The hydrogen sulfide emission of oil-soluble sulfurized organic compounds is reduced by utilizing a hindered amine and optionally a carboxylic acid or acid anhydride in effective amounts.

TECHNICAL FIELD OF THE INVENTION 
The present invention relates to oil-soluble sulfurized organic, such as 
olefin, compounds having a hindered amine therein and optionally an acid 
anhydride or a carboxylic acid. The compositions have low odor and 
improved hydrogen sulfide stability. When a carboxylic acid, a monoester 
of a polycarboxylic acid, or an acid anhydride is used, the compositions 
also have good clarity. 
BACKGROUND OF THE INVENTION 
Heretofore, various organic oil-soluble sulfurized compounds including 
olefinic organic compounds have been prepared. For example, Chemical 
Reviews 65, 237 (1965) relates to sulfurized compositions prepared by 
reacting olefin such as isobutene with sulfur under various conditions. 
The Journal of the American Chemical Society, 60, 2452 (1938), as well as 
U.S. Pat. Nos. 3,221,056; 3,419,614; 4,119,550; 4,191,659 and 4,344, 854 
relate to the reaction of olefins with hydrogen sulfide and elemental 
sulfur to form predominately mercaptans with sulfides, disulfides and 
higher polysulfides being formed as by-products. 
U.S. Pat. No. 3,419,614 describes a process for increasing the yield of 
mercaptan by carrying out the reaction of the olefin with hydrogen sulfide 
and sulfur at high temperatures in the presence of various basic 
materials. 
U.S. Pat. Nos. 4,119,550; 4,119,549 as well as 4,344,854 relate to the 
preparation of sulfurized compounds by the reaction of unsaturated 
olefinic compounds with a mixture of sulfur and hydrogen sulfide at 
superatmospheric pressures in the presence of various catalyst or 
according to various methods. 
U.S. Pat. No. 4,360,438 relates to the use of sulfurized natural and 
synthetic oils as additives in lubricating compositions. 
U.S. Pat. Nos. 3,632,566 and Reissue U.S. Pat. No. 27,331 discloses that 
Diels-Alder adducts can be sulfurized to form sulfur-containing 
compositions which are useful as extreme pressure and anti-wear additives 
in various lubricating oils. 
U.S. Pat. No. 2,999,813 relates to a lubricating composition containing a 
sulfurized mineral oil and a polyvalent metal dithiocarbamate whereas U.S. 
Pat. No. 2,265,851 further relates to the use of coupling agents such as 
alcohols, esters, ketones and other suitable stable oxygen-containing 
materials. 
Similarly, U.S. Pat. No. 2,394,536 relates to lubricating oil compositions 
containing the combination of organic sulfides and salts of 
diothiocarbamic acids. 
U.S. Pat. No. 2,805,996 relates to the use of amine-dithiocarbamate 
complexes in lubricating oil compositions and U.S. Pat. No. 2,947,695 
relates to utilizing mixtures of polyvalent metal dithiocarbamates in 
preparing oil-soluble additive compositions useful in the preparation of 
lubricating oils. 
Although the above-identified documents generally relate to the preparation 
of various oil-soluble sulfurized compounds, they do not relate to 
hydrogen sulfide stabilization thereof. 
U.S. Pat. No. 4,409,114 to Brois et al relates to hydrogen sulfide 
suppressant additives for functional fluids. However, this patent relates 
to the use of sulfurized amine compounds which contain a metal therein. 
SUMMARY OF THE INVENTION 
Accordingly, it is an aspect of the present invention to provide an 
oil-soluble sulfurized organic composition which suppresses volatile 
sulfur compound emission in additive formulations, comprising an 
oil-soluble sulfurized organic compound, and a hindered organic amine, 
said hindered organic amine being soluble in said oil-soluble sulfurized 
organic compound. 
It is a further aspect of the present invention to provide an oil-soluble 
sulfurized organic composition which suppresses volatile sulfur compound 
emission in additive formulations, comprising an oil-soluble sulfurized 
organic compound, a hindered organic amine, said hindered organic amine 
being soluble in said oil-soluble sulfurized organic composition, and at 
least one carboxylic acid, monoester of a polycarboxylic acid, or acid 
anhydride. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
According to the present invention, oil-soluble sulfurized organic 
compositions are improved with regard to H.sub.2 S emission and also often 
with regard to odor. When a carboxylic acid or acid anhydride is utilized, 
the sulfurized organic compositions have good clarity. 
The oil-soluble compositions of the present invention comprise at least one 
oil-soluble sulfurized organic compound. A wide variety of sulfurized 
organic compounds can be utilized in the present invention, and these 
compounds may generally be represented by the formula 
EQU RS.sub.x R.sub.1 (II) 
wherein S represents sulfur, x is a whole number having a value of from 1 
to about 10, and R and R.sub.1 may be the same or different organic 
groups. The organic groups may be hydrocarbon groups or substituted 
hydrocarbon groups containing alkyl, aryl, aralkyl, alkaryl, alkanoate, 
thiazole, imidazole, phosphorothionate, beta-ketoalkyl groups, etc. The 
substantially hydrocarbon groups may contain other substituents such as 
halogen, amino, hydroxyl, mercapto, alkoxy, aryloxy, thio, nitro, sulfonic 
acid, carboxylic acid, carboxylic acid ester, etc. 
