WO2008092944A1 - Organic molybdenum compounds and oil compositions containing the same - Google Patents

Organic molybdenum compounds and oil compositions containing the same Download PDF

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Publication number
WO2008092944A1
WO2008092944A1 PCT/EP2008/051256 EP2008051256W WO2008092944A1 WO 2008092944 A1 WO2008092944 A1 WO 2008092944A1 EP 2008051256 W EP2008051256 W EP 2008051256W WO 2008092944 A1 WO2008092944 A1 WO 2008092944A1
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Prior art keywords
complex
dioxymolybdenum
carbamate
organic molybdenum
compounds
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French (fr)
Inventor
Eiji Nagatomi
Noriaki Shinoda
Yoshihiko Aihara
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority to US12/525,355 priority Critical patent/US8188017B2/en
Priority to BRPI0807027A priority patent/BRPI0807027B1/en
Priority to CN200880003804XA priority patent/CN101611021B/en
Priority to EP08708565.0A priority patent/EP2125762B1/en
Publication of WO2008092944A1 publication Critical patent/WO2008092944A1/en
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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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • 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
    • 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
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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

Definitions

  • the invention relates to novel organic molybdenum compounds, the use thereof as friction-modifiers and lubricating compositions which contain said compounds.
  • Friction-modifiers are used for adjusting the friction characteristics of a lubricant to an appropriate level. Friction-modifiers which reduce friction are used in lubricating compositions such as gear oils and engine oils with a view to reducing fuel costs. Friction-modifiers which raise friction are used for maintaining a certain high friction level in the lubricating compositions which are used in the wet-type clutch part of an automatic gear box. Many types of such friction-modifiers have been proposed.
  • organic molybdenum compounds are the most typical of these friction-modifiers and, as shown in "Shinban Sekiyu Seihin Tenkasai” (New Edition, Additives for Petroleum Products), by Toshio SAKURAI, Saiwai Shobo Co., published 25 th July, 1986, these organic molybdenum compounds are compounds which have two molybdenum atoms in one molecule as shown in formulae (2) and (3) below.
  • the purpose of the invention is to provide novel organic molybdenum compounds, the use thereof as friction-modifiers and lubricating compositions which contain said compounds .
  • the present invention provides molybdenum compounds having the general formula (1) which is indicated below.
  • General Formula ( 1 ) is indicated below.
  • a 1 and A 2 are heterocyclic rings which may have substituent groups, and the aforementioned substituent groups are preferably selected from alkyl groups which have from 1 to 30 carbon atoms.
  • the heterocyclic rings which may have substituent groups are selected from five-membered and six-membered heterocyclic rings.
  • the five-membered rings are selected from the group comprising the tetrazole, triazole, pyrazole, pyrazolidine, imidazole, oxazolidine, thiazolidine, pyrrolidine, pyrroline and pyrrole rings and that the six-membered heterocyclic rings are selected from the group comprising the piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine and piperidine rings.
  • both A 1 and A 2 are:
  • the present invention provides the use of the organic molybdenum compounds as friction- modifiers .
  • the present invention provides lubricating compositions which contain the organic molybdenum compounds .
  • the organic molybdenum compounds of this invention can be obtained, for example, by means of the methods outlined below.
  • a 1 or A 2 can be represented by:
  • Z 1 to Z 4 are elements each selected individually from among the group comprising C, 0, N and S, and in the case of C and N among these, adjacent C and N may form a double bond.
  • R 1 to R 4 and R 1' to R 4' are groups each selected individually from the group comprising hydrogen and alkyl groups which have from 1 to 30 carbon atoms, but these groups are not present in those cases the bonding capacity is saturated by Z 1 to Z 4 forming a ring.
  • a 1 or A 2 can be represented by:
  • Z 5 to Z 9 are elements each selected individually from among the group comprising C, 0, N and S, and in the case of C and N among these, adjacent C and N may form a double bond.
  • R 5 to R 9 and R 5' to R 9' are groups each selected individually from the group comprising hydrogen and alkyl groups which have from 1 to 30 carbon atoms, but these groups are not present in those cases the bonding capacity is saturated by Z 5 to Z 9 forming a ring.
  • R 1 to R 9 there may be substituent groups represented by R 1 to R 9 on the aforementioned five-membered rings such as a tetrazole ring or six-membered rings such as a morpholine ring.
