JPH0138159B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION The use of certain amine salts of sulfurized fatty acids as corrosion inhibitors in lubricating oils is patented in the United States.
2257752. Similarly, the use of sulfurized oleic acid triethanolamine salt in a top cylinder lubricant for fuel addition is patented in US Patent No. 1990365.
has been disclosed. Summary It is already known that engine friction can be reduced by adding small amounts of certain amine salts of sulfurized fatty acids to engine lubricating oils. DESCRIPTION OF PREFERRED EMBODIMENTS A preferred embodiment of the present invention is a formulation of a lubricating oil for the crank chamber of a meat combustion engine to which an oil-soluble sulfurized tertiary alkyl primary amine salt of oleate is added in an amount necessary for reducing friction. The number of carbon atoms in the tertiary alkyl group in this case is about 12 to 30, and the use of this lubricating oil in the crankcase improves the fuel economy of the engine. The amine salt can be prepared by mixing 1 mole of sulfurized fatty acid with about 1 mole of tertiary alkyl primary amine. For example, from about 0.9 per equivalent of sulfurized fatty acid
Use 1.3 equivalents of amine. It is preferred to use a slight excess of stoichiometric amount of amine in order to render the product basic. The preferred amount of amine is about 1.05 to 1.2 moles of amine per mole of sulfurized fatty acid. After mixing, the amine and sulfurized fatty acid are stirred until they become homogeneous.The temperature during this time is, for example, 50-100℃
It is desirable that it be warm by about ℃. Examples of tertiary alkyl primary amines: 1,1-dimethyldecylamine, 1,1-di-n-butyldocosylamine, 1,1-dimethyloctadecylamine, 1,1-dimethyltetradecylamine, 1,
1-dimethylicosylamine, 1-methyl-1
-ethyl-nonylamine, 1,1-dimethyloctacosylamine, and similar compounds. From the above example, the preferred amine structure is

[Formula]. where R ₁ is an alkyl group containing about 8 to 27 carbon atoms; R ₂ and R ₃ are selected from lower alkyl groups containing about 1 to 4 carbon atoms; In a most preferred embodiment, R ₁ is about 16 carbon atoms
Straight-chain or branched-chain alkyl groups with ~20 members,
R ₂ and R ₃ are methyl groups. This type of amine is commercially available. An example is Primene JMT®, available from Rohm and Haas. Sulfurized fatty acids are produced by heating a mixture of fatty acids and elemental sulfur. The mixture is heated in a closed container to about 50°C reflux temperature or slightly higher. Examples of fatty acids are dodecanoic acid, stearic acid, linoleic acid, dilinoleic acid and the like. Preferred fatty acids are oleic acid and fatty acid mixtures based on oleic acid, such as tall oil acid. The following example illustrates the preparation of an additive according to the invention. Example 1 122 g (0.36 equivalents) of Primene in the reaction vessel
Add JMT and add 100 g (0.32 equivalents) of sulfurized oleic acid (8.69% sulfur) while stirring. Stir the mixture at 80°C for 30 minutes to form the amine salt additive. Other additives of the present invention can be made using the general methods described above using _C12-30 tertiary aliphatic primary amines. This additive is added to the lubricating oil in the amount necessary to reduce friction in engines that operate with oil in the crankcase.
