JP2008189562A - Novel organomolybdenum compound, friction modifier comprising the same, and lubricating composition containing the same - Google Patents

Abstract

A novel organomolybdenum compound, a friction modifier comprising the same, and a lubricating composition containing the same are provided.
The following general formula (1)

(Wherein, A ¹ and A ² are groups independently selected from the group consisting of a heterocyclic ring and a dialkylamino group which may have a substituent, respectively) Can be used in lubricating oils. In particular, when A ¹ and A ² are 1-pyrrolidinyl groups, an excellent friction reducing effect is exhibited.
[Selection figure] None

Description

  The present invention relates to a novel organomolybdenum compound, a friction modifier comprising the same, and a lubricating composition containing the same.

  In order to adjust the friction characteristics of the lubricant to an appropriate level, there is a friction modifier (friction modifier), and friction compositions that reduce friction in lubricating compositions such as gear oil and engine oil aiming at fuel saving. In the lubricating composition used for the wet clutch portion of the automatic transmission, a friction modifier having a friction improving effect is used in order to maintain a somewhat high friction level. Many types of friction modifiers have been proposed.

The most typical friction modifier is an organomolybdenum compound. As shown in Non-Patent Document 1, these organomolybdenum compounds are represented by the following formulas (2) and (3). As shown, the compound contains two Mo elements in one molecule.
Patent Documents 1 to 5 also disclose two Mo element-containing compounds in one molecule.
And, as shown by the general formula (2), the compound containing phosphorus in the molecule contains a problem that when added to engine oil, it becomes a catalyst poison of an exhaust gas purification device, and does not contain phosphorus. There is a need for compounds.

July 25, 1986, published by Koshobo Co., Ltd., edited by Toshio Sakurai, “New Version Petroleum Product Additives” Japanese Patent No. 3495764 Japanese Patent Publication No. 45-24562 JP-A 52-19629 JP-A-52-106824 JP-A 48-56202

  An object of the present invention is to provide a novel organomolybdenum compound, a friction modifier comprising the same, and a lubricating composition containing the same.

The first of the present invention is the following general formula (1)
(In the formula, A ¹ and A ² are groups independently selected from the group consisting of a heterocyclic ring and dialkylamino group which may have a substituent)
It relates to the organomolybdenum compound shown by.
In the second aspect of the present invention, the heterocyclic ring that may have a substituent is a heterocyclic ring selected from the group consisting of a 5-membered ring and a 6-membered ring, and the 5-membered ring includes a tetrazole type and a triazole type. , Pyrazole type, pyrazolidine type, imidazole type, oxazolidine type, thiazolidine type, pyrrolidine type, pyrroline type and pyrrole type, wherein the 6-membered ring is piperazine type, pyrazine type, thiomorpholine The organomolybdenum compound according to claim 1, which is a 6-membered ring selected from the group consisting of a type, thiazine type, morpholine type, oxazine type and piperidine type.
According to a third aspect of the present invention, A ¹ and A ² are dialkylamino groups, A ¹ is —N (R ¹⁰ , R ¹¹ ), A ² is —N (R ^{10 ′} , R ^{11 ′} ) 2. The organic molybdenum according to claim 1, wherein R ¹⁰ , R ¹¹ , R ^{10 ′} and R ^{11 ′} are groups independently selected from the group consisting of linear or branched alkyl groups having 1 to 30 carbon atoms. Relates to compounds.
In a fourth aspect of the present invention, A ¹ and A ² are each represented by —N (CH ₃ ) ₂ , —N (C ₂ H ₅ ) ₂ , —N (C ₃ H ₇ ) ₂ , —N (C ₄ H ₉ ). ₂ , —N (C ₅ H ₁₁ ) ₂ , —N (C ₆ H ₁₃ ) ₂ , —N (C ₇ H ₁₅ ) ₂ , —N (C ₈ H ₁₇ ) ₂ The organomolybdenum compound according to claim 1, wherein
A fifth aspect of the present invention relates to the organomolybdenum compound according to claim 1, wherein both A ¹ and A ² are 1-pyrrolidyl groups.
6th of this invention is related with the friction modifier which consists of an organic molybdenum compound in any one of Claims 1-5.
7th of this invention is related with the lubricating composition containing the friction modifier of Claim 6.

The compound of the present invention can be produced, for example, by the following reaction.

(1)

(2) (a) Synthesis of intermediate


(B) Synthesis of Compound of the Present Invention from Intermediate In the following formula, PPh ₃ represents triphenylphosphine.

