JP5829965B2 - Succinimide compound, lubricating oil additive and lubricating oil composition - Google Patents

Description

  The present invention relates to a novel succinimide compound, and a lubricating oil additive and lubricating oil composition containing the compound.

  A succinimide compound is used as an ashless dispersant that disperses an insoluble matter to be generated in oil in the field of lubricating oil for internal combustion engines such as gasoline engine oil and diesel engine oil. On the other hand, succinimide compounds are used as friction modifiers for increasing frictional force in the field of drive system lubricants such as automatic transmissions.

  As a conventional succinimide compound, a succinimide compound obtained by reaction of a succinic anhydride substituted with a high molecular weight alkenyl or alkyl group and a polyalkylene polyamine is known (Patent Document 1 below). Moreover, the method of making a maleimide compound and a silicon enolate react is known as a manufacturing method of substituted succinimide (refer the following patent document 4).

JP-A-2005-146148 Japanese Patent Laid-Open No. 10-265793 JP-A-10-219269 Japanese Patent Laid-Open No. 2007-238524

  The present invention relates to a novel succinimide compound useful for applications such as an ashless dispersant in a lubricating oil for internal combustion engines, a friction modifier in a drive system lubricating oil, and a lubricating oil additive and a lubricating oil composition containing the compound. The purpose is to provide.

［式（１）中、Ｒ^１は数平均分子量５００以上５０００未満のアルキル基又は数平均分子量５００以上５０００未満のアルケニル基を示し、ｎは１〜３の整数を示す。］ In order to solve the above problems, the present invention provides a succinimide compound represented by the following general formula (1).

[In Formula (1), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000, and n represents an integer of 1 to 3. ]

［式（２）中、Ｒ^１は数平均分子量５００以上５０００未満のアルキル基又は数平均分子量５００以上５０００未満のアルケニル基を示す。］

［式（３）中、ｎは１〜３の整数を示す。］ Moreover, this invention provides the succinimide compound obtained by reaction with the compound represented by the following general formula (2), and the compound represented by the following general formula (3).

[In Formula (2), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000. ]

[In formula (3), n shows the integer of 1-3. ]

  Since the succinimide compound of the present invention has very superior characteristics compared to conventional succinimide compounds, it is suitable for use in ashless dispersants in internal combustion engine lubricants, friction modifiers in drive device lubricants, etc. Useful for applications.

  For example, recently, drive system lubricants are required to have a higher coefficient of friction than conventional ones in order to efficiently convert the friction force inside the automatic transmission into drive force from the viewpoint of improving fuel efficiency. However, when a conventional succinimide compound as described in Patent Documents 1 to 3 above is used, a sufficient effect of improving friction characteristics cannot be obtained. In addition, in the case of the conventional succinimide compound, the cause is that the succinimide compound itself has an insufficient effect of improving the friction characteristics, and if the amount of succinimide is increased, the adsorptivity to the metal surface is increased. May change, and the balance of other additives may be lost, resulting in deterioration of friction characteristics.

  On the other hand, the succinimide compound of the present invention is superior in the effect of improving the friction characteristics as compared with the conventional succinimide compound, so that the frictional force inside the automatic transmission is efficiently converted to the driving force. A high coefficient of friction can be achieved, and fuel efficiency can be improved.

  The present invention also provides a lubricating oil additive containing the succinimide compound of the present invention.

  The present invention also provides a lubricating oil composition comprising a lubricating base oil and the succinimide compound of the present invention.

  Moreover, this invention provides the lubricating oil composition for continuously variable transmissions containing lubricating base oil and the said succinimide compound of this invention.

  The lubricating oil composition of the present invention preferably further contains a phosphorus compound.

  According to the present invention, a novel succinimide compound useful for applications such as an ashless dispersant in an internal combustion engine lubricating oil, a friction modifier in a drive system lubricating oil, and a lubricating oil additive and lubricating oil containing the compound It becomes possible to provide a composition.

1 is an IR chart of a succinimide compound obtained in Example 1. FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

[First Embodiment; Succinimide Compound]
The succinimide compound according to the first embodiment of the present invention has a structure represented by the following formula (1).

R ¹ in the general formula (1) is preferably a polybutenyl group or a polyisobutenyl group. The number average molecular weight is 500 or more and less than 5000, preferably 700 to 4000, more preferably 800 to 3500.

  Moreover, n in General formula (1) is an integer of 1-3, Preferably it is an integer of 1-2, More preferably, it is 1. When n exceeds the upper limit, the solubility in the base oil tends to decrease.

