JP5934658B2 - IMIDE-UREA COMPOUND AND PROCESS FOR PRODUCING THE SAME, GREASE THINNER, AND GREASE COMPOSITION - Google Patents

Description

  The present invention relates to an imide-urea compound and a method for producing the same, a thickener for grease, and a grease composition.

  As machine systems become more sophisticated, more powerful, more efficient, and smaller, the use environment of machine elements such as bearings and gears becomes severe, and the grease used in these needs to have higher heat resistance. It is supposed to be. For example, in an automobile, the engine room space is decreasing due to the demand for FF (front wheel drive) for the purpose of reducing the size and weight and the demand for expanding the living space in the vehicle. In order to reduce the engine room space, it is necessary to reduce the size and weight of each component in the engine room, and further reduction in size and weight is being promoted in the above-described electrical components and engine auxiliary machines. On the other hand, high performance and high output are also required for electrical components and engine accessories. However, output reduction due to miniaturization is inevitable, so for example, alternators and car air conditioner electromagnetic clutches compensate for the reduction in output by increasing the speed, but with this, the idler pulley is also increased in speed. And heat generation is promoted at the lubrication point. In addition, the engine room is being sealed in order to achieve quietness during engine operation, but in this case as well, the temperature increase in the engine room is promoted.

  Furthermore, double-row angular contact ball bearings were mainly used for compressor pulleys and car air conditioner electromagnetic clutch bearings. Recently, single-row bearings have been used to reduce the weight and cost of pulleys and electromagnetic clutches. Tend to use. In a single row ball bearing used under the same operating conditions as a double row angular contact ball bearing, the PV value (the product of the bearing surface pressure P and the sliding speed V) representing the limit of the load capacity of the bearing is increased. Due to its small space volume, it tends to be used under conditions where the amount of grease filled is small and the amount of heat generated by the grease is large.

  As described above, since the use conditions of the electrical parts and the engine accessory are becoming severer, the grease applied to these rolling bearings is required to be improved in durability particularly at high temperatures. Furthermore, in recent years, greases that are more inexpensive and excellent in cost performance have been desired.

  As conventional greases, Patent Documents 1 to 5 disclose grease compositions using urea-based thickeners. The heat resistant temperature of these urea greases is about 180 ° C., and fluorine greases are known as greases that can withstand higher temperatures. Fluorine grease is a grease composition containing perfluoropolyether as a base oil and ethylene tetrafluoride as a thickener, but it is very expensive because it uses a special chemically synthesized base oil. A cheaper heat resistant grease is required.

  Patent Documents 6 to 7 disclose grease compositions using an imide thickener as an example of grease having high heat resistance.

JP 2004-359809 A JP 2003-342593 A JP 2010-073320 A JP 2009-197162 A JP 2008-231310 A JP 54-113605 A Japanese Patent Laid-Open No. 57-109896

  An object of the present invention is to provide a novel imide-urea compound and a method for producing the same, and particularly to provide an imide-urea compound excellent in durability at high temperatures and a method for producing the same when used as a thickener for grease. It is to provide. Another object of the present invention is to provide a thickener for grease and a grease composition using the imide-urea compound.

［式中、Ｒ及びＸはそれぞれ１価の有機基を示す。］ The present invention provides an imide-urea compound represented by the following general formula (1).

[Wherein, R and X each represent a monovalent organic group. ]

［式中、Ｘ^１はモノイソシアネートからイソシアネート基を除いた残基を示し、Ｘ^２は２価の有機基を示し、Ｒ^１及びＲ^２は１価の有機基を示し、Ｒ^１及びＲ^２は同一でも異なっていてもよい。］ The imide-urea compound of the present invention preferably has a structure represented by the following general formula (2) or (3).

[Wherein, X ¹ represents a residue obtained by removing an isocyanate group from monoisocyanate, X ² represents a divalent organic group, R ¹ and R ² represent a monovalent organic group, and R ¹ and R ² May be the same or different. ]

［式中、Ｒ及びＸはそれぞれ１価の有機基を示す。］ The present invention also provides a nitrophthalic anhydride represented by the following general formula (6) by reacting a nitrophthalic anhydride represented by the following general formula (4) with a monoamine represented by the following general formula (5). A first step of obtaining a product imide derivative and obtaining an aminophthalic anhydride imide derivative represented by the following general formula (7) by hydrogenation reduction of the nitrophthalic anhydride,
A second step of reacting the aminophthalic anhydride imide derivative with an isocyanate represented by the following general formula (8) to obtain an imide-urea compound represented by the general formula (1): A method for producing a urea compound is provided.

[Wherein, R and X each represent a monovalent organic group. ]

  The present invention also provides a thickener for grease containing the imide-urea compound of the present invention.

  The present invention also provides a grease composition containing a lubricating base oil and the imide-urea compound of the present invention.