  • the alkyl groups which have from 1 to 30 carbon atoms may be linear chain or branched chain groups.
  • These groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-heptyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-nonadecyl and n-eicosyl .
  • the compounds of this invention can be broadly classified into the types I to V. (1) Type I
  • a 1 is five-membered ring and A 2 is:
  • R 10 and R 11 are groups each selected individually from among the group comprising hydrogen and the alkyl groups which have from 1 to 30 carbon atoms.
  • a 1 is six-membered ring and A 2 is:
  • a 1 and A 2 are both five-membered rings .
  • a 1 and A 2 are both six-membered rings .
  • Type V The case where A 1 is a six-membered ring and A 2 is a five-membered ring.
  • R 1 to R 4 and R 1' to R 4' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms, and hydrogen is the preferred one of these groups.
  • R 10 and R 11 are each individually groups which have been selected from the group comprising alkyl groups which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 8 carbon atoms .
  • R 5 to R 9 and R 5' to R 9' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms, and hydrogen is the preferred one of these groups.
  • R 10 and R 11 are each individually groups which have been selected from the group comprising alkyl groups which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 8 carbon atoms .
  • R 1 , A 2 is -N
  • R 1 to R 4 , R 1' to R 4' , R 12 to R 15 and R 12' to R 15' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms. Furthermore, hydrogen is the preferred one of these groups.
  • R 5 to R 9 , R 5' to R 9' , R 16 to R 20 and R 16' to R 20' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms. Furthermore, hydrogen is the preferred one of these groups.
  • R in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms. Furthermore, hydrogen is the preferred one of these groups.
  • Tetrazoyldithiocarbamate/dithioalkylcarbamate dioxy- molybdenum complex triazoylthiocarbamate/dithioalkyl- carbamate dioxymolybdenum complex, pyrazoyldithio- carbamate/dithioalkylcarbamate dioxymolybdenum complex, pyrazolidyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, imidazoyldithiocarbamate/di- thioalkylcarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, thiazolidyldithiocarbamate/dithio- alkylcarbamate dioxymolybdenum complex, pyrrolidinyl- dithiocarbamate/dithioalkylcarba
  • the alkyl groups are from Cl to C30 alkyl groups, and these include, for example, the methyl group and the ethyl group and the alkyl groups which have from 3 to 30 carbon atoms, including propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontacyl groups which include normal and iso-forms.
  • Type II Piperazyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/dithioalkyl- carbamate dioxymolybdenum complex, thiomorpholyldi- thiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, thiazyldithiocarbamate/dithioalkylcarbamate di- oxymolybdenum complex, morpholyldithiocarbamate/di- thioalkylcarbamate dioxymolybdenum complex, oxazyl- dithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex and piperidyldithiocarbamate/dithioalkyl- carbamate dioxymolybdenum complex.
  • the alkyl groups are from Cl to C30 alkyl groups, and these include, for example, the methyl group and the ethyl group and the alkyl groups which have from 3 to 30 carbon atoms, including propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontacyl groups which include normal and iso-forms.
  • Typical compounds of Type IV are: Piperazyldithiocarbamate/piperazyldithiocarbamate di- oxymolybdenum complex, piperazyldithiocarbamate/- pyrazyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/thiomorpholyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- thiazyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/morpholyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/oxazyl- dithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/piperidyldithiocarbamate di- oxymolybdenum complex, pyrazyldithiocarba
  • Typical compounds of Type V are : Piperazyldithiocarbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- triazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- pyrazolidyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- oxazolyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/thiazolidyldithiocarbamate di- oxymolybdenum complex, piperazyldithi
  • Lubricating oils and greases for example, can be cited as lubricating composition of this invention.
  • the amount of the compound of this invention in a lubricating composition is the same as with the conventional friction-modifiers, for example, being compounded in a proportion with respect to the composition generally of some 0.1 to 10 wt%.
  • base oil or grease used in lubricating composition according to the present invention
  • various conventional greases, mineral oils and synthetic oils may be conveniently used.
  • base oil is meant to also include a grease base stock.
  • the base oil used in the present invention may conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils.
  • Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
  • Suitable base oils for use in the lubricating oil composition of the present invention are Group I, Group II or Group III base oils, polyalphaolefins, Fischer- Tropsch derived base oils and mixtures thereof.