Can be expressed as In the formula, Z ^{1 to} Z ⁴ are elements independently selected from the group consisting of C, O, N and S, and among these, in the case of C and N, the adjacent C and N are doubled. A bond may be formed. R ^{1 to} R ⁴ and R ^{1 ′ to} R ^{4 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group having 1 to 30 carbon atoms, but Z ^{1 to} Z ⁴ are bonded to form a ring. These groups are absent when the hand is saturated.

Can be expressed as In the formula, Z ^{5 to} Z ⁹ are elements independently selected from the group consisting of C, O, N, and S. Among these, in the case of C or N, the adjacent C or N is doubled. A bond may be formed. R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group having 1 to 30 carbon atoms, but Z ^{5 to} Z ⁹ are bonded to form a ring. These groups are absent when the hand is saturated.

Specific examples of A ¹ or A ² include the following cases.

The 5-membered ring such as the tetrazole type and the 6-membered ring such as the morpholine type may have substituents represented by R ^{1 to} R ⁹ and R ^{1 ′ to} R ^{9 ′} . The alkyl group having 1 to 30 carbon atoms, which is the locating group, may be linear or branched. For example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n- Examples include decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like.

The compounds of the present invention can be roughly classified into types I to VI.
(1) Type I
R ¹⁰ and R ¹¹ are groups independently selected from the group consisting of hydrogen and an alkyl group having 1 to 30 carbon atoms.
(2) Type II
(3) Type III
A ¹ and A ² are both 5-membered cases (4) Type IV
A ¹ and A ² are both 6-membered cases (5) Type V
Case where A ¹ is a 6-membered ring and A ² is a 5-membered ring (6) Type VI
Case A ¹ is ^-N with ^{(R 10, R 11),} A 2 is ^{-N (R 10 ', R 11} ')

When the compound of type I is further embodied, it can be shown as the following compound group.
In the following, R ^{1 to} R ⁴ and R ¹ ′ to R ^{4 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group, and the alkyl group preferably has 1 to 30 carbon atoms, preferably Are those of 1 to 20, particularly preferably 1 to 10, and hydrogen is preferable as these groups. Further, R ¹⁰ and R ¹¹ are groups independently selected from the group consisting of alkyl groups having 1 to 30, preferably 1 to 20, and particularly preferably 1 to 8 carbon atoms.

When the compound of type II is further embodied, it can be shown as the following compound group.

In the formula, R ^{5 to} R ⁹ , R ⁵ ′ to R ^{9 ′} and R ^{10 to} R ¹¹ are groups independently selected from the group consisting of hydrogen and an alkyl group, and the alkyl group is a carbon The number is 1 to 30, preferably 1 to 20, and particularly preferably 1 to 10, and hydrogen is one of these groups. Further, R ¹⁰ and R ¹¹ are groups independently selected from the group consisting of alkyl groups having 1 to 30, preferably 1 to 20, and particularly preferably 1 to 8 carbon atoms.

Examples of the type III compound include those in which A ¹ and A ² have the following structures.

In the formula, R ^{1 to} R ⁴ , R ¹ ′ to R ^{4 ′} , R ^{12 to} R ¹⁵ and R ¹² ′ to R ^{15 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group. And the alkyl group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. In addition, hydrogen is preferable as these groups.

In the type IV compound, A ¹ and A ² may have the following structures.

In the formula, R ^{5 to} R ⁹ , R ⁵ ′ to R ^{9 ′} , R ^{16 to} R ²⁰ and R ¹⁶ ′ to R ^{20 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group. And the alkyl group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. In addition, hydrogen is preferable as these groups.

Examples of the heterocyclic ring A ¹ and A ² in the compound of type V include the following structures.

In the formula, R ^{5 to} R ⁹ , R ⁵ ′ to R ^{9 ′} , R ^{12 to} R ¹⁵ and R ¹² ′ to R ^{15 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group. And the alkyl group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. In addition, hydrogen is preferable as these groups.

Specific compounds of Type I: dithiooxomolybdenum complex of tetrazoyl dithiocarbamate and dialkyldithiocarbamate, dithiooxomolybdenum complex of triazoyldithiocarbamate and dialkyldithiocarbamate, pyrazoyldithiocarbamate and dialkyldithiocarbamate Dithiooxomolybdenum complex, pyrazolidyl dithiocarbamate and dialkyldithiocarbamate dithiooxomolybdenum complex, imidazoyldithiocarbamate and dialkyldithiocarbamate dithiooxomolybdenum complex, oxazolyldithiocarbamate and dialkyldithiocarbamate Dithiooxomolybdenum complex with mato, dithiooxomolybdenum complex with thiazolidyldithiocarbamate and dialkyldithiocarbamate, pyrrolidyldithiocarbamate and di Dithiooxomolybdenum complex with alkyldithiocarbamate, dithiooxomolybdenum complex with pyrrolyldithiocarbamate and dialkyldithiocarbamate, dithiooxomolybdenum complex with pyrrolyldithiocarbamate and dialkyldithiocarbamate.
In the names of exemplary compounds of type I, alkyl is a C1-30 alkyl group, such as a methyl group, an ethyl group, and an alkyl group having 3 to 30 carbon atoms, including propyl, butyl, and pentyl, including normal and iso forms. , Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hecosyl, heptacosyl, cotacosyl, Contacil etc.