［式（４）中、Ｒ^１は数平均分子量５００以上５０００未満のアルキル基又は数平均分子量５００以上５０００未満のアルケニル基を示す。］ Preferable examples of the succinimide compound represented by the general formula (1) include the following compounds.

[In Formula (4), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000. ]

  The succinimide compound represented by the general formula (1) may be used as it is without being boronated (that is, as a non-borated succinimide compound), or may be used as a boronated succinimide compound. Further, a boronated succinimide compound and a non-borated succinimide compound may be used in combination.

  The boronated succinimide compound can be obtained by reacting a boron-containing compound with a succinimide compound represented by the formula (1) at a temperature of usually 50 to 250 ° C, preferably 100 to 200 ° C. it can. Examples of the boron-containing compound include boron oxide, boron halide, boric acid, boric anhydride and boric acid ester. These boron-containing compounds may be used alone or in combination of two or more.

［式（２）中、Ｒ^１は数平均分子量５００以上５０００未満のアルキル基又は数平均分子量５００以上５０００未満のアルケニル基を示す。］

［式（３）中、ｎは１〜３の整数を示す。］ [Second Embodiment: Succinimide Compound]
The succinimide compound according to the second embodiment of the present invention is a succinimide compound obtained by a reaction between a compound represented by the following general formula (2) and a compound represented by the following general formula (3). is there.

[In Formula (2), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000. ]

[In formula (3), n shows the integer of 1-3. ]

R ¹ in the general formula (2) and n in the general formula (3) each have the same definition as R ^{1 and} n in the general formula (1). These preferable modes are also the same as those in the case of the general formula (1), and redundant description is omitted here.

Specific examples of the compound represented by the general formula (3) include 1,3-bis (3-aminopropyl) tetramethyldisiloxane represented by the following formula (5).

［式（６）中、Ｒ^１は数平均分子量５００以上５０００未満のアルキル基又は数平均分子量５００以上５０００未満のアルケニル基を示し、ｎは１〜３の整数を示す。］ In the reaction of the compound represented by the general formula (2) and the compound represented by the general formula (3), the succinimide compound represented by the general formula (1) is usually obtained as a main product. . Moreover, since there are two reaction sites of the compound represented by the general formula (3), 1 equivalent of the compound represented by the general formula (3) in the reaction product depending on the charging ratio (molar ratio) of the raw material compounds There may be a by-product represented by the following general formula (6) in which 2 equivalents of the compound represented by the general formula (2) are reacted. In this embodiment, the above-mentioned by-product may be removed from the reaction product, and only the succinimide compound represented by the general formula (1) may be used as a lubricating oil additive, or the general formula (1 A mixture of the succinimide compound represented by (2) and the above-mentioned by-product may be used as a lubricating oil additive.

[In Formula (6), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000, and n represents an integer of 1 to 3. ]

  Moreover, the succinimide represented by the general formula (1) in the reaction product is appropriately selected by appropriately selecting the charging ratio of the compound represented by the general formula (2) and the compound represented by the general formula (3). It is possible to adjust the proportion of the compound. From the point that the succinimide compound represented by the general formula (1) can be obtained more reliably, the charging ratio of both is the general formula (3) with respect to 1 mol of the compound represented by the general formula (2). Is preferably 1 to 2 mol, more preferably 1 to 1.8 mol, still more preferably 1.1 to 1.6 mol, and particularly preferably 1.2 to 1.5 mol.

The reaction conditions for the compound represented by the general formula (2) and the compound represented by the general formula (3) are not particularly limited, but the reaction temperature is 145 to 180 ° C, preferably 155 to 175 ° C, and the reaction time. Is 6-12, preferably 8-10 hours.
A reaction solvent can be used if necessary, and the solvent is preferably a solvent that dissolves the compound represented by the general formula (5) and the compound represented by the general formula (6). Examples thereof include ethanol, toluene, and xylenes.

  The succinimide compound according to this embodiment may be used as it is without being boronated (that is, as a non-borated succinimide compound) or may be used as a boronated succinimide compound. Further, a boronated succinimide compound and a non-borated succinimide compound may be used in combination.

  The boronated succinimide compound can be obtained by reacting a boron-containing compound with a succinimide compound represented by the formula (1) at a temperature of usually 50 to 250 ° C, preferably 100 to 200 ° C. it can. Examples of the boron-containing compound include boron oxide, boron halide, boric acid, boric anhydride and boric acid ester. These boron-containing compounds may be used alone or in combination of two or more.