  • Group III base oil in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) categories I, II and III. Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
  • API American Petroleum Institute
  • Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating oil composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO
  • Synthetic oils include hydrocarbon oils such as olefin oligomers (PAOs), dibasic acid esters, polyol esters, and dewaxed waxy raffinate. Synthetic hydrocarbon base oils sold by the Shell Group under the designation "XHVI” (trade mark) may be conveniently used. Effects of the Invention
  • the compounds of this invention exhibit a lower coefficient of friction, and they can be used as additives for various types of energy-saving lubricating oil. See
  • the compounds of this invention are especially suitable for use as friction-modifiers for fuel-saving engine oils as they are phosphorus-free.
  • the method of production outlined below is an example and production is not limited to just this method.
  • the target compound was a yellow coloured powder and the yield was 72%.
  • the compound which had been produced was analyzed using NMR and Mass spectrometry and verification that the target compound had been produced was carried out.
  • 1 H NMR (CDCl 2 ) ⁇ 2.08 - 2.11 (m, 2H x 4), 3.75 - 3.78 (m, 2H x 4)
  • Mass (EI + , 70 eV) m/z (rel. intensity) 406 (M + - 0, 9) 422 (M + , 3), 114 (100, C 4 H 8 NCS)
  • Example 2 The compound obtained in Example 1 was used in Example 2 and the compound with the chemical formula indicated below (trade name Naugalube MoIy FM2543, produced by the Crompton Co.) was used in Comparative Example 1.
  • the above compounds were added to provide a molybdenum content in each case of 500 ppm in API Group III mineral oil (viscosity at 100 0 C 4.23 mm 2 /s) to which 5% of a dispersing agent (alkenyl succinic acid polyalkylene polyimide, trade name Infineum C9266) had been added.
  • API Group III mineral oil viscosity at 100 0 C 4.23 mm 2 /s
  • a dispersing agent alkenyl succinic acid polyalkylene polyimide, trade name Infineum C9266
  • Figure 1 is a graph which shows how the friction coefficient behaved with the passage of time with the sample oils of Example 2 and Comparative Example 1.
  • Figure 2 is an outline drawing of the reciprocating movement tester of the cylinder-on-disc type which was used to measure the friction coefficients.

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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)

Abstract

The present invention provides novel organic molybdenum compounds, the use thereof as friction-modifiers and lubricating compositions which contain said compounds. The organic molybdenum compounds can be represented by the general formula (1) which is indicated below, General Formula (1) wherein A1 and A2 are heterocyclic rings which may have substituent groups.

Description

ORGANIC MOLYBDENUM COMPOUNDS AND OIL COMPOSITIONS CONTAINING THE SAME
The invention relates to novel organic molybdenum compounds, the use thereof as friction-modifiers and lubricating compositions which contain said compounds.
Friction-modifiers (friction-adjusting agents) are used for adjusting the friction characteristics of a lubricant to an appropriate level. Friction-modifiers which reduce friction are used in lubricating compositions such as gear oils and engine oils with a view to reducing fuel costs. Friction-modifiers which raise friction are used for maintaining a certain high friction level in the lubricating compositions which are used in the wet-type clutch part of an automatic gear box. Many types of such friction-modifiers have been proposed. The organic molybdenum compounds are the most typical of these friction-modifiers and, as shown in "Shinban Sekiyu Seihin Tenkasai" (New Edition, Additives for Petroleum Products), by Toshio SAKURAI, Saiwai Shobo Co., published 25th July, 1986, these organic molybdenum compounds are compounds which have two molybdenum atoms in one molecule as shown in formulae (2) and (3) below. Formula (2)
( Dithiophospate Type ) ( 2 ;
Figure imgf000002_0001
Formula (3)
(Dithiocarbamate Type) (3]
Figure imgf000003_0001
(Those compounds for which in this formulae x = 0 and y = 4, those for which x + y = 4, and those for which x ≥ 2 are insoluble in oil and the others are oil- soluble . ) Furthermore, compounds in which the element molybdenum is included twice in one molecule have been disclosed in Japanese Patent No. 3495764, Japanese Examined Patent Publication 45-24562, Japanese Unexamined Patent Application Laid Open 52-19629, Japanese Unexamined Patent Application Laid Open
52-106824 and Japanese Unexamined Patent Application Laid Open 48-56202.
A problem with catalyst poisoning in the apparatus which is used for cleaning-up the exhaust gas arises when compounds which contain phosphorus in the molecule as shown in the aforementioned general formula (2) are added to engine oils and there is a demand for compounds which are phosphorus-free.