Specific compounds of Type II Dithiooxomolybdenum complex of piperazyl dithiocarbamate and dialkyldithiocarbamate, dithiooxomolybdenum complex of pyrazyldithiocarbamate and dialkyldithiocarbamate, thiomorpholyldithiocarbamate and dialkyldithiocarbamate Dithiooxomolybdenum complex with matto, dithiooxomolybdenum complex with thiazyldithiocarbamate and dialkyldithiocarbamate, dithiooxomolybdenum complex with morpholyldithiocarbamate and dialkyldithiocarbamate, oxazyldithiocarbamate and dialkyl Dithiooxomolybdenum complex with dithiocarbamato, dithiooxomolybdenum complex with piperidyldithiocarbamate and dialkyldithiocarbamate.
In the names of exemplary compounds of type II, alkyl is a C1-30 alkyl group, such as a methyl group, an ethyl group, and an alkyl group having 3 to 30 carbon atoms, including propyl, butyl, and pentyl, including normal and iso forms. , Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hecosyl, heptacosyl, cotacosyl, Contacil etc.

Specific compounds of Type III Dithiooxomolybdenum complex of tetrazoyldithiocarbamate and tetrazoyldithiocarbamate, dithiooxomolybdenum complex of tetrazoyldithiocarbamate and triazoyldithiocarbamate, tetrazoyldithiocarbamate and pyrazoyldithio Dithiooxomolybdenum complex with carbamato, dithiooxomolybdenum complex with tetrazoyldithiocarbamate and pyrazolidyldithiocarbamate, dithiooxomolybdenum complex with tetrazoyldithiocarbamate and imidazoyldithiocarbamate, tetrazoyldithiocarbamate Dithiooxomolybdenum complex of matto and oxazolyldithiocarbamate, dithiooxomolybdenum complex of tetrazoyldithiocarbamate and thiazolidyldithiocarbamate, tetrazoyldi Dithiooxomolybdenum complex of thiocarbamate and pyrrolidyldithiocarbamate, dithiooxomolybdenum complex of tetrazoyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex of tetrazoyldithiocarbamate and pyrrolyldithiocarbamate, Diazooxomolybdenum complex of triazoyldithiocarbamate and triazoyldithiocarbamate, dithiooxomolybdenum complex of triazoyldithiocarbamate and pyrazoyldithiocarbamate, triazoyldithiocarbamate and pyrazolidyldithiocarbamate Dithiooxomolybdenum complex, triazoyldithiocarbamate and imidazoyldithiocarbamate dithiooxomolybdenum complex, triazoyldithiocarbamate and oxazolyldithiocarbamate Dithiooxomolybdenum complex, diazooxomolybdenum complex of triazoyldithiocarbamate and thiazolidyldithiocarbamate, dithiooxomolybdenum complex of triazoyldithiocarbamate and pyrrolidyldithiocarbamate, triazoyldithiocarbamate and pyrrolyl Dithiooxomolybdenum complex with dithiocarbamate, diazooxomolybdenum complex with triazoyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with pyrazoyldithiocarbamate and pyrazoyldithiocarbamate, pyrazoyldithiocarbamate Dithiooxomolybdenum complex of mato and pyrazolidyldithiocarbamate, dithiooxomolybdenum complex of pyrazoyldithiocarbamate and imidazoyldithiocarbamate, pyrazoyldithiocarbamate Dithiooxomolybdenum complex with azoazolyldithiocarbamate, diazooxomolybdenum complex with pyrazoyldithiocarbamate and thiazolidyldithiocarbamate, dithiooxomolybdenum with pyrazoyldithiocarbamate and pyrrolidyldithiocarbamate Complexes, dithiooxomolybdenum complexes of pyrazoyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complexes of pyrazoyldithiocarbamate and pyrrolyldithiocarbamate, pyrazolidyldithiocarbamate and pyrazolidyldithiocarbamate Dithiooxomolybdenum complex with matto, dithiooxomolybdenum complex with pyrazolidyldithiocarbamate and imidazoyldithiocarbamate, dithiooxomolybdenum with pyrazolidyldithiocarbamate and oxazolyldithiocarbamate Budene complex, dithiooxomolybdenum complex of pyrazolidyldithiocarbamate and thiazolidyldithiocarbamate, dithiooxomolybdenum complex of pyrazolidyldithiocarbamate and pyrrolidyldithiocarbamate, pyrazolidyldithiocarbamate and pylori Dithiooxomolybdenum complex with rudithiocarbamate, dithiooxomolybdenum complex with pyrazolidyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with imidazoyldithiocarbamate and imidazoyldithiocarbamate, imidazoyl Dithiooxomolybdenum complex of dithiocarbamate and oxazolyldithiocarbamate, dithiooxomolybdenum complex of imidazoyldithiocarbamate and thiazolidyldithiocarbamate, imidazoyldithiocarbamate and Dithiooxomolybdenum complex with lysyldithiocarbamate, dithiooxomolybdenum complex with imidazolyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with imidazolyldithiocarbamate and pyrrolyldithiocarbamate, oxazolyl Dithiooxomolybdenum complex of dithiocarbamate and oxazolyldithiocarbamate, dithiooxomolybdenum complex of oxazolyldithiocarbamate and thiazolidyldithiocarbamate, oxazolyldithiocarbamate and pyrrolidyldithiocarbamate Dithiooxomolybdenum complex, oxazolyldithiocarbamate and pyrrolyldithiocarbamate dithiooxomolybdenum complex, oxazolyldithiocarbamate and pyrrolyldithiocarbamate dithiooxomolybdenum Dithiooxomolybdenum complex of thiazolidyldithiocarbamate and thiazolidyldithiocarbamate, dithiooxomolybdenum complex of thiazolidyldithiocarbamate and pyrrolidyldithiocarbamate, thiazolidyldithiocarbamate and pyrrolyl Dithiooxomolybdenum complex with dithiocarbamate, dithiooxomolybdenum complex with thiazolidyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with pyrrolidyldithiocarbamate and pyrrolidyldithiocarbamate, pyrrolidyldithio Dithiooxomolybdenum complex of carbamato and pyrrolyldithiocarbamate, dithiooxomolybdenum complex of pyrrolidyldithiocarbamate and pyrrolyldithiocarbamate, pyrrolyldithiocarbamate and pyrrolyldithiocarbamate Dithiooxomolybdenum complex, dithiooxomolybdenum complex of pyrrolyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex of pyrrolyldithiocarbamate and pyrrolyldithiocarbamate.

