxylic dispersants", are described in British Patent 1,306,529 and in many U.S. patents including the'f'ollowing:
' .

~ 8 3,163J 603 3,351,552 3J 54~.,012 ~,181-~,474 3J 381,022 3,51~2,678 3,215,707 3,399,14]. 3,542,680 3,219,666 3,415,750 3,567,637 3J271,310 3J433J744 3J574,l 3,272,746 3,444,170 3,576,743 . :~
3,281,357 3,448, o48 3,630,9ol~
: 3,306,908 3.41~8, o49 3,632,510 - 3,311,558 3,451,933 ~,632,511 lo : ~ 3,316,177 3,1~54,607 3,697,1~28 3,340,281 3,467,668 3,725,41~1 3,341,542 3,501,405 Re 26,433 3,31~6,1~93 3,522,179

(2) Reaction products of aliphatic or alicyclic ; 15 ~ halides containing at least about 30 carbon atoms with :amines, preferably polyalkylene polyamines. These may be :
characterized as "amine dispersants" and examples thereof a~re~described, for example, in the following U.S. patents:

3,275,554 3,454,555 20~ : 3,438.,757 3,56~5,804 (3): Reactlon products~of alkyl phenols:ln which : the alkyl group contains at least about 30 carbon atoms : ~ ~with aldehydes (especlally formaldehyde) and amines (especially :
polyalkylene polyamines), which may be characterized as ~ "Mannlch dispersants". The materials described in the ~ollowing U.S. patents are illustrati~e:
: 3,413,3l~7 3,725,480 ~,697,571~ 3,726,882 3,725,277

(4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, car-boxylic acids, hydrocarbon-substituted succinic anhydrides,

5 nitriles, epoxides, boron compounds, phosphorus compounds or the likeO Exemplary materials of this Xind are d~scribed in the following U,SO patents:
. : 3,036,003 3,367,943 3,579,1~50 ~,0~7,936 3,373,111 ~,591,598 10 ~ 3~200~107 3,l~03,102 3,600,372 : - 3,216,936 3,442,808 3,639,242 3,25l~,025 3j455,831 3,649,229 ~.
3,256 " 85 - 3,455,832 -3,649,659 3,278,550 3,493,520 3,658,836 3,280,234 3;502,677 3,697,574 3,281,428 3,513,093 3,702,757 3~282,955 3,533,945 3,703,536 `:
: 3,312,619 3,539,633 3,704,308 3,~366,569 3,57~,010 3,708,522 ;20 ~ (5) Interpolymers of oil-solubilizing monomers containing a pendant alkyl group having at least about 8 carbon~atoms, such as décyl methacrylate, vinyl decyl ether or a relatively high molecular weight olefin, with monomers containing polar substituents, e.g., aminoalkyl .
: 25 : acrylates, aminoalkyl acrylamides or poly-(oxyalkylene)-substituted alkyl acrylatesO These may be characterized as "polymeric dispersants" and examples thereof are disclosed in the following U.S. patents:
3,329,658 3,666,730 ~o 3,449,250 3~687,8J~9 3,519,565 ~,702~300

-6 -~09L~;~8~
The carhoxylic dispersants are the pre~erred ones for use in the preparation of the compositions of this in-vention. They may be most conveniently and accurately des-cribed in terms o radicals A and B present therein. Radical A is at least one acyl, acyloxy or acylimidoyl radical con-taining at least about 34 carbon atoms. The structures of these radicals, as defin~d by the International Union of Pure and Applied chemistry, are as ~ollows (R representing a hydrocarbon or similar group):

Acyl: R-C-pl '.
Acyloxy: R-C-0-Acylimidoyl: R-C-Radical B is preferably at least one radical in which a nitrogen or oxygen atom is attached directly to said rsdical A, s~id nitrogen or oxygen atom also being attached to a hydrocarbon radical or substhtuted hydrocarbon 20 ~ radlcal, especially an amino, alkylamino-, polyalkyleneamino-, hydroxy- or alkyleneoxy-substituted hydrocarbon radical.
With respect to radical B, the dispérsants are convenently :
classified as "nitrogen-bridged dispersants~' and "oxygen-bridged dispersants" wherein the atom attached directly to radical A is nitrogen or oxygen, respectively.
The nitrogen-bridged dispersants, which will be descxibed first, are those disclosed (for example3 in th~
above-mentioned U.S. Patents 3,219,666 and 3,272,746 which also describe a large number o~ methods for their preparation.

