SHINODA NORIAKI (JP)
AIHARA YOSHIHIKO (JP)
NAGATOMI EIJI (JP)
SHINODA NORIAKI (JP)
AIHARA YOSHIHIKO (JP)
| US20060199745A1 | 2006-09-07 | |||
| JP2000303088A | 2000-10-31 | |||
| EP1041135A1 | 2000-10-04 |
BOND, A. M.; BROOMHEAD, J. A.; HOLLENKAMP, A. F.: "Novel synthesis of reduced mixed-valence molybdenum and tungsten complexes by electrochemical oxidation of teh seven-coordinate complexes MX(S2) (R2dtc)2 (M= Mo, X= O; M= W, X= O, S; R= alkyl; dtc= dithiocarbamate)", INORGANIC CHEMISTRY, vol. 27, no. 6, 1988, pages 978 - 985, XP002484228
PAN, WIE HIN; HALBERT, THOMAS R.; HUTCHINGS, L. L.; STIEFEL, EDWARD I.: "Ligand and induced internal electron transfer pathways to new molybdenum-sulfur dithiocarbamate complexes", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, vol. 13, 1985, pages 927 - 929, XP009101553
MUSHA, KIYOSHI; TERAMAE, NORIO; YAMAZAKI, SUNAO; TODA, SHOZO; TANAKA, SHIGEYUKI: "Analysis of molybdenum dithiocarbamate complexes. IV. Thermal conversion of dinuclear molybdenum(V) bis(2-ethylhexyl)dithiocarbamate complexes in air", NIPPON KAGAKU KAISHI, vol. 12, 1984, pages 1889 - 1894, XP009101548
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 groups each selected individually from the group comprising heterocyclic rings, which may have substituent groups, and dialkylamino groups. 2. An organic molybdenum compound according to Claim 1, wherein the heterocyclic rings are selected from the group comprising five-membered and six-membered rings. 3. An organic molybdenum compound according to claim 2, wherein the five-membered rings are selected from the group comprising tetrazole, triazole, pyrazole, pyrazolidine, imidazole, oxazolidine, thiazolidine, pyrrolidine, pyrroline and pyrrole rings. 4. An organic molybdenum compound according to claim 2 or 3, wherein the six-membered heterocyclic rings are selected from the group comprising piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine and piperidine rings . 5. An organic molybdenum compound, according to any of Claims 1-4, wherein, if a dialkylamino group, A 1 is -N(R 10 ,R n ) and A 2 is -N (R 10' , R 11' ) , and R 10 , R 11 , R 10' and R 11' are groups each selected individually from the group comprising linear chain or branched alkyl groups having from 1 to 30 carbon atoms.
6. An organic molybdenum compound according to any of Claims 1-5, wherein A 1 and A 2 are groups each selected individually from among the group comprising -N (CH 3 ) 2 , -N(C 2 Hs) 2 , -N(C 3 H 7 ),, -N(C 4 Hg) 2 , -N(C 5 Hn) 2 , -N(C 6 H 13 ),, -N(C 7 Hi S ) 2 and -N (C 8 Hi 7 ) 2 .
7. An organic molybdenum compound according to any of Claims 1-6, wherein A 1 and A 2 are both 1-pyrrolidinyl groups .
8. Use of the organic molybdenum compound according to any of Claims 1 to 7 as a friction-modifier.
9. A lubricating composition comprising a base oil and the organic molybdenum compound according to any of claims 1-7.
10. Method of improving the friction characteristics of a lubricating composition by using the organic molybdenum compound according to any of claims 1-7. |
ORGANIC MOLYBDENUM COMPOUNDS AND LUBRICATING COMPOSITIONS COMPRISING SAID COMPOUNDS
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)
Formula ( 3 )
(Those compounds for which in this formulae x = 0 and y = 4, those for which x + y = 4, and 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)
In this formula A 1 and A 2 are groups each selected individually from the group comprising heterocyclic rings, which may have substituent groups, and dialkylamino groups . Preferably the heterocyclic rings which may have substituent groups are selected from five-membered and six-membered heterocyclic rings. It is further preferred that the five-membered rings are selected from the group comprising 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 piperazine, pyrazine, thiomorpholine, thiazine, morpholine, oxazine and piperidine rings. According to another preferred embodiment A 1 and A 2 are dialkylamino groups and A 1 is -N(R 1 ^R 11 ) and A 2 is -N(R 10' ,R n' ), and R 10 , R 11 , R 10' and R 11' are groups each selected individually from the group comprising linear chain or branched alkyl groups having from 1 to 30 carbon atoms.