  In addition, according to the study by the present inventors, in the case of a grease composition using a urea-based thickener as disclosed in the above Patent Documents 1 to 7, depending on the use environment, such as when used at a high temperature. It was found that sufficient durability could not be obtained. In contrast, the present inventors have confirmed that the imide-urea compound, the thickener for grease and the grease composition of the present invention can exhibit sufficient durability even when used at high temperatures. doing.

  As described above, according to the present invention, it is possible to provide a novel imide-urea compound, particularly an imide-urea compound excellent in durability at high temperatures when used as a thickener for grease, and a method for producing the same. It becomes possible.

  Further, according to the present invention, it is possible to provide a thickener for grease and a grease composition that can exhibit sufficient durability even when used at high temperatures.

1 is an infrared absorption spectrum of the imide-urea compound obtained in Example 1. FIG.

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

［式中、Ｒ及びＸはそれぞれ１価の有機基を示す。］ [First Embodiment: Imide-Urea Compound]
The imide-urea compound according to the first embodiment of the present invention has a structure represented by the following general formula (1).

[Wherein, R and X each represent a monovalent organic group. ]

［式中、Ｘ^１は１価の有機基を示し、Ｘ^２は２価の有機基を示し、Ｒ^１及びＲ^２は１価の有機基を示し、Ｒ^１及びＲ^２は同一でも異なっていてもよい。］ Preferable examples of the imide-urea compound according to this embodiment include imide-urea compounds represented by the following general formula (2) or general formula (3). The imide-urea compound represented by the general formula (2) has one imide group and one urea group. Moreover, the imide-urea compound represented by General formula (3) has two imide groups, and has two urea groups.

[Wherein, X ¹ represents a monovalent organic group, X ² represents a divalent organic group, R ¹ and R ² represent a monovalent organic group, and R ¹ and R ² are the same or different. May be. ]

X ¹ is a monovalent residue obtained by removing one isocyanate group from monoisocyanate. Monoisocyanates are defined as compounds in which one isocyanate group is added to an aliphatic, aromatic hydrocarbon or heterocyclic compound, or derivatives thereof. Among the monoisocyanate monomers from which the structure X ¹ is derived, there are the following or a mixture thereof, but the invention is not limited to these.

  Examples of the aliphatic monoisocyanate include linear or branched aliphatic monoisocyanates, alicyclic monoisocyanates, or aromatic monoisocyanates, and hydrocarbon residues having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms. Linear or branched alkyl monoisocyanate, linear or branched alkenyl monoisocyanate, cycloalkyl monoisocyanate, alkylcycloalkyl monoisocyanate, aryl monoisocyanate, alkylaryl monoisocyanate, arylalkyl A monoisocyanate etc. are mentioned. Specific examples include hexyl monoisocyanate, heptyl monoisocyanate, octyl monoisocyanate, nonyl monoisocyanate, decyl monoisocyanate, undecyl monoisocyanate, dodecyl monoisocyanate, tridecyl monoisocyanate, tetradecyl monoisocyanate, pentadecyl monoisocyanate, hexadecyl. Linear or branched alkyl monoisocyanates such as monoisocyanate, heptadecyl monoisocyanate, octadecyl monoisocyanate, nonadecyl monoisocyanate, eicosyl monoisocyanate; cyclohexyl monoisocyanate; methylcyclohexyl monoisocyanate, dimethylcyclohexyl monoisocyanate, ethyl Cyclohexyl monoisocyanate, die Rucyclohexyl monoisocyanate, propylcyclohexyl monoisocyanate, isopropylcyclohexyl monoisocyanate, 1-methyl-3-propylcyclohexyl monoisocyanate, butylcyclohexyl monoisocyanate, amylcyclohexyl monoisocyanate, amylmethylcyclohexyl monoisocyanate, hexylcyclohexyl monoisocyanate, heptylcyclohexyl monoisocyanate Isocyanates, octyl cyclohexyl monoisocyanate, nonyl cyclohexyl monoisocyanate, decyl cyclohexyl monoisocyanate, undecyl cyclohexyl monoisocyanate, dodecyl cyclohexyl monoisocyanate, tridecyl cyclohexyl monoisocyanate, tetradecyl cyclohexyl Alkyl cycloalkyl monoisocyanates such as sil monoisocyanate; aryl monoisocyanates such as phenyl monoisocyanate and naphthyl monoisocyanate; toluyl monoisocyanate, ethylphenyl monoisocyanate, xylyl monoisocyanate, propylphenyl monoisocyanate, cumenyl monoisocyanate, methylnaphthyl monoisocyanate Examples thereof include alkyl aryl monoisocyanates such as isocyanate, ethyl naphthyl monoisocyanate, dimethyl naphthyl monoisocyanate and propyl naphthyl monoisocyanate; arylalkyl monoisocyanates such as benzyl monoisocyanate, methylbenzyl monoisocyanate and ethylbenzyl monoisocyanate.

