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JP5108316B2 - Friction modifier comprising organomolybdenum compound and lubricating composition containing the same - Google Patents

Friction modifier comprising organomolybdenum compound and lubricating composition containing the same Download PDF

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Publication number
JP5108316B2
JP5108316B2 JP2007023211A JP2007023211A JP5108316B2 JP 5108316 B2 JP5108316 B2 JP 5108316B2 JP 2007023211 A JP2007023211 A JP 2007023211A JP 2007023211 A JP2007023211 A JP 2007023211A JP 5108316 B2 JP5108316 B2 JP 5108316B2
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friction modifier
complex
friction
dithiooxomolybdenum
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JP2008189562A (en
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悦史 長富
憲明 篠田
良彦 相原
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Showa Shell Sekiyu KK
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Showa Shell Sekiyu KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Description

本発明は、有機モリブデン化合物よりなる摩擦調整剤およびそれを含む潤滑組成物に関する。 The present invention relates to an organic molybdenum compound by Li Cheng friction modifiers and lubricating compositions containing them.

潤滑剤の摩擦特性を適切なレベルに調整するために摩擦調整剤（フリクションモディファイア）があり、省燃費を目指したギヤ油やエンジン油のような潤滑組成物には摩擦低減作用のある摩擦調整剤が使用されており、自動変速機の湿式クラッチ部分に用いる潤滑組成物ではある程度高い摩擦レベルを維持するため摩擦向上作用のある摩擦調整剤が使用されている。これらの摩擦調整剤としては多くのタイプのものが提案されている。   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.

そして、その摩擦調整剤として最も代表的なものが有機モリブデン化合物であるが、非特許文献１にみられるように、これらの有機モリブデン化合物は、下記式（２）および（３）に示されているように１分子中に２個のＭｏ元素を含有する化合物である。
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、前記一般式（２）で示されるように分子中にリンを含有する化合物は、エンジン油に添加される場合、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, 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.

昭和６１年７月２５日、株式会社 幸書房発行、桜井俊男編著「新版石油製品添加剤」July 25, 1986, published by Koshobo Co., Ltd., edited by Toshio Sakurai, “New Version Petroleum Product Additives” 特許第３４９５７６４号公報Japanese Patent No. 3495764 特公昭４５−２４５６２号公報Japanese Patent Publication No. 45-24562 特開昭５２−１９６２９号公報JP-A 52-19629 特開昭５２−１０６８２４号公報JP-A-52-106824 特開昭４８−５６２０２号公報JP-A 48-56202

本発明の目的は、有機モリブデン化合物よりなる摩擦調整剤およびそれを含む潤滑組成物を提供する点にある。 An object of the present invention is to provide an organic molybdenum compound by Li Cheng friction modifiers and lubricating compositions containing them.

本発明の第１は、下記一般式（１）で示される有機モリブデン化合物よりなる摩擦調整剤に関する。
（式中、Ａ１およびＡ２は、環構成原子として窒素原子を１個含む５員環の複素環基および炭素数１〜２のアルキル基を有するジアルキルアミノ基よりなる群から選ばれた基であり、複素環基は窒素原子により基本骨格と結合しており、炭素数１〜３０のアルキル基で置換されていてもよい。）
本発明の第２は、Ａ １ およびＡ ２ がジエチルアミノ基または１−ピロリジニル基である請求項１記載の摩擦調整剤に関する。
本発明の第３は、請求項１又は２に記載の摩擦調整剤を含有する潤滑組成物に関する。 1st of this invention is related with the friction modifier which consists of an organic molybdenum compound shown by following General formula (1) .
(Wherein, A 1 and A 2, was exposed, the group or al election consisting dialkylamino group having a heterocyclic group and alkyl group having 1 to 2 carbon atoms of 5-membered ring containing one nitrogen atom as a ring-constituting atom Motodea is, the heterocyclic group is bonded to the basic skeleton by a nitrogen atom, it may be substituted with an alkyl group having 1 to 30 carbon atoms.)
The second of the present invention relates to the friction modifier according to claim 1 , wherein A 1 and A 2 are a diethylamino group or a 1-pyrrolidinyl group .
3rd of this invention is related with the lubricating composition containing the friction modifier of Claim 1 or 2 .