The nit.rogen-~o~ltaining group therein is derived from com-pounds chaxacterized by a radical of the structure ,_ NH
wherein the two remaining valences of nitrogen are satisfied - by hydrogen, amino or organic radicals bonded to said nitrogen atom through direct carbon-to-nitrogen linkagesO These com-pounds include aliphatic, aromaticJ heterocyclic and carbo-, . .
cyclic amines as well as substituted ureas, thioureas, hydrazines, guanidines, amidines, amidesj thioamides, cyana-mides and the like.
10 : ` EspecialIy preferred as nitrogen-containing com-pounds used in the preparation of the nitrogen-bridged dis-persants are alkylene polyamines and hydroxyalkyl-substituted . al.kylene polyamines. The alkylene polyamines comprise, in general, alkylene amines containing about 10 or less alkylene groups joined through nitrogen atomsO They include princi-, .
pally the ethylene amines, propylene amines, butylene amines and homologs thereof, and also piperazines and aminoalkyl-: substituted piperazines~ Hydroxyalkyl-substituted derivatives of these alkylene polyamines are also contemplated for Use 20 ~ in~preparlng the nitrogen-bridged dispersant, Typical examples o~ suitable amlnes are ethylene diamine, triethylene : tetramlne, pentaethylene hexamlne, propylene diamine, tri-~`~ propylene tetramine, di-(trimethylene) triamine, 1,4-bis-(2-: aminoethyl)piperazine, 1-(2-aminopropyl)piperazine, N-(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)piperazine, .
~ and 2-heptadecyl-1-(2-hydroxyethyl)-imidazoline~ Mixtures ::~ of these amines may also be used~ ` :
: The preferred amlnes are the polyethylene poly-amlnes containing from two to about ei.ght amino groups per molecule, ~ commercially available mixture of polyethylene polyamines containing an a.erage of about 3-7 amino groups .

~04~LZ1~6 per molecule is particularly suitable.
T~e acylating agent used for preparing the nitro-gen-bridged dispersant is a carboxylic acid-producing compound containing at least about 34 and preferably at least about 54 ~' 5 carbon atoms. By "carboxylic acid-producing compound" is . meant an acid, anhydride, acid halide, ester~ amide, imide, - amidine or the like; the acids-and anhydrides are preferredO
.- The acylating agent is usually prepared by the reactlon (more fully described hereinafter) of a relatively . ~. .
low molecul.ar weight carboxyllc acid-producing compound with : ~ . a hydrocarbon source containing at least about 30 and pre-:; . ' . .
' ferably at least about 50 carbon atoms. The hydrocarbon . source should be substantially saturated, i,e,, at least about 95~ of the t.ota'l number of carbon-to-carbon covaient linkages 15 ' should be saturated, It should also'be substantially free . - . .
from pendant groups.containing more than about six aliphatic carbon atoms, It may be:a substituted hydrocarbon source;
by "substituted" is meant sources containing substituents Whlch do not alter slgniflcantly their character or reactivity ~: Examples are halide,~hydroxy, ether, keto, carboxy, ester (especially lower carbalkoxy), amide, nitro, cyano, sulfoxy and sulfone:radlcals, In general~ not~more than three and usually n~t more than~one.such radical will be preeent for each 10 carbon atoms, ~ 25 The preferred hydrocarbon sources are those de-:~ ~ rived from substantially~'satura'ted petroleum fractions and : ' .. ~o'lefin polymers, particularly polymers of monoolefins having '' from 2 to about 30 carbon atoms. .Thus, the hydrocarbon source may be deri~ed from a polymer of ethylene, propene, l-butene, isobutene, l-octene, 3~cyclohexyl-1-butene, 2'-butene, 3-pentene or the likeO Also useful are interpoly-mers o.t olefins such as those il.lustrated above with other - polymerizable olefinic substances such as styrene, chloro~
prene, isoprene, p-methylstyrene, piperylene and the like.
In general~ these interpolymers should contain at least about 80~, preferably at least about 95~, on a weight basis of units derived from the aliphatic monoolefins, Another suitable hydrocarbon source comprises saturated aliphatic hydrocarbons such as highly refined high molecular weight white oils or synthetic alkanes, In many instances, the hydrocarbon source should - contain an activating polar radical to facilitate its reaction with the low molecular weight acid-producing com-~ pound. The preferred activating radlcals are halogen atoms, : especially chlorine, but other suitable radicals include sulfide, disulfide, nitro, mercaptan, ketone and aldehyde . groups.
As already pointed out, the hydrocarbon sources generally contaln at least about ~0 and preferably at least about 50 carbon atoms. Among the olefin polymers those ~ having a molecular weight of about 700-5000 are preferred, a:Lthough higher polymers having molecular weights from about .
lO,OOO~to about 100,000 or higher may sometimes be used.
Especially suitable as hydrocarbon sources are isobutene polymers within the pre.scribed molecular weight range, and : 25 chlorinated derivatives thereof.
Any one of` a number of known reactions may be em~
ployed for the incorporation of the hydrocarbon source into the acid-producing compound to provide the required acylating agentO Thus, an alcohol of the desired molecular weight may be oxidized with potassium permanganate, nitric acid or a similar oxldizing agent; a halogenated o].efin polymer may be ~10~