As the monoisocyanate monomer which is the base of the X ¹ structure, a linear or branched aliphatic monoisocyanate is preferable from the viewpoint of lubricity and grease performance. Carbon number of linear or branched aliphatic monoisocyanate becomes like this. Preferably it is 4-20, More preferably, it is 8-20. The aliphatic monoisocyanate may be either a linear or branched saturated aliphatic monoisocyanate or an unsaturated aliphatic monoisocyanate. However, since the aliphatic monoisocyanate is excellent in oxidative stability, the linear or branched saturated aliphatic monoisocyanate. Isocyanates are preferred.

  From the viewpoint of heat resistance, alicyclic monoisocyanate is preferred. Carbon number of alicyclic monoisocyanate becomes like this. Preferably it is 4-20, More preferably, it is 4-10. The alicyclic monoisocyanate may be either a saturated alicyclic monoisocyanate or an unsaturated alicyclic monoisocyanate, but a saturated alicyclic monoisocyanate is preferred because of excellent oxidation stability.

  Furthermore, aromatic monoisocyanate is preferable from the viewpoint of lubricity and heat resistance. The carbon number of the aromatic monoisocyanate is preferably 6 to 20, more preferably 8 to 20.

X ² represents a divalent organic group, preferably a divalent residue obtained by removing two isocyanate groups from diisocyanate. Diisocyanate is defined as a compound in which two isocyanate groups are added to an aliphatic, aromatic hydrocarbon or heterocyclic compound, or a derivative thereof. Among the diisocyanate monomers that form the structure of X ² , there are the following or a mixture thereof, but the present invention is not limited to these.

  Examples of the aliphatic diisocyanate include diisocyanates having saturated and / or unsaturated linear, branched, or alicyclic hydrocarbon groups. Specifically, methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,5-dimethylhexamethylene diisocyanate, 3-methoxyhexamethylene diisocyanate, heptamethylene diisocyanate, 2,5- Dimethylheptamethylene diisocyanate, 3-methylheptamethylene diisocyanate, 4,4-dimethylheptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 5-methylnonamethylene diisocyanate, decamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1 , 3-Bis (isocyanatomethyl) cyclohexa 1,4-bis (isocyanatomethyl) cyclohexane, 4,4′-methylenebis (cyclohexyl isocyanate), 4,4′-methylenebis (2-methylcyclohexyl isocyanate), bis (isocyanatomethyl) norbornane, 1,3- Diisocyanatoadamantane, isophorone diisocyanate, 1,8-diisocyanato p-menthane and the like can be mentioned.

  Aromatic diisocyanates include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,4-diisocyanatonaphthalene, 1, 5-diisocyanatonaphthalene, 1,8-diisocyanatonaphthalene, 2,6-diisocyanatonaphthalene, 2,7-diisocyanatonaphthalene, 1,8-diisocyanatoanthracene, 2,6-diisocyanato Anthracene, 2,7-diisocyanatoanthracene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 2,4-diisocyanato (m-xylene), 2,5-diisocyanato (m-xylene) 1,1-bis (3-i Cyanatophenyl) ethane, 1,1-bis (4-isocyanatophenyl) ethane, 2,2-bis (3-isocyanatophenyl) propane, 2,2-bis (4-isocyanatophenyl) propane, 2, 2-bis (4-isocyanato 3,5-dimethylphenyl) propane, 2,5-diisocyanatopyridine, 2,6-diisocyanatopyridine, 3,5-diisocyanatopyridine, 2,4-diisocyanato Toluenebenzidine, 3,3'-diisocyanatobiphenyl, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-diisocyanatobenzophenone, 4,4 '-Diisocyanatobenzophenone, 3,3'-Diisocyanatodiphenyl ether, 4,4'-Diisocyanatodiphenyl Ether, 3,3′-diisocyanatodiphenylmethane, 4,4′-diisocyanatodiphenylmethane, 4,4′-diisocyanato 3,3 ′, 5,5′-tetramethyldiphenylmethane, 3,3′-diisocyanato Diphenylsulfone, 4,4′-diisocyanatodiphenylsulfone, 3,3′-diisocyanatodiphenylsulfide, 4,4′-diisocyanatodiphenylsulfide, 4,4′-diisocyanatodiphenylthioether, 4,4 '-Diisocyanato 3,3', 5,5'-tetramethyldiphenyl ether, 4,4'-diisocyanato 3,3 ', 5,5'-tetraethyl diphenyl ether, 1,3-bis (3-isocyanatophenoxy) benzene, 1,3-bis (4-isocyanatophenoxy) benzene, 1,4-bis (3 -Isocyanatophenoxy) benzene, 1,4-bis (4-isocyanatophenoxy) benzene, 2,6-bis (3-isocyanatophenoxy) pyridine, 1,4-bis (3-isocyanatophenylsulfonyl) benzene, 1,4-bis (4-isocyanatophenylsulfonyl) benzene, 1,4-bis (3-isocyanatophenylthioether) benzene, 1,4-bis (4-isocyanatophenylthioether) benzene, 4,4′- Bis (3-isocyanatophenoxy) diphenylsulfone, 4,4′-bis (4-isocyanatophenoxy) diphenylsulfone, 4,4′-bis (4-isocyanatophenoxy) biphenyl, bis [4- (3-isocyanate) Natophenoxy) phenyl] sulfone, bis [4- (4-isocyanatophenoxy) Phenyl] sulfone, bis [4- (4-isocyanatophenoxy) phenyl] ether, bis [4- (4-isocyanatophenoxy) phenyl] methane, bis [3-methyl-4- (4-isocyanatophenoxy) phenyl ] Methane, bis [3-chloro-4- (4-isocyanatophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-isocyanatophenoxy) phenyl] methane, 1,1-bis [4 -(4-isocyanatophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-isocyanatophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4- Isocyanatophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-isocyanatophenoxy) phenyl] ethane, 2, -Bis [4- (4-isocyanatophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-isocyanatophenoxy) phenyl] propane, 2,2-bis [3-chloro-4 -(4-isocyanatophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-isocyanatophenoxy) phenyl] propane, 2,2-bis [4- (4-isocyanato) Phenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-isocyanatophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4- (4-isocyanatophenoxy) Phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-isocyanatophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis (4-isocyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-isocyanatophenoxy) phenyl] propane, bis (3-isocyanatophenyl) tetramethyldisilane, bis (4-isocyanatophenyl) tetramethyldisilane, bis (3-methyl-4-isocyanatophenyl) tetramethyldisilane, bis (3-isocyanatophenoxy) tetramethyldisilane Bis (4-isocyanatophenoxy) tetramethyldisilane, bis (3-isocyanatophenoxy) -1,1,3,3-tetramethyldisiloxane, bis (4-isocyanatophenoxy) -1,1,3 Examples thereof include 3-tetramethyldisiloxane.