[Third Embodiment: Lubricating Oil Additive]
The lubricating oil additive according to the present embodiment contains the succinimide compound according to the first embodiment or the second embodiment. The lubricating oil additive may be composed only of the succinimide compound according to the first embodiment or the second embodiment, and the succinimide compound according to the first embodiment or the second embodiment and other It may be a mixture with an additive. The lubricating oil additive may further contain a diluent for dissolving the additive.

  The succinimide compounds according to the first embodiment and the second embodiment are excellent in compatibility with various additives used in the lubricating oil field. Therefore, when the lubricating oil additive according to the present embodiment is a mixture of the succinimide compound according to the first embodiment or the second embodiment and other additives, the types of other additives used in combination are particularly The type of the other additive used in combination with the succinimide compound according to the first embodiment or the second embodiment and the blending amount of both are appropriately selected according to the use and purpose of the lubricant additive. be able to. Specific examples of other additives used in combination will be described later.

[Fourth Embodiment: Lubricating Oil Composition]
The lubricating oil composition according to the fourth embodiment of the present invention contains a lubricating base oil and the succinimide compound according to the first embodiment or the second embodiment. In addition, the aspect containing the lubricating oil base oil and the lubricating oil additive which concerns on the said 3rd Embodiment is included by the said lubricating oil composition.

  The lubricating base oil is not particularly limited, and any of mineral oil and synthetic oil can be used. Various conventionally known oils can be used as the mineral oil, and examples thereof include paraffin-based mineral oil, intermediate-based mineral oil, and naphthene-based mineral oil. Specifically, light neutral oil, intermediate neutral oil, heavy neutral oil, bright stock, etc. by solvent refining or hydrogen refining can be mentioned. Alternatively, GTL base oil obtained by isomerizing wax may be used, and the effect increases as the degree of purification increases.

  As the synthetic oil, various conventionally known oils can be used. For example, poly α-olefin (including α-olefin copolymer), polybutene, polyol ester, dibasic acid ester, phosphate ester, polyphenyl ether, alkylbenzene, alkylnaphthalene, polyoxyalkylene glycol, neopentyl glycol, silicone Oil, trimethylolpropane, pentaerythritol, hindered ester and the like can be used.

  These lubricating base oils can be used alone or in combination of two or more, and may be used in combination of mineral oil and synthetic oil.

The kinematic viscosity of the lubricating base oil can be appropriately selected according to the use and purpose of the lubricating oil composition. For example, when using a lubricating oil composition according to the present embodiment as the drive system a lubricating oil, a kinematic viscosity at 100 ° C. of the lubricating base oil is preferably 1 to 30 mm ² / s, more preferably 2 to 20 mm ² / s More preferably, it is 3-10 mm < ² > / s. When the kinematic viscosity at 100 ° C. is in the above range, friction at sliding parts such as gear bearings and clutches of the automatic transmission can be sufficiently reduced and the low temperature characteristics are also good. On the other hand, if the kinematic viscosity at 100 ° C. exceeds 30 mm ² / s, the fuel efficiency deteriorates and the low-temperature viscosity tends to be too high. Further, if the kinematic viscosity at 100 ° C. is less than 1 mm ² / s, the lubrication performance is lowered such as an increase in wear amount in sliding parts such as gear bearings and clutches of the automatic transmission, and the evaporating property is increased, resulting in lubrication. Oil consumption may increase.

  Further,% CA of the lubricating base oil is preferably 20 or less, more preferably 10 or less, from the viewpoint of low temperature characteristics.

  In the lubricating oil composition according to the present embodiment, the content of the succinimide compound represented by the formula (1) is preferably 0.01 to 30% by mass from the viewpoint that the additive effect can be effectively exhibited. More preferably, it is 0.05-20 mass%, More preferably, it is 0.1-10 mass%.

  The lubricating oil composition according to the present embodiment may further contain additives other than the succinimide compound according to the first embodiment or the second embodiment, as necessary, for the purpose of further improving the performance. it can. Such additives include ashless dispersants and / or friction modifiers other than the succinimide compounds represented by formula (1), metal detergents, viscosity index improvers, extreme pressure additives, antioxidants, corrosion An inhibitor, an antifoamer, a coloring agent, etc. are mentioned. These additives can be used individually by 1 type or in combination of 2 or more types.