1~4~Z86 reacted with a ketene, an ester o~ an active hydrogen~contairl-ing acid, such as acetoacetic acid~ may be converted to lts sodium derivative and the sodium derivative reacted with a halogenated high molecular weighl; hydrocarbon such as bro-minated wax or brominated polyisobutene; a high molecular weight olefin may be ozonized; a methyl ketone of the desired molecular weight may be oxidized by means of the haloform reaction; an organometallic derivative of a halogenated hydro-carbon may be reacted with carbon dioxide; a halogenated ' 10 hydrocarbon or olefin polymer may be cbnverted to a nitrile/
which is subsequently hydrolyzed~ or an olefin polymer or its halogenated derivative may undergo an addition reaction with an unsaturated acid or derivative thereofO This latter ' reaction is preferred, especially where the acid-producing compound is maleic acid or anhydride. The resulting product is then a hydrocarbon-substituted'succinic acid or derivative thereof. The reaction leading to its formation involves merely heating the two reactants at about 100-200~C The sub-stituted succinic acid or anhydrlde thus obtained, may, if 20 ~ desired, be converted to the correspo'nding acid halide by ,.
reaction with known halogenating agents such as phosphorus trichloride, phosphorus pentachloride or thionyl chloride For the formation of the nitrogen-br.idged dis-persant, the hydrocarbon-substituted succinic anhydride or acid, or other acylating agent, and the' alkylene polyamine or other nitrogen-containing reagent are heated'to`a tem-perature above about 80C., preferably about 100-250C. The product thus obtained has predominantly amide, imide and/or amidine linkages (containing acyl or acylimidoyl groups)0 The process may in some instances be carried out at a tem-perature belo~r 80C. to produce a product havlng predomlnantly :~0~28~
salt linkages (containing acyloxy groups). The use of a diluent such as mineral oil, benzene, toluene, naphtha or the like is often desirable to facilitate control of'the ' reaction temperature.
The relative proportions of the acylating agent and the alkylene polyamine or the like are such that at least about one-half the stoichiometrically equivalent amount of polyamine is used for each equivalent of acylating agent.
In this regard it will be noted that the equivalent wèight of the alkylene polyamine is based upon the-number of amine radicals therein, and the equivalent weight of the acylating agent-is based on the number of acidic or potentially acidic radicals. (Thus, the equivalent weight of a hydrocarbon-subs'tituted succinic acid or anhydride is one-half its :
'15 molecular weight.) Although a minimum of one-half equivalent of polyamine per equivalent of acylating agent should be used, -;
there does not appear to be an upper limit for the amount of polyamineO If an excess is used3 it merely remains in the product unreacted without any~apparent adverse effects, Ordinarily, no more than about 2 equivalents of polyamine . ~ .
are~used per equivalent of acylating agent~