Examples of the diisocyanate monomer that forms the structure of X ² include compounds in which two isocyanate groups are bonded to an aromatic hydrocarbon, particularly (a) diisocyanatotoluene or a derivative thereof and (b) diisocyanatodiphenylmethane or a compound thereof. Derivatives are preferred.

R ¹ and R ^{2 each} represent a monovalent organic group, preferably a monovalent residue obtained by removing one amino group from an aliphatic monoamine, alicyclic monoamine or aromatic monoamine. Examples of the monoamine that is the base of the structure of R ¹ and R ² include, but are not limited to, the following monoamines or mixtures thereof.

  Examples of monoamines include aliphatic amines, alicyclic amines, and aromatic amines, which have a hydrocarbon residue having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, and are linear or branched alkyls. Examples include amines, linear or branched alkenylamines, cycloalkylamines, alkylcycloalkylamines, arylamines, alkylarylamines, arylalkylamines, and the like. Specific examples include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eico Linear or branched alkylamine such as silamine; cyclohexylamine; methylcyclohexylamine, dimethylcyclohexylamine, ethylcyclohexylamine, diethylcyclohexylamine, propylcyclohexylamine, isopropylcyclohexylamine, 1-methyl-3-propylcyclohexyl Amine, butylcyclohexylamine, amylcyclohexylamine, amylmethylcyclohexylamine, hexylcyclo Alkylcycloalkylamines such as xylamine, heptylcyclohexylamine, octylcyclohexylamine, nonylcyclohexylamine, decylcyclohexylamine, undecylcyclohexylamine, dodecylcyclohexylamine, tridecylcyclohexylamine, tetradecylcyclohexylamine; aryls such as phenylamine and naphthylamine Amine; alkylarylamines such as toluylamine, ethylphenylamine, xylylamine, propylphenylamine, cumenylamine, methylnaphthylamine, ethylnaphthylamine, dimethylnaphthylamine, propylnaphthylamine; arylalkylamines such as benzylamine, methylbenzylamine, ethylbenzylamine, etc. Can be mentioned.

Of the monoamines based on the structure of R ¹ and R ² , linear or branched aliphatic monoamines are preferable from the viewpoint of lubricity and grease performance. The carbon number of the linear or branched aliphatic monoamine is preferably 4 to 20, and more preferably 8 to 20. The aliphatic monoamine may be either a saturated aliphatic monoamine or an unsaturated aliphatic monoamine, but is preferably a saturated aliphatic amine because of excellent oxidation stability.

  From the viewpoint of heat resistance, alicyclic monoamines are preferred. Carbon number of alicyclic monoamine becomes like this. Preferably it is 4-20, More preferably, it is 4-10. The alicyclic monoamine may be either a saturated alicyclic monoamine or an unsaturated alicyclic monoamine, but is preferably a saturated alicyclic monoamine because of excellent oxidation stability.

  In particular, from the viewpoint of heat resistance and grease performance, a mixture of an aliphatic chain monoamine, an alicyclic monoamine, and an aromatic monoamine is preferable.

