WO2013172428A1

WO2013172428A1 - Imide-amide compound and method for producing same, grease thickener, and grease composition

Info

Publication number: WO2013172428A1
Application number: PCT/JP2013/063713
Authority: WO
Inventors: 健太郎山口; 実希藤原; 龍一上野; 設楽　裕治
Original assignee: Ｊｘ日鉱日石エネルギー株式会社
Priority date: 2012-05-17
Filing date: 2013-05-16
Publication date: 2013-11-21
Also published as: JP2013237820A; JP5908786B2

Abstract

The invention provides an imide-amide compound represented by general formula (1). This imide-amide compound has excellent durability under high temperature, particularly when used as a thickener for grease. (In the formula, R and X each represent a monovalent organic group.)

Description

IMIDE-AMIDE COMPOUND AND METHOD FOR PRODUCING THE SAME, GREASE THINNER

The present invention relates to an imide-amide compound, a production method thereof, 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 electrical parts and engine accessories 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 a grease composition using an imide thickener as an example of a 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 Unexamined Patent Publication No. 57-109896

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

The present invention provides an imide-amide compound represented by the following general formula (1).

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

The imide-amide compound of the present invention preferably has a structure represented by the following general formula (2) or (3).

[Wherein R ¹ and R ² represent a monovalent organic group, X ¹ represents a divalent organic group, X ² represents a monovalent organic group, and R ¹ and R in formula (2) ² may be the same or different. ]

Further, the present invention provides an imidocarboxylic acid represented by the following general formula (6) by reacting a trimellitic anhydride represented by the following formula (4) with a monoamine represented by the following general formula (5). A second step of obtaining an imide-amide compound represented by the following general formula (1) by reacting the imide carboxylic acid with an isocyanate represented by the following general formula (7): ,
The manufacturing method of an imide compound provided with this is provided.

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

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

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

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 high temperatures. It was found that sufficient durability could not be obtained. In contrast, the present inventors have confirmed that the imide-amide compound, the thickener for grease and the grease composition of the present invention can exhibit sufficient durability even when used at high temperatures. is doing.

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

2 is a graph showing an infrared absorption spectrum of an imide-amide compound obtained in Example 1. FIG. 2 is a diagram showing an FD-MS spectrum of an imide-amide compound obtained in Example 1. FIG.

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

[First embodiment: imide-amide compound]
The imide-amide 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. ]

Preferable examples of the imide-amide compound according to this embodiment include imide-amide compounds represented by the following general formula (2) or general formula (3). The imide-amide compound represented by the general formula (1) has two imide groups and two amide groups. Further, the imide-amide compound represented by the general formula (2) has one imide group and one amide group.

X ¹ 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 from which X ¹ is derived, 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 a saturated and / or unsaturated linear, branched, or alicyclic hydrocarbon group. 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- Examples thereof include diisocyanatoadamantane, isophorone diisocyanate, and 1,8-diisocyanato p-menthane.

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- Socyanatophenyl) 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'-Diisocyanatodipheni 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- Isocyanatophenoxy) 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 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-isocyanate) Natophenoxy) 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) tetramethyl Disilane, bis (4-isocyanatophenoxy) tetramethyldisilane, bis (3-isocyanatophenoxy) -1,1,3,3-tetramethyldisiloxane, bis (4-isocyanatophenoxy) -1,1,3 And 3-tetramethyldisiloxane.

Examples of the diisocyanate monomer that forms the structure of X ¹ include compounds in which two isocyanate groups are bonded to an aromatic hydrocarbon group, particularly (a) diisocyanatotoluene or a derivative thereof and (b) diisocyanatodiphenylmethane or Its derivatives are preferred.

X ² represents a monovalent organic group, preferably 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 that form the structure of X ² , 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, and 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 L-cyclohexyl 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.

The former become monoisocyanate monomer X ² made structure, in terms of lubricity and grease performance, straight-chain or branched aliphatic monoisocyanates are preferred. The carbon number of the linear or branched aliphatic monoisocyanate is preferably 4 to 20, more preferably 8 to 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.