  Ashless dispersants and / or friction modifiers other than succinimide compounds according to the first embodiment or the second embodiment include fatty acid esters, fatty acid amides, phosphate esters, phosphite esters, thiophosphate esters, and the like. Solid lubricants such as phosphorus compounds, organomolybdenum compounds such as MoDTP, MoDTC, organozinc compounds such as ZnDTP, organoboron compounds such as alkyl mercaptoylborate, graphite, molybdenum disulfide, antimony sulfide, boron compounds, polytetrafluoroethylene, etc. System friction modifiers and the like. Among these, phosphorus compounds are preferable. The content of the ashless dispersant and / or the friction modifier is usually 0.1 to 10% by mass based on the total amount of the lubricating oil composition.

  Examples of the antioxidant include amine-based antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated-α-naphthylamine, 2,6-di-t-butyl-4-methylphenol, 4,4 ′. -Phenolic antioxidants such as -methylenebis (2,6-di-t-butylphenol). The content of the antioxidant is usually 0.05 to 5% by mass based on the total amount of the lubricating oil composition.

  Examples of metallic detergents include calcium sulfonate, magnesium sulfonate, barium sulfonate, calcium salicylate, magnesium salicylate, calcium phenate, barium phenate, and the like. It is usually 0.1 to 10% by mass based on the total amount of the oil composition.

  Examples of the viscosity index improver include polymethacrylates, polyisobutenes, ethylene-propylene copolymer systems, and styrene-butadiene hydrogenated copolymer systems. The content of the viscosity index improver is usually 0.5 to 35% by mass based on the total amount of the lubricating oil composition.

  The use of the lubricating oil composition according to the present embodiment is not particularly limited, and can be used in a wide range of fields such as a lubricating oil for internal combustion engines and a drive system lubricating oil. For example, since the lubricating oil composition according to the present embodiment contains a succinimide compound represented by the lubrication formula (1), it has a higher coefficient of static friction (high wet friction material) than a conventional succinimide compound. Torque capacity) and can be used as an automatic transmission oil or a continuously variable transmission oil. Further, it can be used as a lubricating oil for construction machines, agricultural machines, manual transmissions, two-wheeled gasoline engines, diesel engines, gas engines, shock absorber oils, etc., equipped with transmissions having wet clutches and wet brakes.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

Example 1 Synthesis of Succinimide Compound Ia
In a 2000 mL autoclave, 1.0 mol of polyisobutene (number average molecular weight 1000) and 1.0 mol of maleic anhydride are added, heated to 220 ° C. over 1.5 hours, and allowed to react for 4 hours after reaching 220 ° C. It was. After completion of the reaction, n-hexane was added to the obtained product and stirred, and the solution was filtered to remove insoluble matter. After removing n-hexane from the filtrate by atmospheric distillation, maleic anhydride was removed at 220 ° C. under reduced pressure to obtain maleated polyisobutene.
A synthesizer was assembled, 7.40 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was weighed into a 300 ml four-necked flask, and the system was purged with nitrogen. 30.0 g of maleated polyisobutene was weighed into a 200 ml eggplant flask, 80 ml of o-xylene was added and dissolved in a hot water bath, and placed in a dropping funnel portion. Moreover, 20 ml o-xylene was put into the 4-neck flask.
The temperature was raised to 145 ° C., and dropping was started at 300 rpm. Thereafter, the temperature was raised to 155 ° C. in 30 minutes, and the temperature was further raised to 165 ° C. over 1 hour, and dripping was completed in 3 hours. From the IR measurement, it was confirmed that the reaction was progressing, and the reaction was completed after 4 hours. The reaction solution was light yellow.
The product was distilled under reduced pressure using an evaporator. 35.8 g of product was obtained. By IR and GPC analysis, the obtained product is represented by the general formula (1), R ¹ is a polyisobutenyl group having a number average molecular weight of 1000, and n = 1 (hereinafter referred to as “succinic acid”). It was referred to as “imide compound Ia”). An IR chart of the product is shown in FIG.

