JPH0142997B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to lubricating oil additives, and more particularly to lubricating oil additives that are added to internal combustion engine crankcases to provide friction reduction in a running engine. In order to save energy, automobiles are currently being designed to have improved gasoline mileage compared to conventional ones. Achieving this is extremely urgent in the United States, even in light of regulations that force automobile manufacturers to meet specified gas mileage ratings. These rules are meant to conserve oil. To achieve the required mileage, new cars are being made smaller and much lighter. However, there are limits to this approach, beyond which the car will become unsuitable for a standard family. Another way to improve fuel mileage is to reduce engine friction. The present invention relates to this latter approach. The present invention takes advantage of the discovery that incorporation of oil-soluble C16-24 aliphatic hydrocarbyl succinimides or succiniamides into lubricating oils provides a friction-reducing effect. It is necessary that the aliphatic hydrocarbon groups be derived from linear α-olefins which have been isomerized to form a mixture of internal olefins. The additive can also be used in engine fuel. Preferred embodiments of the invention include a friction-reducing amount of an additive selected from the group consisting of oil-soluble succinimides and succinamides and mixtures thereof containing aliphatic hydrocarbon substituents having about 16 to 24 carbon atoms. A lubricating oil composition. The aliphatic substituent on the succin group can be any aliphatic hydrocarbon group having about 16 to 24 carbon atoms;
Includes alkyl, alkenyl and polyunsaturated hydrocarbon groups. The aliphatic hydrocarbon group is attached to the secondary carbon atom of the succinic group. These compounds are
formula:

[expression] or

【formula】 [In the above formula, Z is a group:

[Formula] (wherein R ₁ and R ₂ are independently selected from the group consisting of branched and straight-chain hydrocarbon groups such that the total number of carbon atoms contained in R ₁ and R ₂ is about 15 to 23. (selected). Examples of these additives are:
It is as follows. 1-ethyltetradecylsuccinimide 1-methylpentadecenylsuccinimide 1,2-dimethyloctadecenylsuccinamide 1-methyleicosylsuccinimide In a highly preferred embodiment, R ₁ and R ₂ are linear aliphatic hydrocarbon groups. It is. These additives are
Excellent solubility in lubricating oil. Examples are as follows. 1-Methylpentadecylsuccinimide 1-Propyltridecenylsuccinimide 1-Pentyltridecenylsuccinimide The additive of the present invention isomerizes a linear alpha-orphin having about 16 to 24 carbon atoms to form a mixture of internal orphins. and reacting this mixture of internal orphins with maleic acid, anhydride, or ester to form an intermediate product, and reacting this intermediate product with ammonia to form an amide, imide, or mixture thereof. It is necessary to prepare the mixture by diluting it. Additives made from isomerized linear alpha-olefins have much better oil solubility than those made from just linear alpha-olefins. Isomerization of linear α-olefins can be carried out using conventional methods. One suitable method is the linear α
-Heating the olefin with an acidic catalyst. A particularly useful acidic catalyst is a sulfonated styrene-divinylbenzene copolymer. Catalysts of this type are commercially available and are conventionally used as cation exchange resins. In this method, they are used in their acid form. Typical resins are Amberlyst15, XN-1005 and XN-1010 sold by Rohm and Haas Company.
(registered trademark). The use of this type of resin for the isomerization of linear alpha-olefins is described in U.S. Pat. No. 4,108,889, which is incorporated by reference herein.