［式中、Ｒ及びＸはそれぞれ１価の有機基を示す。］ [Second Embodiment: Method for Producing Imido-Urea Compound]
The method for producing an imide-urea compound according to the second embodiment of the present invention is the following by reacting a nitrophthalic anhydride represented by the following general formula (4) with a monoamine represented by the following general formula (5). First step of obtaining a nitrophthalic anhydride imide derivative represented by the general formula (6) and obtaining an aminophthalic anhydride imide derivative represented by the following general formula (7) by hydrogenation reduction of the nitrophthalic anhydride And a second step of reacting the aminophthalic anhydride imide derivative with an isocyanate represented by the following general formula (8) to obtain an imide-urea compound represented by the above general formula (1). .

[Wherein, R and X each represent a monovalent organic group. ]

［式中、Ｘ^１はモノイソシアネートから１つのイソシアネート基を除いた１価の残基を示し、Ｘ^２は２価の有機基を示し、Ｒ^１及びＲ^２は１価の有機基を示し、Ｒ^１及びＲ^２は同一でも異なっていてもよい。］ The second step in the present embodiment is preferably an aminophthalic anhydride imide derivative represented by the general formula (7) and a monoisocyanate represented by the following general formula (9) or the following general formula (10). And a diisocyanate represented by the general formula (2) or the general formula (3) to obtain an imide-urea compound.

Wherein, X ¹ is a monovalent residue obtained by removing one of the isocyanate groups from a monoisocyanate, X ² represents a divalent organic group, R ¹ and R ² is a monovalent organic group, R ¹ and R ² may be the same or different. ]

  When the diisocyanate represented by the general formula (10) is used, an imide-urea compound mainly represented by the general formula (3) is generated. In this case, an aminophthalic anhydride imide derivative represented by the general formula (7) as a by-product and a compound obtained by reacting only one of the two isocyanate groups of diisocyanate (that is, represented by the general formula (2)). Imide-urea compound) can be produced. In the thickener for grease and grease composition described later, a mixture of the imide-urea compound represented by the general formula (2) and the imide-urea compound represented by the general formula (3) may be used as it is. An imide-urea compound represented by the general formula (3) obtained by isolating a by-product from the mixture may be used.

  On the other hand, when the monoisocyanate represented by the general formula (9) is used, an imide-urea compound represented by the general formula (2) is generated.

Specific examples and preferred examples of the monoisocyanate represented by the general formula (9) are the same as the specific examples and preferred examples of the monoisocyanate which is the base of the structure X ¹ in the first embodiment. Further, specific examples and preferred examples of diisocyanates of the general formula (10) are the same as the specific examples and preferred examples of the underlying diisocyanates X ² becomes the structure of the first embodiment. Furthermore, specific examples and preferred examples of monoamines represented by the general formula (5) (including R ¹ in the general formula (2) and the monoamines that form the structures R ¹ and R ² in the general formula (3)) Examples are the same as the specific examples and preferred examples of the diisocyanate that is the base of the structure X ¹ in the first embodiment.

  In the first step, the charging ratio between the nitrophthalic anhydride represented by the general formula (4) and the monoamine represented by the general formula (5) is the nitrophthalic anhydride 1 represented by the general formula (4). It is preferable that the monoamine represented by the general formula (5) is 0.8 to 1.2 mol, particularly 1.0 to 1.1 mol with respect to mol. The reaction temperature is preferably 100 to 250 ° C, particularly 130 to 200 ° C. By reacting at such a temperature, the reaction intermediate represented by the general formula (6) can be obtained in high yield by dehydration cyclization. The reaction is preferably carried out at 0 to 100 ° C. and then 100 to 250 ° C., particularly 130 to 200 ° C. The reaction time is preferably 1 to 24 hours, particularly 2 to 12 hours.

  The reaction of the nitrophthalic anhydride represented by the general formula (4) and the monoamine represented by the general formula (5) in the first step should be performed in the absence of a solvent, a solvent, or a lubricating base oil described later. Can do. As the solvent, organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran and toluene, or a mixed solvent of two or more of these can be used.

  Reduction of the nitro group of the nitrophthalic anhydride imide derivative represented by the general formula (6) in the first step is catalytic hydrogenation, reduction using a metal hydride, reduction using zinc, iron or tin in an acidic atmosphere. Although it is not particularly limited as long as it is a general nitro group technique, catalytic hydrogenation is preferred. For example, Pd, Pt, Rh, Ru-supported carbon is used as the catalyst, and Pd and Pt are particularly preferable. The reaction solvent is not particularly limited as long as it dissolves the substrate such as no solvent, ester, ether, alcohol, etc., but esters such as ethyl acetate and butyl acetate are preferable from the viewpoint of solubility, and the reaction temperature is 10 to 200 ° C., especially 25-100 degreeC is preferable. The hydrogen pressure is preferably atmospheric pressure to 10 MPa, particularly 1 to 5 MPa.

  In the second step, the reaction between the aminophthalic anhydride imide derivative represented by the general formula (7) and the monoisocyanate represented by the general formula (9) or the diisocyanate represented by the general formula (10) is carried out in a solvent. Can be done. As the solvent, organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran and toluene, or a mixed solvent of two or more of these can be used. In addition, when performed in a lubricating base oil, it can be used as it is as a grease composition.

