CA1187508A

CA1187508A - Sulfurized fatty oil additives

Info

Publication number: CA1187508A
Application number: CA000412035A
Authority: CA
Inventors: Karl P. Kammann, Jr.; Marvin J. Den Herder
Original assignee: Ferro Corp
Current assignee: Vibrantz Corp
Priority date: 1982-09-23
Filing date: 1982-09-23
Publication date: 1985-05-21

Abstract

Improved lubricant additive compositions, derived from fatty oils, comprise sulfurized, transesterified triglycerides. Such additive compositions possess improved solubility in oils in impart improved lubrication properties to both lubricant and fuel compositions.

Description

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It has been common practice to include in lubricant $ormulations additives to provide improved antiwear and rust inhibition properties. In the pastl sulfurized triglycerides~
such as sulfurized lard oil, have been utilized, especially in as~sociation with lightly refined aromatic mineral oils which pro~ided sufficient solubility or the sulfurized triglycerides.
~ Yith the increased concern for toxicity of aromatic ~ompounds found in such mineral oils, lubricant formulatiolls lQ now comprise essentially non-aromatic oils. This change to substantially non-aromatic base oi}s crcated a major problem, resulting from a significant decrease in solubility of the sulfurized triglycerides in the non-aromatic mineral oil, resul~ing in solidification and/or dropout of the sulfuriæed triglycerides.
~hile the solubility problem has been overcome, the ~odified lubricant products have been found to be either deflcient in desirable lubricant properties or incapable of pro~iding needed improvement in these propertiesO
2Q In a typical approach to this problem9 as reported in United States Patent Number 3~455,896, sulfurized9 low ~lecular weight polybutenes were reacted with liquid trigly-ceridesg which ~ere susceptible of sulfurization, to yield an additiveO In United States Patent Number 3,850,~25, another additive was prepared by the sulfurization of a mixture of prime burning lard oil and alkyl oleate. In United States Patent Number 3,7~0~333, Cl~ - C16 alcohol esters of unsaturated fatty acids7 having 18 to 22 carbon atoms~ were blended with a triglyceride 5~3 and either used `'as is" or sulfurizedO Modifications of such composi~ions have been reported in United Skates Patent Num~ers ~,14~,~8~, 4,166,795, 4,166,796, 4,166,797, and 8,300 D
Althoug~ t~ese prior art efforts have increased the solubility o~ sulfurized fatty oils to acceptable values, there has remained a serious need for sulfurized additives possessing both good solubility and a combination of improved lubricant properties, such as, for example, la ~etter low temperature flow properties, better load carrying and antifriction properties9 and a lack of sludging. Such imyroved lubricant properties would also be attractive or use in various fuels systems employed for power generation and heating purposes.
This in~ention relates to improved lubricant additive compositions comprising sul~uriæed fatty oils, to ~he process for their preparation, and to oil product compositions, including bo~h fuels and lubricants, incor-porating such sulurized fatty oilsO The additive compositions ~0 o~ this invention exhibit highly desirable solubility pro-perties when employed in ei*her lubricant or fuel formula tions. The particularly desirable utility of these additive compositions derives from their providing generally improved performance characteristics, ranging from improved load carrying, anti~ear, and friction properties3 to reduced levels of deposits and varnish, and to improved pour point depression.
This invention particularly relates to sulfurized, fatty oil additive compositions3 comprising a sulfurizedO

_ ~ _ 1~3'75(~

transesterified -triglyceride wherein the total acicl com-ponent of the triglyceride comprises no less than about 35 ~nole ~ saturated aliphatic acids and no more than about 65 mole % un~aturated fatty acids, said total acid component being further characterized as comprising:
a) more than about 20 mole % of mono-unsaturated acids;
b~ less than about 15 mole % of poly-unsa~urated fatty acids;
c) more than about 20 mole % saturated aliphatic acids having 6 to 16 carbon atoms> including nore than about 10 mole % saturated aliphatic acids. ha~ing 6 to 14 carbon atoms; and d? less than about 15 mole % saturated aliphatic acids having 18 or more carbon atoms.
This invention further relates to the method for preparation of such transesterified and sulfurized trigly-cer~des.
2Q This invention additionally relates to lubricant and fuel compositions incorporating such sulfurized, fatty oil additives, whereby improved performance in conventional usages is achievedD The additives of this invention may be emplo~ed in concentrations up to about 15 Wto % in lubricant formulations and up to about 0ul wto % in fuel compositionsO
This invention is directed to additive compositions of sulfurized fatt~ oils, and to the process of preparing said compositions, which e~hibit the required solubility properties in non-aromatic base oils without the disadvan-'75~

