CA1060879A - Sulfurized compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Sulfurized compositions prepared by the reaction of unsaturated compounds and a mixture of sulfur and hydrogen sulfide under superatmospheric pressure are disclosed.
Lubricating compositions containing these sulfurized compositions are also disclosed.

Description

8~3 The invention herein is concerned with a process for the sulfurization of unsaturated compounds and to the novel sulfurized compositions produced by this process. Also, this invention is concerned with lubricating compositions containing these sulfurized compositions as additives therein.
More specifically, the process of the present invention is concerned with the reaction, under suitable reaction conditions, of at least one compound having a non-aromatic carbon-to-carbon unsaturated bond with a mixture of sulfur and hydrogen sulfide to produce sulfurized compositions.
These sulfurized compositions have the properties of extreme pressure agents, anti-wear agents, and oxidation inhibitors;
and, accordingly, are useful as additives for lubricating oils to improve these properties in formulated lubricating compositions. The sulfurization process of this invention is advantageous both from an environmental and economic standpoint since nearly complete conversion of reactants to product can be accomplished in many instances.
The sulfurized compositions of the present invention are effectively employed in lubricating compositions de-signed for a variety of uses. Likewise, the subject sulfur-ized compositions are effective in lubricating compositions based upon both natural and synthetic oils of lubricating viscosity. Also, the subject sulfurized compositions are e~fective in lubricating compositions containing additional additives.
The exact chemical formula and/or structure of the sul-furized compositions is not completely known. Accordingly, the sulfurized compositions are best described by the pro-8 7 ~

cess by which they are produced. The sulfurized composi-tions contain sulfur within the range of from about 2~ to - about 60% by weight, with a range of sulfur in preferred sulfurized lower molecular we:ight olefin (iOe., up to C8 olefins, particularly isobuty:Lene) compositions being from about 25% to about 60% by weight, more preferably about 40%
to about 50~ by weight.
- It is known in the prior art to react isobutylene as well as its dimer or trimer with sulfur under a variety of reaction conditions. Recent work in this area indicates - -that a product containing a trithione grouping is obtained.
This work has been reviewed by Landis in Chemical Revlews 65 237-45 (1965) and by Xharasch and Meyers, Chapter 10 of Vol.
II of THE CHEMISTRY OF ORGANIC SULFUR COMPOUNDS (1966).
One of the products formed by the reaction ~f the iso-butylenes and sulfur is hydrogen sulfide. Numerous prior - art references teach that it is highly desirable to remove the hydrogen sulfide product as it is formed;
-Also, it is known in the prior art that h~drogen sul-fide reacts with isobutylene, as well as its dimer and - trimer to predominantly form the corresponding thiols with sulfides, disulfides and higher polysulfides being formed as by-products. In some instances, the use of minor amounts of sulfur in this reaction have been reported. References of

2~ interest in this regard are Jones and Reid, J. Am. Chem.
Soc.- 60 2452-55 (1938), Naylor, J. Chem. Soc. 1947 1532-39, and U.S. Patent 3, 221,056 issued to Loutham. Also of interest is U.S. Patent 3,419,614 issued to Doss and con-cerned with a process for increasing the yield of thiol compounds by the reaction, at high temperatures, of various ethylenically unsaturated compounds with hydrogen sulfide and sulfur in the presence of various basic materlals.
In essence, the preparative process for the novel sulfurized compositions of the present invention comprises-the steps of (A) reacting at least one compound having a non-aromatic carbon-to-carbon unsaturated bond, sulfur and hydrogen sulfide under suitable reaction conditions and in .suitable amounts to produce a first sulfurized reaction product; ~B) separating from the first reaction product of step (A), by suitable means,any low boiling materials; and - (C) optionally treating the separated product of (B) to - reduce active sulfur, whereby the desired sulfurized com-position is obtained. Thus, the desired sulfurized com-positions of this invention are the reaction products of lS step (A) from which low boil-ing materials, if any, are - removed and further, if desired, treated to reduce active sulfur. Analysis of preferred sulfurized isobutylene and diisobutylene compositions of this invention indicates that they are predominantly composed of di-, tri-, tetra- and higher sulfides.
More specifically, the sulfurized compositions are prepared by a process which comprises the steps of (A) reacting, under superatmospheric pressure,~i) at least one compound having a non-aromatic carbon-to-carbon unsaturated bond with (ii) sulfur and (iii) hydrogen sulfide, wherein the molar ratio (a) of (i) to (ii) is in the range of 1 to f~om about 0.1 to about 3.0 (more preferably about 0.3 to about 2.0, still more preferably about O.S to about 1.5) and ; the molar ratio (b) of (i) to (iii) is in the range of 1 to from about 0.1 to about 1.5 (more preferably up to about 1.25, still more preferably rom about 0.4 to about 0.8);

8~3 (B) separating rom the reaction product of step (A) any low boiling materials; and (C) optionally treatin~ the separated product of (B) to reduce active sulfur, whereby the desired sulfurized composition is obtained.
The terminology "low boiling materials" as used herein and in the appended claims refers to materials which, be-cause of their relatively low boiling points, are desirably removed from the reaction product obtained in step (A). The - nature of the low boiling materials removed from the product of step (A) will vary according to the amount and type of starting materials used, and, the particular reaction con-ditions employed. Moreover, the nature of these low boiling materials will also vary according to the criteria used in their removal. Thus, the nature of the 1QW boiling materials will vary according to such criteria as odor considera~io~
- recycling needs of unreacted reactants and by-products, and.
to an extent, performance of the sulfurized compositions in lubricating compositions, especially where particularly high - -sulfur (30% by weight or higher) content is desired.
--A typical basic standard used to determine the extent of removal of materials (i.e., low boiling materials) from the reaction product obtained in step (A) is the avoidance of compositions which are flammable according to standards ' set, for example, by the Department of Transportation and/or Department of Labor. It is desirable that the sulfurized compositions of this invention, and, moreover, concentrates of these compositions as well as lubricating compositions , meet such standards so as to not require excessive pre-caution in transportation and storage~ Accordingly, the ' nature of low boiling materials will depend upon the con-.