~specially preferred for the purposes of this - - - .
invention are substantially neutral or acidic disper-sants; that is, dispersants having a base number less ~than 7 or an acid number when titrated to a bromphenol blue end point. ("Acid number" is the number of milli-grams of potassium hydroxide required for titration of a gram sample, and "base number" is the number of milli-grams of potassium hydroxide equivalent to the amount ~0 of acid required for titration of a l-gram sample.) Nitrogen-bridge~ dispersants of ~his type may often be , _12~
, 1t)4~Z~6 prepared by using one equivalent or less of polyamine per equivalent of acylating agent.
- In an alternative method for producing the nitro-gen-bridged dispersant, the alkylene polyamine is first reacted with a low molecular weight, unsaturated carboxylic acld-producing compound such as maleic anhydride and the resulting intermedi.ate is subsequently reacted with the hydrocarbon source as previously describedO
. - Oxygen-bridged dispersants comprise the esters ~ of the above~described carboxylic acids, as described (for example) in the aforementioned U,S~ Patents 3,381,02? and 3,542,678. As such, they contain acyl or, occasionally acylimidoyl radicals as radical A~ (An oxygen-bridged dis-persant contalning an acyloxy radical as radical A would be ~; 15 a peroxide, ~hich is unlikely to be stable under all con-ditions of use of the compositions of this invention.) These ; esters are pre~erably prepared by conventional methods, .
; usually the reaction (~requently in the presence of an acidic ; ;catalyst) of the carboxylic acid-producing compound with an ~;
~ ~ aliphatic~compound such as a monohydric or polyhydric alcohol or with an aromatic compound such as a phenol or naphtholc The:preferred hydroxy compounds are alcohols containing up to about 40 aliphatic carbon atoms, These may be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, neopentyl alcohol? monomethyl ether of ethylene glycol and the like, or polyhydric alcohols including ;~
ethylene glycol, diethylene glycol, dipropylene glycol, tetramethylene glycol, pentaerythritol, glycerol and the like, Carbohydrates (e~g., sugars, starches, cellulose) ~0 are also suitable as are partia~y esteri~ied derivatives of polyhydric alcohols having at least three hydroxy radicals~

~ ` iL(14~Z8~
The reaction is usually effected at a temperature above about 100C. and typically at 150-300Co The esters may be.neutral or aci.dic, or may contain unesterified hydroxy groups, according as the ratio of equivalents of acid-producing compound to hydroxy compound is equal to, greater than or less than.l: lo ~ . . As will be apparent, the oxygen~bridged disper-:: - . sants are normally substantially neutral.or acidic, They ;~ .are among the preferred dispersants for the purposes of this invention, . It is possible to prepare mixed oxygen- and nitrogen-bridged dispersants by reacting the acylating agent : . .
~ - simultaneously or, preferably, sequentially with nitrogen-. - ~
containing and hydroxy reagents such as those previously described. The relative amounts of the ni.trogen-containing .` - and hydroxy reagents may be between about 10:1 and 1:10, on an equivalent weight basisO The methods of preparation of ~ .
the mixed oxygen- and nitrogen-bridged dispersants are generally the same as for the individual dispersants :: 20 ~ ~ ~described, except that two sources of radical B are used.
As previously noted, s.ubstantially neutral or acidic dis-~: ~ :persants are preferred, and a typical method of producing ~; ~ mixed oxygen- and nitrogen-bridged dispersants of this type (which are especially preferred)~is to react the acylating . : 25 agent with the hydroxy reagent first and subsequently react the inte~mediate thus obtained w:ith a suitable nitrogen-containing reagent in an amount to afford a substantially neutral or acidic productD
Typical carboxylic dispersants suitable for use ~0 in preparing the compositions of this invention are listed in Table I, "Reagent A~ and "Reagent B" are, respectively, ~LLI_ the sources o~ radicals A and B as previously defined. The dispersants of Examples. 1-6, 8, 9J 12 and 14-17 are basic;
those of the other examples are substantially neutral or acidicO

.

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~04~2~3~
The com.pos-ltions of this invention are formed by preparing a mixture of D~I`V with the dispersant and heating said mixture within the temperature range previously recited, for a period of time sufficient to provide a product which is capable Or forming a homogeneous blend with an oleaginous liquid of lubricating VlSCOSity, usually with a lubricating oil such as the natural and synthetic lubricants described .
hereinafter. The mixture will usually also contain an organic liquid diluent which may be either polar or non-polar.
Suitab]e polar liquids Lnclude alcohols, ketones3 esters a~d the likeO As non-polar liquids there may be used petroleum fractîons~ ordinarily high-boiling distillates such as mineral oils of lubricating viscosity, as well as naphthas and intermediate fractions (eOg.~ gas oilJ fuel oil or the like). ALso suitable are aromatic hydrocarbons~ especially ~-~
the higher boiling ones s~ch as xylene and various mlnimally ; volatile alkylaromatic compounds. Halogenated hydrocarbons ~ such as chlorobenzene may also be usedO
~ -~ It is preferred to use the above-desScribed olea-: ~ ~ : : .
~ ~ ginous liquids o~ lubricating viscosity as diluents, since this permits the direct use of the composition as a lubri-: .
cant or a concentrate for incorporation in luhricants.
Especially suitable are mineral olls of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types and oils derived from coal or shale. Also suitable but less preferred~
are animal and vegetable oils (e.g., castor oil, lard oil) and synthetic lubricating oils. The latter include hydro-carbon oils and halo-substituted hydrocarbon oils such as polyrnerized and interpolymerized olefins (eOg., polybutylenes,~
polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.); alkylbenzenes (e,g,~ dodècylbenzenes?