tages associated with the prior art lubricant additive ~ormulations. In addition, the compositions of this invention exhibit improved performance characteristics, over the compositions of the prior art, including improved load carrying/ antiwear, and friction properties~ reduced levels of deposits and varnish in used oils, and~better pour-point depre~sion. This invention is likewise directed to lubricant and fuel formulations which include the invelltive additive compositions.
Triglycerides of the prior art, typically derived from plants and animals, do not provide maximum effective-ness as lubricant additives because of the chain length and/or the degree of unsaturation of the acid moiety.
Modification of said acid moieties of th~ triglycerides, by transesterification, produces novel triglycerides that optimize the properties of the resulting additive when said nov l triglycerides are coupledl through sul~ur bonds, with solubilizing components, such as esters and/or olefins.
The acid moiety o~ the triglyceride components of the additives of this invention consists of an acid mixture having less than about 65 ~ole % unsaturated acids, mainly possessing one ethylenic carbon-carbon double bond, and more than 35 mole % saturated aliphatic acids, Of the total acid moiety, less than about 15 mole % are 5 saturated acids having 18 or more carbon atoms and more than about 35 mole % are saturated acids having less ~han 18 carbon atoms. Similarlyl less than about 15 mole % are -oly~unsaturated acids and more than about 20 mole %
are mono-unsaturated acids~

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The transesterification reaction is carried out on blends of (1) triglycerides, (2) triglycerides and organic acids, or (3) triglycerides and esters of organic acids~ Where acids are incLuded in the reaction and the amount of free acids present in the transesterified blend is greater than about 15 %, then the free acid ig pr~ferably esterifi~d wi~h monoalcohols, glycols or glycerol to decrease the free acid content prior to the subsequent sulfurization reac~ionO The esterification of free acids may also be effected when the concentration thereof is less than about 15% but this is not imperative.
Fotlowing the transesterification, or esteri~ication, the reaction components are coupled by reaction with sulf~lr with, where desired, the added presence of solubilizing components, such as esters, olefins or blends thereof. The sulfurization is conducted in accordance with known procedures which generally consist of heating the mixture with elemental sulfur at temperatures ~rom about 3no F. to about 400 F.
for from about 1 to about 8 hours. The sulur content of the additives o this invention should be within the range from about 4 to about 14 wt. %.
The additives of the present invention preferably utilize as starting compounds naturally occuring trigly-cerides. The ~ompositions of such triglycerides are detailed in BaileY's Industrial Oil and Fat Products, VolO I~ 4th Edition, John Wiley and Sons.
A triglyceride is the ester product of glycerol and one or more fatty acids, represented schematically as 5l~3 H H
H-C-OH HOOC-Rl H~C-OOCRl H-C-OH -t HOOC-P~2 ~ -C-OOCR2 H-C-OH ~OOC-R3 H-C-OOCR3 H H
~ where Rl, R2~ and R3 represent hydrocarhon groups which may be identic.~l or different in chain length and may also be saturated or unsaturatedO
Triglycerides from fish and animal oils contain acids with chain lengths that normally exceed 15 carbon atoms and usually contain large a~ounts of mono- and poly-unsaturated acids. Triglycerides from sc.me plant species contain appreciable amounts of shorter chain acids, having 10, 12 or 14 carbon atoms. These shorter chain plant-derived acids tend to be mainly saturated acids.
In the process of preparing the triglyceride components of the additive of the present invention, com-mercially available triglycerides which do not have the required distribution of acids are transesterified with acids, esters or triglycerides having a higher proportion of the required distribution of acids. The resultant mixtures, following the transesterification, have the required average distribution of acids, preferably as triglycerides~ Free acids in the transesterification reaction product may then 5 be esterified with mono-alcohols, ranging from methyl to C20, or with poly-alcohols, such as a glycol br glycerol.
If the free acid content in the transesterification reaction product is greater than about 15%, esterification is a highly preferred p.rocedure, whereas below the 15~ level esterification is optionalO Transesterification is preferably ~ ~ 8'75~