i~UB'79 ditions used to meet such standards. Reference is made in this regard to ASTM procedures D-56, 93 and 1310. Desirably, the low boiling materials are removed so that the sulurized compositions, as well as any concentrate or lubricating compositions made therefrom, exhibit a flash point above at least about 30C., more preferably ahove at least about 70C., and even more preerably above at least about lOO~C.
as determined by ASTM D-93-73.
When starting with volatile unsaturated compounds such as those having up to about 6 carbon atoms, the low boilin~
materials are mostly composed of unreacted reactants, mer-captans and monosulfides. If the unsaturated compounds are gaseous at ambient pressures and temperatures, then the unreacted unsaturated compounds along with any unreacted hydrogcn sulfide can be rem~ved in part simply by venting the reaction vessel after step (A). Substantially all, i.e., greater than about 50% by weight, of the unreacted reactants, mercaptans and monosulfides are ultimately ` removed in separation step ~B) when starting with such volatile unsaturated compounds. These low boiling materials can be recycled if desired.
When starting with higher molecular weight (e.g., 15 carbons or more) unsaturated compounds, or those having polar groups which raise the boiling point of the unsatu-rated compound, there is normally no requirement to remove all of the mercaptans and monosulfides or even unreacted unsaturated compounds, unless economically justified as in the case of recycling or desire for higher sulfur content.
Moreover, when starting with even higher molecular weight unsaturated compounds (e.g., 30 or more carbon atoms), the .
_ 5 _ ~6~)8~7~
percent of low boiling materials removed (not considering any unreacted H2S) can be relatively low compared to the total weight of the reaction product obtained from step (A), e.g., as low as about 3% or less by weight based upon the total product of step (A).
In certain instances as, for example, sulfurization of a-methylstyrene, the removed low boiling materials include by-products, such as cumene, of either the sulfurization of the ~-methylstyrene in step lA) or some further reaction during the separation stage. Again, separation of these materials according to any of the above-described criteria, particularly flammability, constitutes separation of low boiling materials according to this invention.
If desired, any solids can also be optionally removed during the separation step (B) or optional treatment (C).
Normally, the removal of any solids, if present, can be accomplished by simply removing the liquid phase from the reaction vessel after completion of the reaction in step (A). However, if necessary, removal of solids can be accomplished through filtration or centrifugation methods.
Usually, there will be no sulfur solids after step (A), unless, however, excessively high levels of sulfur are employed or the reaction is not carried to completion. When particularly high sulfur content is desired, minor amounts of elemental sulfur may remain in the sulfurized composition.
It has been found that advantageous results are obtained when certain materials are incorporated in the reaction mixture during the sulfurization step, i.e., step (A). Thus, water and/or basic catalytic materials, such as aqueous solution ~L~16~
of basic alkali metal compounds, as their hydroxides, sulfides, etc., ammonium hydroxide, amines or quaternary ammonium compounds such as quaternary ammonium hydroxides, are advantageously employed in this step. When water or aqueous solutions are employed in the sulfurization step, they are used in a range of from about 1~ to about 25% by weight of the total weight of the unsaturated compounds used. This will provide a concentration of the basic catalytic material of the solution within a range of from about 0.0005 mole to about 0.5 mole per mole of unsaturated compound, with a preferred range of from about 0.001 mole to about 0.1 mole per mole of the unsaturated compound present.
The reaction can be conducted under anhydrous or substantially anhydrous conditions as such conditions are advantageous for this process when using certain types of reaction equipment.
The sulfurization step, i.e., step (A) may be conducted in the presence of a basic catalytic material selected from the group consisting of ammonia, organic hydrocarbyl amines and mixtures thereof. This catalytic material may be present in a range of from 0.0005 mole to about 0.5 mole per mole of unsaturated compound, and preferably, in the range of from about 0.001 mole to about 0.1 mole per mole of unsaturated compound present.
The amines useful as the basic catalytic material in the sulfurization step include the primary, secondary and tertiary hydrocarbyl amines, wherein the hydrocarbyl radicals include alkyl, aryl, arylalkyl, alkaryl, etc. In general, the hydrocarbyl radical contains from 1 to about 20 ~t36~8~
carbon atoms. Examples of suitable amines include aniline, benzylamine, dibenzylamine, dodecylamine, napthylamine, tallowamines, N-ethyldipropylamine, N-phenylbenzylamine, N,N-diethylbutylamine, m-toluidine and 2,3-xylidine. Also useful as a basic catalytic material in the sulfurization step are secondary amines derived from a hydrocarbyl radical which is an alkylene or substituted alkylene and forms a five or six membered heterocyclic group with the amino nitrogen, e.g., pyrrolidinyl and piperidyl. Also useful as a basic catalytic material are nitrogen heterocyclic compounds, such as pyridine and quinoline.
As stated earlier, when a basic catalyst material is used in the sulfurization step, it can be selected from ammonia;
and primary, secondary, or tertiary aliphatic amines having from 1 to about 8 carbon atoms in the alkyl radicals.
Representative amines useful as a basic catalytic material in the process of this invention include methylamine, dimethyl-amine, trimethylamine, ethylamine, diethylamine, triethyl-amine, di-n-butylamine, tri-n-butylamine, tri-sec.-hexylamine, tri-n-octylamine, and the like. Obviously, mixtures of these various amines can be used, as well as mixtures of ammonia and amines.
A wide variety of unsaturated compounds can be sulfurized according to this invention and the particular type unsaturated compound does not, in general, limit the nature of the sulfurization process. Ethylenic and acetylenic unsaturation are contemplated, but ethylenic unsaturation is usually pre~erred. Preferred unsaturated compounds for lubricating compositions of this invention include those which are mono- or di-olefinic compounds (i.e., having one il7~

or two carbon-to-carbon double bonds) and, particularly, ~erminal olefins (i e., ~ C-=~H2) havin~ one carbon-to-carbon double bond. Examples of unsaturated compounds are those wherein each set of olefinically bonded carbon atoms ~i.e., C = C ) have valences independently satisfied by moieties selected from the group consisting of (a) -C(R) 3 wherein each R is independently hydrogen; alkyl; alkenyl;
aryl; substituted alkyl; substituted alkenyl; and substi-tuted aryl; with the proviso that any two R groups can be alkylene or substituted alkylene whereby a ring of up to .. O .
Il 11 about 12 carbon atoms is formed; (b) -COR'; -CN(R') 2;
O - O
-CON(R')4 or -C-OM wherein M is An equivalent of a metal cation ~preferably Group I or II, e.g., sodium, potassium, - ~ - R"
etc.) and wherein R' is as R above; (c) -C --N or -C=NR"
wherein R" is as R above; (d) -X wherein ~ is halogen (e.g~, chloro, bromo or iodo); (e) -YR " ' wherein Y is oxygen or divalent sulfur and R''' is as R above; (f) -A wherein A is - aryl or a substituted aryl of up to about 12 carbon atoms;
and (g) hydrogen; with the proviso that any two of the valences can be satisfied by an alkylene or substituted alkylene moiety.
Particularly useful unsaturated compounds have from 3 up to about 30 carbon atoms ~more preferably from 3 to about 16 carbon atoms). Included among the useful unsaturated compounds of this invention are those of the formula . . .
R~R2C = CR3R4 Formula I
wherein Rl, R2, R3 and R~ are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted _ 9 _ ~alkenyl, aryl and substituted aryl~ ~pre preferably, in Formula I, R4 is, ~or example, hydrogen and at least one o Rl, R2 and R3 is not hydrogen but is alkyl or alkenyl, more preerably, al~yl.
The nature of any particulax substituent in the sub-stituted alkyl, alkenyl or aryl moieties as above-described does not constitute an essential or normally cri*ical aspect of this invention and any sach substituent, providing it is or can be made compatible in lubricating environments and is - 10 non-interfering under the contemplated reaction conditions, is useul in this invention. Thus, of course, substituted unsaturated compounds which are so unstable as to deleteri-ously decompose under the reaction conditions employed are ~ not contemplated herein. However, certain substituents such as keto or aldo can desirably undergo sulfurization according to the process of this invention. The selection of suitable substituents to provide useful lubricating compositions is generally believed within the skill of the art, or, alter-natively, may be established through routine testing.
Typical of such substituents include any of the above-listed moieties as well as hydroxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, alkali metal salts of mercap-tans, phosphates, phosphites and the like.
Isobutylene, propylene and the respective dimers, trimers and tetramers of either of these as well as mixtures ~f any of such monomers or oligomers are more preferred of all the unsaturated compounds. Of these compounds, iso-butylene and diisobutylene are preferred, especially con-sidering the particularly high sulfur containing composi-