In addition, alicyclic monoisocyanate is preferable from the viewpoint of heat resistance. The carbon number of the alicyclic monoisocyanate is preferably 4 to 20, more preferably 4 to 10. Further, the alicyclic monoisocyanate may be either a saturated alicyclic monoisocyanate or an unsaturated alicyclic isocyanate, but a saturated alicyclic isocyanate 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.

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, 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.

Also, from the viewpoint of heat resistance, alicyclic monoamines are preferable. The carbon number of the alicyclic monoamine is preferably 4 to 20, more preferably 4 to 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.

[Second Embodiment: Method for Producing Imido-Amide Compound]
The method for producing an imide-amide compound according to the second embodiment of the present invention comprises the steps of reacting trimellitic anhydride represented by the following formula (4) with a monoamine represented by the following general formula (5). The first step of obtaining an imide carboxylic acid represented by the general formula (6) and the imide carboxylic acid reacted with an isocyanate represented by the following general formula (7) are represented by the following general formula (1). And a second step of obtaining an imide-amide compound.

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

Moreover, the second step in the present embodiment is preferably performed by reacting the imide carboxylic acid with a diisocyanate represented by the following general formula (8) or a monoisocyanate represented by the following general formula (9). In this step, an imide-amide compound represented by the general formula (2) or (3) is obtained.

When the diisocyanate represented by the general formula (8) is used, an imide-amide compound represented mainly by the general formula (2) is formed. In this case, as a by-product, an imide carboxylic acid represented by the general formula (6) and a compound obtained by reacting only one of the two isocyanate groups of the diisocyanate (that is, an imide represented by the general formula (3)) -Amide compounds) can be formed. In the thickener for grease and the grease composition described later, a mixture of the imide-amide compound represented by the general formula (2) and the imide-amide compound represented by the general formula (3) may be used as it is. Alternatively, an imide-amide compound represented by the general formula (2) 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-amide compound represented by the general formula (3) is formed.

Specific examples and preferred examples of the diisocyanate represented by the general formula (8) are the same as the specific examples and preferred examples of the diisocyanate which is the base of the structure of X ¹ in the first embodiment. Further, specific examples and preferred examples of monoisocyanates of the general formula (9) are the same as the specific examples and preferred examples of the underlying monoisocyanate X ² becomes the structure of the first embodiment. Specific examples and preferred examples of monoamines represented by the general formula (5) (including R ¹ and R ^{2 in the} general formula (2) and a monoamine that is the basis of the structure R ¹ in the general formula (2)) are also included. 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 of trimellitic anhydride represented by formula (4) and monoamine represented by general formula (5) is trimellitic anhydride represented by general formula (4). The monoamine represented by the general formula (5) is preferably 0.8 to 1.2 mol, particularly 0.9 to 1.1 mol, per 1 mol. The reaction temperature is preferably 100 to 350 ° C., particularly 130 to 260 ° 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 ° C. to 100 ° C. initially, and then 100 to 350 ° C., particularly 130 to 260 ° C. The reaction time is preferably 1 to 24 hours, particularly 4 to 12 hours.

The reaction of the trimellitic anhydride represented by the general formula (4) and the monoamine represented by the general formula (5) in the first step is performed without solvent, in a solvent, or in a lubricating base oil described later. be able to. As the solvent, organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, toluene, or a mixed solvent of two or more of these can be used.

In the second step, the reaction between the imide carboxylic acid represented by the general formula (6) and the diisocyanate represented by the general formula (8) or the monoasocyanate represented by the general formula (9) 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, 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.

Although the usage-amount of the diisocyanate represented by General formula (8) in a 2nd process in particular is not restrict | limited, It represents with General formula (8) with respect to 1 mol of imide carboxylic acids represented with General formula (6). It is preferable to use 0.3 to 0.7 mol of diisocyanate, particularly 0.4 to 0.6 mol, more preferably 0.45 to 0.55 mol. 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 monoisocyanate represented by General formula (9) in a 2nd process in particular is not restrict | limited, It represents with General formula (9) with respect to 1 mol of imide carboxylic acid represented by General formula (6). It is preferable to use 0.8 to 1.2 mol, particularly 0.9 to 1.1 mol, more preferably 0.95 to 1.05 mol of monoisocyanate. 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-amide compound represented by the general formula (1). Specific examples and preferred examples of the imide-amide compound represented by the general formula (1) are the same as the specific examples and preferred examples of the imide-amide compound according to the first embodiment.