Effective concentrations are 0.05 to 3 weight percent. A more preferred range is 0.1 to 1.5 weight percent. From the above, it is proved that the present invention is extremely improved as a lubricating oil for a crank chamber. Accordingly, an aspect of the present invention is an improved motor oil composition formulated for the crankcase of an internal combustion engine, which improvement comprises adding the present additive to the crankcase oil in an amount necessary to reduce fuel consumption of the engine. It can be obtained by adding More preferred embodiments of such improved motor oils include ashless dispersants, zinc dialkyldithiophosphates, alkaline earth metal salts of petroleum sulfonic acids (eg, alkylbenzene sulfonic acids), and the like. The additive can also be used in mineral or synthetic oils whose viscosity is adjusted for use in the crankcases of internal combustion engines. The maximum viscosity of crank chamber lubricating oil is approximately 80SUS at 210〓. The additive according to the invention has the function of improving fuel economy by adding it to the lubricating oil composition for the crankcase of an internal combustion engine. Similar benefits per unit distance can be obtained with spark ignition and diesel engines. The viscosity of the crank chamber lubricating oil of the present invention is up to approximately
It is SAE40. This type of motor oil is sometimes SAE LOW40
Or, like SAE 5W30, it may be rated at both -18℃ and 100℃. The identity of the crankcase lubricant of the present invention can be confirmed because it usually contains zinc dihydrocarbyl dithiophosphate in addition to the above-mentioned additives. Furthermore, this crank chamber lubricant contains petroleum-based sulfonic acid calcium salt, paraffin-based hydrocarbon sulfonic acid calcium salt, petroleum-based sulfonic acid magnesium salt, paraffin-based hydrocarbon sulfonic acid magnesium salt, petroleum-based sulfonic acid barium salt,
Paraffinic hydrocarbon sulfonic acid barium salt,
Valium alkylaryl sulfonates, alkyl phenate sulfide calcium salts, alkyl phenate sulfide magnesium salts and similar compounds can be included. Mineral oils include those of suitable viscosity obtained by refining crude oil from the Gulf Coast, mid-continent, Pennsylvania, California, Alaska, and all other sources. Synthetic oils include hydrocarbon synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils also include liquid polymers of alpha-olefins of appropriate viscosity. Particularly useful are α-decene trimers, such as
It is a hydrogenated liquid oligomer of C ₆ to C ₁₂ α-olefins. Similarly, alkylbenzenes of appropriate viscosity, such as didodecylbenzene, can also be used. Useful synthetic esters include esters of monocarboxylic acids, polycarboxylic acids, monohydroxyalkanols, and polyols. Representative examples include didodecyl adipate, trimethylolpropane tripelargonate, pentaerythritol tetracaproate, and di-adipate.
(2-ethylhexyl), dilauryl sebacate,
and similar esters. Complex esters of monocarboxylic and dicarboxylic acids with mono- and polyhydroxyalkanols can also be used. Mixtures of mineral and synthetic oils are particularly effective. For example, a mixture of 10-25 weight percent hydrogenated α-decene trimer and 75-90 weight percent 150SUS (100〓) mineral oil makes an excellent lubricant. Similarly about 10
A mixture of ~25 weight percent di-(2-ethylhexyl) adipate and mineral oil of suitable viscosity makes an excellent lubricant. Mixtures of synthetic hydrocarbon oils and synthetic esters can also be used. Mixing mineral oils with synthetic oils provides low viscosity without increasing volatility, so low viscosity oils (e.g. SAE
This is particularly advantageous when preparing 5W20). A more preferred lubricant composition uses a combination of current additives and zinc dihydrocarbyldithiophosphate (ZDDP). Both zinc dialkyldithiophosphate and zinc dialkyldithiophosphate and alkyl-allyl mixture
ZDDP is also valid. Representative alkyl-type ZDDP includes isobutyl and isoamyl groups. Zinc dinonylphenyl dithiophosphate is a typical allylic ZDDP. ZDDP such that the zinc content is approximately 0.01-0.5 weight percent
Good results can be obtained using . A preferred concentration is one that provides about 0.05 to 0.3 weight percent zinc. Other additives used in lubricating oil compositions include alkaline earth metal petroleum sulfonates or alkaline earth metal alkylaryl sulfonates. Examples of these include calcium petroleum sulfonate, magnesium petroleum sulfonate, barium alkylaryl sulfonate, calcium alkylaryl sulfonate or magnesium alkylaryl sulfonate. Either neutral or slightly hyperalkaline sulfonates with alkaline numbers up to about 400 can be used effectively. These have an alkaline earth metal content of about 0.05~