Specific compounds of Type IV: dithiooxomolybdenum complex of piperazil dithiocarbamate and piperazil dithiocarbamate, dithiooxomolybdenum complex of piperazyl dithiocarbamate and pyrazyldithiocarbamate, piperazyl dithiocarbamate and thiomorpholine Dithiooxomolybdenum complex with rudithiocarbamate, dithiooxomolybdenum complex with piperazyldithiocarbamate and thiazyldithiocarbamate, dithiooxomolybdenum complex with piperazyldithiocarbamate and morpholyldithiocarbamate, piperazil Dithiooxomolybdenum complex of dithiocarbamate and oxazyldithiocarbamate, dithiooxomolybdenum complex of piperazyldithiocarbamate and piperidyldithiocarbamate, pyrazyldithiocarbamate and pyrazyldithio Dithiooxomolybdenum complex with rubamato, dithiooxomolybdenum complex with pyrazyldithiocarbamate and thiomorpholyldithiocarbamate, dithiooxomolybdenum complex with pyrazyldithiocarbamate and thiazyldithiocarbamate, pyrazyldithiocarbamate Dithiooxomolybdenum complex of matto and morpholyldithiocarbamate, dithiooxomolybdenum complex of pyrazyldithiocarbamate and oxazyldithiocarbamate, dithiooxomolybdenum complex of pyrazyldithiocarbamate and piperidyldithiocarbamate, Dithiooxomolybdenum complex of thiomorpholyldithiocarbamate and thiomorpholyldithiocarbamate, dithiooxomolybdenum complex of thiomorpholyldithiocarbamate and thiazyldithiocarbamate, thiomorpholyldithio Dithiooxomolybdenum complex of rubamat and morpholyldithiocarbamate, dithiooxomolybdenum complex of thiomorpholyldithiocarbamate and oxazyldithiocarbamate, dithiol of thiomorpholyldithiocarbamate and piperidyldithiocarbamate Oxomolybdenum complex, dithiooxomolybdenum complex of thiazyldithiocarbamate and thiazyldithiocarbamate, dithiooxomolybdenum complex of thiazyldithiocarbamate and morpholyldithiocarbamate, thiazyldithiocarbamate and oxazyldithio Dithiooxomolybdenum complex with carbamato, dithiooxomolybdenum complex with thiazyldithiocarbamate and piperidyldithiocarbamate, dithiooxomolybdenum complex with morpholyldithiocarbamate and morpholyldithiocarbamate , Dithiooxomolybdenum complex of morpholyldithiocarbamate and oxazyldithiocarbamate, dithiooxomolybdenum complex of morpholyldithiocarbamate and piperidyldithiocarbamate, oxadyldithiocarbamate and oxazyldithiocarbamate Dithiooxomolybdenum complex, dithiooxomolybdenum complex of oxazyldithiocarbamate and piperidyldithiocarbamate, dithiooxomolybdenum complex of piperidyldithiocarbamate and piperidyldithiocarbamate.