3~ tions which can be prepared from these olefins.
, ~(~60~
The more preferred reactants, i.e., isobutylene or diisobutylene, and the sul~ur and hydrogen sulfide, are well known and are commercially available. Since it is con-templated that for commercial manufacture, commercial sources of these reactants will be used, impurities normally associ-ated with these commercial products may be present. More-over, diisohutylene is generally believed to be composed of two isomeric forms and this mixture is contemplated.
The sulfur and hydrogen sulfide reactants react with the unsaturated compounds within a specified range of molar ratios. Thus, sulfur is used preferably in the range of ~rom about 0.3 mole to about 2.0 moles per mole of unsatu-rated compounds. A more preferred range is from about 0.5 - mole to about 1.5 moles per mole of the unsaturated com-pounds. The most preEerred rang~l espec ally whcn using isobutylene, is from about 0.7 mole to about 1.2 moles per mole of the unsaturated compounds. Hydrogen sulfide is used in the range of from about 0.1 mole to about 1.5 moles per mole of unsaturated compound with a preferred range of from about 0.4 mole to about 1.25 moles per mole of unsaturated - compound, more preferably, about 0.4 mole to about 0.8 mole.
In batch operations, the reactants are present at such levels that the unsaturated compounds react with a mixture o sulfur and hydrogen sulfide within the above ratios. In semi-continuous and continuous operations, the reactants may be admixed at any ratio. However, on a mass balance basis, they are ultimately consumed during the course of the two latter operations within the ratios as specificed above.
Thus, for instance, the reaction vessel may be initially .

.

lO~OB7 .. .. . . .
.charged with sulfur alone, and the unsaturated compounds along with hydrogen sulfide incrementally added and reacted .
over a period of time until the desired ratio is obtained.
However, in all these operations the unsaturated compounds must be reacted with sulfur in the presence of added hydro-gen sulfide.
The subject sulfurization reaction is conducted at a reaction temperature in the range of at least about 50~C. to about 300C. with a more preferred range of from about 100C. to about 200C. A range of between about 125C. to about 180~C. is especially suitable. The reaction is con-ducted in a reactor system under superatmospheric pressure, -usually this is autogenous pressure, i.e., the pressure developed during the course of the reaction. The exact - 15 pressure developed can vary during the course of the reac-~tion and is dependent upon such factors as the design and operation of the system, the reaction temperature, and vapor pressure of the reactants and products. -The reaction is conducted for a period of time suffi-cient to form à product having the desired degree of sul-furization. The actual time required to complete the reaction depends upon many factors, including, for example, the nature of the unsaturated compounds used~ the reaction - temperature employed, the ratio in which the reactants are present, the presence of catalysts, and to a lesser extent, upon the purity of the reactants. The course of the reac-tion in batch or semi-continuous operations may conveniently be followed by monitoring the change in pressure during the ; reaction. Ordinarily, in these type operations, the reac-.i .

8~7~
tion is considered complete when the pressure within the vessel levels off to a constant value.
- The subject process can be conducted without resorting to added diluents. However, diluents can be used, for example, in order to control reaction rates, i~ desired.
In effecting the second step of the subject process, i.e., step (B), the separation o volatiles is most effec-tively accomplished using separation methods based on dif-ferences in the vapor pressures of the materials to be separated. Thus, in this step, distillation techniques such as vacuum distillation or distillation at atmospheric pressure, are effectively employed to separate low boiling materiaIs from the crude reaction product of the sulfuri-zation step. Likewise, vacuum stripping techni~ues which involve the separation of low boiling materials ~rorll the pxoduct under reduced pressure and at a variety of tempera-~ures are useful in effecting the separation step. Also, techniques involving the passage of an inert gas, such as nitrogen, through the reaction mixture at a variety of ~0 temperatures and pressures are useful in removing various low boiling materials. Additionallyl techniques involving large-scale gas chromatography and molecular distillation are useful in e~fecting the separation step.
Considering the lower boiling unsaturated compounds such as isobutylene and other such unsaturated compounds of up to about 6 carbon atoms, substantially all of the unre-acted reactants, mercaptan and monosulfide products are separated in the separation step (B) from the di-, tri-, tetra-, and higher sulfides. The terminology of "substantially all"or "majority" is used to define a separation of at least about 50% of these materials. Preferably, a separation of about 60% of these materials is obtained, and more preferably a separation of about 75% is effected. The percentage or degree of separation may be determined and the progress of the separation step followed by analytical methods known to those skilled in the art. One useful method is to employ gas chromatography.
The optional treatment to reduce active sulfur can be accomplished according to any of the known methods in the art.
As used herein and in the appended claims, "active sulfur"
refers to the activity of the sulfur (in the separated compositions of step (B))to materials such as copper which are susceptible to attack under certain lubricating conditions or environments. Standard tests can be used to determine the activity of sulfur of any particular sulfurized composition.
Of course, metal deactivators or passivators can be used in the lubricating compositions in lieu of, or in supplement to, the reduction of active sulfur in the sulfurized compositions themselves. Where high levels of active sulfur are desired (e.g., metal working fluids) the reduction of active sulfur may be omitted.
One useful method to reduce active sulfur is shown in U.S. Patent 3,498,915, issued March 3, 1970. In the interest of brevity, this method basically entails treatment of the sulfurized composition with aqueous sodium sulfide for a period of time 7~
suficient to scavenge active sulfur. Other alk~li metal sulfides can be used to replace the sodium sulfide. After treatment, the aqueous phase is separated from the organic phase whereby the organic phase has sulfur of reduced activity. The extent of reduction can be conveniently measured by procedures known to those in the art. Of course, step ~C) can precede step (B), or they can be run concurrently, if desired.
Other optional treatments may be employed to improve such qualities as the odor, color and staining character-- istics of the sulfurized compositions of this invention, if ~esired. For example, treatment of sulfurized unsaturated compounds such as diisobutylene with acidic clays (eOg., Super Filtrol) may be advantageous in reducing any tendency of such SU1LUriZed co~p3sitions ~o e-vol-ve hy~lcyen su' ide.
- Moreover, filtration through Fuller's Earth, activated - charcoal, other alumina clays and the like may improve such ` qualities as odor, color and staining. However, such treat-ments are often not required when a basic catalyst is em-ployed and the preferred sulfurized isobutylene compositions are particularly advantageous in that no such post treatment is required for compositions o desirable odor, color and staining characteristics.
A clearer understanding of the novel sulfurized com-positions of this invention, the processes for their pre-paration, and lubricant compositions containing these sulfurized compositions may be obtained from the examples given below, which illustrate this invention but are not to be considered as limiting thereof.