~104~Z86 :
tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g , biphenyls, terphenyls, etc;); and the like~ Alkylene oxide polymers and inter-polymers and derivatives thereof where the terminal hydroxyl ` 5 groups have been modified by esterification, etherification, `~
~- etc., constitute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the ~alkyl and aryl ethers of these poiyoxyalkylene polymers (e,e., methylp?lyisopropylene glycol ether having an average molecular ~eight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-. ~ .
1500, etc.~ or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-c8 fatty acid .
; ~ esters, or the C13 OXO acid diester of tetraethylene glycol~
Another suitable class of synthetic lubricating oils com-prises the esters of dicarboxylic acids (e,g,j phthalic acid, succinic acid,~ maleic acid, azelaic acid, suberic acid, s~ebacic acid, fumaric acid, adipic acid, linoleic acid dimer, : , .
etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc,)~.
.
Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl ;~ 25 sebacate~ diisooctyl azela~e, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester Pormed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and t~o moles o~ 2-ethyl-hexanoic acid, and the likeO Silicon-based oils such as the polyalkyl-, polyaryl-, polyal~oxy- or polyaryloxy-.

siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.gO~ tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-tetraethyl) silicate, tetra-(p-tert-butyl-phenyl) silicate, hexyl-(4-methyl-2-pentoxy~di-siloxane, poly(methyl)-siloxanes3 poly(methylphenyl)-siloxanes, etcD).
Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g,, tricresyl phosphate, trioctyI phosphate, diethyl ester of decane phosphonic acid, etc,), polymeric tetrahydrofurans, and the like.
In a particularly preferred embodiment, the non-polar organic liquid d1luent is mineral oil of lubricating ~; viscosity. It is also contemplated, though not preferred~
to use a volatile liquid initially and subsequently replace ~ 15 it~by mineral oil, with the vo:Latile liquid being remo~ed ;~ by distillation, vacuurn stripp:Lng or the like or to dissolve~the DMTD in a volatile polar liquid such as an alcohol and to add the resulting solution to the dispersant-oil mixture~
removing the volatile liquid by flash stripping or other - -~ ~ 20 ~ evaporation methods.
.
:
The relative amounts of dispersant and DMTD may vary~widely, as long as a homogeneous product is ultimately obtained. Thus, about O.l-lO parts by weight of dispersant may be used per part of DMTD. More often, ab~ut 5-lO parts of dispersant are used per part of DMTD. The product usually contains DMTD moieties in amounts substantially greater than the stoichiometric amount based on salt formation, If the dispersant is neutral or acidic there is, of course, no "stoichiometric amount" of DMTD and any amount thereof in the product is present in excess. If the dispersant is basic~ the product usually contains at least about a five-~0a~2~36 ` ;
fold excess and may contain a 500-~old or even greater excess of DMTD moieties, based on the stoichiometric amount.
The precise chemical nature of the compositions of this in~ention is not known. In particular, it is not certain whether a chemical reaction takes place between ~- the DMTD al~d the dispersant~ However, it has been shown thai DMTD may bè dispersed to form a homogeneous composition at lower temperatures than those prescribed fo~ the formation .
of the compositions o~ this invention, When the former com-~ ~ position is heated~ a solLd product precipitates and upon~
further heating at a higher temperature, it is redispersed - , . . .
to form a stable, homogeneous composition. Hydrogen sulfide evolution is noted as the product precipitates when the temperature is raised, It is believed that the initial stage in this process is the~homogenization of DMTD by the dispersant~ and that the DMTD ~subsequently condenses to form dimers and other oligomers which first precipitate and are then~ redispersed as the temperature risesO Since the normal operating temperatures of an 1nternal combust1on engine are 20 ~ hlgher than the temperature of precipitat1on, the dispersions irst formed are not skable enough to serve as lubricant addlt1ves, and it lS nècessary to go through the precipita-tion and redispersion steps to form an additive of th1s invention, .
The preparation of the compositions of this inven-tion is illustrated by the following examplesO All parts and percentages are by weightO The weight ratios of dispérsant to DMTD referred to are, in each instance, initial ratiosO
Equivalents of base in the dispersant are calculated from the base number. Equivalents Or DMTD are based on an e~uivalent weight of 75 (one-hal~ the molecular weight), ~22-~ ~ 6 Example 26 Six thousand parts of the product of Example 10 (o.64 equivalent of base) is heated to 100C., and 484 parts of wet DMTD (420 parts on a dry basis, or 506 equivalents) is added over 15 minutes, wikh stirring. The mixture is heated' ' ; at 110-120a for 6 hours under nitrogen, durlng which time hydrogen sulfide evolution is noted~ Mineral oil, 1200 parts, is added and the mixture is filtered while hot. The filtrate is a 53~ solutlon of the desired product in oil and 'contains 1.68~ nitrogen 'and 2.83~ sulfur. The weight ratio of dispersant to DMTD is 8.6.
.~ ' ' ' .' , Example 27 DMTD (506~ equivalents) is prepared by adding 447 parts of carbon disulfide over 2-3/4 hours to a mixture of 140 parts of hydrazine hydrate, ?24 parts of 50~ aqueous ' sodium hydroxide and 1020 parts of mineral oil, with stirring under nitrogen at 25-46C.~ heating the resulting mixture at 96-104C. for about 3 hours, and then cooling to 78C, and acidifying with 280-parts of 50~ aqueous sulfuric acid O The ~ resultlng material is heated to 94C. and 6000 parts of the product of Example lO (o.64 equlvalent of base) is addèd over about 1/2 hour at 90-94C,, under nitrogen. The mixture is heated gradually to 150C. and maintained at that tempera~
ture for ab~ut 3 hours; lt is then filtered while hot to yield a 50~ solution in mineral oil of the desired product.
The solution contains 2.06~ nitrogen and 3.26~ sulfur, and the weight ratio of dispersant to DMTD therein is 8.6.