Specific compounds of Type V: dithiooxomolybdenum complex of piperazil dithiocarbamate and tetrazoyldithiocarbamate, dithiooxomolybdenum complex of piperazyldithiocarbamate and triazoyldithiocarbamate, piperazyldithiocarbamate and pyrazoyldithio Dithiooxomolybdenum complex with carbamato, dithiooxomolybdenum complex with piperazyldithiocarbamate and pyrazolidyldithiocarbamate, dithiooxomolybdenum complex with piperazyldithiocarbamate and imidazoyldithiocarbamate, piperazyldithiocarbamate Dithiooxomolybdenum complex of matto and oxazolyldithiocarbamate, dithiooxomolybdenum complex of piperazyldithiocarbamate and thiazolidyldithiocarbamate, piperazyldithiocarbamato Dithiooxomolybdenum complex with pyrrolidyldithiocarbamate, dithiooxomolybdenum complex with piperazyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with piperazyldithiocarbamate and pyrrolyldithiocarbamate, pyrazyl Dithiooxomolybdenum complex of dithiocarbamate and tetrazoyldithiocarbamate, dithiooxomolybdenum complex of pyrazyldithiocarbamate and triazoyldithiocarbamate, dithiooxomolybdenum of pyrazyldithiocarbamate and pyrazoyldithiocarbamate Complexes, dithiooxomolybdenum complexes of pyrazyldithiocarbamate and pyrazolidyldithiocarbamate, dithiooxomolybdenum complexes of pyrazyldithiocarbamate and imidazoyldithiocarbamate, pyrazyldi Dithiooxomolybdenum complex of ocarbamate and oxazolyldithiocarbamate, dithiooxomolybdenum complex of pyrazyldithiocarbamate and thiazolidyldithiocarbamate, dithiooxomolybdenum of pyrazyldithiocarbamate and pyrrolidyldithiocarbamate Complexes, dithiooxomolybdenum complexes of pyrazyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complexes of pyrazyldithiocarbamate and pyrrolyldithiocarbamate, thiomorpholyldithiocarbamate and tetrazoyldithiocarbamate Dithiooxomolybdenum complex with mato, dithiooxomolybdenum complex with thiomorpholyldithiocarbamate and triazoyldithiocarbamate, dithioomolybdenum with thiomorpholyldithiocarbamate and pyrazoyldithiocarbamate Somolybdenum complex, dithiooxomolybdenum complex of thiomorpholyldithiocarbamate and pyrazolidyldithiocarbamate, dithiooxomolybdenum complex of thiomorpholyldithiocarbamate and imidazoyldithiocarbamate, thiomorpholyldithio Dithiooxomolybdenum complex of carbamato and oxazolyldithiocarbamate, dithiooxomolybdenum complex of thiomorpholyldithiocarbamate and thiazolidyldithiocarbamate, thiomorpholyldithiocarbamate and pyrrolidyldithiocarbamate Dithiooxomolybdenum complex with thiomorpholyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with thiomorpholyldithiocarbamate and pyrrolyldithiocarbamate, thiazyldithio Dithiooxomolybdenum complex of ocarbamate and tetrazoyldithiocarbamate, dithiooxomolybdenum complex of thiazyldithiocarbamate and triazoyldithiocarbamate, dithiooxomolybdenum complex of thiazyldithiocarbamate and pyrazoyldithiocarbamate, Dithiooxomolybdenum complex of thiazyldithiocarbamate and pyrazolidyldithiocarbamate, dithiooxomolybdenum complex of thiazyldithiocarbamate and imidazoyldithiocarbamate, thiazyldithiocarbamate and oxazolyldithiocarbamate Dithiooxomolybdenum complex, thiazyldithiocarbamate and thiazolidyldithiocarbamate dithiooxomolybdenum complex, thiazyldithiocarbamate and pyrrolidyldithiocarbamate dithiooxomolybdenum , Dithiooxomolybdenum complex of thiazyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex of thiazyldithiocarbamate and pyrrolyldithiocarbamate, morpholyldithiocarbamate and tetrazoyldithiocarbamate Dithiooxomolybdenum complex with morpholyldithiocarbamate and triazoyldithiocarbamate, dithiooxomolybdenum complex with morpholyldithiocarbamate and pyrazoyldithiocarbamate, morpholyldithiocarbamate Dithiooxomolybdenum complex of mato and pyrazolidyldithiocarbamate, dithiooxomolybdenum complex of morpholyldithiocarbamate and imidazoyldithiocarbamate, morpholyldithiocarbamate and oxazolyldithiocarbamate Dithiooxomolybdenum complex, morpholyldithiocarbamate and thiazolidyldithiocarbamate dithiooxomolybdenum complex, morpholyldithiocarbamate and pyrrolidyldithiocarbamate dithiooxomolybdenum complex, morpholyldithiocarbamate Dithiooxomolybdenum complex between mato and pyrrolyldithiocarbamate, dithiooxomolybdenum complex between morpholyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex between oxazyldithiocarbamate and tetrazoyldithiocarbamate Dioxaxomolybdenum complex of oxazyldithiocarbamate and triazoyldithiocarbamate, dithiooxomolybdenum complex of oxazyldithiocarbamate and pyrazoyldithiocarbamate, Dithiooxomolybdenum complex with lazolidyldithiocarbamate, dithiooxomolybdenum complex with oxazildithiocarbamate and imidazoyldithiocarbamate, dithiooxomolybdenum complex with oxazyldithiocarbamate and oxazolyldithiocarbamate, Dithiooxomolybdenum complex of dildithiocarbamate and thiazolidyldithiocarbamate, dithiooxomolybdenum complex of oxazyldithiocarbamate and pyrrolidyldithiocarbamate, dithiox of oxazyldithiocarbamate and pyrrolyldithiocarbamate Oxomolybdenum complex, dithiooxomolybdenum complex of oxazyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex of piperidyldithiocarbamate and tetrazoyldithiocarbamate, Dithiooxomolybdenum complex of peridyldithiocarbamate and triazoyldithiocarbamate, dithiooxomolybdenum complex of piperidyldithiocarbamate and pyrazoyldithiocarbamate, dithiooxo of piperidyldithiocarbamate and pyrazolidyldithiocarbamate Molybdenum complexes, dithiooxomolybdenum complexes of piperidyldithiocarbamate and imidazoyldithiocarbamate, dithiooxomolybdenum complexes of piperidyldithiocarbamate and oxazolyldithiocarbamate, piperidyldithiocarbamate and thiazolidyldithiocarbamate Dithiooxomolybdenum complex, piperidyldithiocarbamate and pyrrolidyldithiocarbamate complex, piperidyldithiocarbamate and pyrrolyldithiocarbamate Dithio oxo molybdenum complexes, dithiocarbamate oxo molybdenum complexes with piperidyl dithiocarbamate Mato and pillow Lil dithiocarbamate Mato.