tra~le ~ar~

~ 15 -~36~7~

.EXAMPLE 1 Powdered sulfur ~526 grams r 16.4 moles) is charged to a jacketed high pressure reactor, which is fitted with an agitator and internal cooling coils. Refrigerated brine is circulated through the coils to cool the reactor prior to the introduction of the gaseous reactants. After sealing the reactor, evacuation to about 2mm Hg and cooling, 920 - grams (16.4 moles) of isobutylene and 279 grams (8.2 moles) of hydrogen sulfide are charged to the reactor. The reactor is heated using steam in the external jacket to a tempera-ture of about 182C. ~360F.) over a period o~ about 1.5-hours. A maximum pressure of 1350 psig (pounds per square inch gauge) in the reactor is reached at about 168C.
(335F.) during this heat-up. Prior to reaching the peak reaction temperature, the pressure starts to decrease and continues to decrease steadily as the gaseous reactants are consumed. After about 10 hours at a reaction temperature of about 182C., the pressure is 310-340 psig and the rate of pressure change is about 5-10 psig per hour. The unreacted hydrogen sulfide and isobutylene are vent~d rom the reactor ...
to a suitable recovery system. After the pressure in the reactor has obtained atmospheric pressure, the product is removed from the reactor, and a reddish colored fluid product is obtained.
This product is then post treated hy charging it to a suitable flask and blowing nitrogen gas through the product at approximately 100C. (212F.) to separate the lower-boiling fraction. The stripped material is mixed with 5% of -~' ; an acidic clay (Super Filtrol) for one hour at 100C. and then filtered using about 1% of a diatomaceous earth fil-1æ ~arl~
~ 16 --tering aid. A separation of more than 75~ of the unreacted isobutylene, mercaptans and monosulfide materials present in the crude reaction mixture was obtained in the separation step. The inal product cGntained 42.5% by weight sulfur.
A second sulfurized composition is prepared using the procedure of Example 1 except that (1) a basic catalytic material (n-butylamine) is used in step ~A) and (2) the step using acidic clay is omitted. It is found that the sulfurized lsobutylene compositions which are prepared in $he presence of a basic catalytic material and which omit treatment with acidic clay (Super Filtrol) have superior iong term stability as compared to similarly catalyzed sulfurized isobutylene compositions which have been treated W~ti-l the dCidi~ clay.
EX~MPLES 2-12 In Examples 2-12, the general procedure-of Example 1, was followed with variables, such as reactant ratio, reac-tion temperature, and the composition of the reaction mixture being varied. The separation step in these pre-parations was effected by the preliminary blowing of nitro-~ gen gas through the reaction mixture, followed by vacuum stripping of the resulting mixture. In those examples where water was present in the reaction mixture, the crude product was first separated from the aqueous layer and then worked - up in the usual manner.
The experimental details, as well as the results obtained in these Examples are summarized in Table I below.
, ~r~le~rK
, ~6(~87~
, g ~; h 1~) ~ ~ .
q~ .... .....

H
h ,, a ,. ' . ' ' - . O ~
U~ ~ X
~ O m E3 d Ot`~ O O O ~ r~ ~ g - O .1~ ---------- a)s~o '1 ~D ~1 1` 0 OD ~1 In O ~ ~ E~

C~ h ~ h æ ~ ~
~ n o u ~ o~ n ~ o ~ o o ~
u~ ~ w,1 u ~ ~r In ~ ~1 0 ~1 0 0 0 ,1 , s Z~ ~ ' Q.) O o `
HO O ~1 h ~ o~o ' .

a) ~" t,~ ~0 U~P nl r~ n o ~ O a) oP
h 0 ~ ~I Lt~ > N C~ LO ~1 ~2~ ~ O ~ >1 ~1 H h . . ~: Q) a) Q rl O

-,, ~ I C) ~ O
~ ~ x ~ ~ o s~
~ ~ z z z o ~ ~
k u) Q) - Q) Q) a) O-` u~ O ~ rl s~
O N ~ m m ~ o ~ ~ o o o o ~ I X I 1 4~ U o ~
z æ ~ c æ z; ~ Z ~ ~ ~ o ~
o ~W
Z ~ O
9 ~ ~ ~ rl h u~
d O ~ O
.¢ o h ~ ~ 1) ~1 rd H O Q, 1~ ~ ~1~ co I~ rl W
~ ~ ~1 ~1 ~1~1 ~1 ~1 ~1~1 ~1 ~ H Id O ~
O O ~ ~ ~
O O ~\
~I OOOOO~OOOOO ~O~rl ~ r-l H N t~ H ~--1 H H r-l a) ~ Ul o o ~
H I ~ u~ dP oP O O U~
O O
, ,,. .. ~ ' . E~ , '- X O ,1 ,1 ,~
~;

~ 18 --~ From the above data, it is apparent that the sulfur-ization step of the subject process may be conducted by a variety of methods using a reaction mixture comprising isobutylene, sulfur and hydrogen sulfide. Thus, the three 5 ` components, i.e., isobutylene, sulfur and hydrogen sulfide, may be reacted without the presence of any additional active material, i.e., the reaction mixture consists essentially of isobutylene, sulfur and hydrogen sulfide. The final sul-furized composition obtained by this sulfurization step has good properties as a lubricating additive~ A second method to effect the sulfurization is to conduct the reaction in thç presence of water or aqueous solutions of various basically reacting compounds, as described above. Again, the final sulfurized compositions obtained using these sul-furization steps have good properties as lubricating addi-tives. Another method is to effect the reaction in the presence of a catalytic amount of a basic catalyst, such as - ammonia or amines. The final sulfurized composition obtained using this particular sulfurization step, likewise, has good additive properties. The principal difference between the final sulfurized compositions obtained by these different methods appears to reside in the amount of trithione-type compound produced as a by-product of the sulfurization step.
As discussed above, it is known in the prior art khat the reaction of sulfur and isobutylene produces a compound containing a trithione group and formation of this type of compound during the sulfurization step appears to contribute some coloration to the final product. The formation of the - trithione type compound appears to decrease when the reac-tion is conducted in the presence of water and is further 19 ~

~iO~'7~
.. .
decreased when the reaction is conducted in the presence of the basic catalytic materials.

In Examples 13-27, various unsaturated compounds are sulfurized according to the procedures of this invention.
The separation step (B) includes using vacuum distillation : for separation of low boiling materials.
The experimental details, as well as the results obtained in these Examples, are summarized in Table II
below.

: ' : .

- ' , ~ ..

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

.
, :

.

.

.

p . ~ h ,. ~ ~ ........... ...
æ U~ ,,O ,~ J ",~
~L~ dP ' Q) ' ` ` . U) p~
IL1 Q~ , W
U~ O
O
2; ~ . a) ' 1 ~ . ` U ~IIS
O ~ O
~4 ~ a) . o o .
~:1 0 ~ O a) h O
O
m h ~
, 0 "~ QJ Z . - ~ o . o o ~;
~ m - o ~ ,~ o o H~ ~ t H ~ 5 Q
H ~ C.) I` = ~
- ~ ~ ~ a) a) - o -. ~ ~ OOOOOOOOOOOOOOO Q~
,,." " ......................... o ~ o o m U
. . h --wO a~
~ ~ ~ O`-Q ~ Q a ;1 R O rl ~ o ~ Id ~ 0 au ~: a) ~ ~ a) h o ~ ~ Q~1 Ei ~1 O) H ~ X -1 ~1~1 ~ R ~ ~ ~1 n~ IJ ~ R ~1~ ~ 0 t~ 0 ~ q) ~ 0 ~ ~ 0 !:~ ~ U ~ a) O ~ h U) C,) ~ 0~ ~ Q -~ S ~ ~1 ~ ~ u~ O o a~ I ~ A S l ~ O O ~ a 5~ O ~ O 5 ~ 1 0 U S~ 4 o u) o o o ~1 ~ u o ~ ~ o ,~ Q O a~ ~ ~ O o ~ ~ O
U~ I U~ rl ~ ~ U~ ~ I U~ O ~ rl O R ~ ~ V O ~1 0 æ o z ~,. .
n. .