The grease thickener according to the present embodiment may contain a thickener component other than the imide-amide 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-amide 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 used for constant speed gears, transmission gears, steel making equipment, 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]
The grease composition according to the fourth embodiment of the present invention contains a lubricating base oil and an imide-amide compound represented by the above general formula (1), and the content of the imide-amide compound is the grease composition. 2 to 50% by mass based on the total amount of the product.

In the grease composition according to this embodiment, the content of the imide-amide 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-amide 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.

The lubricating base oil of the grease composition according to this embodiment includes 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; alkyl naphthalenes; 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.

The 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, the grease composition according to the present embodiment, other than the imide-amide compound represented by the above general formula (1), as necessary, in order to further improve the performance, as long as the properties are not impaired. Thickeners, solid lubricants, extreme pressure agents, antioxidants, oily agents, rust inhibitors, viscosity index improvers, detergent dispersants and the like.

Thickeners other than the imide-amide compound represented by the general formula (1) include soap-type thickeners such as metal soaps and composite metal soaps; Benton, silica gel, urea compounds, urea / urethane compounds, urethanes 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, an imide-amide compound other than the imide-amide compound represented by the general formula (1) may be contained.

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

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- Examples thereof include 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; partial alcohol 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 sulfonate, salicylate, phenate, and the like.

In order to prepare the grease composition according to this embodiment, for example, the lubricant base oil contains the imide-amide compound represented by the general formula (1) or a thickener containing the imide-amide 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.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]
In 250 mL of NMP (N-methyl-2-pyrrolidone) solvent, 43.8 g of trimellitic anhydride represented by the following formula (4) and 42.3 g of dodecylamine represented by the following formula (10) The reaction was carried out at 25 ° C. for 4 hours while cooling. Subsequently, 250 mL of toluene was added, and the mixture was heated for 4 hours while being azeotropically dehydrated using a Dean-Stark apparatus at reflux temperature. Distilling under reduced pressure, removing 150 ml of toluene and NMP, and cooling and drying the precipitated solid with 100 ml of toluene and 100 ml of methanol, followed by imidocarboxylic acid intermediate containing an imide carboxylic acid intermediate represented by the following formula (11) Body-1 was obtained as a solid (yield: 50.0 g). Subsequently, in 15 mL of NMP (N-methyl-2-pyrrolidone) solvent, 15.0 g of this intermediate, 2.9 g of 2,4-diisocyanatotoluene represented by the following formula (12), and the following formula ( A mixture of 0.7 g of 2,6-diisocyanatotoluene represented by 13) was reacted at 160 ° C. for 2 hours. After cooling to room temperature and adding 30 mL of toluene to suspend, the solid was filtered, washed with 100 mL of toluene and 100 mL of acetone, and dried to give an imide-amide compound containing an imide-amide compound represented by the following formula (14) -1 was obtained as a solid (yield: 14.3 g).

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, about 1720 cm ^-1 and derived from cyclic imido group, absorption of about 1660 cm ^-1 derived from about 1780 cm ^-1, and an amide group is confirmed, about attributed to isocyanide groups of the reaction raw material Absorption at 2270 cm ⁻¹ was not confirmed. From this result, it was confirmed that the obtained solid was an imide-amide compound.