Specific compounds of Type VI Dimethyldithiocarbamatodithiooxomolybdenum complex, Diethyldithiocarbamatodithiooxomolybdenum complex, Dipropyldithiocarbamatodithiooxomolybdenum complex, Dibutyldithiocarbamatodithiooxomolybdenum complex, Dipentyldithiocarbamatodithiooxomolybdenum complex Dihexyldithiocarbamatodithiooxomolybdenum complex, diheptyldithiocarbamatodithiooxomolybdenum complex, dioctyldithiocarbamatodithiooxomolybdenum complex, dinonyldithiocarbamatodithiooxomolybdenum complex, didecyldithiocarbamatodithiooxomolybdenum complex, diun Decyldithiocarbamatodithiooxomolybdenum complex, didodecyldithiocarbamatodithiooxomolybdenum complex, di Ridecyldithiocarbamatodithiooxomolybdenum complex, ditetradecyldithiocarbamatodithiooxomolybdenum complex, dipentadecyldithiocarbamatodithiooxomolybdenum complex, dihexadecyldithiocarbamatodithiooxomolybdenum complex, diheptadecyldithiocarbamatodithio Oxomolybdenum complex, dioctadecyldithiocarbamatodithiooxomolybdenum complex, dinonadecyldithiocarbamatodithiooxomolybdenum complex, dieicosyldithiocarbamatodithiooxomolybdenum complex, dihenicosyldithiocarbamatodithiooxomolybdenum complex, didoco Sildithiocarbamatodithiooxomolybdenum complex, ditricosyldithiocarbamatodithiooxomolybdenum complex, ditetracosyldithiocarbamatodithiooxo Ribden complex, dipentacosyldithiocarbamatodithiooxomolybdenum complex, dihexocyldithiocarbamatodithiooxomolybdenum complex, diheptacosyldithiocarbamatodithiooxomolybdenum complex, dioctacosyldithiocarbamatodithiooxomolybdenum complex, Dinonacosyldithiocarbamatodithiooxomolybdenum complex, ditriacontacyldithiocarbamatodithiooxomolybdenum complex and mixed alkyldithiocarbamatodithiooxomolybdenum complexes thereof.