Example 28 . . _ .
One thousand parts of the product of Example 1(0.89 equivalent of base) is heated to 95C,, under nltrogen, and -2~-8~
.
288 parts o~ wet DMTD (250 parts on a dry basis, or 3,33 equivalents) is added over about 20 minutes. The mixture is heated to 150C. and held at that temperature ~or about 5 hours, and is then filtered while hot to yield the desired product, a 59~ solution in oil containing 4061~ nitrogen and 9ol9~ sulfurO The welght ratio of dispersant to DMTD is 2.4.

Example 29 Following the procedure o~ Example 28, a product .
~ ~ is prepared ~rom 200 parts e~ch of the dispersant of Example - ~.~ . , 1 (0.18~equivalent of base) and DMTD (2067 equivalents), and 2000 parts of mineral oil is added. The product (a 20 solution in oil) contains 1012~ nitrogen and 3,48~ sulfur~
and the weight ratio o~ dispersant to DMTD is o.6.

~ ~ .
~ Example 30 ::: :
Following the procedure o~ Example 28, a product (50~ solution in oil) is prepared from 7300 parts of the -product o~ Example 11 (0.26 equivalent of base), 588 parts , : , -o~ wet DMTD (510 parts on a dry basis, or 608 equivalents) and 1250 parts o~ mineral oil. It contains 1072~ nitrogen ~ . ~
20 ; ~and 3Oo8~ sulfur, and the weight ratio o~ dispersant to DMTD is~7.8~, .
~ Example 31 - ~ .
Following the procedure o~ Example 28, a product is prepared from 1000 parts o~ the product of Example 11 (o.o36 equivalent of base), 241 parts (3.21 equivalents) o~

, .
DMTD and 310 parts of mineral oil. The product is a 50~ solution in rnineral oil and contains 2.71~ nitrogen ` and 6.79~ sulfurO The ratio o~ dispersant to DMTD is 2062.
' 21~ -.

104~Z~36 Example 32 Following the procedure of Example 27, DMTD (8.16 equivalents) is prepared from 204 parts of hydrazine hydrate, .
324 parts of 50~ aqueous sodium hydroxide, 648 parts of car- :
bon disulfide, 1200 parts of mi.neral oil and 408 parts of 50~ aqueous sulfuric acid. It is then reacted with 600 ~i;
parts of the product of Example 11 (0.02 equivalent of base) .
in the presence of 600 parts of toluene, and the toluene and ~: water are removed by azeotropic distillation to yield-a ..
: 10 product (50~ solution in mineral oil) containing 1.8~ nitro-.
gen and 531~ sulfur, and having a 5.5:.1 ratlo of dispersant to DM~D.
.
; Example 33 Following the procedure of Example 27, DMTD (5.6 equivalents) 1s prepared from 140 parts of hydrazine hydrate, ~ 447 parts of carbon disulfide, 224 parts of 50~ aqueous :~: sodium hydroxide, 280 parts of 50~ aqueous sulfuric acid and , 1020 parts of mineral oil. It is then reacted with 6000 .
parts of the product of Example 11 (0.22 equi~alent of base) .
: : 20 ::to yield a product (50~ solution in oil) containing 1.35 :nitrogen and 2.64~ sulfur, and having a weight ratio of dispersant to DMTD of 7.860 ;~
:
.
Example 34 .
Hydrazine hydrate, 28 parts, is mixed with 45 parts of 50~ aqueous sodium hydroxide and 206 parts:of mineral : oil, and 102 parts of carbon disulfide is added over 2 hours.
An exotherrnic reaction takes place which causes the tempera-ture to rise to 38C. The mixture is heated to 109C. and maintained at that temperature for 1 hour, during which time hydrogen sulfi.de evolution is noted. It is then cooled to , ~25- `
.