  The amount of the monoisocyanate represented by the general formula (9) in the second step is not particularly limited, but the general formula (9) is used with respect to 1 mol of the aminophthalic anhydride imide derivative represented by the general formula (7). It is preferable to use 0.8 to 1.2 mol, particularly 0.9 to 1.1 mol, and more preferably 0.95 to 1.05 mol of the monoisocyanate represented by the formula. The reaction temperature is preferably 80 to 200 ° C, particularly 130 to 180 ° C. The reaction time is preferably 0.5 to 10 hours, particularly 1 to 4 hours.

  Although the usage-amount of the diisocyanate represented by General formula (10) in a 2nd process in particular is not restrict | limited, General formula (8) with respect to 1 mol of aminophthalic anhydride imide derivatives represented by General formula (7). It is preferable to use 0.3 to 0.7 mol, particularly 0.4 to 0.6 mol, more preferably 0.45 to 0.55 mol of the diisocyanate represented. The reaction temperature is preferably 80 to 200 ° C, particularly 130 to 180 ° C. The reaction time is preferably 0.5 to 10 hours, particularly 1 to 4 hours.

[Third embodiment: thickener for grease]
The thickener for grease according to the third embodiment of the present invention contains an imide-urea compound represented by the general formula (1). Specific examples and preferred examples of the imide-urea compound represented by the general formula (1) are the same as the specific examples and preferred examples of the imide-urea compound according to the first embodiment.

  The thickener for grease according to the present embodiment may contain a thickener component other than the imide-urea compound. Such thickener components include soap-type thickener components such as metal soaps and composite metal soaps; non-soap-type thickener components such as benton, silica gel, urea compounds, urea / urethane compounds, urethane compounds, imide compounds, etc. Any thickener component can be used. Examples of the soap-based thickener component include sodium soap, calcium soap, aluminum soap, lithium soap and the like. Examples of the urea compound, urea / urethane compound, and urethane compound include diurea compounds, triurea compounds, tetraurea compounds, other polyurea compounds, urea / urethane compounds, diurethane compounds, and mixtures thereof.

  The imide-urea compound according to the first embodiment and the thickener for grease according to the third embodiment are excellent in heat resistance, so that they are for constant speed gears used at high temperatures, for transmission gears, for steel manufacturing facilities, It is particularly preferably used as a grease thickener for ball bearings and roller bearings. The use temperature in these applications is preferably -40 ° C to 300 ° C, more preferably -40 ° C to 250 ° C.

[Fourth embodiment: grease composition]
A grease composition according to a fourth embodiment of the present invention includes a lubricating base oil and an imide-urea compound represented by the above general formula (1), and the content of the imide-urea compound is a grease composition. It is a thing of 2-50 mass% on the basis of the total amount of things.

  In the grease composition according to this embodiment, the content of the imide-urea compound represented by the general formula (1) is 2% by mass or more, preferably 5% by mass or more based on the total amount of the grease composition. , 50% by mass or less, preferably 40% by mass or less. If the content of the imide-urea compound is less than 2% by mass, the effect as a thickener is small, so that it does not become a sufficient grease, and if it exceeds 50% by mass, it becomes too hard as a grease and sufficient lubrication Since performance cannot be demonstrated, it is not preferable respectively.

  Examples of the lubricating base oil of the grease composition according to the present embodiment include mineral oil and / or synthetic oil.

  Mineral oil can be obtained by a method commonly used in the oil refining industry's lubricating oil production process. For example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation can be desolvated, solvent extracted, Examples include those purified by one or more treatments such as hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment.

  Specific examples of synthetic oils include poly-α-olefins such as polybutene, 1-octene oligomer, 1-decene oligomer or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, Diesters such as di3-ethylhexyl sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate; alkylnaphthalenes; alkylbenzenes, polyoxyalkylene glycols; Polyphenyl ethers; dialkyl diphenyl ethers; silicone oils; or mixtures thereof.

  From the viewpoint of durability at high temperatures, synthetic oils are preferable, and polyol esters, polyphenyl ethers, alkyl diphenyl ethers, and alkyl naphthalenes are more preferable.

Kinematic viscosity at 100 ° C. of the lubricating base oil is preferably 2 to 40 mm ² / s, more preferably 3 to 20 mm ² / s. The viscosity index of the lubricating base oil is preferably 90 or higher, more preferably 100 or higher.

  In addition, as long as the grease composition which concerns on this embodiment does not impair the property, it is other than the imide-urea compound represented by the said General formula (1) as needed in order to improve a performance further. Thickeners, solid lubricants, extreme pressure agents, antioxidants, oily agents, rust inhibitors, viscosity index improvers, detergent dispersants and the like.