As was briefly described above, the sulfurized com-positions of the present invention are particularly useful as additives for oils of lubricating viscosity in the for-mulation of lubricating compositions. It is known that high pressures encountered during the usage of certain types of gears and bearings may cause the film of lubricant to rup-ture and cause damages, such as excessive wear, scuffing and seizure to the metal surfaces of those parts. It is common practice to incorporate in lubricating oils, compounds such as extreme pressure (EP) agents and anti-wear agents capable of improving the properties of the lubricant to protect the metal surfaces under such conditions of extreme pressure, high temperature and high speed conditions. Also, it is well known in the art that when lubricating oils are sub-jected to extended periods of use, particularly at high operating temperatures, they tend to decompose with a formation of various oxidation products, such as acidic materials, peroxides, and other decomposition pro~
ducts. The products may have adverse effects on both the base lubricating oil and upon the various materials which come into contact with these lubricating compositions.
Thus, such products promote the corrosion of various metal-lic surfaces, such as engine parts, gears, etcO, contacted with a composition containing these various oxidation and other decomposition products. It is common practice to incorporate in base lubricating oils compounds, i.e.~
oxidation inhibitors, capable of increasing the resistance l8~
of these oils to oxidation. Thus, the compositions of the pxesent invention are particularly useful as additives for lubricating oils where they function primarily as extreme pressure agentsl anti-wear agents and oxidation inhibitors.
Lubricating compositions containing the subject sul-furized compositions as additives (sometimes referred to hereafter as "subject additive(s)" or "sulfurized addi-$ive(s)") therein comprise a major proportion of lubricating oils and a minor proportion, sufficient to improve the extreme pressure, anti-wear and oxidation inhibiting pro-perties of the lubricating composition, of the sulfurized composition. In general, the subject sulfurized composi-tions are used in amounts of from about 0.01% to about 20%
by weight of the total weight of lubricating composition.
lS The optimum conc2n~ration r~r a par'icular additive will ~epend to a large measure upon the type of service or ~hich the composition is designed. In most applications, lubri-- - cating compositions containing from about 0.1% to about lO~
by weight of the subject sulfurized composition are useful, although for certain applications, such as in gear lubricants and in diesel engines, compositions containing up to 20% or -more may be preferred.
The subject sulfurized compositions can be effec-tively employed in a variety of lubricating compositions formulated for a variety of uses. Thus, lubricating com-positions containing the subject additive are effective as crankcase lubricating oils for spark-ignited and compres-sion-ignited internal combustion engines, including .

~1~6~

automobile and truck engines, two-cycle engines, aviation piston engines, marine and low-load diesel engines, and the like. Also, automatic transmission fluids, transaxle lubri-cants, gear lubricants, metal-working lubricants, hydraulic fluids, and other lubricating oil and grease compositions can benefit from the incorporation of the subject additives therein.
The lubricating composition of the present invention may, of course, be prepared by a variety of methods known in the art. One convenient method is to add the subject sul-furized additive in the form of a concentrated solution or substantially stable suspension to a sufficient amount of the base lubricant to form the lubricating compositions.
This additive concentrate contains the sulfurized additive in the proper amount to provide the proper ratio of additive in the final lubricating composition when added to a pre-determined amount of base lubricant. Also, the concentrate may contain appropriate amounts of any additional additives desired in the final lubricating composition.
Generally, the concentrate will compri~e from about 20%
to about 90% of the sulfurized additive with the balance being a substantially inert normally liquid solvent or diluent, plus any additional additives used. Suitable solvents and diluents include any of the herein discussed natural or synthetic oils, kerosene, xylene, benzene, mixtures of two or more of these and other solvents and diluents known in the art. Hereinafter, these substantially inert, normally liquid solvents and diluents used in the preparation of additive concentrates are re~erred to col-lectively as carriersO Normally the carriers are oil-soluble at least to the extent of their concentration in the final lubricating compositions prepared for them.
The sulfurized additives of the present invention are effectively employed using base oils of lubricating viscosity derived from a variety of sources. Thus, base oil derived from both natural and synthetic sources are useful for the preparation of lubricating compositions of the present invention.
The natural oils include animal oils, such as lard oil; vegetable oils, such as castor oil; and mineral oils, such as solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types.
Also useful are oils of lubricating viscosity derived from coal or shale.
Many synthetic lubricants are known in the art and these are useful as a base lubricating oil for lubricating compositions containing the subject additives. Surveys of synthetic lubricants are contained in the publications, SYNTHETIC LUBRICANTS by R.C. Gunderson and A.W. Hart, published by Reinhold (N.Y., 1962); LUBRICATION AND LUBRICANTS, E.R. Braithwaite, ed., published by Elseiver Publishing Co., (N.Y., 1967), Chapter 4, pages 166 through 196, "Synthetic Lubricants", and SYNTHETIC LUBRICANTS by M.W. Ranney, published by Noyes Data Corp. (Park Ridge, N.J., 1972).
These publications are mentioned to establish the state of the art in regard to identifying both general and specific types of synthetic lubricants which can be used in conjunction with additives of the present invention.

t7~

Thus, useful synthetic lubricating base oils include hydrocarbon oils derived from the polymerization or copoly-merization of olefins, such as polypropylene, polyisobu-tylene and propylene-isobutylene copolymers; and the halo-hydrocarbon oils, such as chlorinated polybutylene. Other useful synthetic base oils include those based upon alkyl benzenes, such as dodecylbenzene, tetra-decylbenzene, and those based upon polyaromatics, such as biphenyls and terphenyls.
Another known class of synthetic oils useful as base oils for the subject lubricant compositions are those based upon alkylene oxide polymers and interpolymers, and those oils obtained by the modiication of the terminal hydroxy groups of these polymers, ~i.e., by the esterification or etherification of the hydroxy groups). Thus, useful base oils are obtained from polymerized ethylene oxide or pro-pylene oxide or from the copolymers of ethylene oxide and propylene oxide. Useful oils include the alkyl and aryl ether~ of the polymerized alkylene oxides, such as methyl-polyisopropylene glycol ether, diphenyl ether of poly-ethylene glycol, and diethyl ether of propylene glycol.
Another useful series of synthetic base oils is derived from the esterification of the terminal hydroxy group of the polymerized alkylene oxides with mono- or polycarboxylic acids. Exemplary of this series is the acetic acid esters or mixed C3-C~ fatty acid esters of the C13Oxo acid diesters of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprise the esters of dicarboxylic acids, such as phthalic acid, succinic acid, oleic acid, azelaic acid, suberic acid, ~O~)B~

sebacic acid, with a variety of alcohols. Specific examples of these esters inclu~edibutyl adipate, di(2-ethylhexyl)-sebacate, and the like. Silicone based oils such as poly-alkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and the silicate oils, i.e., tetraethyl silicate, comprise another useful class of synthetic lubricants. Other synthe-tic lubricating oils include liquid esters of phosphorus-containing acids, such as tricresyl phosphate, polymerized tetrahydrofurans, and the like.
Unrefined, refined, and re-refined oils of the type described above are useful as base oils for the preparation of lubricant compositions of the present invention. Unre-fined oils are those obtained directly from a natural or synthetic source without further purification or treatment.
For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from dis-tillation, or an ester oil obtained directly from ester-ification process, and used without further treatment are unrefined oils. Refined oils are similar to the unrefined oils, except they have been further treated in one or more purification steps, to improve one or more properties. Many such purification techniques are known in the art, such as solvertextraction, acid or base extraction, filtration percolation, etc. Rerefined oils are obtained by a variety of processes similar to those used to obtain refined oils.
The rerefined oils are also known as reclaimed or repro-cessed oils and have been treated by additional techniques directed to the removal of spent additives and oil breakdown products.