  Examples of the lubricating composition of the present invention include lubricating oil and grease. The abundance of the compound of the present invention in the lubricating composition is the same as that of the conventional friction modifier, and for example, it is blended at a ratio of about 0.1 to 10% by weight with respect to the normal composition.

(1) A new Mo-based friction modifier containing no phosphorus was obtained.
(2) When compared with existing Mo-based friction reducers with the same Mo content in the oil, the compound of the present invention exhibits a lower friction coefficient and can be used as an additive for various energy-saving lubricating oils.
(3) Since the compound of the present invention does not contain phosphorus, it is particularly suitable for use as a friction modifier of fuel-saving engine oil.

  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1
Dimethyldithiocarbamatodithiooxomolybdenum complex
Synthesis example (first step)
Na ₂ MoO ₄ + 2NaS ₂ CNEt ₂ + 4HCl
→ MoO ₂ (Et ₂ NCS ₂ ) ₂ + 2H ₂ O + 4NaCl
Sodium diethyldithiocarbamate (5.0 g, 0.02 mol) and sodium molybdate (2.7 g, 0.01 mol) were added to a 500 ml eggplant flask and dissolved in 50 ml of water. Thereto was added 0.04 mol of diluted hydrochloric acid (water added to 4 ml of concentrated hydrochloric acid to a total volume of 300 ml) dropwise over about 2 hours from the dropping funnel, and the resulting precipitate was suction filtered, and water, ethanol, After thoroughly washing with diethyl ether, it was dried. The obtained crystals were purified by recrystallizing twice with dichloromethane and n-hexane to obtain a diethyldithiocarbamatooxomolybdenum complex in a yield of 85%. This compound is a tan powder.
Under Ar, the diethyldithiocarbamatooxomolybdenum complex (1.0 g, 2.3 mmol) and triphenylphosphine (1.0 g, 3.8 mmol) were added to a two-necked flask equipped with a reflux tube, and 1,2- The mixture was refluxed for 10 to 15 minutes at about 90 ° C. in 10 ml of dichloroethane. An additional 3.2mmol of _{S 8} or propylene sulfide mixed solution turned red, 30 minutes in the case of _{S 8,} in the case of sulfide propylene was heated to reflux for 1.5 hours. The obtained reaction mixture was purified by a silica gel column, and the obtained crystals were further purified by recrystallization.
Complexes: dark green crystals were confirmed product of intended product (a synthetic _{S 8)} NMR and IR 37% yield.
¹ HNMR (CDCl ₃ ) δ = 1.09, 1.38, 1.40 and 1.45 (4t, 4 × 3H), 3.48 and 3.57 (m, 2H), 3.8-4.0 (m, 3 × 2H)
IR (KBr): ν (CN) 1529 s, 1497 s; ν (Mo═O) 922 s; ν (SS) 554 cm ⁻¹