Specific examples of types of sulfurized compositions which are useful in 
the present invention include aromatic, alkyl or alkenyl sulfides and 
polysulfides, sulfurized olefins, sulfurized carboxylic acid esters, 
sulfurized ester olefins, sulfurized oil, and mixtures thereof. The 
preparation of such oil-soluble sulfurized compositions is described in 
the art. 
The sulfurized organic compounds utilized in the present invention can be 
aromatic and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, 
dicetyl sulfide, diparaffin wax sulfide and polysulfide, cracked wax oleum 
sulfides, etc. One method of preparing the aromatic and alkyl sulfides 
includes the condensation of a chlorinated hydrocarbon with an inorganic 
sulfide whereby the chlorine atom from each of two molecules is displaced, 
and the free valence from each molecule is joined to a divalent sulfur 
atom. Generally, the reaction is conducted in the presence of elemental 
sulfur. 
Examples of dialkenyl sulfides are described in U.S. Pat. No. 2,446,072. 
These sulfides can be prepared by interacting an olefinic hydrocarbon 
containing from 3 to 12 carbon atoms with elemental sulfur in the presence 
of zinc or a similar metal generally in the form of an acid salt. Examples 
of sulfides of this type include 6,6'-dithiobis(5-methyl-4-nonene), 
2-butenyl monosulfide and disulfide, and 2-methyl-2-butenyl monosulfide 
and disulfide. 
The sulfurized olefins of the present invention includes sulfurized olefins 
prepared by the reaction of an olefin (preferably containing 2 to 6 carbon 
atoms) or a lower molecular weight polyolefin derived therefrom, with a 
sulfur-containing compound such as sulfur, sulfur monochloride, sulfur 
dichloride, hydrogen sulfide and combinations thereof. 
The sulfurized organic compounds utilized in the compositions of the 
present invention can be sulfurized oils which may be prepared by treating 
natural or synthetic oils including mineral oils, lard oil, carboxylic 
acid esters derived from aliphatic alcohols and fatty acids or aliphatic 
carboxylic acids (e.g., myristyl oleate and oleyl oleate) sperm whale oil 
and synthetic sperm whale oil substitutes and synthetic unsaturated esters 
or glycerides. Stable sulfurized mineral lubricating oils can be obtained 
by heating a suitable mineral lubricating oil with from about 1 to about 
5% of sulfur at a temperature above about 175.degree. C. and preferably at 
about 200.degree. to about 260.degree. C. for several hours so as to 
obtain a reaction product which is substantially non-corrosive to copper. 
The mineral lubricating oils sulfurized in this manner may be distillate 
or residual oils obtained from paraffinic, naphthenic or mixed base 
crudes. Similarly, sulfurized fatty oils such as a sulfurized lard oil can 
be obtained by heating lard oil with about 10 to 15% of sulfur at a 
temperature of about 150.degree. C. for a time sufficient to obtain a 
homogeneous product. 
The sulfurized fatty acid esters which are useful in the compositions of 
this invention can be prepared by reacting sulfur, sulfur monochloride, 
and/or sulfur dichloride with an unsaturated fatty ester at elevated 
temperatures. Typical esters include C.sub.1 -C.sub.20 alkyl esters of 
C.sub.8 -C.sub.24 unsaturated fatty acids such as palmitoleic oleic, 
ricinoleic, petroselic, vaccenic, linoleic, linolenic, oleostearic, 
licanic, etc. Sulfurized fatty acid esters prepared from mixed unsaturated 
fatty acid esters such as are obtained from animal fats and vegetable oils 
such as tall oil, linseed oil, olive oil, castor oil, peanut oil, rape 
oil, fish oil, sperm oil, etc also are useful. Specific examples of the 
fatty esters which can be sulfurized include lauryl talate, methyl oleate, 
ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl 
ricinoleate, oleolinoleate, oleostearate, and alkyl glycerides. 
Another class of organic sulfur-containing compounds include sulfurized 
aliphatic esters of an olefinic mono-dicarboxylic acid. For example, 
aliphatic alcohols of from 1 to 30 carbon atoms can be used to esterify 
monocarboxylic acids such as acrylic acid, methacrylic acid, 
2,4-pentadienic acid, etc. or fumaric acid, maleic acid, muconic acid, 
etc. Sulfurization of these esters is conducted with elemental sulfur, 
sulfur monochloride and/or sulfur dichloride. 
Still another class of sulfurized organic compounds can be utilized in the 
compositions of the invention are diestersulfides characterized by the 
following general formula 
EQU --S.sub.y [(CH.sub.2).sub.x COOR].sub.2 (III) 
wherein x is from about 2 to about 5; y is from 1 to about 6, preferably 1 
to about 3; and R is an alkyl group having from about 4 to about 20 carbon 
atoms. The R group may be a straight chain or branched chain group that is 
large enough to maintain the solubility of the compositions of the 
invention in oil. Typical diesters include the butyl, amyl, hexyl, heptyl, 
octyl, nonyl, decyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, 
stearyl, lauryl, and eicosyl diesters of thiodialkanoic acids such as 
propionic, butanoic, pentanoic and hexanoic acids. Of the diester 
sulfides, a specific example is dilauryl, 3,3'-thiodipropionate. 