The purpose of the invention is to provide novel organic molybdenum compounds, the use thereof as friction-modifiers and lubricating compositions which contain said compounds .
In a first aspect, the present invention provides molybdenum compounds having the general formula (1) which is indicated below. General Formula ( 1 )
Figure imgf000004_0001
O
In this formula A1 and A2 are heterocyclic rings which may have substituent groups, and the aforementioned substituent groups are preferably selected from alkyl groups which have from 1 to 30 carbon atoms. Preferably, the heterocyclic rings which may have substituent groups are selected from five-membered and six-membered heterocyclic rings.
It is even more preferred that the five-membered rings are selected from the group comprising the tetrazole, triazole, pyrazole, pyrazolidine, imidazole, oxazolidine, thiazolidine, pyrrolidine, pyrroline and pyrrole rings and that the six-membered heterocyclic rings are selected from the group comprising the piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine and piperidine rings.
Further it is preferred that both A1 and A2 are:
( 1-pyrrolidinyl groups]
Figure imgf000004_0002
In a further aspect, the present invention provides the use of the organic molybdenum compounds as friction- modifiers . In another aspect the present invention provides lubricating compositions which contain the organic molybdenum compounds . The organic molybdenum compounds of this invention can be obtained, for example, by means of the methods outlined below. When A1 and A2 are the same :
C - A1 +4HC1
I
Figure imgf000005_0001
When A1 and A2 are different:
4HCl
Figure imgf000005_0002
0 In a case where the aforementioned A1 or A2 is a five-member ring, then A1 or A2 can be represented by:
Figure imgf000006_0001
In this formula Z1 to Z4 are elements each selected individually from among the group comprising C, 0, N and S, and in the case of C and N among these, adjacent C and N may form a double bond. R1 to R4 and R1' to R4' are groups each selected individually from the group comprising hydrogen and alkyl groups which have from 1 to 30 carbon atoms, but these groups are not present in those cases the bonding capacity is saturated by Z1 to Z4 forming a ring.
In a case where the aforementioned A1 or A2 is a six-membered ring, then A1 or A2 can be represented by:
Figure imgf000006_0002
In this formula Z5 to Z9 are elements each selected individually from among the group comprising C, 0, N and S, and in the case of C and N among these, adjacent C and N may form a double bond. R5 to R9 and R5' to R9' are groups each selected individually from the group comprising hydrogen and alkyl groups which have from 1 to 30 carbon atoms, but these groups are not present in those cases the bonding capacity is saturated by Z5 to Z9 forming a ring.
The cases indicated below can be cited as actual examples of the aforementioned A1 and A2.
Table 1 In the case of a five-membered ring
Figure imgf000007_0001
Table 2 In the case of a six-membered ring
Figure imgf000007_0002
There may be substituent groups represented by R1 to R9 on the aforementioned five-membered rings such as a tetrazole ring or six-membered rings such as a morpholine ring. The alkyl groups which have from 1 to 30 carbon atoms may be linear chain or branched chain groups. These groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-heptyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-nonadecyl and n-eicosyl .
The compounds of this invention can be broadly classified into the types I to V. (1) Type I
The case where A1 is five-membered ring and A2 is:
Figure imgf000008_0001
Moreover, R10 and R11 are groups each selected individually from among the group comprising hydrogen and the alkyl groups which have from 1 to 30 carbon atoms.
(2) Type II
The case where A1 is six-membered ring and A2 is:
Figure imgf000008_0002
( 3 ) Type I I I
The case where A1 and A2 are both five-membered rings .
(4) Type IV
The case where A1 and A2 are both six-membered rings .
(5) Type V The case where A1 is a six-membered ring and A2 is a five-membered ring.
In more practical terms, the group of compounds indicated below can be shown as compounds of Type I. Below, R1 to R4 and R1' to R4' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms, and hydrogen is the preferred one of these groups. Moreover, R10 and R11 are each individually groups which have been selected from the group comprising alkyl groups which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 8 carbon atoms .
O
O
Figure imgf000010_0001
Figure imgf000011_0001
In more practical terms, the group of compounds indicated below can be shown as compounds of Type II.
Figure imgf000012_0001
H 7
Figure imgf000013_0001
Moreover, R5 to R9 and R5' to R9' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms, and hydrogen is the preferred one of these groups. Moreover, R10 and R11 are each individually groups which have been selected from the group comprising alkyl groups which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 8 carbon atoms .