Example 2
Complexes of pyrrolidinyldithiocarbamate with dithiooxomolybdenum.
Synthesis example (first step)
Synthesis of complexes of the intermediate composition pyrrolidinyldithiocarbamate with dithiooxomolybdenum.
Na ₂ MoO ₄ + 2NH ₄ S ₂ CN (C ₄ H ₈ ) + 4HCl
→ MoO ₄ (C ₄ H ₈ NCS ₂ ) ₂ + 2NaCl + 2NH ₄ Cl
Sodium molybdate (7.3 g, 0.03 mol) and ammonium pyrrolidinedithiocarbamate (9.9 g, 0.06 mol) are added to a 500 ml eggplant flask, dissolved in 100 ml of water, and 300 ml of 0.12 mol dilute hydrochloric acid is added from the dropping funnel. It was dripped over 2 hours. The obtained precipitate was suction filtered, washed well with water, ether, methanol, and acetone to remove moisture. Further, in order to remove moisture, it was left for 2 days in a desiccator under vacuum. Recrystallization was performed with dichloromethane / methanol to obtain a complex of pyrrolidinyldithiocarbamate and dithiooxomolybdenum shown in [Chemical Formula 52].
Complex: yellow powder, yield 72%
The complex shown in [Chemical Formula 52] (1.0 g, 2.3 mmol) and triphenylphosphine (1.0 g, 3.8 mmol) were refluxed for 10 minutes in 10 ml of 1,2-dichloroethane, and further sulfided. Propylene (0.77 ml, 9.9 mmol) was added and heated to reflux for 1-2 hours. The resulting reaction mixture was isolated and purified by column chromatography to obtain a complex of pyrrolidinyldithiocarbamato and dithiooxomolybdenum.
Complex: Blue-green crystals, 82% yield
NMR and elemental analysis were performed to confirm the formation of the target compound.
¹ HNMR (CDCl ₃ ) δ = 1.95 to 2.00 (m, 2H × 1), 2.04 to 2.16 (m, 2H × 2), 3.36 to 3.50 (m, 2H ×) 1), 3.77 to 4.02 (m, 2H × 4)
Elemental Anal. _{Calcd (%) forC 10 H 16} N 2 S 6 OMo: C, 25.63; H, 3.44; N, 5.98; S, 41.06; O, 3.41; Mo, 20.47. found (%): C, 25.60; H, 3.27; N, 5.75.
An API group III mineral oil (viscosity at 100 ° C. 4.23 mm ² / s) containing 5% of a dispersant (alkenyl succinic acid polyalkylene polyimide, trade name: Infinum C9266) ) "Was added so that the Mo content was 500 ppm to prepare a lubricating oil composition.

Comparative Example 1
Instead of the complex of pyrrolidinyldithiocarbamate and dithiooxomolybdenum,
A lubricating oil composition was prepared in the same manner as described above except that was used.

The lubricating oil composition of Example 2 using the complex of pyrrolidinyldithiocarbamato and dithiooxomolybdenum of the present invention as a friction modifier and the lubricating oil composition of Comparative Example 1 using a commercially available friction modifier Using a SRV tester (cylinder-on-disk type reciprocating tester shown in FIG. 2), a friction coefficient was measured and evaluated for 30 minutes under the conditions shown in Table 3 below, and the results are shown in FIG. The specimen is 52100 steel.

As shown in FIG. 1, Example 2 shows a much lower friction coefficient than that of Comparative Example 1.

It is the graph which investigated the change of the time course of the lubricating oil which used this invention compound as a lubricating oil regulator, and the lubricating oil which used the commercial item as a lubricating oil regulator, and its friction coefficient. It is a conceptual schematic diagram of a cylinder-on-disk type reciprocating test machine used for measuring a friction coefficient.

Claims (7)

The following general formula (1)
(In the formula, A ¹ and A ² are groups independently selected from the group consisting of a heterocyclic ring and dialkylamino group which may have a substituent)
An organomolybdenum compound represented by   The heterocyclic ring that may have a substituent is a heterocyclic ring selected from the group consisting of a 5-membered ring and a 6-membered ring, and the 5-membered ring is a tetrazole type, a triazole type, a pyrazole type, a pyrazolidine type, It is a 5-membered ring selected from the group consisting of imidazole type, oxazolidine type, thiazolidine type, pyrrolidine type, pyrroline type and pyrrole type, and the 6-membered ring is piperazine type, pyrazine type, thiomorpholine type, thiazine type, morpholine type The organomolybdenum compound according to claim 1, which is a 6-membered ring selected from the group consisting of oxazine type and piperidine type. A ¹ and A ² are dialkylamino groups, A ¹ is —N (R ¹⁰ , R ¹¹ ), A ² is —N (R ^{10 ′} , R ^{11 ′} ), and R ¹⁰ , R ¹¹ , The organomolybdenum compound according to claim 1, wherein R ^{10 '} and R ^11' are groups independently selected from the group consisting of linear or branched alkyl groups having 1 to 30 carbon atoms. A ¹ and A ² are —N (CH ₃ ) ₂ , —N (C ₂ H ₅ ) ₂ , —N (C ₃ H ₇ ) ₂ , —N (C ₄ H ₉ ) ₂ , —N (C ₅ A group independently selected from the group consisting of H ₁₁ ) ₂ , —N (C ₆ H ₁₃ ) ₂ , —N (C ₇ H ₁₅ ) ₂ , —N (C ₈ H ₁₇ ) _2. 1. The organomolybdenum compound according to 1. ^{2. The} organomolybdenum compound according to claim 1, wherein A ¹ and A ² are both 1-pyrrolidyl groups.   A friction modifier comprising the organomolybdenum compound according to any one of claims 1 to 5.   A lubricating composition containing the friction modifier according to claim 6.