Preferably, the sulfurized organic compound utilized in the compositions of 
the present invention comprise sulfurized olefins. For example, organic 
polysulfides can be prepared by the sulfochlorination of olefins 
containing four or more carbon atoms and further treatment with inorganic 
higher polysulfides according to U.S. Pat. No. 2,708,199. 
In one embodiment, sulfurized olefins are produced by (1) reacting sulfur 
monochloride with a stoichiometric excess of a low carbon atom olefin, (2) 
treating the resulting product with an alkali metal sulfide in the 
presence of free sulfur in a mole ratio of no less than 2:1 in an 
alcohol-water solvent, and (3) reacting that product with an inorganic 
base. This procedure is described in U.S. Pat. No. 3,471,404, and the 
disclosure of U.S. Pat. No. 3,471,404 is hereby incorporated by reference 
for its discussion of this procedure for preparing sulfurized olefins and 
the sulfurized olefins thus produced. Generally, the olefin reactant 
contains from about 2 to 6 carbon atoms and examples include ethylene, 
propylene, butylene, isobutylene, amylene, etc. Briefly, in the first 
step, sulfur monochloride is reacted with from one to two moles of the 
olefin per mole of the sulfur monochloride, and the reaction is conducted 
by mixing the reactants at a temperature of from about 20.degree. to 
80.degree. C. In the second step, the product of the first step is reacted 
with an alkali metal, preferably sodium sulfide, and sulfur. The mixture 
consists of up to about 2.2 moles of the metal sulfide per gram-atom of 
sulfur, and the mole ratio of alkali metal sulfide to the product of the 
first step is about 0.8 to about 1.2 moles of metal sulfide per mole of 
step (1) product. Generally, the second step is conducted in the presence 
of an alcohol or an alcohol-water solvent under reflux conditions. The 
third step of the process is the reaction between the phosphosulfurized 
olefin which contains from about 1 to about 3% of chlorine with an 
inorganic base in a water solution. Alkali metal hydroxide such as sodium 
hydroxide may be used. The reaction is continued until the chlorine 
content is reduced to below 0.5%, and this reaction is conducted at under 
reflux conditions for a period of from about 1 to 24 hours. 
The sulfurized olefins which are useful in the compositions of the present 
invention also can be prepared by the reaction, under superatmospheric 
pressure, of olefinic compounds with a mixture of sulfur and hydrogen 
sulfide in the presence of a catalyst, followed by removal of low boiling 
materials. This procedure for preparing sulfurized compositions which are 
useful in the present invention is described in U.S. Pat. No. 4,191,659, 
the disclosure of which is hereby incorporated by reference for its 
description of the preparation of useful sulfurized compositions. An 
optional final step described in this patent is the removal of active 
sulfur by, for example, treatment with an alkali metal sulfide. 
Other methods of preparing sulfurized olefin compounds for use in the 
present invention are set forth in U.S. Pat. Nos. 4,119,550 and 4,344,854 
which generally relate to the reaction of saturated or unsaturated 
olefinic compounds with a mixture of sulfur and hydrogen sulfide under 
superatmospheric pressure, followed by removal of low boiling materials. 
These patents are accordingly hereby fully incorporated by reference for 
their description of the preparation of useful sulfurized olefinic 
compounds. 
The olefinic compounds which can be sulfurized by this method and used in 
the compositions of this invention are diverse in nature. They contain at 
least one olefinic double bond, which is defined as a non-aromatic double 
bond; that is, one connecting two aliphatic carbon atoms. In its broadest 
sense, the olefin may be defined by the formula 
EQU R.sup.1 R.sup.2 C.dbd.CR.sup.3 R.sup.4 (IV) 
wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is hydrogen or an 
organic group. In general, the R values in the above formula which are not 
hydrogen may be satisfied by such groups as --C(R.sup.5).sub.3, 
--COOR.sup.5, --CON(R.sup.5).sub.2, --COON(R.sup.5).sub.4, --COOM, --CN, 
--X, --YR.sup.5 or --Ar, wherein: 
each R.sup.5 is independently hydrogen, alkyl, alkenyl, aryl, substituted 
alkyl, substituted alkenyl or substituted aryl, with the proviso that any 
two R.sup.5 groups can be alkylene or substituted alkylene whereby a ring 
of up to about 12 carbon atoms is formed; 
M is one equivalent of a metal cation (preferably Group I or II, e.g., 
sodium, potassium, barium, calcium); 
X is halogen (e.g., chloro, bromo, or iodo); 
Y is oxygen or divalent sulfur; 
Ar is an aryl or substituted aryl group of up to about 12 carbon atoms. 
Any two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may also together form an 
alkylene or substituted alkylene group; i.e., the olefinic compound may be 
alicyclic. 
The natures of the substituents in the substituted moieties described above 
are not normally critical and any such substituent is useful so long as it 
is or can be made compatible with lubricating environments and does not 
interfere under the contemplated reaction conditions. Thus, substituted 
compounds which are so unstable as to deleteriously decompose under the 
reaction conditions employed are not contemplated. However, certain 
substituents such as keto or aldehydo can desirably undergo sulfurization. 