~J6V~
The subject additives can be used alone or in combination with other lubricant additives known in the prior art. A brief survey of conventional addi ives for lubricating compositions is contained in the publications, LUBRICANT ADDITIVES, by C.V. Smalheer and R. Kennedy Smith, published by the Lezius-Hiles Co., Cleveland, Ohio (1967~
and LUBRICANT ADDITIVES, by M.W. Ranney, published by Noyes Data Corp., Park Ridge, New Jersey (1973). These publications are mentioned to establish the state of the art in regard to identifying both general and specific types of other additives which can be used in conjunction with the additives of the present invention.
In general, these additional additives include detergents of the ash--containing type, ashless dispersants, viscosity index improvers, pour point depressants, anti-foam agents, extreme pressure agents, anti-wear agents, rust-inhibiting agents, oxidation inhibitors, and corrosion inhibitors.
The ash-containing detergents are the well known neutral basic alkali or alkaline earth metal salts of sulfonic acids, carboxylic acids or organo-phosphorus-containing acids. The most commonly used salts of these acids are the sodium, potassium, lithium, calcium, magnesium, strontium and barium salts. The calcium and barium salts are used more extensively than the others. The i'basic salts" are those metal salts known to the art wherein the metal is present in a stoichiometrically larger amount than that necessary to neutralize the acid. The calcium- and barium-overbased petrosulfonic acids are typical examples of such basic salts.

-~ - 28 -1060~79 The extreme pressure agents, corrosion inhibiting agents and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons, such as chlorinated wax;
organic sulfides and polysulfides, such as benzyl-disulfide, ~is-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sul-furized sperm oil, sulfurized methyl ester o~ oleic acid~
sulurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosul-furized hydrocarbons, such as the reaction product of phos-phorus sulfide with turpentine or methyl oleate; pnosphoric acids, phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, i.e., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl - 15 phosphite and polypropylene substituted phenol phosphite;
metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol dithiocarbamate; Group II metal salts of phosphorodithioic acid, such as zinc dicyclohexyl phosphorodithioate, and the zinc salts of a phosphorodi-thioic acid; and esters of phosphorodithioic acids such as phosphorodithioic acids treated with either styrene or epoxides.
The ashless detergents or dispersants are a well known - class of lubricant additives and are extensively discussed and exemplified in the above-cited publications by Smalheer et al, and Ranney and the reference cited therein. Particu-larly useful types of ashless dispersants are based upon the reaction products of hydrocarbon-substituted succinic acid compounds and polyamines or polyhydric alcohols. These reaction products may be post treated with materials, such as alkylene oxides, carboxylic acids, boron compounds, ~(~6()8~
carbon disulfide and alkenyl cyanides to produce further useful ashless dispersants.
Pour point depressing agents are illustrated by the polymers of ethylene, propylene, isobutylene, and poly(alkyl methacrylate). Anti-foam agents include polymeric alkyl siloxanes, poly(alkyl methacrylates), terpolymers of diace-tone acrylamide and alkyl acrylates or methacrylates, and the condensation products of alkyl phenols with formaldehyde and an amine. Viscosity index improvers include polymerized and copolymerized alkyl methacrylates and polyisobutylenes.
When additional additives are used in lubricant com-positions comprising the subject additive they are used in concentrations in which they are normally employed in the art. Thus, they will generally he used in a concentration of from about 0.001% up to about 25% by weight of total composition, depending of course, upon the nature of the additive and the nature of the lubricant composition. For example, ashless dispersants can be employed in amounts from about 0.1% to about 10% and metal-containing detergents can be employed in amounts from about 0.1% to about 20% by weight. Other additives, viscosity index improving agents, anti-foaming agents, and the like, are normally employed in amounts of from about 0.001% to about 10% by weight of the total composition, depending upon the nature and purpose of thç particular additive.
The following lubricant compositions exemplify the incorporation of the additives of the present invention in these type compositions.

EX~MPLE A
A lubricating composition suitable for use as a crank case lubricant is prepared using a lOW-40 mineral lubri~
cating oil base and, as additives: 5.41% of a polyiso-decylacrylate viscosity index improver; 4.2% of an ashless dispersant based upon the react:ion product of a polyiso-butenyl: succinic anhydride, pentaerythritol, and poly-ethylene polyamine; 1.57% of an overbased calcium sulfonate detergent; 0.96% of a zinc isobutylamyl phosphorodithioate oxidation inhibitor; 0.27% of the sulfurized isobutylene product of Example ll; and 40ppm of a conventional anti-foam agent~
Example B
A lubricating composition suitable for use as a gear lubricant is prepared using a SAE 90 base mineral oil, and as additives: 2.0% of a dialkyl phosphite derived from Cl4 18 alcohols; 0~25% of a commercially available aliphatic primary amine, wherein the aliphatic groups are a mixture of tertiary alkyl radicals having 11 to 14 carbon atoms; 0.08%
of a conventional anti-foaming agent based upon a polymer of 2-ethylhexyl acrylate and ethyl acrylate; and 4.1% of the sulfurized isobutylene compositions of Example 5.
Example C
A lubricating composition suitable for use as an industrial gear lubricant is prepared using a SAE 90 base mineral lubricating oil and 4.0% of an additive concentrate.
The additive concentrate is mineral oil based and comprises the following additives: 2% of a mixture of sulfurized esters of fatty acids andlard oil; 0.5% of a dialkyl phosphite derived from long chain alcohols; 0.02% of a conventional anti-foaming agent based upon a polymer of 2-ethylhexyl acrylate and ethyl acrylate; and 1.25% of the sulfurized isobutylene composition of Example 10 Example D
A lubricating composition suitable for use as a crank-case lubricant is prepared using a lOW-30 mineral lubri-cating oil base and, as additives: 5.00% of a styrene-maleic anhydride copolymer, partially esterified with C4-C18 alcohols and neutralized with C~l-CI,, t-alkyl primary amine mixture, as a viscosity index improver; 1.77% of a propylene oxide-treated sulfurized overbased calcium phenate deter-- -. gent; 0.46% of an overbased magnesium sulfonate detergent;
3.81~ of an ashless dispersant based upon the reaction product of a polyisobutenyl succinic anhydride, pentaery-thritol and polyethylene polyamine, 0.20% of a commercially available copper deactivator, 1.66% of an ashless dispersant based upon the reaction product of a polyisobutenyl succinic anhydride, polyethylene polyamine and boric acid; 0.35% of an alkenylated succinic acid wherein the alkenyl group is derived from a propylene tetramer; 2.00% of the product o Example 14; 0.21% of a diluent mineral oil and 0.01% of a silicone anti-foam agent.
- Example E
A lubricating composition suitable for use as an indus-trial gear lubricant is prepared using a SAE 90 base mineral oil and, as additives: 2.29% of a mixture of sulfur-treated esters o fatty acids and lard oil; 0.05% of a commercially available aliphatic propylene diamine, wherein the aliphatic group is derived from tallow; 0.005% of a commercially ~ available demulsifier; 0.042% of an alkenylated succinic anhydride wherein the alkenyl group is derived from a propylene tetramer; 0.28% of a product formed by reacting a mixture of mono- and dialkyl phosphoric acids with a C~1-C~ 4 t-alkyl primary amine mixture; 0.10% diluent mineral oil;
1.21~ of the product of Example 16; and 0.023% of an anti-foam agent based upon a polymer of 2-ethylhexyl acrylate and ethyl acrylate.
Example F
A lubricating composition suitable for use as a gear lubricant is prepared using a SAE 90 base mineral oil and, as additives. 1.32% of a product formed by reacting a mixture of mono- and dialkyl phosphoric acids with a -CI 4 t-alkyl primary amine mixture, 0.35% o~ an oleyl amine; 0.10% of a mixture of oleamide and linoleamide; 0.07~
diluent mineral oil; 0.15~, of a copper deac~ivator; 9~20~ of - the product of Example 17; and 0.08% of an anti-foam agent based upon a polymer of 2-ethylhexyl acrylate and ethyl acrylate.
Example G
A lubricating composition suitable for u5e as an indus-- trial lubricant is pr~paxed using tap water, and as addi-tives: 5.03% of a lOON lubricating oil; 0.27% of fatty acids; 0.23% of a naphthenic oil; 0.13% of a polyisobutenyl succinic anhydride; 0.12~ of a C4-C5 alcohol mixture; 0.08~
of a 45% a~ueous potassium hydroxide solution; 0.04% of iso-propanolamine; and 0.35% of the product of Example 16.
Example H
.
The lubricating composition of Example E is prepared except 2.23~ of the product of Example 19 is substituted for the product of Example 16.