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

[Examples 2 to 18]
In Examples 2 to 18, monoamines represented by the above formulas (10) to (12) or the following formulas (15) to (18) as monoamines represented by the general formula (4) are represented by the general formula (8). The diisocyanate represented by the above formulas (12), (13) or the following formulas (19) to 22) was used as the diisocyanate represented by the same formula as in Example 1 except that the combinations shown in Tables 1 to 6 were used. Thus, imide compounds -2 to 18 were obtained as solids. Examples 5 to 7, 14 and 16 use two types of monoamines, and after synthesizing each of the intermediates in the same manner as in Example 1, the molar ratio was 1: 1 and the two types of intermediates were combined. In the same manner as in Example 1, the intermediate and diisocyanate in an amount of 15 g were reacted. If no solid precipitated after the reaction, methanol was added until a solid precipitated. The yields of imide compounds-2 to 18 obtained by the reaction are shown in Tables 1 to 6.

For the imide-amide compounds-2 to 18 obtained in Examples 2 to 18, the infrared absorption spectra were measured in the same manner as in Example 1. In any of the imide-amide compounds, it was found that about Absorption at 1720 cm ⁻¹ , about 1780 cm ⁻¹ , and about 1660 cm ⁻¹ derived from an amide group were confirmed, and absorption at about 2270 cm ⁻¹ attributed to the isocyanide group of the reaction raw material was not confirmed. From these results, it was confirmed that the solids obtained in Examples 2 to 18 were imide-amide compounds.

Further, imide-amide compounds-2 to 18 obtained in Examples 2 to 18 were subjected to FD-MS measurement in the same manner as in Example 1. The imide-amide compounds contained are shown in Tables 1 to 6, respectively. Peaks attributed to imide-amide compounds (compounds represented by the following formulas (23) to (39)) were observed. The intensity ratios of the contained imide-amide compounds to the total ion intensity observed in each example are shown in Tables 1 to 6.

[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 urea compound-1 represented by the formula (40). The yield of the resulting urea compound is shown in Table 7.

[Comparative Example 2]
A grease-like substance was obtained by reacting 38.3 g of 4,4′-diisocyanatodiphenylmethane with 68.3 g of octadecylamine in 300 g of a diphenyl ether base oil having a kinematic viscosity at 100 ° C. of 13 mm ² / s. Diphenyl ether base oil was removed from the grease-like substance with hexane to obtain urea compound-2 represented by the formula (41). The yield of the resulting urea compound is shown in Table 7.

[Heat resistance evaluation]
The imide-amide compounds -1 to 18 obtained in Examples 1 to 18 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 results obtained are shown in Tables 8-14. In the table, the higher the decomposition temperature, the better the heat resistance.

[Capacity evaluation]
The imide-amide compounds-1 to 18 obtained in Examples 1 to 18 and the urea compounds 1 and 2 obtained in Comparative Examples 1 and 2 had a kinematic viscosity at 100 ° C. of 13 mm ² / The substance obtained by mixing with s diphenyl ether base oil and uniformly dispersing in the base oil through a roll mill was measured for consistency after 60 blending (60 W) by the consistency measuring method of JIS2220. The results obtained are shown in Tables 8-14. For the urea compounds of Comparative Examples 1 and 2, the consistency was measured before removing the diphenyl ether base oil with hexane.

From the results shown in Tables 8 to 14, the imide-amide compounds -1 to 18 obtained in Examples 1 to 18 were more heat resistant 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

An imide-amide compound represented by the following general formula (1):

[Wherein, R and X each represent a monovalent organic group. ]
The imide-amide compound according to claim 1, which is represented by the following general formula (2) or (3).

[Wherein R 1 and R 2 represent a monovalent organic group, X 1 represents a divalent organic group, X 2 represents a monovalent organic group, and R 1 and R in formula (2) 2 may be the same or different. ]
First step of obtaining imidocarboxylic acid represented by the following general formula (6) by reacting trimellitic anhydride represented by the following formula (4) with a monoamine represented by the following general formula (5) When,
A second step of reacting the imide carboxylic acid with an isocyanate represented by the following general formula (7) to obtain an imide-amide compound represented by the following general formula (1);
The manufacturing method of an imide compound provided with.

[Wherein, R and X each represent a monovalent organic group. ]
A thickener for grease containing the imide-amide compound according to claim 1 or 2.
A grease composition comprising a lubricating base oil and the imide-amide compound according to claim 1 or 2.