More preferably from about 0.1 to 1.0 weight percent is used in an amount that amounts to 1.5 weight percent. The most preferred lubricating oil composition embodiments include petroleum calcium sulfonates or alkylaryl (eg, alkylbenzene) sulfonates. The viscosity index improver includes polyalkyl methacrylate type or ethylene-propylene copolymer type. Similarly, styrene-diene modifiers or styrene-acrylic acid copolymers can be used. Sulfur phosphated alkaline earth metal salts of polyisobutylene are also effective. The most preferred crankcase oils also include ashless dispersants such as succinimides of polyolefin substituted succiamides and polyethylene polyamines such as tetraethylene pentamine. As the succinic acid substituted polyolefin, a polyisobutylene group having a molecular weight of about 800 to 5,000 is preferred. These ashless dispersants are more fully described in US Pat. No. 3,172,892 and US Pat. No. 3,219,666, along with the patents cited by reference. Other useful types of ashless dispersants include polyolefin succinates of monohydric and polyhydric alcohols having from 1 to about 40 carbon atoms. These dispersants are described in US Pat. No. 3,381,022 and US Pat. No. 3,522,179. Esters and amides of polyolefin-substituted succinic acids with alkanols, amines, or aminoalkanols are useful ashless dispersants. These dispersants are described in US Pat. No. 3,381,022 and US Pat. No. 3,522,179. Also alkanol, amine and/or
Ester and amide mixtures of polyolefin-substituted succinic acids prepared with aminoalkanols also belong to a useful class of ashless dispersants. Succinamide, imide and/or ester type ashless dispersants can be boronated by reaction with boron compounds such as boric acid. Similarly, succinic amides, imides and/or esters can be oxyalkylated by reaction with alkylene oxides such as ethylene oxide or propylene oxide. Other useful ashless dispersants include polyolefin substituted phenols, formaldehyde and Mannitz condensation reaction products such as polyethylene polyamines. Polyolefin inphenol has a molecular weight of about 800
Polyisobutylene substituted phenols with 5000 polyisobutylene groups are preferred. The polyethylene polyamine is preferably tetraethylenepentamine. Such Mannitzg reaction ashless dispersants are described in detail in the following patents: U.S. Pat.
3368972; US Patent 3413347; US Patent 3442808;
US Patent 3448047; US Patent 3539633; US Patent
3591598; US Patent 3600372; US Patent 3634515;
US Patent 3697574; US Patent 3703536; US Patent
3704308; US Patent 3725480; US Patent 3726882;
US Patent 3736357; US Patent 3751365; US Patent
3756953; US Patent 3792202; US Patent 3798165;
US Patent 3798247 and US Patent 3803039. The polyolefin-substituted succinimides, polyolefin-substituted succinic esters, and the dispersant produced by the Mannich reaction can be reacted with boric acid to form a borated dispersant with improved contact resistance. Excellent results are obtained when the additive of the present invention is used in combination with a phosphonic acid additive in a crankcase lubricating oil. Preferred phosphonic acid compounds include di-C _1-4
It is an alkyl C _12-36 alkyl phosphonic acid ester or an olefinic hydrocarbon phosphonic acid ester. These compounds have the structural formula: It is. In the formula, R ₃ is independently selected from aliphatic hydrocarbon groups having 12 to 36 carbon atoms, and R ₄ and R ₅ are lower alkyl groups having 1 to 4 carbon atoms. Typical examples of these additives include: Dimethyl octadecyl phosphonate Dimethyl octadecyl phosphonate Diethyl 2-ethyl decyl phosphonate Ethyl propyl 1-butyl hexadecyl phosphonate Methyl ethyl octadecyl phosphonate Methyl butyl eicosyl phosphonate Dimethyl hexatriacontyl phosphonate Phosphonic oxidation If other substances are added in combination, only a very small amount is sufficient. Effective range is approximately 0.005 to 0.75 for prescription oils
Weight percentage. A more preferred amount is about 0.05
~0.5 weight percent. In commercial practice, the preferred method of adding the present additives to lubricating oils is in the form of additive packages. These are dissolved in oil in a concentrated form so that when added to the base oil, an effective concentration of this and other known additives is obtained. For example, if the desired usage level is 0.2 weight percent and the final formulated oil is made up of 10 parts of the additive package and 90 parts of lubricating oil, the additive package will contain 2.0 weight percent of the additive. Such additive packages typically contain, in addition to the present additive, an ashless dispersant as described above. Additionally, the additive packaging includes phosphonic acid compound co-additives, zinc dialkyldithiophosphates, hydrocarbon sulfonic acid alkaline earth metal salts (either neutral or overbased), alkaline earth metal phenol salts (either neutral or overbased), and alkaline earth metal salts (either neutral or overbased). or similar sulfur-bridged phenol salts, antioxidants such as 4,4'-methylenebis-(2,6-di-ter-butylphenol) or N-octylphenyl-α-naphthylamine, phosphorus-sulfurized terpenes. or olefins such as phosphosulfurized polyisobutylene (molecular weight 1000) or alkaline earth metal salts of phosphosulfurized olefins, viscosity index improvers such as polyalkyl methacrylates,