  Examples of the thickener other than the imide-urea compound represented by the general formula (1) include soap thickeners such as metal soap and composite metal soap; Benton, silica gel, urea compound, urea / urethane compound, urethane Any thickeners such as non-soap thickeners such as compounds and imide compounds can be used. Examples of the soap-based thickener include sodium soap, calcium soap, aluminum soap, lithium soap and the like. Examples of the urea compound, urea / urethane compound, and urethane compound include diurea compounds, triurea compounds, tetraurea compounds, other polyurea compounds, urea / urethane compounds, diurethane compounds, and mixtures thereof. Furthermore, you may contain imide-urea compounds other than the imide-urea compound represented by the said General formula (1).

  Specific examples of the solid lubricant include graphite, carbon black, fluorinated graphite, polytetrafluoroethylene, molybdenum disulfide, antimony sulfide, and alkali (earth) metal borate.

  Specific examples of the extreme pressure agent include organic zinc compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate; sulfur-containing compounds such as dihydrocarbyl polysulfide, sulfide ester, thiazole compound and thiadiazole compound; phosphates and phosphites Etc.

  Specific examples of the antioxidant include phenol compounds such as 2,6-di-t-butylphenol and 2,6-di-t-butyl-p-cresol; dialkyldiphenylamine, phenyl-α-naphthylamine, p- Amine compounds such as alkylphenyl-α-naphthylamine; sulfur compounds; phenothiazine compounds.

  Specific examples of oily agents include amines such as laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine; higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol; laurin Higher fatty acids such as acid, myristic acid, palmitic acid, stearic acid, oleic acid; fatty acid esters such as methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate; laurylamide, myristylamide, Amides such as palmitylamide, stearylamide, oleylamide; oils and fats.

  Specific examples of the rust inhibitor include metal soaps; polyhydric alcohol partial esters such as sorbitan fatty acid esters; amines; phosphoric acid;

  Specific examples of the viscosity index improver include polymethacrylate, polyisobutylene, and polystyrene.

  Specific examples of the cleaning dispersant include sulfonates, salicylates, phenates, and the like.

  In order to prepare the grease composition according to the present embodiment, for example, the lubricant base oil contains the imide-urea compound represented by the general formula (1) or a thickener containing the imide-urea compound, and further necessary. Depending on the conditions, other additives may be mixed and the mixture stirred and then passed through a roll mill or the like.

  Since the grease composition according to the fourth embodiment is excellent in heat resistance, it is used for constant speed gears, transmission gears, automobiles, steelmaking equipment, industrial machinery, precision machinery, ball bearings used at high temperatures. It is particularly preferably used as grease for roller bearings and the like. The use temperature in these applications is preferably -40 ° C to 300 ° C, more preferably -40 ° C to 250 ° C.

  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]
After mixing 10.7 g of 4-nitrophthalic anhydride represented by the following formula (11) and 10.8 g of dodecylamine represented by the following formula (12), the mixture is heated from room temperature to reach 150 ° C. and reacted for 2 hours. It was. Subsequently, while maintaining 150 ° C., the pressure was gradually reduced to 0.7 kPa to remove moisture and unreacted dodecylamine. When it was cooled after maintaining the reduced pressure for 2 hours, the nitrated imide intermediate-1 containing the nitrated imide intermediate represented by the following formula (13) was obtained as a solid (yield: 19.7 g). 10 g of the obtained nitrated imide intermediate-1 was dissolved in 150 mL of ethyl acetate solvent, 1 g of palladium 5 wt% -carbon-supported catalyst was added, and a hydrogenation reaction was performed using an autoclave. When the reaction was performed from room temperature while maintaining a hydrogen pressure of 3 MPa, the temperature gradually decreased after the liquid temperature rose to 45 ° C. by reaction heat. After 3 hours, the temperature dropped to room temperature and the hydrogen pressure did not drop, so the reaction was stopped. The catalyst was filtered off from the solution, and the solvent was distilled off with a rotary evaporator to obtain 8.8 g of aminated imide intermediate-1 containing an aminated imide intermediate represented by the following formula (14). 7.9 g of the obtained aminated imide intermediate, 1.7 g of 2,4-diisocyanatotoluene represented by the following formula (15) and 2,6-diisocyanatotoluene represented by the following formula (16) 0.4 g of the mixture was mixed with 30 g of diphenyl ether base oil having a kinematic viscosity at 100 ° C. of 13 mm ² / s and reacted at 160 ° C. for 2 hours. After cooling to room temperature, 40 g of a grease-like substance containing imide-urea compound-1 containing the following formulas (17) and (18) at a weight ratio of 8: 2 was obtained. Diphenyl ether base oil was removed from this grease-like substance with hexane to obtain imide-urea compound-1.

The infrared absorption spectrum of imide-amide compound-1 (manufactured by JASCO Corporation, FT / IR-410) was measured by the KBr method. The result is shown in FIG. As shown in FIG. 1, absorption of about 1700 cm ⁻¹ and about 1760 cm ⁻¹ derived from the cyclic imide group and absorption of about 1650 cm ⁻¹ derived from the urea group were confirmed, and attributed to the isocyanate group of the reaction raw material. Absorption at about 2270 cm ⁻¹ was not confirmed. From this result, it was confirmed that the obtained solid was an imide-urea compound.