The compounds where A1 and A2 have the structures indicated below can be cited as compounds of Type III.
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
R1 , A2 is -N
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Moreover, R1 to R4, R1' to R4', R12 to R15 and R12' to R15' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms. Furthermore, hydrogen is the preferred one of these groups.
The compounds where A1 and A2 have the structures indicated below can be cited as compounds of Type IV.
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Moreover, R5 to R9, R5' to R9', R16 to R20 and R16' to R20' in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms. Furthermore, hydrogen is the preferred one of these groups.
The compounds where A1 and A2 have the structures indicated below can be cited as compounds of Type V.
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
V
V
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Moreover, R5 to R9, R5' to R9', R12 to R15 and R12' to
R in these formulae are each individually a group selected from the group comprising hydrogen and alkyl groups, and the aforementioned alkyl groups are those which have from 1 to 30, preferably from 1 to 20 and most desirably from 1 to 10 carbon atoms. Furthermore, hydrogen is the preferred one of these groups.
Actual compounds of Type I are :
Tetrazoyldithiocarbamate/dithioalkylcarbamate dioxy- molybdenum complex, triazoylthiocarbamate/dithioalkyl- carbamate dioxymolybdenum complex, pyrazoyldithio- carbamate/dithioalkylcarbamate dioxymolybdenum complex, pyrazolidyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, imidazoyldithiocarbamate/di- thioalkylcarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, thiazolidyldithiocarbamate/dithio- alkylcarbamate dioxymolybdenum complex, pyrrolidinyl- dithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, pyrrolinyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex and pyrrolyldithiocarbamate/di- thioalkylcarbamate dioxymolybdenum complex.
In the names of the illustrative compounds of Type I the alkyl groups are from Cl to C30 alkyl groups, and these include, for example, the methyl group and the ethyl group and the alkyl groups which have from 3 to 30 carbon atoms, including propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontacyl groups which include normal and iso-forms.
Actual compounds of Type II are: Piperazyldithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/dithioalkyl- carbamate dioxymolybdenum complex, thiomorpholyldi- thiocarbamate/dithioalkylcarbamate dioxymolybdenum complex, thiazyldithiocarbamate/dithioalkylcarbamate di- oxymolybdenum complex, morpholyldithiocarbamate/di- thioalkylcarbamate dioxymolybdenum complex, oxazyl- dithiocarbamate/dithioalkylcarbamate dioxymolybdenum complex and piperidyldithiocarbamate/dithioalkyl- carbamate dioxymolybdenum complex.
In the names of the illustrative compounds of Type II the alkyl groups are from Cl to C30 alkyl groups, and these include, for example, the methyl group and the ethyl group and the alkyl groups which have from 3 to 30 carbon atoms, including propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontacyl groups which include normal and iso-forms.
Actual compounds of type III are: Tetrazoyldithiocarbamate/tetrazolyldithiocarbamate di- oxymolybdenum, tetrazoylditiocarbamate/triazoyldithio- carbamate dioxymolybdenum complex, tetrazoyldithio- carbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, tetrazoyldithiocarbamate/pyrazolidyldithio- carbamate dioxymolybdenum complex, tetrazoyldithio- carbamate/imidazoyldithiocarbamate dioxymolybdenum complex, tetrazoyldithiocarbamate/oxazolyldithio- carbamate dioxymolybdenum complex, tetrazoyldithio- carbamate/thiazolidyldithiocarbamate dioxymolybdenum complex, tetrazoyldithiocarbamate/pyrrolidinyldithio- carbamate dioxymolybdenum complex, tetrazoyldithiocarbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, tetrazoyldithiocarbamate/pyrrolyldithio- carbamate dioxymolybdenum complex, triazoyldithio- carbamate/triazoyldithiocarbamate dioxymolybdenum complex, triazolyldithiocarbamate/pyrazoyldithio- carbamate dioxymolybdenum complex, triazoyldithio- carbamate/pyrazolidyldithiocarbamate dioxymolybdenum complex, trizoyldithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, triazoyldithio- carbamate/oxazolyldithiocarbamate dioxymolybdenum complex, triazoyldithiocarbamate/thiazolidyldithio- carbamate dioxymolybdenum complex, triazoyldithio- carbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, triazoyldithiocarbamate/pyrrolinyldithio- carbamate