本発明で用いる化合物は、例えば下記の反応により製造することができる。
（１）
The compound used in the present invention can be produced, for example, by the following reaction.
(1)

（２）（イ）中間体の合成
（ロ）中間体から本発明で用いる化合物の合成
下記式中、ＰＰｈ３は、トリフェニルホスフィンを示す。
(2) (a) Synthesis of intermediate
(B) Synthesis of compound used in the present invention from an intermediate In the following formula, PPh 3 represents triphenylphosphine.

Ａ １ またはＡ ２ を例えば下記〔化９〕として表すと、その具体例としては、下記〔表１〕のものが挙げられる。Ｒ １ 〜Ｒ ４ およびＲ １′ 〜Ｒ ４′ は、水素および炭素数１〜３０のアルキ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。
For example, when A 1 or A 2 is represented by the following [Chemical 9], specific examples thereof include those shown in [Table 1] below. 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.

本発明で用いられる化合物は、大きく分けると、タイプＩ、III、VIに分けることができる。
（１）タイプＩ
Ａ １ が５員環で、Ａ ２ が−Ｎ（Ｒ １０ ，Ｒ １１ ）のケース
なお、Ｒ１０およびＲ１１は、炭素数１〜２のアルキル基からそれぞれ独立して選ばれた基である。
（２）タイプIII
Ａ１およびＡ２が共に５員環のケース
（３）タイプVI
Ａ１が−Ｎ（Ｒ１０，Ｒ１１）で、Ａ２が−Ｎ（Ｒ１０′，Ｒ１１′）のケース
なお、Ｒ １０ 、Ｒ １１ およびＲ １０ ′、Ｒ １１ ′は、炭素数１〜２のアルキル基からそれぞれ独立して選ばれた基である。 The compounds used in the present invention can be roughly classified into types I , III and VI .
(1) Type I
In A 1 is 5-membered ring, the case of A 2 is -N (R 10, R 11) Note that, R 10 and R 11 are each independently selected groups from the alkyl group of carbon number 1-2 .
( 2 ) Type III
A 1 and A 2 are both 5-membered cases ( 3 ) Type VI
Case A 1 is -N with (R 10, R 11), A 2 is -N (R 10 ', R 11 ')
R 10 , R 11 and R 10 ′, R 11 ′ are groups independently selected from alkyl groups having 1 to 2 carbon atoms.

タイプＩの化合物をさらに具体化すると下記の化合物群として示すことができる。
式中のＲ１〜Ｒ４およびＲ１′〜Ｒ４′は、水素およびアルキル基よりなる群からそれぞれ独立して選ばれた基であり、前記アルキル基の炭素数は１〜３０、好ましくは１〜２０、特に好ましくは１〜１０であり、また、水素は好ましいものの１つである。さらに、Ｒ１０およびＲ１１は、炭素数１〜２のアルキル基からそれぞれ独立して選ばれた基である。 When the compound of type I is further embodied, it can be shown as the following compound group.
R 1 to R 4 and R 1 '~R 4' of the formula are each independently a group selected from the group consisting of hydrogen and alkyl groups, the carbon number of the alkyl group having 1 to 30, preferably 20, particularly preferably 1 to 10, also hydrogen is one of those preferred. Furthermore, R 10 and R 11 is an alkyl group or al independently selected groups of 1-2 carbon atoms.

タイプIIIの化合物としては、Ａ１およびＡ２が下記の構造のものが挙げられる。
なお、式中Ｒ１〜Ｒ４、Ｒ１′〜Ｒ４′、Ｒ１２〜Ｒ１５およびＲ１２′〜Ｒ１５′は、水素およびアルキル基よりなる群からそれぞれ独立して選ばれた基であり、前記アルキル基の炭素数は１〜３０、好ましくは１〜２０、特に好ましくは１〜１０である。また、水素は好ましいものの１つである。 Type III compounds 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. The number of carbon atoms of the alkyl group is 1-30, preferably 1-20, particularly preferably 1-10. Moreover, hydrogen is one of those preferred.