carried out in the presence of a strong acid catalyst, at temperatures within the range from about 400 F. to about 450 F. for from about 1 to about 8 hours.
Prior to sulfurization, the transesterlfied mixture may be blended Witll a solubilizin~ component whe~ further improved so ubility is desired. Whenever there ~s a sufi5icient amount of free unsaturated acid in the tr~nsesterification reaction product, the esterification of such acids can provide the solubilizing factor. Otherwi3e additional solubilizing components, such as unsaturated esters or ole~ins are added prior to sulfurization.
Although the amount of solubilization component present, prior to sulfurization may, if desired, be as high as about 70 wt~ %, such solubilization components, when employed, are preferably present in an amount within the range from about 5 wt. % to about 55 wt. ~.
Examples of naturally occurring triglycerides, which may be utilized as starting triglycerides for the prPparation of the additives of this invention, include, but are not limited to, lard oil, tallow, palm oil and peanut oil.
The acid moiety of the triglyceride, following transesterification, consists of a total ~ono- and poly-unsaturated fatty acids in an amount of less than about 65 mole ~. The acid moiety consists of more than abcut 20 ~ole ~, preferably more than about 35 mole %, of mono-unsaturated fatty acids and less than about 15 mole ~ poly-unsaturated fatty acids; i.eO, acids ha~ing more than one ethylenic carbon-carbon bond. Total saturated aliphatic acids comprise more than about 35 mole ~, and preferably morQ than about ~'75~

50 mole %, of said acid moiety. Of the total acid moiety, saturat~d acids having 6 to 14 carbon atoms are present ~n an amount of more than a~out 10 mole ~ a~d prefexably more than about 15 mole %; saturated acids having 6 to 16 carbon atoms including the aforementioned acids having ~ to 14 carbon atoms, are present in an amount o more t~an about 20 mole % and preferably more than about 35 mole %i and sat~lrated acids having 18 or more carbon atoms are present in an amount of less than about 15 mole %O
The acids utilized are normally straight chain acids, although the presence of some branched chain acids, such as 2-ethylhexanoic and 2-methyldecanoic, is not deleterious.
A~most any alcohol can be utilized in the optional esterification step, including glycerol, diols and mono-hydroxy alcohols, especially terminal primary alcohols.
Branche~ alcohols, such as ~-ethylhexyl, isodecyl, isodo-decyl and mixtures containing a wide range o alcohols, such as 11 to 22 carbon atoms, can also be utilized.
Olefins, when used as solubilizing agents, normally contain 8 to 20 carbon atoms per molecule. Olefin mixtures may be employed.
In one embodiment of this invention, the trans-esterification and esterification is caused to occur in 2 reduced number of steps by mixing together the starting triglyceride, replacement acids, and alcohol, and then subjecting the mixture to heat in the presence oE a tranC-esterifi~ation catalyst.
Transesteriflcation catalysts are normally utilized to speed th6 reaction, although the reaction will proceed without a catalyst. The amount and type of catalyst can ~e 5~

widely varied. Known transesterification catalysts are tetrabutyl titanate, zinc acetate, sodium carbonate, sodium hydroxides, potassium hydroxide, sodium methylate, sodium sulfate, stannous oxalate, p-toluenesulfonic acid (PTSA), methanesulfonic acid (MSA3, butylchlorotin dihydroxide, sulfuric acid, phosphoric acid and the like. p-~oluene-sulfonic acid and methanesulfonic acid are the preferred catalyst. The amount of catalyst utilized is in the range of about 0.01 wt~ % to about 1 wt. ~ with the preferred range being about 0.03 wt. % to 0.5 wt. ~
Comparison runs made with and without a trans-esterification catalyst showed the follow1ng degree of completion:
a) catalyst: 0.15 % methanesulfonic acid, 4 hours at 400 F. - about 72 % completion;
b) catalyst. 0.1 ~ butylchlorotin dihydroxide, 8 hours at 400 F~ -- about 44 % completion;
and c) catalysi: NONE - 8 hours at 400 F. --about 21 % completion.
The above comparison study shows that the trans-esterification reaction occurs even in the absence of a catalyst and that the rate o~ reaction is increased by the addition of a catalyst.
During thè transesterification reaction the presence of 0.15 to 1.0 wt. % water increases the rate of transesterification. However, during subsequent esterifica-tion it is desirable that the water that nad been added, ox is generated by the esterification reactioI?, be removed as promptly as possible, in order to drive the reaction to _ g _ ~'7S~