[Example 2; Synthesis of succinimide compound Ib]
In a 2000 mL autoclave, 1.0 mol of polyisobutene (number average molecular weight 2300) and 1.0 mol of maleic anhydride are added, heated to 220 ° C. over 1.5 hours, and allowed to react for 4 hours after reaching 220 ° C. It was. After completion of the reaction, n-hexane was added to the obtained product and stirred, and the solution was filtered to remove insoluble matter. After removing n-hexane from the filtrate by atmospheric distillation, maleic anhydride was removed at 220 ° C. under reduced pressure to obtain maleated polyisobutene.
A synthesizer was assembled and 3.70 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was weighed into a 300 ml four-necked flask, and the system was purged with nitrogen. 30.0 g of maleated polyisobutene was weighed into a 200 ml eggplant flask, 80 ml of o-xylene was added and dissolved in a hot water bath, and placed in a dropping funnel portion. Moreover, 20 ml o-xylene was put into the 4-neck flask.
The temperature was raised to 145 ° C., and dropping was started at 300 rpm. Thereafter, the temperature was raised to 155 ° C. in 30 minutes, and the temperature was further raised to 165 ° C. over 1 hour, and dripping was completed in 3 hours. From the IR measurement, it was confirmed that the reaction was progressing, and the reaction was completed after 4 hours. The reaction solution was light yellow.
The product was distilled under reduced pressure using an evaporator. 32.4 g of product was obtained. By IR and GPC analysis, the obtained product is represented by the general formula (1), R ¹ is a polyisobutenyl group having a number average molecular weight of 2300, and n = 1 (hereinafter referred to as “succinic acid”). It was referred to as “imide compound Ib”).

[Comparative Example 1; Synthesis of Succinimide Compound II]
In a 2000 mL autoclave, 1.0 mol of polyisobutene (number average molecular weight 1000) and 1.0 mol of maleic anhydride are added, heated to 220 ° C. over 1.5 hours, and allowed to react for 4 hours after reaching 220 ° C. It was. After completion of the reaction, n-hexane was added to the obtained product and stirred, and the liquid was filtered to remove sludge. After removing n-hexane from the filtrate by atmospheric distillation, maleic anhydride was removed at 220 ° C. under reduced pressure to obtain maleated polyisobutene.
In a 2 L separable flask, 1.7 mol of diethylenetriamine and xylene were added. Next, it was made to react at 145-155 degreeC for 11 hours, dripping 0.17 mol of maleated polybutenes melt | dissolved in xylene. After completion of the reaction, the solvent was removed by atmospheric distillation, and residual diethylenetriamine was removed by distillation under reduced pressure to obtain succinimide compound II.

[Examples 3-8, Comparative Examples 2-4; Preparation and Evaluation Test of Lubricating Oil Composition]
In Examples 3 to 8, mineral oil of 10 SAE fractions (100 ° C. kinematic viscosity 4.1 mm ² / s) as a lubricating base oil, succinimide compound Ia or Ib, and additions shown below A lubricating oil composition having the composition shown in Table 1 was prepared using the agent.
In Comparative Examples 2 and 3, a mineral oil of SAE 10 fraction (100 ° C. kinematic viscosity 4.1 mm ² / s) as a lubricant base oil, succinimide compound II, and the additives shown below were used, respectively. A lubricating oil composition having the composition shown in 2 was prepared. Further, in Comparative Example 4, a lubricating oil having the composition shown in Table 2 using a mineral oil of SAE 10 fraction (100 ° C. kinematic viscosity 4.1 mm ² / s) as a lubricating base oil and the additives shown below. A composition was prepared.
Polymethacrylate: average molecular weight 20,000
Amine-based antioxidant: diphenylamine tricresyl phosphanote calcium sulfonate: 300TBN
Ashless oil-based agent: glycerol monooleate

  Next, about the lubricating oil composition of Examples 3-8 and Comparative Examples 2-4, the friction coefficient between metals was evaluated using the LFW-1 test machine. The test conditions were a surface pressure of 0.8 GPa, a sliding speed of 0.2 m / s, a test temperature of 80 ° C., a test time of 1 hour, and an average friction coefficient obtained by averaging the friction coefficients within the time. The obtained result is shown to Tables 1-2.

  The succinimide compound, lubricating oil additive and lubricating oil composition of the present invention can be used in a wide range of lubricating oil fields, and are particularly suitable as automatic transmission oils and continuously variable transmission oils that require a high coefficient of static friction. is there.

Claims (5)

A succinimide compound represented by the following general formula (1).

[In Formula (1), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000, and n represents an integer of 1 to 3. ] A succinimide compound obtained by a reaction between a compound represented by the following general formula (2) and a compound represented by the following general formula (3).

[In Formula (2), R ¹ represents an alkyl group having a number average molecular weight of 500 or more and less than 5000 or an alkenyl group having a number average molecular weight of 500 or more and less than 5000. ]

[In formula (3), n shows the integer of 1-3. ]   A lubricating oil additive comprising the succinimide compound according to claim 1.   A lubricating oil composition comprising a lubricating base oil and the succinimide compound according to claim 1.   A lubricating oil composition for a continuously variable transmission, comprising a lubricating base oil and the succinimide compound according to claim 1.

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