タイプＩの具体的化合物
ピロリジルジチオカルバマトとジアルキルジチオカルバマトとのジチオオキソモリブデン錯体、ピロリルジチオカルバマトとジアルキルジチオカルバマトとのジチオオキソモリブデン錯体、ピローリルジチオカルバマトとジアルキルジチオカルバマトとのジチオオキソモリブデン錯体。
タイプＩの例示化合物の名称において、アルキルとは炭素数１〜３０のアルキル基であり、例えばメチル基、エチル基および炭素数３〜３０のアルキル基で、ノルマル体およびＩｓｏ体を含むプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、エイコシル、ヘンイコシル、ドコシル、トリコシル、テトラコシル、ペンタコシル、ヘキコシル、ヘプタコシル、オクタコシル、ノナコシル、トリアコンタシル等である。 Specific compounds of type I Dithiooxomolybdenum complex of pyrrolidyldithiocarbamate and dialkyldithiocarbamate, dithiooxomolybdenum complex of pyrrolyldithiocarbamate and dialkyldithiocarbamate, pyrrolyldithiocarbamate and dialkyldithiocarbamate And dithiooxomolybdenum complex.
In the names of the exemplified compounds of type I, alkyl is an alkyl group having 1 to 30 carbon atoms , such as a methyl group, an ethyl group, and an alkyl group having 3 to 30 carbon atoms, including propyl and butyl containing normal and iso isomers. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hecocosyl, hepanosyl , Triacontacil and the like.

タイプIIIの具体的化合物
ピロリジルジチオカルバマトとピロリジルジチオカルバマトとのジチオオキソモリブデン錯体、ピロリジルジチオカルバマトとピロリルジチオカルバマトとのジチオオキソモリブデン錯体、ピロリジルジチオカルバマトとピローリルジチオカルバマトとのジチオオキソモリブデン錯体、ピロリルジチオカルバマトとピロリルジチオカルバマトとのジチオオキソモリブデン錯体、ピロリルジチオカルバマトとピローリルジチオカルバマトとのジチオオキソモリブデン錯体、ピローリルジチオカルバマトとピローリルジチオカルバマトとのジチオオキソモリブデン錯体。 Specific compounds of type III Dithiooxomolybdenum complex of pyrrolidyldithiocarbamate and pyrrolidyldithiocarbamate, dithiooxomolybdenum complex of pyrrolidyldithiocarbamate and pyrrolyldithiocarbamate, pyrrolidyldithiocarbamate and pyrrolyl Dithiooxomolybdenum complex with dithiocarbamato, dithiooxomolybdenum complex with pyrrolyldithiocarbamate and pyrrolyldithiocarbamate, dithiooxomolybdenum complex with pyrrolyldithiocarbamate and pyrrolyldithiocarbamate, pyrrolyldithiocarbamate Dithiooxomolybdenum complex of matto and pyrrolyldithiocarbamato.

タイプVIの具体的化合物
ジメチルジチオカルバマトジチオオキソモリブデン錯体、ジエチルジチオカルバマトジチオオキソモリブデン錯体。 Specific compounds of type VI Dimethyldithiocarbamatodithiooxomolybdenum complex, diethyldithiocarbamatodithiooxomolybdenum complex.

本発明の潤滑組成物としては、潤滑油やグリースなどを挙げることができる。本発明で用いる有機モリブデン化合物の潤滑組成物中の存在量は、従来の摩擦調整剤と同様であり、例えば通常組成物に対し、０．１〜１０重量％程度の割合で配合する。 Examples of the lubricating composition of the present invention include lubricating oil and grease. The amount of the organomolybdenum compound used in 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）新規なリンを含まないＭｏ系摩擦調整剤が得られた。
（２）油中Ｍｏ含有量を同量にして既存のＭｏ系摩擦低減剤と比較すると、本発明のＭｏ系摩擦調整剤は更に低い摩擦係数を示し、各種省エネルギー潤滑油の添加剤として利用できる。
（３）本発明のＭｏ系摩擦調整剤はリンを含まないことにより、特に省燃費エンジンオイルの摩擦調整剤としての利用に適する。 (1) A new Mo-based friction modifier containing no phosphorus was obtained.
(2) When the oil content of Mo in the same amount compared with the conventional Mo-based friction modifier, Mo-based friction modifier of the present invention exhibit a lower coefficient of friction, can be used as additives for various energy conservation lubricants .
(3) Since the Mo-based friction modifier of the present invention does not contain phosphorus, it is particularly suitable for use as a friction modifier of fuel-saving engine oil.