completion and thus increase the yield.
The following examples serve, without limitation, to describe the invention ~lore fully as it relates to lubricant additive compositio~s. In the examples all parts and percentages are on a weight basis unless ot~erwise indicated.
In the following examples HOE alcohol refers to an 11 to 22 carbon alkyl alcohol, averaging about 16 carbons, mainly branched primary alcohol, sold commercially as Heavy Oxo Ends. Emery 876 acid is a saturated acid mixture containing about 11% C9, ~ Clo-C13, 16~ C14, l5 16 1~ C17 and 12% C18 monobasic acids and 15% C~-C14 dibasic acids. Diol concentrate is a mixture o predominantly s~raight chain alcohols, containing about 84% diols, mainly C13-C17 primary, and about 16% monohydroxy alcohols, mainly C15-C16 primarY- ~

~ .
A blend of 67 parts prime lard oil, 28 parts crude coconut oil, and 5 parts oleic acid W2S heated for 4 hours at 4Q0 to 410 F., in the presence of 0.2~ p-~oluenesulfonic acids. The acid value (A.V.~ of the mixture rose from 16 to 20. Acid value is determined by titration (A.O.C.S. method Cd 3a-63~ and is defined as the numher of milligrams of potassium hydroxide necessary to neutralize ~he free acids in one gram of sample.
To the transes~erification reaction mixture I was added 8 parts of HO~ alcohol and the heatlng continued for an additional 3 hoursO The A.V. value W~5 reduced duxing this process to 10~ The resultant produc1: II, except for -- 10 ~

'75~3 small amounts of free acid and alcohol, contained about 87%
transesterified triglyceride and about 13% ester.
This product was sulfurized, by heating with elemental sulfur at 360-370 F. for 3 hours, followed by cooling below 330~ F. and passing air through the mixture for about 1.5 hours, to remove any ~2S or other noxious light ends. The resultant product III contained 6.3% bound sulfur.
Example 2 Sixty (60~) percent of ~he transesterified trigly-ceride product I, obtained by the procedure o~ Example 1, was blended with 40~ of an alkyl alcohol ~HOE) ester of unsaturated fatty acids (tall oil fatty acids~ and the mixture sulfurized to yield product IV, having 7.3% bound sul~ur.

A blend of 10Q parts prime lard oil and 25 parts Emery 621 coconut fatty acid was heated for 4 hours at 400-410 F., in the presence of 0.2% p-toluenesulfonic acid. To this mixture was added 25 parts HOE alcohol and the mixture was heated for an additional 3 hours. The A.V. of this product V was 11.
To 150 parts of reaction product V was added 20 parts of the alkyl alcohol (HOE) ester of unsaturated fa~ty acids (tall oil fatty acids) and the mixt~re sulfurized to yield product VI, having 6~75 bound sulfur.

~ blend of 7~ parts of a solid triglyceride, having a melting point o about 100 F., and 22 parts Emery 621 1~7Si~l~

coconut fatty acids was heated at 400-410 F. for 4 hours, in the presence of 0.2% methanesulfonic acid. Twenty (20) parts of HOE alcohol was added and the reaction continued until the A.V. decreased to 10. Twenty-eight (28) parts of HOE alcohol ester of tall oil fatty acids was then added and the ~ix~cure sulfuri~ed to yield product ~7II, having 6.5%
bound sulur. The mixture, pxior to sulfuriza~ion, con-tained about 53% transeste~ified triglyce~ide and about 47%
HOE ester.

Exam~
Sixty-eight (68) parts of a solid triglyceride, having a melting point of about 100 F., was mixed with 19 parts Emery 621 coconut fatty acid and 13 parts tall oil fatty acid. The mixture was heated at 400-410~ F. for 4 hours, in the presence of 0.15% methanesulfonic acid.
Thirty ~30) parts HOE alcohol was then added and the heating continued until an A.V. of 9 was obtained. The product was then sulfurized, using 6.5~ sulfur, to yield the sulfuri2ed product VIII.