The selection of suitable substituents is within the skill of the art or 
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, phosphate, phosphite, alkali 
metal mercapto and the like. 
The olefinic compound is usually one in which each R value which is not 
hydrogen is independently alkyl, alkenyl or aryl, or (less often) a 
corresponding substituted group. Monoolefinic and diolefinic compounds, 
particularly the former, are preferred, and especially terminal 
monoolefinic hydrocarbons; that is, those compounds in which R.sup.3 and 
R.sup.4 are hydrogen and R.sup.1 and R.sup.2 are alkyl or aryl, especially 
alkyl (that is, the olefin is aliphatic). Olefinic compounds having about 
3 to 30, desirably about 3 to 16, especially 9 or less, and preferably 8 
carbon atoms are particularly desirable. 
Ethylene, isobutene, propylene and oligomers thereof are especially 
preferred olefinic compounds. Of these compounds, isobutylene and 
diisobutylene are particularly desirable because of their availability and 
the particularly high sulfur-containing compositions which can be prepared 
therefrom. 
Commercial sources of sulfur and hydrogen sulfide are normally used for the 
purpose of this sulfurization reaction, and impurities normally associated 
therewith may be present without adverse results. Thus, commercial 
diisobutene is believed to contain essentially two isomeric forms and this 
mixture is contemplated for use according to the present invention. 
The amines used in the present invention are hindered organic amines. By 
the term "hindered", it is meant that the organic amine has stearic 
hindrance therein. The hindered organic amine is also soluble in the 
oil-soluble sulfurized organic compound. That is, based upon 100 parts by 
weight of said oil-soluble sulfurized organic compound, the solubility of 
the amine is at least 0.01 parts by weight, desirably at least 5.0 parts 
by weight, and preferably at least 10.0 parts by weight up to a large 
excess of said amine, as for example 10,000 parts by weight. Desirably, 
the organic amine compound is added in an effective amount such as to 
suppress volatile sulfur compound emission and/or reduce odor. 
Accordingly, the amount of the hindered organic amine used in the present 
invention can be from about 0.1 to about 20% by weight and desirably from 
about 0.25 to about 2.0% by weight based upon the weight of the 
oil-soluble sulfurized compound in the composition. 
The hindered organic amine can either be a polyamine or more desirably a 
monoamine. The organic amine can also contain unsaturated hydrocarbon 
groups therein but desirably is saturated. Suitable amines include 
hydrocarbyl amines having from 3 to about 100 carbon atoms and preferably 
from 3 to about 30 carbon atoms, such as aliphatic amines, aromatic 
amines, or combinations thereof, e.g., aliphatic substituted aromatic 
amines. Desirably, the hydrocarbyl group is an alkyl group. 
Desirable hindered hydrocarbyl amines according to the present invention 
have the formula 
##STR1## 
wherein R', R" and R'" can be the same or different. R', R" and R'" can be 
a hydrocarbyl such as aromatic, aliphatic, or combinations thereof, or 
hydrogen, but regardless of the makeup or content of any particular R', 
R", or R'" substituent, collectively they have a total of 2 to about 30 
carbon atoms. That is, at least one of the R', R" or R'" substituents must 
contain one or two carbon atoms therein. Desirably, R', R" and R'" are 
alkyl. a preferred total number of carbon atoms of R', R" and R'" is from 
about 12 to about 14. Considering R.sup.2 and R.sup.3, they can be the 
same or different, and also can be hydrocarbyl or hydrogen. However, 
collectively they have from 0 to about 30 carbon atoms. Desirably, R.sup.2 
and R.sup.3 are alkyl having a total of 0 to 4 carbon atoms, but 
preferably are both hydrogen. Thus, desirable amines of the present 
invention include t-octylamine, and the like. A commercially available 
compound is Primene JM-T which is a mixture of isomeric amines having from 
18 to 22 carbon atoms or Primene 81-R which is a mixture of isomeric 
amines having from 12 to 14 carbon atoms. The Primene compounds are 
produced by the Rohm & Haas Corporation. 
The oil-soluble sulfurized organic compound is often used as a metal 
working additive. Accordingly, the sulfurized organic compounds of the 
present invention in association with the hindered organic amine find 
common use in additive formulations. Preparation of an additive 
concentrate or the like containing the oil-soluble sulfurized organic 
compound and the hindered organic amine can utilize any conventional or 
common mixing or blending method as by merely adding one to the other. 
Usually agitation is utilized to blend or mix the components together. 
It has been unexpectedly found that the use of at least one carboxylic acid 
or acid anhydride in combination with a hindered amine in the oil-soluble 
sulfurized organic compound generally yields good clarity as well as 
improved hydrogen sulfide stability and low or nil odor. Although 
monocarboxylic acids can be utilized, polycarboxylic acids are preferred. 
The hydrocarbon portion of the acid can be saturated or unsaturated. The 
acid contains at least two carbon atoms as from about 2 to about 100 
carbon atoms and desirably from about 3 to about 30 carbon atoms. Examples 
of saturated monocarboxylic acids include acetic, propionic, butyric, 
lauric, palmitic, stearic, and the like. Examples of saturated 
dicarboxylic acids include oxalic, malonic, succinic, glutaric, adipic, 
pimelic, and the like. Examples of suitable unsaturated acid include 
acrylic acid, maleic, fumaric, and the like. 