Ethylene propylene copolymers, ethylene propylene non-conjugated diene terpolymers, styrene conjugated diene copolymers, styrene acrylate copolymers, and the like may also be included in the additive package or added separately to the oil. Next, the formulation of a typical additive package of the present invention will be illustrated. Parts are weights. Γ Sulfurized oleate of Primene JMT 1.2-12 parts Γ Succinimide of polyisobutenyl (molecular weight 950) of tetraethylenepentamine
2.9-120 parts Γ Zinc dialkyldithiophosphate (10% Zn)
6.0 to 24 parts Γ Calcium alkylbenzenesulfonate (TBN300) 13.0 to 60 parts Γ Dimethyl octadecyl phosphonate
1.2 to 12 parts Γ Acryloid 70260.0 to 180 parts Γ Neutral 100SUS mineral oil 5.0 to 50 parts (Note 1 Registered trademark given to polymethacrylate modifier by Rohm and Haas) The antifriction additive of the present invention can be used as a fuel component. is also valid. Fuel injected or introduced into the combustion chamber wets the cylinder walls. Fuel containing small amounts of this additive reduces the friction caused by piston rings sliding against the cylinder wall. This additive can be used in both diesel engine oil and gasoline used to operate internal combustion engines.
Fuels containing about 0.001 to 0.25 weight percent N-hydroxymethylhydrocarbyl succinimide can be used. The fuel according to the invention can be mixed with any additives commonly used in such fuels. In the case of gasoline, dyes, antioxidants, detergents, anti-nox agents (e.g. tetraethyl lead, methylcyclopentadienyl manganese tricarbonyl, rare earth chelating agents, methyl-tert-butyl ether and similar substances) may be mixed. can. In the case of diesel fuel, pour point depressants, detergents, ignition enhancers (eg hexyl nitrate) and the like can be added to the composition. Experiments were also conducted to prove the friction reduction effect of the present invention. One test was conducted with a four-ball tester. Three balls formed a fixed triangle, and the fourth ball was pressurized to the center of the triangle with a load of 20 kg at 1200 rpm. These balls are immersed in test oil, and the frictional torque transmitted from the rotating balls to the fixed balls is measured at the start of the test and again 3 hours later. The test was conducted with a reference oil and this same oil with 1% test additive. The percentage reduction in torque transmitted is the criterion for determining the friction reduction effect of the test additive. The second test was conducted in a low-velocity friction tester (LVFA), which presses a flat plate against an annular body. The flat plate and the annular body rotate on a common axis. The contact surface between the flat plate and the annular body is immersed in the test oil. The torque transmitted from the rotating flat plate to the stationary ring is measured first (static friction) and then after the flat plate has rotated (dynamic friction). The test is first carried out on a reference oil and then on the same oil with 1% of the additive to be tested. The criterion is determined by the reduction rate of both static friction and dynamic friction. Next the test results are sulfurized oleic acid Primene JMT
The salt is due to: Four Ball Test Friction Reduction % Initial Final 4.4 4.7 LVFA Test Friction Reduction % Static Friction Kinetic Friction 18.6 12.9 These results demonstrate that the test additives significantly reduce the friction between sliding metal surfaces. are doing.

Claims (1)

[Scope of Claims] 1. A lubricating oil formulated for the crank chamber of an internal combustion engine contains an oil-soluble tertiary alkyl primary amine salt of sulfurized oleic acid in an amount necessary for reducing friction, and the tertiary alkyl group is carbon-based. A lubricating oil having about 12 to 30 atoms, which improves the fuel economy of an engine operating using the oil in a crank chamber. 2 The tertiary alkyl primary amine has the following structure: (wherein R ₁ is an alkyl group having about 8 to 27 carbon atoms, and R ₂ and R ₃ are selected from lower alkyl groups having 1 to 4 carbon atoms) Top lubricant. 3. The lubricating oil according to item 2 above, wherein R ₁ in the structural formula is an alkyl group containing about 16 to 20 carbon atoms, and R ₂ and R ₃ are methyl groups.