Exam~ 6 A mixture of 80 parts prime burning lard oil and 20 parts Emery 876 acids was heated for 4 hours at 400-410 Fr in the presence of 0.3~ p-toluenesulfonic acidO ~wen~y-two (22) parts HOE alcohol was then added and the heating con-tinued until an ~V. of 10 was obtained~ Tp this mixture was added 30 parts c,f a dies'cer prspared from 2 mol~s of tall oil fatty acids and 1 mole diol concentra~eO The resultant mixture was sulfurized to give produc~ ~X, con-taining 7.4% bound sulfur.

~8'~5~3 Example 7 A blend of 12% Chevron C15 - C18 ~C -olefin and 88~ of product V was sulfurized to give product X, con-taining 7.1% sulfur.

Example 8 The procecure of Example 4 was repeated on a large scale, utilizing 6% sulfur in the sulfurization step. The product XI containec 5.9~ bound sulfur.

Example 9 A blend o~ 78 parts of a solid triglyceride, having a melting point of about 100 F., and 22 parts Emery 621 coconut fatty acids was heated at 400-410 F. for 4 hours, in the presence of 0.15% methanesulfonic acid.
Twenty-three (23) parts of isodecyl alcohol was then added and the heating continued for an additional 4 hours at 340-380 F. The A.V. was reduced during this process to 8.
Sixteen (16) parts of isodecyl ester of tall oil fatty acids was then added and the mixture sulfuri~ed, by heating with sulfur, using the procedure of Example 1, to yield product XII, containing 6.?% bound sulfur7 The mixture prior to sulfurization, except for small amounts of free acid and alcohol, contained about 56~ transesterified triglyceride and 44% ester.
The following products were prepared for com-parison purposes.

Exame~ A
A ~ixtuxe of 88% prime burning 13rd oil and 12 methyl oleate was sulfurized to produce product A, con-taining 9.7% bound sulfur.

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Example B
A mixture of 55~ prime burning lard oil and 45%
HOE alcohol ester of tall oil fatty acids was sulfuriz~d to yield sulfurized product B, oontaining 9.C% bound sulfur and having an A.V. of 9. '-~ Example C
A mixture of 50% prime buxning lard oil and 50%isodecyl alcohol ester of tall oil fatty acids was sulfurized to ~ield product C, containing 9.1% bound sulfur and having an A.V. of 8.
Products exemplary of t~e sulfu~ized f~.~ty oi~
additive compositions of this invention, prepared as descri~ed in ~xamples 1 - 9, above, togethe~ with comparison products A and B, were tested by conventional procedures at various concentration levels, ranging from 1 to 4 wt. %, in a mineral oil and in three commercially available engine oils, to determine the respective effects on flow properties~ Results are presented in Tables I, II, III, and IV.
The mineral oil _ontained no po-lr depressant additive and did not flow at temperatures below 0c F. The engine oils contained pour depressants and still flowed at -20 F. Solubility of the products of this invention in these oils was good.
Table I shows clearly that the additives of this ~ invention have excellent properties as pou~ depressants, keeping the oil fluid at lower temperatures when added to a mineral oil having a pour point of 0 F. However r when large amounts Of the additives are added, the abili~y to cause flow at low temperatures is ~educed.

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Tables II, III and IV show that sulfurized fatty oils (Products A and B) diminish the low temperature flow properties of pour dPpressed engine oils. However, addi~ives of the present invention can be used at higher COnGentratiOnS
without any harmful effect upon the flow propertIes of the same engine oils.
The improved load carrying and friction reduction properties imparted by the use of the additives of the present invention are illustrated by the data in Tables V
and VI, showing the improved load carrying and friction reduction (torque) as measurPd by the Falex step~up tes~.
Tests presented in Table V were conducted with a pour-depressed engille oil. Tests presented in Table VI illustrate the additive performance with non-formulated base oils, including a mineral oil and a synthetic lubricating oil base stock.
Falex procedures for evaluating lubricants are described in Lubrication Engineering, 24, No. 8, 349-358 (196~). The procedure employed in these tests was as follows:
After a 5 minute warmup at 250 lbs., the load is increased in 250 lb. increments and h~ld at each increment for one minute/ until failure~ which is of the weld typeO
Torque comparisons were also made to show diff~rences in friction.
~ Crankcase oil, formulated to be a high~quality SE
Grade l~W40 crankcase oil, was evaluated using a four-ball machine in testing for friction and wear as described in the ASTM-D-2266 procedure. The crankcase oil alone was compared with crankcase oil containing 2% additive B or 2% additi~e '75~