以下に実施例および比較例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。   Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

実施例１
ジエチルジチオカルバマトジチオオキソモリブデン錯体
の合成例
（第１工程）
Ｎａ２ＭｏＯ４＋２ＮａＳ２ＣＮＥｔ２＋４ＨＣｌ
→ＭｏＯ２（Ｅｔ２ＮＣＳ２）２＋２Ｈ２Ｏ＋４ＮａＣｌ
ジエチルジチオカルバミン酸ナトリウム（５．０ｇ、０．０２ｍｏｌ）とモリブデン酸ナトリウム（２．７ｇ、０．０１ｍｏｌ）を５００ｍｌのナスフラスコに加え、５０ｍｌの水に溶かした。そこに０．０４ｍｏｌの希塩酸（濃塩酸４ｍｌに水を加え、全量を３００ｍｌにしたもの）を滴下ロートから約２時間かけて滴下した後、得られた沈殿物を吸引ろ過し、水、エタノール、ジエチルエーテルでよく洗った後乾燥させた。得られた結晶をジクロロメタンとｎ−ヘキサンで再結晶を２回行って精製し、ジエチルジチオカルバマトオキソモリブデン錯体を収率８５％で得た。この化合物は黄褐色粉体である。
Ａｒ下で、還流管を付けた二口フラスコに前記ジエチルジチオカルバマトオキソモリブデン錯体（１．０ｇ、２．３ｍｍｏｌ）とトリフェニルホスフィン（１．０ｇ、３．８ｍｍｏｌ）を加え、１，２−ジクロロエタン１０ｍｌ中で９０℃前後で１０〜１５分間加熱還流を行った。赤色に変化した混合溶液にさらにＳ８もしくは硫化プロピレンを３．２ｍｍｏｌ加え、Ｓ８の場合は３０分間、硫化プロピレンの場合は１．５時間加熱還流を行った。得られた反応混合物をシリカゲルカラムによって精製し、得られた結晶を再結晶にてさらに精製を行った。
錯体：暗緑色結晶、収率３７％（Ｓ８より合成）ＮＭＲ及びＩＲにより目的物の生成の確認を行った。
１ＨＮＭＲ（ＣＤＣｌ３）δ＝１．０９，１．３８，１．４０ａｎｄ１．４５（４ｔ，４×３Ｈ），３．４８ａｎｄ３．５７（ｍ，２Ｈ），３．８−４．０（ｍ，３×２Ｈ）
ＩＲ（ＫＢｒ）：ν（ＣＮ）１５２９ｓ，１４９７ｓ；ν（Ｍｏ＝Ｏ）９２２ｓ；ν（Ｓ−Ｓ）５５４ｃｍ−１ Example 1
Di an ethyl dithiocarbamate Mato dithio-oxo-molybdenum 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

実施例２
ピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体
の合成例
（第１工程）
中間組成物ピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体の合成
Ｎａ２ＭｏＯ４＋２ＮＨ４Ｓ２ＣＮ（Ｃ４Ｈ８）＋４ＨＣｌ
→ＭｏＯ４（Ｃ４Ｈ８ＮＣＳ２）２＋２ＮａＣｌ＋２ＮＨ４Ｃｌ
モリブデン酸ナトリウム（７．３ｇ、０．０３ｍｏｌ）とピロリジンジチオカルバミン酸アンモニウム（９．９ｇ、０．０６ｍｏｌ）を５００ｍｌのナスフラスコに加え、１００ｍｌの水に溶かし、０．１２ｍｏｌ希塩酸３００ｍｌを滴下ロートから約２時間かけて滴下した。得られた沈殿物を吸引ろ過し、水・エーテル・メタノール・アセトンでよく洗い、水分を除去した。さらに水分を除去するため、真空下のデシケーター内で２日間放置した。ジクロロメタン・メタノールで再結晶を行い、〔化５２〕に示すピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体を得た。
錯体：黄色粉末、収率７２％
前記〔化５２〕に示す錯体（１．０ｇ，２．３ｍｍｏｌ）とトリフェニルホスフィン（１．０ｇ，３．８ｍｍｏｌ）を１０ｍｌの１，２−ジクロロエタン中で１０分間過熱還流し、さらにそこに硫化プロピレン（０．７７ｍｌ，９．９ｍｍｏｌ）を加えて１〜２時間過熱還流を行った。得られた反応混合物をカラムクロマトグラフィーにて単離精製を行い、ピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体を得た。
錯体：青緑色結晶、収率８２％
ＮＭＲと元素分析を行い目的化合物の生成を確認した。
１ＨＮＭＲ（ＣＤＣｌ３）δ＝１．９５〜２．００（ｍ，２Ｈ×１），２．０４〜２．１６（ｍ，２Ｈ×２），３．３６〜３．５０（ｍ，２Ｈ×１），３．７７〜４．０２（ｍ，２Ｈ×４）
Ｅｌｅｍｅｎｔａｌ Ａｎａｌ．Ｃａｌｃｄ（％）ｆｏｒＣ１０Ｈ１６Ｎ２Ｓ６ＯＭｏ：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．
前記ピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体を、「分散剤（アルケニルコハク酸ポリアルキレンポリイミド 商品名ＩｎｆｉｎｕｍＣ９２６６）５％を添加したＡＰＩグループＩＩＩ鉱油（１００℃における動粘度４．２３ｍｍ２／ｓ）」中に、Ｍｏ含有量５００ｐｐｍとなるよう加え、潤滑油組成物を調製した。 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 heated to reflux in 10 ml of 1,2-dichloroethane for 10 minutes, 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.
A complex of pyrrolidinyldithiocarbamate and dithiooxomolybdenum was added to an API group III mineral oil ( kinematic viscosity at 100 ° C. of 4.23 mm 2 /5% added with a dispersant (alkenyl succinic acid polyalkylene polyimide, trade name: Infinum C9266) 5%). s) "was added so that the Mo content was 500 ppm to prepare a lubricating oil composition.

