SHINODA NORIAKI (JP)
AIHARA YOSHIHIKO (JP)
NAGATOMI EIJI (JP)
SHINODA NORIAKI (JP)
AIHARA YOSHIHIKO (JP)
| DE3717143A1 | 1988-12-15 | |||
| JP3495764B2 | 2004-02-09 | |||
| JP4524562B2 | 2010-08-18 | |||
| JPS5219629A | 1977-02-15 | |||
| JPS52106824A | 1977-09-07 | |||
| JPS4856202A | 1973-08-07 | |||
| DE3717143A1 | 1988-12-15 |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; UNOURA, KEI ET AL: "Substituent effects of cis-dioxobis(dithiocarbamato)molybdenum(VI) on redox properties: redox potentials for one-electron reduction and second-order rate constants for oxygen atom transfer", XP002476206, retrieved from STN Database accession no. 1998:57633
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; SOVILJ, S. P. ET AL: "Molecular modelling of new dioxomolybdenum(VI) complexes with heteroalicyclic dithiocarbamates. In Silico models for metal-implant coating within living systems", XP002476207, retrieved from STN Database accession no. 2006:696107
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; GNECCO, J. A. ET AL: "Catalytic epoxidation of cyclohexene using molybdenum complexes", XP002476208, retrieved from STN Database accession no. 2004:424323
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; SOVILJ, S. P. ET AL: "Dioxomolybdenum(VI) complexes of methylpiperidinodithiocarboxylates", XP002476209, retrieved from STN Database accession no. 2002:939565
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MACIAS, BENIGNO ET AL: "An EXAFS study of Mo(VI) and Mo(V) complexes with proline dithiocarbamate", XP002476210, retrieved from STN Database accession no. 1999:413035
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; STERGIOU, ANAGNOSTIS C. ET AL: "Spectroscopic investigation of dichloro and hydrazido(2-) derivatives of bis(dithiocarbamato)dioxomolybdenum(VI) compounds. Crystal and molecular structure of bis(diisobutyldithiocarbamato)(N, N-dimethylhydrazido(2-)-N')oxomolybdenum(VI)", XP002476211, retrieved from STN Database accession no. 1994:448977
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BHAT, G. S. ET AL: "Synthesis and characterization of lead(II), bismuth (III), titanium(IV), selenium(IV), thorium(IV), dioxomolybdenum(VI) and dioxouranium(VI) hexamethyleniminecarbodithioate and their biological activities", XP002476212, retrieved from STN Database accession no. 1994:337719
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; NAIR, B. GOPALAKRISHNAN ET AL: "A novel series of cis-dioxomolybdenum(VI) carbodithioate complexes", XP002476213, retrieved from STN Database accession no. 1991:669180
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MOLOY, KENNETH G.: "Oxygen atom transfer reactions. Epoxide deoxygenation by bis(diethyldithiocarbamato)oxomolybdenum", XP002476214, retrieved from STN Database accession no. 1988:94302
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BERZINA, S. ET AL: "Two-phase stability constants of some 3-pyrrolecarbodithioates and 3-indolecarbodithioates", XP002476215, retrieved from STN Database accession no. 1976:531419
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; BYR'KO, V. M. ET AL: "Composition and structure of molybdenum(V,VI) 5-phenyl-1- pyrazolinedithiocarbamates", XP002476216, retrieved from STN Database accession no. 1974:9928
TOSHIO SAKURAI: "Shinban Sekiyu Seihin Tenkasai", 25 July 1986, SAIWAI SHOBO CO.
| C L A I M S
1. An organic molybdenum compound having the general formula (1) below General Formula (1)
wherein A 1 and A 2 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 A 1 and A 2 are:
;i-pyrrolidinyl groups)
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. |
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 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. Formula (2)
( Dithiophospate Type ) ( 2 ;
Formula (3)
(Dithiocarbamate Type) (3]
(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 )
O
In this formula 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. 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 A 1 and A 2 are:
( 1-pyrrolidinyl groups]
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 A 1 and A 2 are the same :
C - A 1 +4HC1
I
When A 1 and A 2 are different:
4HCl
In a case where the aforementioned A 1 or A 2 is a five-member ring, then A 1 or A 2 can be represented by:
In this formula 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.
In a case where the aforementioned A 1 or A 2 is a six-membered ring, then A 1 or A 2 can be represented by:
In this formula 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.
The cases indicated below can be cited as actual examples of the aforementioned A 1 and A 2 .
Table 1 In the case of a five-membered ring
Table 2 In the case of a six-membered ring
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
The case where A 1 is five-membered ring and A 2 is:
Moreover, 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.
(2) Type II
The case where A 1 is six-membered ring and A 2 is:
( 3 ) Type I I I
The case where A 1 and A 2 are both five-membered rings .
(4) Type IV
The case where A 1 and A 2 are both six-membered rings .
(5) Type V The case where A 1 is a six-membered ring and A 2 is a five-membered ring.
In more practical terms, the group of compounds indicated below can be shown as compounds of Type I.
Below, 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. Moreover, 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 .
O
O
In more practical terms, the group of compounds indicated below can be shown as compounds of Type II.
H 7
Moreover, 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. Moreover, 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 .
The compounds where A 1 and A 2 have the structures indicated below can be cited as compounds of Type III.
R 1
, A 2 is -N
Moreover, 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.
The compounds where A 1 and A 2 have the structures indicated below can be cited as compounds of Type IV.
Moreover, 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.
The compounds where A 1 and A 2 have the structures indicated below can be cited as compounds of Type V.
V
V
Moreover, R 5 to R 9 , R 5' to R 9' , R 12 to R 15 and R 12' 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 A 1 and R 2 are:
The method of production outlined below is an example and production is not limited to just this method.
Na 2 MoO 4 + 2 NH 4 S 2 CN(C 4 H 8 ) + 4 HCl
→ MoO 4 (C 4 H 8 NCS 2 ) 2 + 2 NaCl = 2 NH 4 Cl
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. 1 H NMR (CDCl 2 ) 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, C 4 H 8 NCS) 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 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.
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
Table 4
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.