XI. Tests were conducted at 1800 R.P.M., using a 40 kg. load, for one hour at 350 F. The results obtained were as follows:

Additives Wear-Scar Diameter Crankcase Oil 0.8~
+2~ Additive B 0.8~ mm + 2% A~ditive XI 0.57 mm Several products were tested for solubility in synthetic hydrocarbon oils by dissolving in Gulf Synlube 4cs with warming and stixring. The solutions were then kept a~
45 F. for 4 days and finally observed after warming to room temperature. The observed results were:

2% A Heavy Bottom Layer 2% B Slight dropout 2% C Slight dropout 2~ VI Very slight dropout 2% VIII Tr. Ha~e 2% VII Hazy 2% XI Tr. Haze The sulfurized fatty oil additivs compositions of this invention are ef~ective when employed in lubricating oils at concentrations ranging from about 0.05 ~o about 15 wt. ~O The preferred concentra~ion range is generally from about 0.5 to abou~
5 wto ~6~
In other embodime~ts of t~is invention the sulfurized fatty oil additive compositions are effec~ive in various types of fuels, particularly to improve the lubrication of fuel pumps;

:~8'~5~

to reduce wear on pistons, rings, and cylinders; and to reduce deposit formation. Such fuels broadly include gasolines, for use in spark-ignition internal combustion engines; diesel oils, for use in compression-ignition internal combustion engines; and heating (or furnace) oils, for use inoil-fired burner assemblies. Other advantages include, when employed in fuel oils or diesel f-lels, reduction of pour points and attendant reduction in plugging of oll filters. In such novel and improved fuel com~ositions, the additives of this invention are effective at relatively low ~oncentrations within the range from about 0.0005 to about a . 1 wto % r and preferably from about 0.0015 to about 0.05 wt. ~. ~

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Table I
Low Temperature Flow of a Mineral Oil ( ) ~viscosity 27 cst. at 40 C.) After 16 Hours at -lS F.

Additive 1% 2% 3~ 4%
A Flows No Flow B - Flows No ~low C - Flows No Flow VI - Flows No Flow VIII - Flows No Flow XI - Flows Flows No Flow XII - Flows Flows No Flow )Without additives, no flow at 0 F.

Table II
Commercial 10W40 Oil "Brand A" (1) After 16 Hours at -2Q~ F.

Additive1% 2~ 3~ 4 A Flows No Flow B - Flows( ) No Flow C - Flows( ) No ~low III - Flows No Flow IV - Flows Flows Flows VI _ Flows Flows Flows( ) VII ~ Flows Flows Flows( ) VIII - Flows Flows No Flow IX Flows Flows No Flow X ~ Flows Flows No Flow XI - Flows F~ows Flows(2) XII - Flows Flows Flows )Without additives, flows at -~0 F.
)Marginal Flow~

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Table III
Commercial 5W30 Oil ''Brand B" (1) After 16 Hours at -22 F.

Additive .1% 2% 3~ 4%
A Flows No Flow - s B Flows Flows No Flow C Flows Flows No Fl ~
III - Flows Flows Flows IV - Flows Flows Flows VI - Flows Flows N~ Flow VII - Flows Flows Flows~ ) VIII - Flo~s Flows Flows(2) IX ~ Flows Flows No Flow )Without additives, flows at -22 F.
)Marginal Flow.

Table IV
Commercial lQW40 Oil "Brand Cll (1) After 16 Hours at -20 F.

Additive 1~ 2~ 3~ 4 A Flows No Flow B - Flows Flows Flows ~ Flows Flows VI - Flows Flows Flows VII - - Flows Flows _ _ (l~Without additives, flows at -20 F.
.

s~

Table V
Falex Step-Up Test, 10W40 Oil, "Brand A"

Lbso Load Torque at Before Failure 1500 lbs.
Oil alone ' 1250 , (45 at 1250) 2% B 1500 30 2% ~ 1500 ~ 30 2~ III 1750 25

3% IV 2000 24 2% VII 1750 26 3~ VII 1750-2000 25 3~ VIII 2000 23 2% IX 1750-200Q 27 3~ IX 2000 27 3% ~ 1750 2~
~ XI 1750 25 3~ XI 2250 24 2% XII 1500-1750 27 3% XII 1750 26