It is stated in the specification of the No. The following example illustrates the method of manufacturing the additive. Example 1 185 g of octadecenyl succinic anhydride was placed in a reaction vessel. Heat this to 60℃ to melt it,
_NH3 was injected. As the exothermic reaction progresses, the temperature increases
The temperature rose to 160℃. After the reaction was complete, the product was heated to 180°C under a 29 inch Hg vacuum to remove volatiles. The product was octadecenyl succinimide. Example 2 1000 g of linear α-octadecene was placed in a reaction vessel. Add to this 187g of Amberlyst15 (5% water content)
added. The mixture was stirred under nitrogen and heated to 120 °C for 3
heated for an hour. The isomerized product contained 3.6% by weight of olefin dimer with the remainder being _C18 internal olefin. The product was separated from the resin. 504 g of the above isomerized C ₁₈ olefin and 300 ml of heptane were placed in a second reaction vessel. Heptane was distilled off under reduced pressure to remove water. then 2.4
g of tri(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene stabilizer was added. The mixture was heated to 225°C under nitrogen. Next, 160 g of molten maleic anhydride was gradually added over 2.5 hours. Stir the mixture for an additional 2 hours at 225°C,
And then, while keeping the reaction mixture at 200℃, 762
Unreacted maleic anhydride was distilled off under reduced pressure of mm (30 inches) Hg. The product is mainly secondary
It was _C18 alkylene succinic anhydride. The above isomerized octadecenyl succinic anhydride
532.5g was placed in another reactor. This was done under nitrogen at 165
°C, then inject ammonia to bring the temperature up to
The temperature was raised to 180°C. Ammonia injection was continued until the fever stopped. The mixture is heated to 170° C. under reduced pressure to remove water and isomerized octadecenyl succinimide (which satisfies the definition of Z in the above formula)
I got it. Example 3 1005 g of linear α-eicosene and 187 g of Amberlyst 15 (water content 5%) were placed in a reaction vessel. The mixture was heated to 110-125°C under nitrogen for 6 hours. The product was internally unsaturated eicosene containing 3.3% eicosene dimer. 560g of the above isomerized eicosene and 200ml of heptane
was placed in a separate reaction vessel. The heptane was distilled off to dry the eicosene. At 140°C, 3.1 g of tri-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene stabilizer was added and the mixture was heated to 210°C. The addition of 156.8 g of maleic anhydride was carried out at about 225° C. over a period of 2.5 hours. Thereafter, unreacted maleic anhydride was distilled off at 210° C. under reduced pressure, and isomerized eicosenyl succinic anhydride remained. 570g of the above isomerized eicosenyl succinic anhydride
was placed in another reactor. Heat this to 160℃,
Ammonia injection was started. The temperature rose to 175°C. Inject ammonia until the temperature drops.
Continued at 175°C. Then gradually 762mm (30 inches)
Water and ammonia were distilled off by reducing the pressure to Hg.
Additional injections of ammonia were made to completely eliminate residual anhydride. When no further reaction occurs, the ammonia is removed by stripping at 170° C. under a 762 mm (30 in.) Hg vacuum and the isomerized eicosenyl succinimide (which satisfies the definition of Z in the formula above) is removed. ) was obtained. Example 4 Linear α-C ₁₆ to C ₁₈ α-olefin mixture 1100g
was placed in the reaction vessel. This olefin mixture was isomerized according to the procedure of Example 3. 485 g (2 moles) of the above isomerized olefin was placed in a separate container. 762mm (30 inches) under Hg vacuum
This was heated to 100°C to remove water. Next, 2.4 g of tri-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitylene was added thereto.
The mixture was heated to 225° C. under nitrogen and then 152 g of molten maleic anhydride was added over a period of 3 hours.
The mixture was stirred at 225 °C for 30 min, and maleic anhydride 50
Added additional g. This mixture was stirred at 225°C for 30 minutes, and then 762 mm of unreacted maleic anhydride was removed.
(30 inches) Hg was distilled off at 200°C under reduced pressure. Isomerized _C16 - _C18 alkenyl succinic anhydride above
598 g was placed in another reaction vessel. Ammonia injection was started at 140°C and the temperature rose to 145°C. Ammonia injection was continued at 130°C until the point where no more ammonia was adsorbed. Then mix the mixture to 180
C. and distilled off water and ammonia to obtain isomerized _C.sub.16 to _C.sub.18 alkenyl succinimide (which satisfies the definition of Z in the above formula). These additives are added to the oil in amounts to reduce friction in engines running on the lubricating oil in the crankcase. Effective concentrations are approximately 0.05 to 3
Weight%. A more preferred range is about 0.1 to 1.0% by weight. From the above description, it can be seen that the present invention provides an improved crankcase lubricant. Accordingly, one aspect of the invention is characterized in that it contains a friction-reducing additive as described herein in an amount sufficient to reduce fuel consumption of the engine.