A suitable acid of the present invention is a substituted succinic acid of 
the formula 
##STR2## 
wherein R is a hydrocarbyl group having at least 10 carbon atoms. 
Generally R has from about 10 to about 100 carbon atoms, desirably from 
about 10 to about 30 carbon atoms with approximately 9 to 15 carbon atoms 
being preferred. The R substituent of the above set forth formula 
desirably is alkenyl. Moreover, it is often a low molecular weight 
olefinic hydrocarbon reactant such as tetrapropylene, triisobutylene, 
tetraisobutylene, and the like. Such low molecular weight substituents are 
monoolefins and have a branched chain structure. A highly preferred acid 
of the present invention is polypropenyl succinic acid. 
Included within the definition of carboxylic acids are monoesters of 
polycarboxylic acids. These compounds are derived from the above 
polycarboxylic acids or anhydrides thereof and hence can contain the same 
number of carbon atoms in the acid portion as well as be saturated or 
unsaturated as set forth above. With regard to the monoester group, it 
generally has from about 1 to 100, desirably from 1 to about 30 and 
preferably from 1 to about 10 carbon atoms. The monoester group can also 
contain one or more hydroxy groups with one such hydroxy group being 
preferred. Accordingly, the monoester group is generally a hydrocarbyl or 
a hydroxyhydrocarbyl with an alkyl or a hydroxyalkyl group being 
preferred. A suitable monoester of a polycarboxylic acid has the formula 
##STR3## 
wherein R is as set forth above. That is, a hydrocarbyl group having from 
about 10 to about 100 carbon atoms and the like. R.sup.3 is the monoester 
group and accordingly has from 1 to about 100, desirably from 1 to about 
30 and preferably from 1 to about 10 carbon atoms. As noted, R.sup.3 can 
be hydrocarbyl or hydroxyhydrocarbyl and preferably alkyl or hydroxyalkyl. 
In combination with, or in lieu of a carboxylic acid, an acid anhydride can 
be utilized. The acid anhydrides are derivatives of the above-noted 
polycarboxylic acids. Thus, the acid anhydrides will have from about 4 to 
about 100 carbon atoms with from about 4 to about 30 carbon atoms being 
preferred. Inasmuch as the acid anhydrides are derivatives of the 
above-noted carboxylic acids, the description thereof will not be 
repeated, but is rather hereby incorporated by reference including the 
above-substituted succinic acid formulation. Examples of acid anhydrides 
include acetic anhydride, propionic anhydride, succinic anhydride, 
glutaric anhydride, and the like. 
The relative amount of the carboxylic acid or acid anhydride to the 
hindered organic amine generally is important or critical. The amount of 
the carboxylic acid, monoester of a polycarboxylic acid, acid anhydride, 
or combinations thereof to the amine is generally from about 0.1 to about 
20, desirably from about 0.25 to about 2.0 and preferably about 1:1 on a 
weight basis. The effective amount of the carboxylic acid or acid 
anhydride will vary somewhat depending upon the type of specific acid or 
anhydride, type of sulfurized compound, and the like. Usually, from about 
0.1 to about 20% by weight and desirably from about 0.25 to about 2% by 
weight of the acid and/or anhydride based upon the total weight of the 
oil-soluble sulfurized organic compound is used. Typically, an amount is 
used such that good clarity of the oil-soluble sulfurized organic 
composition is obtained. Although the carboxylic acid, monoester of a 
polycarboxylic acid, or acid anhydride itself need not be soluble in the 
oil-soluble sulfurized organic compound, it, in combination with the 
hindered amine should be soluble in said oil-soluble sulfurized organic 
compound. 
The preparation of the oil-soluble sulfurized organic composition 
containing the sulfurized organic compound, the hindered organic amine and 
the carboxylic acid/or acid anhydride can be by any conventional method. 
Often times the various components can simply be blended or mixed together 
at ambient temperature. 
As noted, the compositions of the present invention have improved hydrogen 
sulfide stability, low odor, and good clarity. The compositions are 
especially suitable as metal working additives, as additive concentrates 
and the like. 
The invention will be better understood by reference to the following 
examples.

EXAMPLES 1-7 
A 40% sulfurized olefin is prepared by reacting sulfur, H.sub.2 S and 
diisobutylene. That is, 96 grams of sulfur (3 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, evacuating to about 2 torr and cooling, 224 
grams (2 moles) of diisobutylene and 34 grams (1 mole) of hydrogen sulfide 
are charged to the reactor. The reactor is heated using steam in the 
external jacket, to a temperature of about 171.degree. C. over about 1.5 
hours. A maximum pressure of 1350 psig. is reached at about 168.degree. C. 
during this heat-up. Prior to reaching the 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 171.degree. C., the pressure is approximately 310 to 
about 340 psig. and the rate of pressure change is about 5 to 10 psig. per 
hour. The unreacted hydrogen sulfide and diisobutylene are vented to a 
recovery system. After the pressure of the reactor has decreased to 
atmospheric, the sulfurized mixture is covered as a liquid. The mixture is 
blown with nitrogen and then vacuum stripped to remove the low boiling 
materials including unreacted diisobutylene, mercaptans and monosulfides. 