Also it is preferred that A 1 and A 2 are groups each selected individually from the group comprising -N (CH 3 ) 2 , -N(C 2 Hs) 2 , -N(C 3 H 7 ),, -N(C 4 Hg) 2 , -N(C 5 Hn) 2 , -N(C 6 H 13 ),, -N(C 7 H 15 ), and -N (C 8 H 17 ),. It is especially preferred that A 1 and A 2 are both
1-pyrrolidinyl groups .
In another aspect, the preal provides the use of the organic molybdenum compounds as friction-modifiers.
In another aspect, the preal 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 reactions outlined below. (D
(2) (a) Synthesis of the Intermediate [1] When A 1 and A 2 are the same:
[2] When A 1 and A 2 are different:
(b) Synthesis of a compound of this invention from the intermediate. In the formulae indicated below PPh 3 signifies triphenylphosphine .
:i]
In a case where the aforementioned A 1 or A 2 is a five-membered 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 the 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 VI . (D Type I
The case where A 1 is a five-membered ring and A 2 is:
Moreover, R 10 and R 11 are groups each selected individually from 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 III 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. (6) Type VI
The case where A 1 is -N(R 1 ^R 11 ) and A 2 is -N(R lϋ' ,R n' ) 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 the 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 among 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 .
In more practical terms , the group of compounds indicated below can be shown as compounds of Type I I
Moreover, R 5 to R 9 and R 5' to R 9' , and R 10 and R 11 , 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.
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 b to R , R to R R 16 to R 20 and R 16' to
R -,2 z 0 u ' 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.
Moreover, R 5 to R 9 , R 5' to R 9' , 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. Actual compounds of Type I are :
Tetrazoyldithiocarbamate/dialkyldithiocarbamate dithio-oxomolybdenum complex, triazoylthiocarbamate/ dialkyldithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/dialkyldithiocarbamate dithio- oxomolybdenum complex, pyrazolidiyldithiocarbamate/- dialkyldithiocarbamate dithio-oxomolybdenum complex, imidazoyldithiocarbamate/dialkyldithiocarbamate dithio- oxomolybdenum complex, oxazolyldithiocarbamate/di- alkyldithiocarbamate dithio-oxomolybdenum complex, thiazolidyldithiocarbamate/dialkyldithiocarbamate dithio-oxomolybdenum complex, pyrrolidinyl- dithiocarbamate/dialkyldithiocarbamate dithio-oxomolybdenum complex, pyrrolinyldithiocarbamate/- dialkyldithiocarbamate dithio-oxomolybdenum complex and pyrrolyldithiocarbamate/dialkyldithiocarbamate dithio- oxomolybdenum 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/dialkyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/d
ialkyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/dialkyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/- dialkyldithiocarbamate dithio-oxomolybdenum complex, morpholyldithiocarbamate/dialkyldithiocarbamate dithio- oxomolybdenum complex, oxazyldithiocarbamate/- dialkyldithiocarbamate dithio-oxomolybdenum complex and piperidyldithiocarbamate/dialkyldithiocarbamate dithio- oxomolybdenum 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/ triazoyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/pyrazoyldithiocarbamate dithio- oxomolybdenum complex, tetrazoyldithiocarbamate/- pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/ oxazolyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/thiazolidyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxo-
