CA1187508A - Sulfurized fatty oil additives - Google Patents
Sulfurized fatty oil additivesInfo
- Publication number
- CA1187508A CA1187508A CA000412035A CA412035A CA1187508A CA 1187508 A CA1187508 A CA 1187508A CA 000412035 A CA000412035 A CA 000412035A CA 412035 A CA412035 A CA 412035A CA 1187508 A CA1187508 A CA 1187508A
- Authority
- CA
- Canada
- Prior art keywords
- mole
- acids
- triglyceride
- sulfurized
- additive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000654 additive Substances 0.000 title claims abstract description 58
- 239000010685 fatty oil Substances 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 89
- 230000000996 additive effect Effects 0.000 claims abstract description 40
- 150000003626 triacylglycerols Chemical class 0.000 claims abstract description 25
- 239000000446 fuel Substances 0.000 claims abstract description 24
- 239000003921 oil Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims description 69
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 46
- 150000007513 acids Chemical class 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 125000001931 aliphatic group Chemical group 0.000 claims description 24
- 238000005809 transesterification reaction Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- -1 aliphatic primary alcohols Chemical class 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000007928 solubilization Effects 0.000 claims description 9
- 238000005063 solubilization Methods 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000010687 lubricating oil Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 5
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims description 4
- 239000002199 base oil Substances 0.000 claims description 3
- YWFUVTMPYOLBDB-UHFFFAOYSA-M butyl(chloro)tin;dihydrate Chemical compound O.O.CCCC[Sn]Cl YWFUVTMPYOLBDB-UHFFFAOYSA-M 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 claims 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims 1
- 125000005457 triglyceride group Chemical group 0.000 claims 1
- 239000000314 lubricant Substances 0.000 abstract description 13
- 239000003879 lubricant additive Substances 0.000 abstract description 5
- 238000005461 lubrication Methods 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000000306 component Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010699 lard oil Substances 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 239000003784 tall oil Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910001651 emery Inorganic materials 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000003381 solubilizing effect Effects 0.000 description 4
- 229910014033 C-OH Inorganic materials 0.000 description 3
- 229910014570 C—OH Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004440 Isodecyl alcohol Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003138 primary alcohols Chemical group 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241000415246 Callisia navicularis Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000332 continued effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
- Liquid Carbonaceous Fuels (AREA)
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
5~
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~
~'7~
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.
'75~
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.
- 1~
'7~
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:
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~
~'7~
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.
'75~
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.
- 1~
'7~
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. ~. ~
5~
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~
'75~
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
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. ~. ~
5~
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~
'75~
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
~ 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
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 (37)
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.
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.
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.
(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.
(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.
(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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000412035A CA1187508A (en) | 1982-09-23 | 1982-09-23 | Sulfurized fatty oil additives |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000412035A CA1187508A (en) | 1982-09-23 | 1982-09-23 | Sulfurized fatty oil additives |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1187508A true CA1187508A (en) | 1985-05-21 |
Family
ID=4123650
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000412035A Expired CA1187508A (en) | 1982-09-23 | 1982-09-23 | Sulfurized fatty oil additives |
Country Status (1)
Country | Link |
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CA (1) | CA1187508A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113913229A (en) * | 2021-10-18 | 2022-01-11 | 武汉工程大学 | Environment-friendly anti-wear additive based on hermetia illucens oil and preparation method thereof |
CN114058431A (en) * | 2021-11-01 | 2022-02-18 | 梧州市澳拿科技有限公司 | Environment-friendly inactive vulcanized lard oil and preparation method thereof |
-
1982
- 1982-09-23 CA CA000412035A patent/CA1187508A/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113913229A (en) * | 2021-10-18 | 2022-01-11 | 武汉工程大学 | Environment-friendly anti-wear additive based on hermetia illucens oil and preparation method thereof |
CN114058431A (en) * | 2021-11-01 | 2022-02-18 | 梧州市澳拿科技有限公司 | Environment-friendly inactive vulcanized lard oil and preparation method thereof |
CN114058431B (en) * | 2021-11-01 | 2023-02-24 | 梧州市澳拿科技有限公司 | Environment-friendly inactive vulcanized lard oil and preparation method thereof |
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