dioxymolybdenum complex, triazoyldithio- carbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/- pyrazolidyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, pyrazoyldithio- carbamate/oxazolyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/- thiazolidyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/- pyrrolinyldithiocarbamate dioxymolybdenum complex, pyrazoyldithiocarbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, pyrazolidyldithiocarbamate/- pyrazolidyldithiocarbamate dioxymolybdenum complex, pyrazolidyldithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, pyrazolidyldithio- carbamate/oxazolyldithiocarbamate dioxymolybdenum complex, pyrazolidyldithiocarbamate/thiazoyldithio- carbamate dioxymolybdenum complex, pyrazolidyldithio- carbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, pyrazolidyldithiocarbamate/pyrrolinyldithio- carbamate dioxymolybdenum complex, pyrazolidyldithio- carbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, imidazoyldithiocarbamate/imidazoyldithio- carbamate dioxymolybdenum complex, imidazoyldithio- carbamate/oxazolyldithiocarbamate dioxymolybdenum complex, imidazoyldithiocarbamate/thiazolidyldithiocarbamate dioxymolybdenum complex, imidazoyldithio- carbamate/pyrrolidinyldthiocarbamate dioxymolybdenum complex, imidazoyldithiocarbamate/pyrrolinyldithio- carbamate dioxymolybdenum complex, imidazoyldithio- carbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/oxazolyldithiocarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/thia- zolidyldithiocarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/- pyrrolinyldithiocarbamate dioxymolybdenum complex, oxazolyldithiocarbamate/pyrrolyldithiocarbamate dioxy- molybdenum complex, thiazolidyldithiocarbamate/- thiazolidyldithiocarbamate dioxymolybdenum complex, thiazoylidyldithiocarbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, thiazoylidyldithiocarbamate/- pyrrolinyldithiocarbamate dioxymolybdenum complex, thiazolidyldithiocarbamate/pyrroIyldithiocarbamate dioxymolybdenum complex, pyrrolidinyldithiocarbamate/- pyrrolidinyldithiocarbamate dioxymolybdenum complex, pyrrolidinyldithiocarbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, pyrrolidinyldithiocarbamate/- pyrrolinyldithiocarbamate dioxymolybdenum complex, pyrrolinyldithiocarbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, pyrrolinyldithiocarbamate/- pyrrolinyldithiocarbamate dioxomolybdenum complex, pyrrolyldithiocarbamate/pyrrolyldithiocarbamate dioxy- molybdenum complex and pyrrolyldithiocarbamate/pyrrolyl- dithiocarbamate dioxy-molybdenum complex.
Typical compounds of Type IV are: Piperazyldithiocarbamate/piperazyldithiocarbamate di- oxymolybdenum complex, piperazyldithiocarbamate/- pyrazyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/thiomorpholyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- thiazyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/morpholyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/oxazyl- dithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/piperidyldithiocarbamate di- oxymolybdenum complex, pyrazyldithiocarbamate/pyrazyl- dithiocarbamate dioxymolybdenum complex, pyazyldithiocarbamate/thiomorpholyldithiocarbamate, dioxymolybdenum complex, pyrazyldithiocarbamate/thiazyl- dithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/morpholyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/oxazyl- dithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/piperidyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/- thiomorpholyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/thiazyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/morphoIyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/oxazyldithio- carbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/piperidyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/thiazyldithiocarbamate dioxymolybdenum complex, thiazyldithio- carbamate/morpholyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/oxazyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/- piperidyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/morpholyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/oxalyl- dithiocarbamate dioxymolybdenum complex, morpholyl- dithiocarbamate/piperidyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/oxazyldithiocarbamate dioxymolybdenum complex, oxazyldithio- carbamate/piperidyldithiocarbamate dioxymolybdenum complex and piperidyldithiocarbamate/piperidyldithio- carbamate dioxymolybdenum complex.