4% XII 2000 25 Table VI
Falex Step-Up Test in Non-Formulated Base Hydrocarbons Lb~. Load Torque at Before Failure 1250 Mid-Continent Oil 750 Oil ~ 2~ VI 1250-1500 24 Gulf Synfluid 4cs 250-500 ~ -Gulf Synfluid 4cs + 2% VIII 1250~1500 - 19

Claims

WHAT IS CLAIMED IS:

1. A sulfurized, triglyceride additive composition, comprising a sulfurized, transesterified triglyceride wherein the total acid component of the triglyceride comprises no less than about 35 mole % saturated aliphatic acids and no more than about 65 mole % unsaturated fatty acids, said total acid component being further characterized as comprising:
a) more than about 20 mole % of mono-unsaturated acids;
b) less than about 15 mole % of poly-unsaturated fatty acids;
c) more than about 20 mole % saturated aliphatic acids having 6 to 16 carbon atoms, including more than about 10 mole % saturated aliphatic acids having 6 to 14 carbon atoms; and d) less than about 15 mole % saturated aliphatic acids having 18 or more carbon atoms.

2. The sulfurized triglyceride additive composition of claim 1, wherein said mono-unsaturated fatty acids are present in an amount greater than about 35 mole %.

3. The sulfurized triglyceride additive composition of claim 1, wherein said poly-unsaturated fatty acids are present in an amount less than about 10 mole %.

4. The sulfurized triglyceride additive composition of claim 1, wherein said total saturated aliphatic acids are present in an amount greater than about 50 mole %.

The sulfurized triglyceride additive composition of claim 1, wherein said saturated acids having 6 to 14 carbon atoms are present in an amount greater than about 15 mole %.

6. The sulfurized triglyceride additive composition of claim 1, wherein said saturated acids having 6 to 16 carbon atoms are present in an amount greater than about 35 mole %.

7. The sulfurized triglyceride additive composition of claim 1, additionally comprising a solubilization agent.

8. The sulfurized triglyceride additive composition of claim 7 wherein the solubilization agent is selected from the group consisting of triglycerides, olefins, esters of unsaturated carboxylic acids, and mixtures thereof.

9. The sulfurized triglyceride additive composition of claim 8 wherein the solubilization agent is a triglyceride.

10. The sulfurized triglyceride additive composition of claim 8 wherein the solubilization agent is an olefin.

11. The sulfurized triglyceride additive composition of claim 10 wherein the olefin contains from about 8 to about 20 carbon atoms, alone or in mixtures thereof.

12. The sulfurized triglyceride additive composition of claim 8 wherein the solubilization agent is an ester of an unsaturated carboxylic acid.

13. The sulfurized triglyceride additive composition of claim 7 wherein the solubilization agent is present in an amount within the range from about 5 wt. % to about 70 wt. %
based on the transesterified triglyceride.

14. The sulfurized triglyceride additive composition of claim 13 wherein the solubilization agent is present in an amount within the range from about 5 wt. % to about 55 wt. %, based on the transesterified triglyceride.

15. The sulfurized triglyceride additive composition of claim 1 wherein bound sulfur is present in an amount within the range from about 4 wt. % to about 14 wt. %, based on the total product.

16. A method for preparing a sulfurized, trans-esterified triglyceride additive composition, comprising the steps of:
(1) transesterifying one or more triglycerides with one or more organic acids, or esters thereof, to yield a trans-esterified triglyceride wherein the total acid component com-prises no less than about 35 mole % saturated aliphatic acids and no more than about 65 mole % unsaturated fatty acids, said total acid component being further characterized as comprising:
a) more than about 20 mole % of mono-unsaturated fatty acids;
b) less than about 15 mole % of poly-unsaturated fatty acids;
c) more than about 20 mole % saturated aliphatic acids having 6 to 16 carbon atoms, including more than about 10 mole 3 saturated aliphatic acids having 6 to 14 carbon atoms; and d) less than about 15 mole % saturated aliphatic acids having 18 or more carbon atoms; and (2) sulfurizing the transesterified triglyceride product mixture of step 1 with elemental sulfur to incorporate bound sulfur in an amount within the range from about 4 wt. %
to about 14 wt. %, based upon the transesterified triglyceride product mixture.

