JP5395935B2 - Friction modifier comprising organomolybdenum compound and lubricating composition containing the same - Google Patents

Description

  The present invention relates to a friction modifier comprising an organomolybdenum compound 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.

また、特許文献１〜５においても１分子中に２個のＭｏ元素含有化合物が開示されている。
そして、前記式（２）で示されるように分子中にリンを含有する化合物は、リンがエンジン油に使用される場合、排ガス浄化装置の触媒毒となるという問題を含んでおり、リンを含まない化合物が求められている。 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 the compound containing phosphorus in the molecule as shown in the formula (2) has a problem that when phosphorus is used in engine oil, it becomes a catalyst poison of an exhaust gas purifying device. There is a need for no 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

The first object of the present invention is to provide a friction modifier comprising an organomolybdenum compound that does not contain phosphorus, reduces the coefficient of friction, and is useful as a lubricating additive for optimally adjusting the friction of a wet clutch or the like. is there.
The second object of the present invention is to provide a lubricating composition containing the same.

（式中、Ｒ^１〜Ｒ^１０は、水素、メチル基およびエチル基よりなる群からそれぞれ独立して選ばれた基である。）
本発明の第２は、請求項１に記載の摩擦調整剤を含有する潤滑組成物に関する。 The first of the present invention relates to a friction modifier comprising a dicyclopentadienyl molybdenum bridged complex represented by the following general formula (1).

(Wherein R ^{1 to} R ¹⁰ are groups independently selected from the group consisting of hydrogen, a methyl group and an ethyl group.)
The second aspect of the present invention relates to a lubricating composition containing the friction modifier according to claim 1.

(1) A Mo-based friction modifier containing no new phosphorus is obtained.
(2) The compound used in the present invention exhibits a low friction coefficient and can be used as a friction modifier for various energy-saving lubricating oils.
(3) Since the compound used in the present invention does not contain phosphorus, it is particularly suitable for use as a friction modifier of fuel-saving engine oil.
(4) The catalyst (NOx reduction) built in the automobile exhaust gas purification device is not damaged.

（式中Ｒ^１〜Ｒ^１０は、前記のとおりである。）

<第２工程>
ジシクロペンタジエニルモリブデン架橋錯体の合成
下記反応式のとおり、
一般式（２）のジ（シクロペンタジエニル）μ−チオキソモリブデン錯体
一般式（１）のジ（シクロペンタジエニル）μ−チオキソジオキソモリブデン錯体
一般式（３）のジ（シクロペンタジエニル）μ−オキソモリブデン錯体
一般式（４）のジ（シクロペンタジエニル）μ−オキソジオキソモリブデン錯体
を同時に生成する。

前記Ｒ^１〜Ｒ^１０としては、水素、メチル基およびエチル基を挙げることができ、一般式（１）の錯体の例としては、以下の表１〜表５のような組み合せによる化合物を挙げることができる。 The compound of the present invention can be produced, for example, by the following method.
<First step>
Synthesis of synthetic intermediate raw material dicyclopentadienyl molybdenum hexacarbonyl complex

(Wherein R ^{1 to} R ¹⁰ are as described above.)

<Second process>
Synthesis of dicyclopentadienylmolybdenum bridged complex As shown in the following reaction formula,
Di (cyclopentadienyl) μ-thioxomolybdenum complex of general formula (2) Di (cyclopentadienyl) μ-thioxodioxomolybdenum complex of general formula (1) Enyl) μ-oxomolybdenum complex A di (cyclopentadienyl) μ-oxodioxomolybdenum complex of the general formula (4) is simultaneously formed.

Examples of R ^{1 to} R ¹⁰ include hydrogen, a methyl group, and an ethyl group. Examples of the complex of the general formula (1) include compounds by combinations as shown in Tables 1 to 5 below. Can do.

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

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

ペンタメチルシクロペンタジエン（３．７５ｇ、１８．８ｍｍｏｌ）にテトラヒドロフラン（ＴＨＦ）４５ｍｌを加え、−７８℃に冷却した後、Ｂｕ−Ｌｉ（１２．５ｍｌ、１８．８ｍｍｏｌ）を滴下し、リチウムペンタメチルシクロペンタジエニルを調整した。そこにモリブデンヘキサカルボニル（５ｇ、１８．８ｍｍｏｌ）を加え、４８時間加熱還流し、反応終了後、母液を０℃に冷却した。別に精製水１００ｍｌと酢酸２０ｍｌを混合した溶液に硫酸鉄（II）（３．２ｇ、１８．８ｍｍｏｌ）を加えて得られた溶液を母液に滴下した。得られた赤色溶液を吸引ろ過し、洗浄、乾燥させ、再結晶によりジ（ペンタメチルシクロペンタジエニル）モリブデンヘキサカルボニル錯体を得た。収率２４％

（ロ）第２工程

前記ジ（ペンタメチルシクロペンタジエニル）モリブデンヘキサカルボニル錯体（０．５ｇ、０．７９ｍｍｏｌ）と３−スルホレン（０．６９ｇ、５．８４ｍｍｏｌ）をトルエン１００ｍｌに溶かし、１２０℃で３時間加熱還流した。反応終了後、溶媒除去し、反応生成物をカラムクロマトグラフィーによりオレンジ色の錯体を単離した。収率４％ Example 1 (Synthesis of Compound 2 in Table 1 above: When R ^{1 to} R ¹⁰ are CH ₃ )
(A) First step