The filtrate is the desired sulfurized composition which contains 
approximately 40% sulfur by weight. Various amounts of Primene 81-R was 
added thereto as set forth in Table IA. Primene 81-R is a tertiary-alkyl 
amine manufactured by Rohm & Haas Corporation and is essentially mixtures 
of isomeric amines containing from 12 to 14 carbon atoms. The components 
were mixed for a very short period of time and then tested with regard to 
clarity and hydrogen sulfide. Hydrogen sulfide was quantitatively 
determined. The results are set forth in Tables IA and IB. 
TABLE IA 
______________________________________ 
Vapor Space Hydrogen Sulfide Determination 
Samples stored 65.degree. C./1 week 
Sulfurized Vapor Space H.sub.2 S 
Olefin Plus (ppm) Compatibility 
______________________________________ 
1. Nothing 800 Clear 
2. 5.0% Primene 81-R 
Nil Very hazy + 
suspension 
3. 2.5% Primene 81-R 
Nil Hazy + sus- 
pension 
4. 1.5% Primene 81-R 
Nil Hazy 
5. 1.0% Primene 81-R 
Nil Slight haze 
6. 0.5% Primene 81-R 
Nil Trace haze 
7. 0.25% Primene 81-R 
180 Clear 
______________________________________ 
TABLE IB 
______________________________________ 
Samples stored 65.degree. C./1 month 
Sulfurized Vapor Space H.sub.2 S (ppm) 
Olefin Plus 65.degree. C./1 week 
65.degree. C./1 month 
______________________________________ 
Nothing 800 1000 
1.0% Primene 81-R 
Nil 10 
0.5% Primene 81-R 
Nil 20 
______________________________________ 
As apparent from Table IA and IB, the addition of the hindered amine had a 
dramatic effect upon reducing the hydrogen sulfide generated over a period 
of one week or one month. However, the solutions did exhibit various 
degrees of haze. 
EXAMPLES 8-13 
Upon the addition of various carboxylic acids, the degree of haze was 
greatly reduced as set forth in Table II. 
TABLE II 
______________________________________ 
JTU @ 
1 Wk/ 1 Mth/ 
Initial 
65.degree. C. 
65.degree. C. 
______________________________________ 
8. SO 4 4 1 
9. SO + 0.5% P 7 120 210 
10. SO + 0.5% P + 0.25% OA 
2 1 2 
11. SO + 0.5% P + 0.5% OA 
1 1 2 
12. SO + 0.5% P + 0.25% TS 
13 100 110 
13. SO + 0.5% P + 0.5% TS 
1 1 1 
______________________________________ 
SO = sulfurized olefin 
P = Primene 81R- 
TS = tetrapropenyl succinic acid 
OA = oleic acid 
As apparent from Table II, the haze conditions encountered by using a 
hindered amine were greatly reduced. Moreover, the amount of vapor space 
hydrogen sulfide in all examples except Example 8 were very little or nil. 
It should thus be apparent that volatile sulfur compound emission has been 
suppressed. The odor of Examples 2-7 and 9-13 was also reduced. 
The sulfurized compositions of the invention can be effectively employed in 
a variety of lubricating compositions formulated for a variety of uses. 
These lubricating compositions are based on diverse oils of lubricating 
viscosity, including natural and synthetic lubricating oils and mixtures 
thereof. These lubricating compositions containing the subject additive 
concentrates are effective as crankcase lubricating oils for spark-ignited 
and compression-ignited internal combustion engines, including automobile 
and truck engines, two-cycle engines, aviation piston engines, marine and 
low-load diesel engines, and the like. Also, automatic transmission 
fluids, transaxle lubricants, gear lubricants, metal-working lubricants, 
hydraulic fluids, and other lubricating oil and grease compositions can 
benefit from the incorporation of the subject additive concentrates. 
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard 
oil) as well as mineral lubricating oils such as liquid petroleum oils and 
solvent-treated or acid-treated mineral lubricating oils of the 
paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of 
lubricating viscosity derived from coal or shale are also useful. 
Synthetic lubricating oils include hydrocarbon oils and halosubstituted 
hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., 
polybutylenes, polypropylenes, propyleneisobutylene copolymers, 
chlorinated polybutylenes, etc.); poly(1-hexenes), poly(1-octenes), 
poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g., 
dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, 
di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls, 
terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers and 
alkylated diphenyl sulfides and the derivatives, analogs and homologs 
thereof and the like. 
Alkylene oxide polymers and interpolymers and derivatives thereof where the 
terminal hydroxyl groups have been modified by esterification, 
etherification, etc., constitute another class of known synthetic 
lubricating oils that can be used. These are exemplified by the oils 
prepared through polymerization of ethylene oxide or propylene oxide, the 
alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., 
methylpolyisopropylene glycol ether having an average molecular weight of 
about 1000, diphenyl ether of polyethylene glycol having a molecular 
weight of about 500-1000, diethyl ether of polypropylene glycol having a 
molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic 
esters thereof, for example, the acetic acid esters, mixed C.sub.3 
-C.sub.8 fatty acid esters, or the C.sub.13 Oxo acid diester of 
tetraethylene glycol. 