17. The method of claim 16, wherein said mono-unsaturated fatty acids are present in an amount greater than about 35 mole %.

18. The method of claim 16, wherein said poly-unsaturated fatty acids are present in an amount less than about 10 mole %.

19. The method of claim 16, wherein said total saturated aliphatic acids are present in an amount greater than about 50 mole %.

20. The method of claim 16, additionally comprising the step of esterifying free acids in the tranesterification reaction product with an alcohol component prior to the sulfurization step.

21. The method of claim 20 wherein said alcohol component for esterification comprises branched chain aliphatic primary alcohols.

22. The method of claim 16, additionally comprising the step of blending said transesterification reaction product with a compound selected from the group consisting of triglycerides, esterified fatty acids, ? -olefins and mixtures thereof, prior to the sulfurization step.

23. The method of claim 16 wherein said trans-esterification step is carried out in the presence of a transesterification catalyst.

24. The method of claim 23 wherein said trans-esterification catalyst is selected from the group consisting of tetrabutyl titanate, zinc acetate, sodium carbonate, sodium sulfate, stannous oxalate, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, butylchlorotin dihydroxide, and phosphoric acid.

25. The method of claim 23 wherein said trans-esterification catalyst is present in an amount within the range from about 0.01 to about 1 wt. %, based on the tri-glycerides.

26. The method of claim 25 in which said catalyst is present in an amount within the range from about 0.03 to about 0.5 wt. %.

27. The method of claim 24 wherein said catalyst is p-toluenesulfonic acid.

23. The method of claim 24 wherein said catalyst is methanesulfonic acid.

29. A lubricating oil composition, comprising:
(1) a refined base oil, having lubricating oil.
viscosity and volatility properties; and.
(2) a minor amount of a sulfurized triglyceride additive composition, comprising a sulfurized, transesteri-fied triglyceride wherein the total acid component of the triglyceride comprises no less than about 35 mole % saturated aliphatic acids and no more than about 65 mole % unsaturated fatty acids, said total acid component being further characterized as comprising:
(a) more than about 20 mole % of mono-unsaturated acids;
(b) less than about 15 mole % of poly-unsaturated fatty acids;
(c) more than about 20 mole % saturated aliphatic acids having 6 to 16 carbon atoms, including more than about 10 mole % saturated aliphatic acids having 6 to 14 carbon atoms; and (d) less than about 15 mole % saturated alipha-tic acids having 18 or more carbon atoms.

30. The lubricating oil composition of claim 29 wherein the sulfurized triglyceride additive composition is present in an amount within the range from about 0.05 to about 15 wt. % of the lubricating oil composition.

31. The lubricating oil composition of claim 30 wherein the sulfurized triglyceride additive composition is present in an amount within the range from about 0.5 to about 5 wt. % of the lubricating oil composition.

32. A fuel composition, comprising:
(1) a blended base fuel, having suitable volatility and combustion properties; and (2) a minor amount of a sulfurized triglyceride additive composition, comprising a sulfurized, transesterified triglyceride wherein the total acid component of the triglyceride comprises no less than about 35 mole % saturated aliphatic acids and no more than about 65 mole % unsaturated fatty acids, said total acid component being further characterized as comprising-(a) more than about 20 mole % of mono-unsaturated acids;
(b) less than about 15 mole % of poly-unsaturated fatty acids;
(c) more than about 20 mole % saturated aliphatic acids having 6 to 16 carbon atoms, including more than about 10 mole %
saturated aliphatic acids having 6 to 14 carbon atoms; and (d) less than about 15 mole % saturated aliphatic acids having 18 or more carbon atoms.

33. The fuel composition of claim 32 wherein the blended base fuel is a gasoline fuel, for use in a spark-ignition internal combustion engine.

34. The fuel composition of claim 32 wherein the blended base fuel is a diesel fuel for use in a compression-ignition internal combustion engine.

35. The fuel composition of claim 32 wherein the blended base fuel is a heating oil, for use in an oil-fired burner assembly.

36. The fuel composition of claim 32 wherein the sulfurized triglyceride additive composition is present in an amount within the range from about 0.0005 to about 0.1 wt. % of the fuel composition.

37. The fuel composition of claim 35 wherein the sulfurized triglyceride additive composition is present in an amount within the range from about 0.0015 to about 0.05 wt. % of the fuel composition.