  Further, imide-urea compound-1 was subjected to FD-MS measurement (JEOL Ltd. JMS-T100GC, ionization method: FD +, solvent: on-propylphenol). The peak attributed to the imide-urea compound represented by the general formula (14) was 97% with respect to the total ionic strength.

[Example 2]
In Example 2, the diisocyanate represented by the following formula (19) was changed from the above formulas (15) and (16) as the diisocyanate represented by the general formula (10), and the aminated imide represented by the above formula (14) Imide-urea compound represented by the following general formula (20) in the same manner as in Example 1 except that 7.3 g of intermediate-1 and 2.7 g of diisocyanate represented by the following formula (19) were used. 40 g of a grease-like substance containing 2 was obtained.

From the grease-like substance containing the imide-urea compound-2 obtained in Example 2, the imide-urea compound-2 was taken out in the same manner as in Example 1, and the infrared absorption spectrum was measured. Also in the urea compound, absorption of about 1700 cm ⁻¹ and about 1760 cm ⁻¹ derived from the cyclic imide group and about 1650 cm ⁻¹ derived from the urea group was confirmed, and about 2270 cm ⁻¹ attributed to the isocyanate group of the reaction raw material. No absorption or the like was confirmed. From these results, it was confirmed that the solid material obtained in Example 2 was an imide-urea compound.

[Comparative Example 1]
45.8 g of cyclohexylamine was reacted with 55.8 g of 4,4′-diisocyanatodiphenylmethane in 300 g of diphenyl ether base oil having a kinematic viscosity at 100 ° C. of 13 mm ² / s to obtain a grease-like substance. Diphenyl ether base oil was removed from the grease-like substance with hexane to obtain 100 g of urea compound-1 represented by the formula (21).

[Comparative Example 2]
To 31.7 g of 4,4′-diisocyanatodiphenylmethane, 68.3 g of octadecylamine was reacted in 300 g of diphenyl ether base oil having a kinematic viscosity at 100 ° C. of 13 mm ² / s to obtain a grease-like substance. Diphenyl ether base oil was removed from the grease-like substance with hexane to obtain 100 g of urea compound-2 represented by the formula (22).

[Heat resistance evaluation]
The imide-urea compounds-1 and 2 obtained in Examples 1 and 2 and the urea compounds-1 and 2 obtained in Comparative Examples 1 and 2 were subjected to thermal analysis (DTG60, manufactured by Shimadzu Corporation, heating rate: 5 ° C). / Min, atmospheric gas: nitrogen), and 5% decomposition temperature was measured. The obtained result is shown to Tables 1-2. In the table, the higher the decomposition temperature, the better the heat resistance.

[Capacity evaluation]
The grease-like substance before removing the diphenyl ether base oil with hexane obtained in Examples 1 and 2 and hexane obtained in Comparative Examples 1 and 2 was passed through a roll mill into the base oil. The substance obtained by uniform dispersion was measured for consistency after 60 mixing (60 W) by the consistency measuring method of JIS2220. The obtained result is shown to Tables 1-2.

From the results shown in Tables 1 and 2, the imide-urea compounds -1 and 2 obtained in Examples 1 and 2 were more resistant to heat than the urea compounds -1 and 2 obtained in Comparative Examples 1 and 2. It can be seen that it has excellent properties and can be used as a thickener for grease.

Claims (5)

An imide-urea compound represented by the following general formula (3) .

[ Wherein , X ² represents a divalent organic group, R ¹ and R ² represent a monovalent organic group, and R ¹ and R ² may be the same or different. ] X ² Is a divalent residue obtained by removing two isocyanate groups from an aliphatic, aromatic hydrocarbon or heterocyclic compound, or a compound obtained by adding two isocyanate groups to a derivative thereof,
R ¹ And R ² The imide-urea compound according to claim 1, wherein is a monovalent residue obtained by removing one amino group from an aliphatic monoamine, alicyclic monoamine or aromatic monoamine. A nitrophthalic anhydride imide derivative represented by the following general formula (6) is obtained by reacting a nitrophthalic anhydride represented by the following general formula (4) with a monoamine represented by the following general formula (5), A first step of obtaining an aminophthalic anhydride imide derivative represented by the following general formula (7) by hydrogenation reduction of the nitrophthalic anhydride;
A second step of obtaining a urea compound, - imide and di isocyanate is reacted represented by the following general formula (3) represented by the aminophthalic anhydride imide derivatives and the following general formula (10)
A process for producing an imide-urea compound.

[Wherein, X ² represents a divalent organic group. ]

[ Wherein , X ² represents a divalent organic group, R ¹ and R ² represent a monovalent organic group, and R ¹ and R ² may be the same or different. ]   A thickener for grease containing the imide-urea compound according to claim 1. A grease composition containing a lubricating base oil and the imide-urea compound according to claim 1.

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