Another suitable class of synthetic lubricating oils that can be used 
comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic 
acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic 
acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid 
dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) 
with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl 
alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol 
monoether, propylene glycol, etc.) Specific examples of these esters 
include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, 
dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl 
phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester 
of linoleic acid dimer, the complex ester formed by reacting one mole of 
sebacic acid with two moles of tetraethylene glycol and two moles of 
2-ethylhexanoic acid and the like. 
Esters useful as synthetic oils also include those made from C.sub.5 to 
C.sub.12 monocarboxylic acids and polyols and polyol ethers such as 
neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, 
tripentaerythritol, etc. 
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or 
polyaryloxy-siloxane oils and silicate oils comprise another useful class 
of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl 
silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, 
tetra-(p-tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, 
poly(methyl)siloxanes, poly(methylphenyl)siloxanes, etc.). Other synthetic 
lubricating oils include liquid esters of phosphorus-containing acids 
(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane 
phosphonic acid, etc.), polymeric tetrahydrofurans and the like. 
Unrefined, refined and rerefined oils, either natural or synthetic (as well 
as mixtures of two or more of any of these) of the type disclosed 
hereinabove can be used in the concentrates of the present invention. 
Unrefined oils are those obtained directly from a natural or synthetic 
source without further purification treatment. For example, a shale oil 
obtained directly from retorting operations, a petroleum oil obtained 
directly from primary distillation or ester oil obtained directly from an 
esterification process and used without further treatment would be an 
unrefined oil. Refined oils 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 to those 
skilled in the art such as solvent extraction, secondary distillation, 
acid or base extraction, filtration, percolation, etc. Rerefined oils are 
obtained by processes similar to those used to obtain refined oils applied 
to refined oils which have been already used in service. Such rerefined 
oils are also known as reclaimed or reprocessed oils and often are 
additionally processed by techniques directed to removal of spent 
additives and oil breakdown products. 
Generally the above lubricants contain an amount of one or more of the 
oil-soluble sulfurized compositions of this invention sufficient to 
provide them with improved properties. Normally the amount employed will 
be a minor amount such as about 0.01% to about 20%, preferably about 0.1% 
to about 10% of the total weight of the lubricating composition. 
The invention also contemplates the use of other additives in combination 
with the sulfurized compositions of this invention. Such additives 
include, for example, detergents and dispersants of the ash-producing or 
ashless type, corrosion- and oxidation-inhibiting agents, pour point 
depressing agents, extreme pressure agents, antiwear agents, color 
stabilizers and anti-foam agents. 
The ash-producing 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.g., polyisobutene having a molecular 
weight of 1000) with a phosphorizing agent such as phosphorus trichloride, 
phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride 
and sulfur, white phosphorus and a sulfur halide, or phosphorothioic 
chloride. The most commonly used salts of such acids are those of sodium, 
potassium, lithium, calcium, magnesium, strontium and barium. 
The term "basic salt" is used to designate metal salts wherein the metal is 
present in stoichiometrically larger amounts than the organic acid 
radical. The commonly employed methods for preparing the basic salts 
involve heating a mineral oil solution of an acid with a stoichiometric 
excess of a metal neutralizing agent such as the metal oxide, hydroxide, 
carbonate, bicarbonate, or sulfide at a temperature of about 50.degree. C. 
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, alkylphenol, thiophenol, 
sulfurized alkylphenol, and condensation products of formaldehyde with a 
phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, 
cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl 
alcohol; and amines such as aniline, phenylenediamine, phenothiazine, 
phenyl-beta-naphthylamine, and dodecylamine. A particularly effective 
method for preparing the basic salts comprises mixing an acid with an 
excess of a basic alkaline earth metal neutralizing agent and at least one 
alcohol promoter, and carbonating the mixture at an elevated temperature 
such as 60.degree.-200.degree. C. 
Ashless detergents and dispersants are so called despite the fact that, 
depending on its constitution, the dispersant may upon combustion yield a 
non-volatile material such as boric oxide or phosphorus pentoxide; 
however, it does not ordinarily contain metal and therefore does not yield 
a metal-containing ash on combustion. Many types are known in the art, and 
any of them are suitable for use in the lubricant compositions of this 
invention. The following are illustrative: 
(1) Reaction products of carboxylic acids (or derivatives thereof) 
containing at least about 34 and preferably at least about 54 carbon atoms 
with nitrogen containing compounds such as amine, organic hydroxy 
compounds such as phenols and alcohols, and/or basic inorganic materials. 