.

88C. and 88 parts of 3~ aqueous sulfuric acid is added over 1/2 hour. The temperature rises to 9~C~ during this additionO
The resulting slurry (1.12 equivalents of DMTD) is added to 1209 part.s (0.043 equivalent of base) of the dispersant of Example 11, Volatile materials are removed by vacuum stripping at 150C. and the remaining mixture is heated for ~ hours at that temperature~ The residue is filtered while hot and the filtrate is the desired product ; 10 con~aining 1,4~ nitrogen and 2,90~ sulfur, and having a weight ratio of dispersant to DMTD of 7.86, Example 35 A mixture of 1000 parts of the dispersant of Example 11 (oOo~6 equivalent of base) and 170 parts of mineral oil is heated to 70C, J and a solution of 70 parts (0O93 equivalent) of DMTD in 865 parts of isopropyl alcohol s added over about 1/2 hour~ with stirring. Heating at 70C, is continued as the isopropyl alcohol is stripped under vacuum, yielding a hornogeneous mixture. This mixture is gradually heated to 155C,~ during the heating, a solid ~ ~ :
precipitates and a sample thereof is removed and analyzed.
Elemental analysis indicates that it is an oligomer of DMTD, principally a dimer.
As heating continues above 140C. J the solid is gradually solubilized to yield a homogeneous product again.
This product is the desired material (50~ solution in oil) having a dispersant to DMTD ratio of 7086 lo As previously mentioned~ the compositions of this invention are principally useful for the inhibition of copper ~0 a~tivity and "lead paint" deposition in lubricants. They may also be used as extreme pressure agents and corrosion i.nhlbitors ror copper-lead bearings. They can be employed in a variety of lubri.cating compositions based on diverse oils of lubricating viscosity, including the natural and synthetlc lubricating oils and mixtures thereo~ disclosed .
hereinabove as suitable oleaginous diluentsO The lubrica--ting compositions contemplated include principally crankcase . lubricating olls for spark-ignited and compression-ignited internal combustion engines including automobile and truck - . . i . :
;~ ~ engines9 two-cycle engine lubricants, aviation piston engines, ; . marine ~and railroad diesel engines, and the like. However automatic transmission fluids, transaxle lubricants3 gear .~ lubricants, metal-working lubricants, hydraulic fluids, and . other lubricating oil and grease compositions can benefit from the incorporation of the present compositionsO
In general, about 0.05~20,0 parts (by weight) of : - . .
~ the composition of this invention is dissolved in 100 parts , .
o~ oil to produce a satisfactory lubricantO The inventio.~ :
. also contemplates the use of other additives in combination.
~ ~ ~20 ~ with~the products of this invention, Such additives include, -~ :. for example~ detergents and dispersants of the ash-contain-.
: .. ing or ashless type, oxidation inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers and~anti-foam agents, 25 ~ r~he ash-containing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline . earth metals with sulfonic acids, carboxylic acids, or - organic phosphorus acids characterized by at least one direct ~: carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.gO, polyisob~tene having a molecular ~eight of lO00) with a phosphorizing agent such .

-~7-~0~86 as phosphorus trich:Loride, phosphorus heptasulfide, phos-pho~us pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chlorldeO
The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium 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 ~ : 10 employed methods for preparing the basic salts involve :~ heating a mineraloil solution of an acid with a stoichio- .
metric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass, The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol,. naphthol, alkyl-phenol, thiophenol,.sulfurized alkylphenol, and condensation 20 ~ products of formaldehyde with a phenolic'substance; alcohols ~: ~such as methanolj 2~propanol, octyl alcohol, cellosolve, car-: bitol, ethylene g'lycol, stearyl alcohol, and cyclohexyl :: alcohol; and amlnes such as aniline, phenylenedlamine, :~ ~ phenothiazine, phenyl-~-naphthylamine, and dodecylamine.:
A particularly effective method fo.r preparing the basic .
~: salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent, a phenolic promoter compound, and a small amount of water and carbonating the mixture at an elevated temperature such as 60-200C, : 30 Ashless detergents and dispersants are illustrated hereinabove, -2~-.