Tetramethylcyclopentadiene (3.75 g, 18.8 mmol) was added with 45 ml of tetrahydrofuran (THF), cooled to −78 ° C., Bu-Li (12.5 ml, 18.8 mmol) was added dropwise, and lithium pentamethylcyclohexane was added. Pentadienyl was prepared. Molybdenum hexacarbonyl (5 g, 18.8 mmol) was added thereto and heated to reflux for 48 hours. After completion of the reaction, the mother liquor was cooled to 0 ° C. Separately, iron sulfate (II) (3.2 g, 18.8 mmol) was added to a mixed solution of 100 ml of purified water and 20 ml of acetic acid, and the resulting solution was added dropwise to the mother liquor. The obtained red solution was suction filtered, washed and dried, and di (pentamethylcyclopentadienyl) molybdenum hexacarbonyl complex was obtained by recrystallization. Yield 24%

(B) Second step

The di (pentamethylcyclopentadienyl) molybdenum hexacarbonyl complex (0.5 g, 0.79 mmol) and 3-sulfolene (0.69 g, 5.84 mmol) were dissolved in 100 ml of toluene and heated to reflux at 120 ° C. for 3 hours. . After completion of the reaction, the solvent was removed, and the orange complex was isolated from the reaction product by column chromatography. Yield 4%

シクロペンタジエン（１８．８ｍｍｏｌ）にテトラヒドロフラン（ＴＨＦ）４５ｍｌを加え、−７８℃に冷却した後、Ｂｕ−Ｌｉ（１２．５ｍｌ、１８．８ｍｍｏｌ）を滴下し、リチウムシクロペンタジエニルを調整した。そこにモリブデンヘキサカルボニル（５ｇ、１８．８ｍｍｏｌ）を加え、４８時間加熱還流し、反応終了後、母液を０℃に冷却した。別に精製水１００ｍｌと酢酸２０ｍｌを混合した溶液に硫酸鉄（II）（３．２ｇ、１８．８ｍｍｏｌ）を加えて得られた溶液を母液に滴下した。得られた赤色溶液を吸引ろ過し、洗浄、乾燥させ、再結晶によりジ（シクロペンタジエニル）モリブデンヘキサカルボニル錯体を得た。収率２０％

（ロ）第２工程

実施例３と同様の手順で反応を、カラムクロマトグラフィーにより赤色生成物ジ（シクロペンタジエニル）μチオキソジオキソモリブデン錯体を単離した。収率１４％ Example 2 (Synthesis of Compound 1 in Table 1 above: When R ^{1 to} R ¹⁰ are H)
(A) First step

Tetrahydrofuran (THF) 45 ml was added to cyclopentadiene (18.8 mmol) and cooled to −78 ° C., and then Bu—Li (12.5 ml, 18.8 mmol) was added dropwise to prepare lithium cyclopentadienyl. Molybdenum hexacarbonyl (5 g, 18.8 mmol) was added thereto and heated to reflux for 48 hours. After completion of the reaction, the mother liquor was cooled to 0 ° C. Separately, iron sulfate (II) (3.2 g, 18.8 mmol) was added to a mixed solution of 100 ml of purified water and 20 ml of acetic acid, and the resulting solution was added dropwise to the mother liquor. The resulting red solution was suction filtered, washed and dried, and di (cyclopentadienyl) molybdenum hexacarbonyl complex was obtained by recrystallization. Yield 20%

(B) Second step

The reaction was carried out in the same manner as in Example 3, and the red product di (cyclopentadienyl) μ thioxodioxomolybdenum complex was isolated by column chromatography. Yield 14%

Example 3
The complex obtained in Example 1 was put into “ester oil (diisononyl adipic acid) (viscosity 3.04 mm ² / s at 100 ° C.) added with 5% dispersant (alkenyl succinic acid polyalkylene polyimide, trade name: Infinum C9266)”. It mixed so that it might become Mo content 500ppm. The composition is shown in Table 7.

Comparative Example 1
The case where the complex obtained in Example 1 was not used in the composition of Example 3 was referred to as Comparative Example 1.
The composition is shown in Table 7.

実施例の場合は試験開始１分以降、無添加基油と比較して、図１に示すとおり低い摩擦係数を示し、摩擦調整剤としての機能を有することが分かった。すなわち、本発明の摩擦調整剤を配合した方が、配合しない場合に較べて低い摩擦係数を示すことが分かった。 With respect to the sample oil, the friction coefficient was measured for 30 minutes under the conditions shown in Table 6 below using an SRV tester (cylinder-on-disk type reciprocating tester shown in FIG. 2). The result is shown in FIG. The specimen is 52100 steel.
Test conditions

In the case of the examples, after 1 minute from the start of the test, compared to the additive-free base oil, it showed a low coefficient of friction as shown in FIG. 1 and was found to have a function as a friction modifier. That is, it turned out that the direction which mix | blended the friction modifier of this invention shows a low friction coefficient compared with the case where it does not mix | blend.

It is a graph which shows what kind of friction coefficient sample oil of Example 3 and comparative example 1 has with progress of time. It is an operation schematic diagram of a cylinder on disk type reciprocating test machine.

Claims (2)

A friction modifier comprising a dicyclopentadienyl molybdenum crosslinked complex represented by the following general formula (1).

(Wherein R ^{1 to} R ¹⁰ are groups independently selected from the group consisting of hydrogen, a methyl group and an ethyl group.)   A lubricating composition containing the friction modifier according to claim 1.

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