molybdenum complex, tetrazoyldithiocarbamate/ pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, triazoyldithiocarbamate/ triazoyldithiocarbamate dithio-oxomolybdenum complex, triazoyldithiocarbamate/pyrazoyldithiocarbamate dithio- oxomolybdenum complex, triazoyldithiocarbamate/pyrazolidyldithiocarbamate dithio- oxomolybdenum complex, trizoyldithiocarbamate/- imidazolyldithiocarbamate dithio-oxomolybdenum complex, triazoyldithiocarbamate/oxazoyldithiocarbamate dithio- oxomolybdenum complex, triazoyldithiocarbamate/- thiazolidyldithiocarbamate dithio-oxomolybdenum complex, triazoyldithiocarbamate/pyrrolidyldithiocarbamate dithio-oxomolybdenum complex, triazoyldithiocarbamate/pyrolidinyldithiocarbamate dithio-oxomolybdenum complex, triazoyldithiocarbamate/pyrrolinyl- dithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, pyrazoyldithiocarbamate/pyrazoyl- dithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/- imidazoyldithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/oxazolyldithiocarbamate dithio- oxomolybdenum complex, pyrazoyldithiocarbamate/- thiazolidyldithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/- pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, pyrazoyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, pyrazolidyldithiocarbamate/- pyrazolidyldithiocarbamate dithio-oxomolybdenum complex,
pyrazolidyldithiocarbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, pyrazolidyldithio- carbamate/oxazolyldithiocarbamate dithio-oxomolybdenum complex, pyrazolidyldithiocarbamate/thiazolidyldithio- carbamate dithio-oxomolybdenum complex, pyrazolidyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, pyrazolidyldithio- carbamate/pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, pyrazolidyldithiocarbamate/ pyrrolyldithiocarbamate dithio-oxomolybdenum complex, imidazoyldithiocarbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, imidazoyldithio- carbamate/oxazolyldithiocarbamate dithio-oxomolybdenum complex, imidazoyldithiocarbamate/thiazolidyldithio- carbamate dithio-oxomolybdenum complex, imidazoyldithio- carbamate/pyrrolidinyldthiocarbamate dithio- oxomolybdenum complex, imidazoyldithio- carbamate/pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, imidazoyldithiocarbamate/ pyrrolyldithiocarbamate dithio-oxomolybdenum complex, oxazoyldithiocarbamate/oxazolyldithiocarbamate dithio- oxomolybdenum complex, oxazoyldithiocarbamate/thia- zolidyldithiocarbamate dithio-oxomolybdenum complex, oxazolyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, oxazolyldithiocarbamate/- pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, oxazolyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, thiazolidyldithiocarbamate/- thiazolidyldithiocarbamate dithio-oxomolybdenum complex, thiazolidyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, thiazoylidyldithio- carbamate/pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, thiazolidyldithiocarbamate/-
pyrrolyldithiocarbamate dithio-oxomolybdenum complex, pyrrolidinyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, pyrrolidinyldithio- carbamate/pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, pyrrolidinyldithiocarbamate/- pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, pyrrolinyldithiocarbamate/pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, pyrrolinyldithiocarbamate/- pyrrolyldithiocarbamate dithio-oxomolybdenum complex and pyrrolyldithiocarbamate/pyrrolyldithiocarbamate dioxy- molybdenum complex. Typical compounds of Type IV are:
Piperazyldithiocarbamate/piperazyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/- pyrazyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/thiomorpholyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/- thiazyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/morpholyldithiocarbamate dithio-oxomolybdenum complex, piperazyl- dithiocarbamate/oxazyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/piperidyl- dithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/pyrazyldithiocarbamate dithio- oxomolybdenum complex, pyazyldithiocarbamate/- thiomorpholyldithiocarbamate, dithio-oxomolybdenum complex, pyrazyldithiocarbamate/thiazyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/- morpholyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/oxazyldithiocarbamate dithio- oxomolybdenum complex, pyrazyldithiocarbamate/- piperidyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/thiomorpholyldithio-
carbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/thiazyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithio- carbamate/morpholyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/oxazyldithio- carbamate dithio-oxomolybdenum complex, thiomorpholyl- dithiocarbamate/piperidyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/thiazyldi- thiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/morpholyldithiocarbamate dithio- oxomolybdenum complex, thiazyldithiocarbamate/oxazyl- dithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/piperidyldithiocarbamate dithio- oxomolybdenum complex, morpholyldithiocarbamate/- morpholyldithiocarbamate dithio-oxomolybdenum complex, morpholyldithiocarbamate/oxalyldithiocarbamate dithio- oxomolybdenum complex, morpholyldithiocarbamate/- piperidyldithiocarbamate dithio-oxomolybdenum complex, oxazyldithiocarbamate/oxazyldithiocarbamate dithio- oxomolybdenum complex, oxazyldithiocarbamate/- piperidyldithiocarbamate dithio-oxomolybdenum complex and piperidyldithiocarbamate/piperidyldithiocarbamate dithio-oxomolybdenum complex. Typical compounds of Type V are: Piperazyldithiocarbamate/tetrazoyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/- triazoyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/pyrazoyldithiocarbamate dithio- oxomolybdenum complex, piperazyldithiocarbamate/- pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/- oxazolyldithiocarbamate dithio-oxomolybdenum complex,
piperazyldithiocarbamate/thiazolidyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/- pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/ pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, piperazyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, pyrazyldithio- carbamate/tetrazoyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/triazoyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/- pyrazoyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/- imidazoyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/oxazolyldithiocarbamate dithio- oxomolybdenum complex, pyrazyldithiocarbamate/- thiazolidyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/- pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, pyrazyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, thiomorpholyldithiocarbamate/- tetrazoyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/triazoyldithiocarbamate di- thio-oxomolybdenum complex, thiomorpholyldithio- carbamate/pyrazoyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/pyrazolidyl- dithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithio- carbamate/oxazolyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/thiazolidyldithio- carbamate dithio-oxomolybdenum complex,
thiomorpholyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithio- carbamate/pyrrolinyldithiocarbamate dithio-oxomolybdenum complex, thiomorpholyldithiocarbamate/- pyrrolyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/tetrazoyldithiocarbamate dithio- oxomolybdenum complex, thiazyldithiocarbamate/- triazoyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/pyrazoyldithiocarbamate dithio- oxomolybdenum complex, thiazyldithiocarbamate/- pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/imidazoyldithiocarbamate dithio- oxomolybdenum complex, thiazyldithio- carbamate/oxazolyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/thiazolidyldithio- carbamate dithio-oxomolybdenum complex, thiazyldithio- carbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/pyrrolinyl- dithiocarbamate dithio-oxomolybdenum complex, thiazyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, morpholyldithiocarbamate/- tetrazoyldithiocarbamate dithio-oxomolybdenum complex, morpholyldithiocarbamate/triazoyldithiocarbamate dithio- oxomolybdenum complex, morpholyldithio- carbamate/pyrazoyldithiocarbamate dithio-oxomolybdenum complex, morpholyldithiocarbamate/pyrazolidyldithio- carbamate dithio-oxomolybdenum complex, morpholyldithio- carbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, morpholyldithiocarbamate/oxazolyldithio- carbamate dithio-oxomolybdenum complex, morpholyldithio- carbamate/thiazolidyldithiocarbamate dithio- oxomolybdenum complex, morpholyldithio- carbamate/pyrrolidinyldithiocarbamate dithio-oxo-