An improved motor oil composition formulated for crankcase lubricating oil in internal combustion engines. In a highly preferred embodiment, this type of improved motor oil also contains an ashless dispersant and an alkaline earth metal salt of a petroleum sulfonic acid or an alkaryl sulfonic acid (eg, an alkylbenzene sulfonic acid). These additives can be used in mineral or synthetic oils of a viscosity suitable for use in the crankcase of an internal combustion engine. Crankcase lubricants have a viscosity of up to approximately 80 SUS at 100°C (210°C). Mineral oils include those of suitable viscosities obtained by refining crude oil from all sources, including Gulf Coast, Mid-Continent, Pennsylvania, California, Alaska, and the like. For mineral oil processing,
A variety of standard purification procedures can be used. Synthetic oils include both hydrocarbon synthetic oils and synthetic esters. Useful synthetic hydrocarbon oils include liquid polymers of alpha-olefins of moderate viscosity. Particularly useful are hydrogenated liquid oligomers of C ₆ -C ₁₂ α-olefins, such as α-decene trimers. Similarly, alkylbenzenes of suitable viscosity, such as didodecylbenzene, can also be used. Useful synthetic esters include esters of both monocarboxylic and polycarboxylic acids and monohydroxyalkanols and polyols. Typical examples are didodecyl adipate, trimethylolpropane tripelargonate, pentaerythritol tetracaproate, di(2-
ethylhexyl) adipate, dilauryl sebacate, etc. Moreover, complex esters produced from mono- and dicarboxylic acids and mono- and polyhydroxy alkanols can also be used. Mixtures of mineral and synthetic oils are particularly useful. For example, 5-25% by weight of hydrogenated α-decene trimer and mineral oil 75-150 SUS at 38°C (100〓) viscosity.
A mixture with 95% by weight makes an excellent lubricant.
Similarly, a mixture of about 5 to 25 weight percent di(2-ethylhexyl) adipate and mineral oil of the appropriate viscosity makes an excellent lubricating oil. Also, mixtures of synthetic hydrocarbon oils and synthetic esters can be used. Mixtures of mineral oils and synthetic oils are particularly useful in producing low viscosity oils (eg SAE5W20) as they can reduce viscosity without creating excessive volatility. More preferred lubricating oil compositions contain zinc dihydrocarbyl dithiophosphate (ZDDP) along with the additives of the present invention. Both zinc dialkyldithiophosphates and zinc dialkyldithiophosphates as well as alkyl-aryl mixed dithiophosphates can be used. An example of an alkyl type ZDDP is one in which the hydrocarbyl group is a mixture of isobutyl and isoamyl alkyl groups. G-(nonylphenyl)-
Zinc dithiophosphate is an example of an aryl ZDDP. Good results are obtained using sufficient zinc dihydrocarbyldithiophosphate to provide about 0.01 to 0.5 weight percent zinc. The desired concentration is approximately 0.05 zinc
~0.3% by weight. Other additives used in oil compositions are alkaline earth metal petroleum sulfonates or alkaline earth metal carkaryl sulfonates. Examples of these are calcium petroleum sulfonate, magnesium petroleum sulfonate, barium alkaryl sulfonate, calcium alkaryl sulfonate or magnesium alkaryl sulfonate. Both neutral sulfonates and overbased sulfonates having up to about 400 bases can be used advantageously. These are approximately 0.05-1.5% by weight,
More preferably, the amount used is about 0.1 to 1.0% by weight of alkaline earth metal. Viscosity index features such as polyalkyl methacrylate type or ethylene-propylene copolymer type can be included. Similarly, styrene
Diene viscosity index improvers can also be used. Alkaline earth metal salts of phosphosulfurized polyisobutylene are useful. Preferred crankcase oils also contain ashless dispersants such as the succinimide of polyolefins succinamide and polyethylene polyamines, such as tetraethylene pentamine. Preferably, the polyolefin succinic substituent is a polyisobutene group having a molecular weight of about 800-5000. No. 3,219,666, which is incorporated herein by reference for ashless dispersants of this type.
More details are given in the specification. Other useful ashless dispersants include polyolefins.