Examples of these "carboxylic dispersants" are described in British Patent 
No. 1,306,529 and in many U.S. patents including the following: 
______________________________________ 
3,163,603 3,351,552 3,541,012 
3,184,474 3,381,022 3,543,678 
3,215,707 3,399,141 3,542,680 
3,219,666 3,415,750 3,567,637 
3,271,310 3,433,744 3,574,101 
3,272,746 3,444,170 3,576,743 
3,281,357 3,448,048 3,630,904 
3,306,908 3,448,049 3,632,510 
3,311,558 3,451,933 3,632,511 
3,316,177 3,454,607 3,697,428 
3,340,281 3,467,668 3,725,441 
3,341,542 3,501,405 4,234,435 
3,346,493 3,522,179 Re 26,433 
______________________________________ 
(2) Reaction products of relatively high molecular weight aliphatic or 
alicyclic halides with amines, preferably polyalkylene polyamines. These 
may be characterized as "amine dispersants" and examples thereof are 
described for example, in the following U.S. patents: 
______________________________________ 
3,275,554 
3,454,555 
3,438,757 
3,565,804 
______________________________________ 
(3) Reaction products of alkyl phenols in which the alkyl group contains at 
least about 30 carbon atoms with aldehydes (especially formaldehyde) and 
amines (especially polyalkylene polyamines), which may be characterized as 
"Mannich dispersants". The materials described in the following U.S. 
patents are illustrative: 
______________________________________ 
2,459,112 3,442,808 
3,591,598 
2,962,442 3,448,047 
3,600,372 
2,984,550 3,454,497 
3,634,515 
3,036,003 3,459,661 
3,649,229 
3,166,516 3,461,172 
3,697,574 
3,236,770 3,493,520 
3,725,277 
3,355,270 3,539,633 
3,725,480 
3,368,972 3,558,743 
3,726,882 
3,413,347 3,586,629 
3,980,569 
______________________________________ 
(4) Products obtained by post-treating the carboxylic, amine or Mannich 
dispersants with such reagents as urea, thiourea, carbon disulfide, 
aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic 
anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or 
the like. Exemplary materials of this kind are described in the following 
U.S. patents: 
______________________________________ 
3,036,003 
3,282,955 3,493,520 
3,639,242 
3,087,936 
3,312,619 3,502,677 
3,649,229 
3,200,107 
3,366,569 3,513,093 
3,649,659 
3,216,936 
3,367,943 3,533,945 
3,658,836 
3,254,025 
3,373,111 3,539,633 
3,697,574 
3,256,185 
3,403,102 3,573,010 
3,702,757 
3,278,550 
3,442,808 3,579,450 
3,703,536 
3,280,234 
3,455,831 3,591,598 
3,704,308 
3,281,428 
3,455,832 3,600,372 
3,708,422 
______________________________________ 
(5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, 
vinyl decyl ether and high molecular weight olefins with monomers 
containing polar substituents, e.g., aminoalkyl acrylates or acrylamides 
and poly-(oxyethylene)-substituted acrylates. These may be characterized 
as "polymer dispersants" and examples thereof are disclosed in the 
following U.S. patents: 
______________________________________ 
3,329,658 
3,666,730 
3,449,250 
3,687,849 
3,519,565 
3,702,300 
______________________________________ 
The above-noted patents are incorporated by reference herein for their 
disclosures of ashless dispersants. 
Extreme pressure agents and corrosion- and oxidation-inhibiting agents 
which may be included in the lubricants of the invention are exemplified 
by chlorinated aliphatic hydrocarbons such as chlorinated wax; oganic 
sulfides and polysulfides such as benzyl disulfide, 
bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester 
of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and 
sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction 
product of a phosphorus sulfide with turpentine or methyl oleate, 
phosphorus esters including principally dihydrocarbon and trihydrocarbon 
phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl 
phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl 
phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 
4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted 
phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal 
thiocarbamates, such as zinc dioctyldithiocarbamate, and barium 
heptylphenyl dithiocarbamate; Group II metal phosphorodithioates such as 
zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, 
barium di(heptylphenyl)-phosphorodithioate, cadmium 
dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid 
produced by the reaction of phosphorus pentasulfide with an equimolar 
mixture of isopropyl alcohol and n-hexyl alcohol. 
Many of the above-mentioned auxiliary extreme pressure agents and 
corrosion-oxidation inhibitors also serve as antiwear agents. Zinc 
dialkylphosphorodithioates are a well known example. 
Pour point depressants are a particularly useful type of additive often 
included in the lubricating oils described herein. The use of such pour 
point depressants in oil-based compositions to improve low temperature 
properties of oil-based compositions is well known in the art. See, for 
example, page 8 of "Lubricant Additives" by C. V. Smalheer and R. Kennedy 
Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967). 
Examples of useful pour point depressants are polymethacrylates; 
polyacrylates; polyacrylamides; condensation products of haloparaffin 
waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers 
of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. 
Pour point depressants useful for the purposes of this invention, 
techniques for their preparation and their uses are described in U.S. Pat. 
Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 
2,721,877; 2,721,878; and 3,250,715 which are hereby incorporated by 
reference for their relevant disclosures. 
Anti-foam agents are used to reduce or prevent the formation of stable 
foam. Typical anti-foam agents include silicones or organic polymers. 
Additional anti-foam compositions are described in "Foam Control Agents", 
by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162. 
The amount of the oil-soluble sulfurized organic composition of the present 
invention when utilized as a concentrate is generally from about 50 to 
about 100% by weight and often exists as a neat composition. 
While in accordance with the patent statutes, the invention has been 
described in detail, the scope of the present invention is set forth by 
the attached claims.