, lQ601:~79 . . ., : ., Example I
~he lubricating composition of Example F is prepared except 2.45% of the product of Example 21 is substituted for -. :the produc$ of Example 17. .- .
Example J .
The lubricating composition of Example E is prepared - except 1.87~ of the product of Example 20 is substituted for the product of Example 16.
Example K
~ . .. . . . .
The lubricating composition of Example F is prepared except 9.20% of the product of Example 26 is substituted for the product of Example 17. - . .... ' Exa~ple L
. .-- . .
. The lubricating composition of Example D is prepared ~xcep~ 2. O~Q of thc p~oduct of EYample 27 is subs~itutea for - the product of Example 14. .. . :
..In the above examples, as well as in the specification and claims, all percentages are expressed as percentage by weight, and all parts are expressed as parts by weight, unless otherwise indicated. Likewise, all temperatures are expressed in degrees centigrade (C.) unless otherwise - - - indica~ed, and all pressures are expressed in pounds per square inch gauge (psig) unless otherwise indicated. Also, the singular forms of "a", "an" and "the" include the plural, unless the context clearly dictates otherwise. For example, the phrase "having a non-aromatic carbon-to-carbon unsaturated bond" refers to compounds havin~ one or more unsaturated carbon-to-carbon bonds. Normally, there will be less than four, preferably one or two (more preferably one) .unsaturated bonds per unsaturated compound.

- 3~ -

Claims (39)

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 proportion of lubricating oil and a minor proportion of an additive, which is a sulfurized composition comprising from about 2 to about 60%
by weight sulfur and prepared by a process which comprises the steps of (A) reacting at about 50 to about 300°C., under superatmospheric pressure, (i) at least one compound having a non-aromatic carbon-to-carbon unsaturated bond;
(ii) sulfur; and (iii) hydrogen sulfide, wherein the molar ratio (a) of (i) to (ii) is in the range of 1 to from about 0.1 to about 3.0 and the molar ratio (b) of (i) to (iii) is in the range of 1 to from about 0.1 to about 1.5; and (B) separating from the reaction product of step (A) any low boiling materials to thereby provide a sulfurized composition having a flash point above at least 30°C.

2. The lubricating composition of claim 1, wherein the reaction is conducted within a temperature range from about 100°C.
to about 300°C., and the sulfurized composition resulting from step (B) is further treated with an alkali metal sulfide to reduce active sulfur.

3. The lubricating composition of claim 2, wherein at least one of the unsaturated compounds is an olefinic compound having one or two carbon-to-carbon double bonds.

4. The lubricating composition of claim 3, wherein at least one of the unsaturated compounds is a terminal mono-olefin.

5. The lubricating composition of claim 4, wherein the molar ratio (a) is in the range of 1 to from about 0.3 to about 2.0 and the molar ratio (b) is in the range of 1 to from about 0.4 to about 1.25.

6. The lubricating composition of claim 3, wherein each olefinic compound has from 3 to about 30 carbon atoms.

7. The lubricating composition of claim 6, wherein each valence of the olefinically bonded carbon atoms is satisfied independently by a moiety selected from the group consisting of (a) -C(R)3 wherein each R is independently hydrogen; alkyl; alkenyl; aryl; substituted alkyl; substi-tuted alkenyl; substituted aryl; with the proviso that any two R groups can be alkylene or substituted alkylene whereby a ring of up to about 12 carbon atoms is formed; (b) ;

; or wherein M is an equivalent of a Group I or Group II metal cation and wherein R' is as R

above; (c) -C?N or wherein each R" is as R above;
(d) -X wherein X is halogen; (e) -YR''' wherein Y is oxygen or divalent sulfur and each R''' is as R above; (f) -A wherein A is aryl or a substituted aryl of up to 12 carbon atoms; and (g) hydrogen with the proviso that any two valences can be satisfied by an alkylene or substituted alkylene moiety.

8. The lubricating composition of claim 7 wherein the reaction is conducted within a temperature range of from about 100°C. to about 200°C.

9. The lubricating composition of claim 1, wherein the molar ratio (a) is 1 to from about 0.3 to about 2Ø

10. The lubricating composition of claim 9, wherein the molar ratio (a) is 1 to from about 0.5 to about 1.5 and the molar ratio (b) is 1 to from about 0.4 to about 0.8.

11. The lubricating composition of claim 10, wherein the unsaturated compound has from 3 to about 16 carbon atoms.

12. The lubricating composition of claim l, wherein at least one of the unsaturated compounds is at least one olefinic compound of the formula R1R2C=CR3R4 wherein R1, R2, R3 and R4 are each independently selected from hydrogen; alkyl; substituted alkyl; alkenyl; sub-stituted alkenyl; aryl; and substituted aryl.

13. The lubricating composition of claim 12, wherein the total number of carbon atoms in each olefinic compound is from 3 to about 30.

14. The lubricating composition of claim 13, wherein the olefinic compound is at least one compound of the formula R1R2C=CR3H
wherein R1, R2 and R3 are each independently selected from the group consisting of alkyl, alkenyl and hydrogen, with the proviso that at least one of R1, R2 and R3 is not hydrogen and the total number of carbon atoms in each olefinic com-pound is from 3 to about 16.

15. The lubricating composition of claim 12, wherein the olefinic compound is a member selected from the group con-sisting of propylene and isobutylene and the respective dimers, trimers, and tetramers thereof and mixtures of two or more of any of these.

16. The lubricating composition of claim 15, wherein the olefinic compound is a member selected from the group consisting of isobutylene, dimers thereof, and mixtures of these.

17. A lubricating composition comprising a major proportion of lubricating oil and a minor effective proportion of a sulfurized isobutylene composition having from about 2 to about 60% by weight sulfur, and prepared by a process which comprises the steps of (A) reacting at about 100° to about 300°C., under superatmospheric pressure, isobutylene with a mixture of sulfur and hydrogen sulfide, wherein the molar ratio of sulfur and hydrogen sulfide to isobutylene is in the range of from about 0.3 mole to about 2.0 moles of sulfur and from about 0.1 mole to about 1.25 moles of hydrogen sulfide per mole of isobutylene; and (B) separating from the reaction product of step (A), substantially all of the unreacted reactants, the mercaptan product and the monosulfide product, whereby the desired sulfurized isobutylene product having a flash point above at least about 30°
is obtained.