Typical compounds of Type V are : Piperazyldithiocarbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- triazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- pyrazolidyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- oxazolyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/thiazolidyldithiocarbamate di- oxymolybdenum complex, piperazyldithiocarbamate/- pyrrolidinyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, piperazyldithiocarbamate/- pyrrolyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/triazoyl- dithiocarbamate dioxymolybdenum complex, pyrazyldithio- carbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/pyrazolidyldithio- carbamate dioxymolybdenum complex, pyrazyldithio- carbamate/imidazoyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/oxazolyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/- thiazolidyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/- pyrrolinyldithiocarbamate dioxymolybdenum complex, pyrazyldithiocarbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/- tetrazoyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/triazoyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithio- carbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/pyrazolidyl- dithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/- oxazolyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/thiazolidyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithio- carbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, thiomorpholyldithiocarbamate/pyrrolinyldithio- carbamate dioxymolybdenum complex, thiomorpholyldithio- carbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, thiazyldithio- carbamate/triazoyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/- pyrazolidyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/imidazoyldithiocarbamate dioxy- molybdenum complex, thiazyldithiocarbamate/oxazolyldi- thiocarbamate dioxymolybdenum complex, thiazyldithio- carbamate/thiazolidyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/pyrrolidinyldithio- carbamate dioxymolybdenum complex, thiazyldithio- carbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, thiazyldithiocarbamate/pyrrolyldithiocarbamate dioxymolybdenum complex, morpholyldithio- carbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/triazoyldithio- carbamate dioxymolybdenum complex, morpholyldithio- carbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/pyrazolidyldithio- carbamate dioxymolybdenum complex, morpholyldithio- carbamate/imidazoyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/oxazolyldithio- carbamate dioxymolybdenum complex, morpholyldithio- carbamate/thiazolidyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/pyrrolidinyldithio- carbamate dioxymolybdenum complex, morpholyldithio- carbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, morpholyldithiocarbamate/pyrrolyldithio- carbamate dioxymolybdenum complex, oxazyldithio- carbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/triazoyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/- pyrazoyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/pyrazolidyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/imidazoyl- dithiocarbamate dioxymolybdenum complex, oxazyldithio- carbamate/oxazolyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/thiazolidyldithio- carbamate dioxymolybdenum complex, oxazyldithio- carbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/pyrrolinyldithiocarbamate dioxymolybdenum complex, oxazyldithiocarbamate/pyrrolyl- dithiocarbamate dioxymolybdenum complex, piperidyl- dithiocarbamate/tetrazoyldithiocarbamate dioxymolybdenum complex, piperidyldithiocarbamate/triazoy1- dithiocarbamate dioxymolybdenum complex, piperidyl- dithiocarbamate/pyrazoyldithiocarbamate dioxymolybdenum complex, piperidyldithiocarbamate/pyrazolidyl- dithiocarbamate dioxymolybdenum complex, piperidyl- dithiocarbamate/imidazoyldithiocarbamate dioxymolybdenum complex, piperidyldithio- carbamate/oxazolyldithiocarbamate dioxymolybdenum complex, piperidyldithiocarbamate/thiazolidyl- dithiocarbamate dioxymolybdenum complex, piperidyl- dithiocarbamate/pyrrolidinyldithiocarbamate dioxymolybdenum complex, piperidyldithiocarbamate/- pyrrolinyldithiocarbamate dioxymolybdenum complex and piperidyldithiocarbamate/pyrrolyldithiocarbamate dioxy- molybdenum complex.
Lubricating oils and greases, for example, can be cited as lubricating composition of this invention. The amount of the compound of this invention in a lubricating composition is the same as with the conventional friction-modifiers, for example, being compounded in a proportion with respect to the composition generally of some 0.1 to 10 wt%.
There are no particular limitations regarding the base oil or grease used in lubricating composition according to the present invention, and various conventional greases, mineral oils and synthetic oils may be conveniently used. For the puprose of this description, the term "base oil" is meant to also include a grease base stock.
The base oil used in the present invention may conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils.
Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
Suitable base oils for use in the lubricating oil composition of the present invention are Group I, Group II or Group III base oils, polyalphaolefins, Fischer- Tropsch derived base oils and mixtures thereof. By "Group I" base oil, "Group II" base oil and
"Group III" base oil in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) categories I, II and III. Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating oil composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO
00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.
Synthetic oils include hydrocarbon oils such as olefin oligomers (PAOs), dibasic acid esters, polyol esters, and dewaxed waxy raffinate. Synthetic hydrocarbon base oils sold by the Shell Group under the designation "XHVI" (trade mark) may be conveniently used. Effects of the Invention
(1) Novel phosphorus-free Mo-based friction-modifiers have been obtained.
(2) When compared with the existing Mo-based friction- reducing agents with the same Mo content in the oil, the compounds of this invention exhibit a lower coefficient of friction, and they can be used as additives for various types of energy-saving lubricating oil. See
Fig.l hereafter. (3) The compounds of this invention are especially suitable for use as friction-modifiers for fuel-saving engine oils as they are phosphorus-free.