- Extreme pr~qæur~agen~;and corrosion and oxida-tion inhibiting agents are exemplified by chlorinated ali-phatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) ; 5 disulfide, dibutyl tetrasulfide, sulfurized methyl ester of`oleic acid, sulfuriæed alkylphenol, sulf'urized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons. such as the reaction product of a phosphorus sul:~ide with turpen-tine or methyl ol~ate; phosphorus esters including principally : . . .
:~ ~ lO dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite~ diheptyl phosphite, dicyclohexyl phosphite, pentyl ; phenyI phosphite, dipentyl phenyl phosphite, tridecyl phos-phite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylerie (molecular weight 500)-substituted phenyl phosphite~ dilsobutyl-substituted ; phenyl phosphite; metal thiocarbamates) such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithio-carbamate; Group II metal phosphorodithioates such as zinc dicyclohéxylphosphorodithioate, zinc dioctylphosphoro-dithloate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phos-phorus pentasulfide wi.th an equimolar mixture of isopropyl . :
alcohol and n~hexyl alcohol. ~ .
It is possible to form the lubricants of this .
: invention by dissolving the various additives, or oil solutions thereof'~ directly in a mineral oil~ However, it is generally more convenient and is preferred to prepare additive concentrates comprising a diluent (typically mineral oil) and one or rnore of' the desired additives~ the latter cornprising up to about 90~ by weight of the concen-:~ .

-29~
' 4 ~
trate, and to disso~e ~hese concentrates in mineral oil to form the firlal lubricating composition.
Typical lubricating compositions according to this invention are listed in Tables II and III. All amounts listed, except those for mineral oil, are exclusive of oil present as diluentO
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Claims

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

1. A composition obtained by preparing a mixture comprising 0.1 - 10 parts by weight of at least one oil-soluble dispersant and one part by weight of at least one dimercaptothiadiazole and heating said mixture at a temper-ature above about 100°C. until it is capable of forming a homogeneous blend with an oleaginous liquid of lubricating viscosity.

2. A composition according to claim 1 wherein the amount of dimercaptothiadiazole is substantially greater than the stoichiometric amount.

3. A composition according to claim 2 wherein the dimercaptothiadiazole is 2,5-dimercapto-1,3,4-thiadiazole.

4. A composition according to claim 3 wherein the mixture also contains an oleaginous liquid of lubricating viscosity .

5. A composition according to claim 4 wherein the dispersant is selected from the group consisting of car-boxylic dispersants,amine dispersants, Mannich dispersants, post-treatment products of any of the foregoing, and polymeric dispersants.

6. A composition according to claim 5 wherein the dispersant is a carboxylic dispersant characterized by the presence within its molecular structure of (A) at least one acyl, acyloxy or acylimidoyl radical containing at least about 30 carbon atoms, and (B) at least one radical in which a nitrogen or oxygen atom is attached directly to said rad-ical A, said nitrogen or oxygen atom also being attached to a hydrocarbon radical or substituted hydrocarbon radical.

7. A composition according to-claim 6 wherein the oleaginous liquid is a mineral oil.

8. A composition according to claim 7 wherein the dispersant is a substantially neutral or acidic dis-persant prepared by the reaction of a substantially satu-rated hydrocarbon-substituted succinic acid-producing compound with at least one of an alcohol and an alkylene polyamine.

9. A composition according to claim 8 wherein the dispersant is a mixed oxygen- and nitrogen-bridged dispersant prepared by sequentially reacting a succinic acid-producing compound having a hydrocarbon substituent which contains at least about 50 carbon atoms with at least one alcohol and at least one alkylene polyamine.

10. A composition according to claim 9 wherein the hydrocarbon substituent on the succinic acid-producing compound is a polyisobutenyl substituent.

11. A composition according to claim 10 wherein the alcohol is pentaerythritol and the alkylene polyamine is a polyethylene polyamine containing about 3-7 amino groups per molecule.

12. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a composi-tion according to claim 1.

13. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a com-position according to claim 3.

14. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a com-position according to claim 7.

15. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a composition according to claim 8.

16. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a com-position according to claim 10.

17. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a com-position according to claim 11.