比較例１
前記ピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体の代わりに、
を用いたほかは、実施例２と同様にして、潤滑油組成物を調製した。 Comparative Example 1
Instead of the complex of pyrrolidinyldithiocarbamate and dithiooxomolybdenum,
A lubricating oil composition was prepared in the same manner as in Example 2 except that was used.

下記表３に示す、本発明のピロリジニルジチオカルバマトとジチオオキソモリブデンとの錯体を摩擦調整剤として用いた実施例２の潤滑油組成物と、市販の摩擦調整剤を用いた比較例１の潤滑油組成物について、ＳＲＶ試験機（図２に示すシリンダー・オン・ディスク型の往復動試験機）により、下記表２の条件で３０分間摩擦係数を測定した。その結果を図１に示す。試験片は５２１００鋼である。
図１に示すように、実施例２のものは、比較例１のものと較べて、はるかに低い摩擦係数を示した。 The lubricating oil composition of Example 2 using the complex of pyrrolidinyldithiocarbamato and dithiooxomolybdenum according to the present invention shown in Table 3 below as a friction modifier, and Comparative Example 1 using a commercially available friction modifier the lubricating oil composition, SRV tester by (reciprocating tester cylinder-on-disc type shown in FIG. 2), was measured 30 minutes friction coefficient under the condition of lower Symbol table 2. The result is shown in FIG. The specimen is 52100 steel.
As shown in FIG. 1, Example 2 showed a much lower coefficient of friction than that of Comparative Example 1.

本発明化合物を潤滑油調整剤として用いた潤滑油と潤滑油調整剤として市販品を用いた潤滑油の時間経過とその摩擦係数の変化を調べたグラフである。It is the graph which investigated the change of the time passage 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. 摩擦係数の測定に用いたシリンダー・オン・ディスク型の往復動試験機の概念概略図である。It is a conceptual schematic diagram of a cylinder-on-disk type reciprocating test machine used for measuring a friction coefficient.

Claims (3)

下記一般式（１）で示される有機モリブデン化合物よりなる摩擦調整剤。
（式中、Ａ１およびＡ２は、環構成原子として窒素原子を１個含む５員環の複素環基および炭素数１〜２のアルキル基を有するジアルキルアミノ基よりなる群から選ばれた基であり、複素環基は窒素原子により基本骨格と結合しており、炭素数１〜３０のアルキル基で置換されていてもよい。） A friction modifier comprising an organomolybdenum compound represented by the following general formula (1) .
(Wherein, A 1 and A 2, was exposed, the group or al election consisting dialkylamino group having a heterocyclic group and alkyl group having 1 to 2 carbon atoms of 5-membered ring containing one nitrogen atom as a ring-constituting atom Motodea is, the heterocyclic group is bonded to the basic skeleton by a nitrogen atom, it may be substituted with an alkyl group having 1 to 30 carbon atoms.) ＡA １1 およびＡAnd A ２2 がジエチルアミノ基または１−ピロリジニル基である請求項１記載の摩擦調整剤。The friction modifier according to claim 1, wherein is a diethylamino group or a 1-pyrrolidinyl group. 請求項１又は２に記載の摩擦調整剤を含有する潤滑組成物。 A lubricating composition containing the friction modifier according to claim 1 .
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