Illustrative Examples
The present invention is described below by means of Examples and Comparative Examples but the invention is not limited in any way by these examples .
Example 1
The synthesis of the compound indicated below, a compound where both A1 and R2 are:
Figure imgf000056_0001
The method of production outlined below is an example and production is not limited to just this method.
Na2MoO4 + 2 NH4S2CN(C4H8) + 4 HCl
→ MoO4 (C4H8NCS2) 2 + 2 NaCl = 2 NH4Cl Sodium molybdate (7.3 g, 0.03 mol) and ammonium pyrrolidinedithiocarbamate (9.9 g, 0.06 mol) were added to a 500 ml pear-shaped flask and dissolved in 100 ml of water. Then 300 ml of 0.12 mol dilute hydrochloric acid was added dropwise from a dropping funnel over a period of about 2 hours . The precipitated material obtained was recovered by suction filtration and washed thoroughly with water, ether, methanol, acetone and the water was removed. Moreover, the material was left to stand in a desiccator under vacuum for 2 days to eliminate the water fraction. Recrystallization was carried out using dichloromethane/methanol .
The target compound was a yellow coloured powder and the yield was 72%. The compound which had been produced was analyzed using NMR and Mass spectrometry and verification that the target compound had been produced was carried out. 1H NMR (CDCl2) δ = 2.08 - 2.11 (m, 2H x 4), 3.75 - 3.78 (m, 2H x 4) Mass (EI+, 70 eV) m/z (rel. intensity) = 406 (M+ - 0, 9) 422 (M+, 3), 114 (100, C4H8NCS) Example 2 and Comparative Example 1
The compound obtained in Example 1 was used in Example 2 and the compound with the chemical formula indicated below (trade name Naugalube MoIy FM2543, produced by the Crompton Co.) was used in Comparative Example 1. The above compounds were added to provide a molybdenum content in each case of 500 ppm in API Group III mineral oil (viscosity at 1000C 4.23 mm2/s) to which 5% of a dispersing agent (alkenyl succinic acid polyalkylene polyimide, trade name Infineum C9266) had been added.
Figure imgf000058_0001
These sample oils were subjected to 30 minute friction coefficient measurement and evaluation under the conditions shown in Table 3 below using an SRV tester (a reciprocating movement tester of the cylinder- on-disc type shown in Figure 2) and the results are shown in Figure 1. The test piece was 52100 steel.
Table 3
Figure imgf000058_0002
Table 4
Figure imgf000058_0003
Brief Explanation of the Drawings
Figure 1 is a graph which shows how the friction coefficient behaved with the passage of time with the sample oils of Example 2 and Comparative Example 1.
Figure 2 is an outline drawing of the reciprocating movement tester of the cylinder-on-disc type which was used to measure the friction coefficients.

Claims

C L A I M S
1. An organic molybdenum compound having the general formula (1) below General Formula (1)
Figure imgf000059_0001
wherein A1 and A2 are heterocyclic rings which may have substituent groups.
2. An organic molybdenum compound according to Claim 1, wherein the aforementioned substituent groups are selected from alkyl groups having from 1 to 30 carbon atoms .
3. An organic molybdenum compound according to Claim 1 or 2, wherein the heterocyclic rings which may have substituent groups are selected from five-membered and six-membered heterocyclic rings.
4. An organic molybdenum compound according to Claim 3, wherein the five-membered rings are selected from the group comprising tetrazole, triazole, pyrazole, pyrazolidine, imidazole, oxazolidine, thiazolidine, pyrrolidine, pyrroline and pyrrole rings.
5. An organic molybdenum compound according to Claim 3 or 4, wherein the six-membered heterocyclic rings are selected from the group comprising piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine and piperidine rings .
6. An organic molybdenum compound according to any of Claim 3 to 5, in which both A1 and A2 are:
;i-pyrrolidinyl groups)
Figure imgf000060_0001
7. Use of the organic molybdenum compound according to any of the Claims 1 to 6 as a friction-modifier.
8. A lubricating composition comprising a base oil and the organic molybdenum compound according to any of the Claims 1 to 6.
9. Method of improving the friction characteristics of a lubricating composition by using the organic molybdenum compound according to any of Claims 1 to 6.
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