Includes Mannitz condensation products of substituted phenols, formaldehyde and polyethylene polyamines. As the polyolefin phenol, a polyisobutylene-substituted phenol in which the molecular weight of the polyisobutylene group is about 800 to 5000 is preferred. A preferred polyethylene polyamine is atraethylenepentamine. For this type of Mannitz ashless dispersant, U.S. Pat.
No. 3442808, No. 3448047, No. 3539633,
No. 3591598, No. 3600372, No. 3634515, No.
No. 3697541, No. 3703536, No. 3704308, No.
No. 3725480, No. 3726882, No. 3736357, No.
No. 3751365, No. 3756953, No. 3793202, No.
It is described in more detail in the specifications of No. 3798165, No. 3798247, and No. 3803039. The friction reducing additives of the present invention are also useful in fuel compositions. Fuel injected or introduced into the combustion chamber wets the cylinder walls. Fuels containing small amounts of this additive reduce the friction caused by the piston rings sliding against the cylinder wall. These additives can be used in both diesel fuel and gasoline used to operate internal combustion engines. Fuels containing about 0.001 to 0.25 weight percent of friction reducing additives can be used. Fuels used with the additives of the present invention can include any additives conventionally used in this type of fuel. In the case of gasoline, dyes, antioxidants, detergents, anti-knock agents (e.g., tetraethyl lead, methylcyclopentadienylmanganese tricarbonyl, rare earth metal chelates, methyl tert-
butyl ether, etc.). In the case of diesel fuel, it may contain a pour point depressant, a detergent, a combustion improver (for example, hexyl nitrate), and the like. Tests were conducted using a 1977 American car. These tests are simplified adaptations of the Federal EPA's urban cycle and are called the "Hot 505" cycle. This cycle consists of the first 5.8 km (3.8 miles) of the Federal EPA city cycle starting with a warmed engine instead of a cooled engine.
The car is filled with fully formulated SE grade oil in the crankcase and driven at approximately 88 km/hour (55 mph) for approximately 1 hour on a sea dynamometer to stabilize the oil temperature. The fuel economy of the base oil is then determined by running four consecutive "Hot 505" cycles. Average the results of 4 cycles. Half of the base oil is then drained from the crankcase and refilled with the same base oil containing double the dose of test additive. Next, drive the car approximately 88km/
(55 mph) for about an hour to allow the temperature to stabilize again. A second series of four consecutive "Hot 505" cycles is run to determine the initial fuel economy of the base oil containing the test additive. Then about 88
Km/hour (55 mph)
mile) run. Then 4 consecutive "Hottu 505"
A third series of cycles is run to determine fuel economy after approximately 500 miles of operation for oils containing the test additives. Next, drain the heat from the crankcase, fill it with flushing oil, run it for a short time with flushing oil, and then drain the oil. The crankcase is then filled with base oil, operated with it for a short period of time, and then drained. Next, fill the crankcase with base oil again. Drive at approximately 88 km/hour (55 mph) for approximately 1 hour to reach a stable temperature.
A fourth series of four consecutive "Hot 505" cycles is then run to determine fuel economy. This provides a second baseline and the tests performed with the friction reducing additive are bracketed between the two baseline tests. The following table shows the percentage improvement in fuel economy of base oils obtained using 1% by weight of friction reducing additive.

[Table] Alkenyl Succinimide The reduction in fuel consumption is small but significant.

Claims (1)

Claims: 1. (a) isomerizing the olefinic double bonds of a linear α-olefin or mixture thereof containing about 16 to 24 carbon atoms to obtain a mixture of internal olefins; (b) reacting a mixture of internal olefins with maleic acid, anhydride or ester to obtain an intermediate hydrocarbon-substituted succinic acid, anhydride or ester; and (c) reacting said intermediate with ammonia to produce an amide, A structure characterized in that it is produced by forming an imide or a mixture thereof: [Formula] or [Formula] [In the above formula, Z is the structure: [Formula] (wherein R ₁ and R ₂ are independently selected from the group consisting of straight-chain and branched hydrocarbon groups such that the total number of carbon atoms contained in R ₁ and R ₂ is about 15 to 23) An oil-soluble friction-reducing additive added to lubricating oil to reduce engine friction. 2. The oil-soluble friction-reducing additive according to claim 1, wherein the linear α-olefin is mainly α-hexadecene, α-octadecene, or α-eicosene.