18. The lubricating composition of claim 17, wherein the molar ratio of sulfur to isobutylene is in the range of from about 0.5 mole to about 1.5 moles.

19. The lubricating composition of claim 18, wherein the molar ratio of hydrogen sulfide is in the range of from about 0.4 mole to about 0.8 mole.

20. The lubricating composition of claim 17, wherein the reaction is conducted within a temperature range of from about 100°C. to about 200°C. and molar ratio of sulfur and hydrogen sulfide to isobutylene is in the range of from about 0.7 mole to about 1.2 moles of sulfur and from about 0.1 mole to about 1.25 moles of hydrogen sulfide per mole of isobutylene.

21. The lubricating composition of claim 20, wherein the molar ratio of hydrogen sulfide is in the range of from about 0.4 mole to about 0.8 mole per mole of isobutylene.

22. The lubricating composition of claim 17, wherein the molar ratio of sulfur and hydrogen sulfide to isobutylene is in the range of from 0.7 mole to about 1.2 moles of sulfur per mole of isobutylene and from about 0.4 mole to about 0.8 mole of hydrogen sulfide per mole of isobutylene.

23. The lubricating composition of claim 22, wherein the additives are present in a range of from about 0.01% to about 20.0% by weight.

24. An additive concentrate comprising a substantially inert carrier and from about 20% to about 90% by weight of a sulfurized composition comprising from about 2 to about 60% sulfur by weight, and prepared by a process which comprises the steps of (A) reacting at about 50° to about 300°C., under superatmospheric pressure, (i) at least one compound having a non-aromatic carbon-to-carbon unsaturated bond;
(ii) sulfur; and (iii) hydrogen sulfide, wherein the molar ratio (a) of (i) to (ii) is in the range of 1 to from about 0.1 to about 3.0 and the molar ratio (b) of (i) to (iii) is in the range of 1 to from about 0.1 to about 1.5; and (B) separating from the reaction product of step (A) any low boiling materials to thereby provide a sulfurized composition having a flash point above at least 30°C.

25. The additive concentrate of claim 24, wherein the reaction is conducted with a temperature range from about 100°C.
to about 300°C., and the sulfurized composition resulting from step (B) is further treated with an alkali metal sulfide to reduce active sulfur.

26. The additive concentrate of claim 25, wherein at least one of the unsaturated compounds is an olefinic compound of 3 to about 30 carbons.

27. The additive concentrate of claim 26, wherein at least one of the olefinic compounds is a compound having one carbon-to-carbon double bond.

28. The additive concentrate of claim 25, wherein the olefinic compound is a terminal olefin.

29. An additive concentrate comprising a substantially inert carrier and from 20% to about 90% by weight of a sulfurized isobutylene composition having from about 2 to about 60% by weight sulfur, prepared by a process which comprises the steps of (A) reacting at about 100° to about 300°C., under superatmospheric pressure isobutylene with a mixture of sulfur and hydrogen sulfide, wherein the molar ratio of sulfur and hydrogen sulfide to isobutylene is in the range of from about 0.3 mole to about 2.0 moles of sulfur and from about 0.1 mole to about 1.25 moles of hydrogen sulfide per mole of isobutylene; and (B) separating from the reaction product of step (A), substantially all of the unreacted reactants, the mercaptan product and the monosulfide product, whereby the desired sulfurized isobutylene product having a flash point of at least above 30°C. is obtained.

30. The additive concentrate of claim 29, wherein the molar ratio of sulfur to isobutylene is in the range of from about 0.5 mole to about 1.5 moles.

31. The additive concentrate of claim 29, wherein the reaction temperature is conducted within a temperature range of from about 100°C. to about 200°C., the molar ratio of hydrogen sulfide is in the range of from about 0.4 mole to about 0.8 mole.

32. The additive concentrate of claim 29, wherein the molar ratio of sulfur and hydrogen sulfide to isobutylene is in the range of from about 0.7 mole to about 1.2 moles of sulfur and from about 0.1 mole to about 1.25 moles of hydrogen sulfide per mole of isobutylene.

33. The additive concentrate of claim 32, wherein the molar ratio of sulfur and hydrogen sulfide to isobutylene is in the range of from 0.7 mole to about 1.2 moles of sulfur per mole of isobutylene and from about 0.4 mole to about 0.8 mole of hydrogen sulfide per mole of isobutylene.

34. A process for the preparation of a sulfurized composition having from about 2 to about 60% by weight sulfur which comprises the steps of (A) reacting at about 50° to about 300°C., under superatmospheric pressure, (i) at least one compound having a non-aromatic carbon-to-carbon unsaturated bond;
(ii) sulfur; and (iii) hydrogen sulfide, wherein the molar ratio (a) of (i) to (ii) is in the range of 1 to from about 0.1 to about 3.0 and the molar ratio (b) of (i) to (iii) is in the range of 1 to from about 0.1 to about 1.5; and (B) separating from the reaction product of step (A) any low boiling materials to thereby provide a sulfurized composition having a flash point above at least 30°C.

35. The process of claim 34, wherein the reaction is conducted within a temperature range from about 100°C. to about 300°C., and the sulfurized composition resulting from step (B) is further treated with an alkali metal sulfide to reduce active sulfur.

36. A process for the preparation of a sulfurized isobutylene composition having from about 2 to about 60% by weight sulfur, which comprises the steps of (A) reacting at about 100° to about 300°C., under superatmospheric pressure isobutylene with a mixture of sulfur and hydrogen sulfide, wherein the molar ratio of sulfur and hydrogen sulfide to isobuty-lene is in the range of from about 0.3 mole to about 2.0 moles of sulfur and from about 0.1 mole to about 1.25 moles of hydrogen sulfide per mole of isobutylene;
and (B) separating from the reaction product of step (A), substantially all of the unreacted reactants, the mercaptan product and the monosulfide product, whereby the desired sulfurized isobutylene product having a flash point above at least 30°C. is obtained.

37. The process of claim 36, wherein the molar ratio of sulfur to isobutylene is in the range of from about 0.5 mole to about 1.5 moles.

38. A sulfurized composition having from about 2 to about 60%
by weight sulfur prepared by the process which comprises the steps of (A) reacting at about 50° to about 300°C., under superatmospheric pressure, (i) at least one compound having a non-aromatic carbon-to-carbon unsaturated bond;
(ii) sulfur; and (iii) hydrogen sulfide, wherein the molar ratio (a) of (i) to (ii) is in the range of 1 to from about 0.1 to about 3.0 and the molar ratio (b) of (i) to (iii) is in the range of 1 to from about 0.1 to about 1.5; and (B) separating from the reaction product of step (A) any low boiling materials to thereby provide a sulfurized composition having a flash point above at least 30°C.

39. A sulfurized isobutylene composition having from about 2 to about 60% by weight sulfur prepared by the process which comprises the steps of (A) reacting at about 100° to about 300°C., under superatmospheric pressure isobutylene with a mixture of sulfur and hydrogen sulfide, wherein the molar ratio of sulfur and hydrogen sulfide to iso-butylene is in the range of from about 0.3 mole to about 2.0 moles of sulfur and from about 0.1 mole to about 1.25 moles of hydrogen sulfide per mole of isobutylene; and (B) separating from the reaction product of step (A), substantially all of the unreacted reactants, the mercaptan product and the monosulfide product, whereby the desired sulfurized isobutylene product having a flash point above at least 30°C. is obtained.