molybdenum complex, morpholyldithiocarbamate/pyrrolinyl- dithiocarbamate dithio-oxomolybdenum complex, morpholyldithiocarbamate/pyrrolyldithiocarbamate dithio- oxomolybdenum complex, oxazyldithio- carbamate/tetrazoyldithiocarbamate dithio-oxomolybdenum complex, oxazyldithiocarbamate/triazoyldithiocarbamate dithio-oxomolybdenum complex, oxazyldithiocarbamate/- pyrazoyldithiocarbamate dithio-oxomolybdenum complex, oxazyldithiocarbamate/pyrazolidyldithiocarbamate dithio- oxomolybdenum complex, oxazyldithiocarbamate/imidazoyl- dithiocarbamate dithio-oxomolybdenum complex, oxazyldithiocarbamate/oxazolyldithiocarbamate dithio- oxomolybdenum complex, oxazyldithio- carbamate/thiazolidyldithiocarbamate dithio-oxo- molybdenum complex, oxazyldithiocarbamate/pyrrolidinyl- dithiocarbamate dithio-oxomolybdenum complex, oxazyldithiocarbamate/pyrrolinyldithiocarbamate dithio- oxomolybdenum complex, oxazyldithiocarbamate/pyrrolyl- dithiocarbamate dithio-oxomolybdenum complex, piperidyl- dithiocarbamate/tetrazoyldithiocarbamate dithio- oxomolybdenum complex, piperidyldithiocarbamate/- triazoyldithiocarbamate dithio-oxomolybdenum complex, piperidyldithiocarbamate/pyrazoyldithiocarbamate dithio- oxomolybdenum complex, piperidyldithio- carbamate/pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, piperidyldithiocarbamate/imidazoyl- dithiocarbamate dithio-oxomolybdenum complex, piperidyl- dithiocarbamate/oxazolyldithiocarbamate dithio- oxomolybdenum complex, piperidyldithiocarbamate/- thiazolidyldithiocarbamate dithio-oxomolybdenum complex, piperidyldithiocarbamate/pyrrolidinyldithiocarbamate dithio-oxomolybdenum complex, piperidyldithiocarbamate/- pyrrolinyldithiocarbamate dithio-oxomolybdenum complex
and piperidyldithiocarbamate/pyrrolyldithiocarbamate dithio-oxomolybdenum complex. Typical Compounds of Type VI are:
Dimethyldithiocarbamate dithio-oxomolybdenum complex, diethyldithiocarbamate dithio-oxomolybdenum complex, dipropyldithiocarbamate dithio-oxomolybdenum complex, dibutyldithiocarbamate dithio-oxomolybdenum complex, dipentyldithiocarbamate dithio-oxomolybdenum complex, dihexyldithiocarbamate dithio-oxomolybdenum complex, diheptyldithiocarbamate dithio-oxomolybdenum complex, dioctyldithiocarbamate dithio-oxomolybdenum complex, dinonyldithiocarbamate dithio-oxomolybdenum complex, didecyldithiocarbamate dithio-oxomolybdenum complex, diundecyldithiocarbamate dithio-oxomolybdenum complex, didodecyldithiocarbamate dithio-oxomolybdenum complex, ditridecyldithiocarbamate dithio-oxomolybdenum complex, ditetradecyldithiocarbamate dithio- oxomolybdenum complex, dipentadecyldithiocarbamate dithio-oxomolybdenum complex, dihexadecyldithiocarbamate dithio-oxomolybdenum complex, diheptadecyldithiocarbamate dithio-oxomolybdenum complex, dioctadecyldithiocarbamate dithio-oxomolybdenum complex, dinonadecyldithiocarbamate dithio-oxomolybdenum complex, dieicosyldithiocarbamate dithio-oxomolybdenum complex, diheneicosyldithiocarbamate dithio- oxomolybdenum complex, didocosyldithiocarbamate dithio- oxomolybdenum complex, ditricosyldithiocarbamate dithio- oxomolybdenum complex, ditetracosyldithiocarbamate dithio-oxomolybdenum complex, dipentacosyldithiocarbamate dithio-oxomolybdenum complex, dihexacosyldithiocarbamate dithio-oxomolybdenum complex, dioctacosyldithiocarbamate dithio-oxomolybdenum complex, dinonacosyldithiocarbamate dithio-oxomolybdenum
complex, ditriacontacyldithiocarbamate dithio- oxomolybdenum complex and mixed-alkyl dithiocarbamate dithio-oxomolybdenum complexes thereof.
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. 1 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
Synthesis of the dimethyldithiocarbamate dithio- oxomolybdenum complex.
(Process 1]
Na 2 MoO 4 + 2 NaS 2 CNEt 2 + 4 HCl
→ MoO 2 (Et 2 NCSz) 2 + 2 H 2 O + 4 NaCl
Sodium diethyldithiocarbamate (5.0 g, 0.02 mol) and sodium molybdate (2.7 g, 0.01 mol) were added to a 500 ml pear-shaped flask and dissolved in 50 ml of water. Then 0.04 mol of dilute hydrochloric acid (4 ml of concentrated hydrochloric acid added to water and made up to a total of 300 ml) was added dropwise from a dropping funnel over a period of about 2 hours, after which the precipitated material obtained was recovered by suction filtration and washed thoroughly with water, ethanol and diethyl ether and then dried. The crystals obtained were refined by recrystallization twice from dichloromethane/n-hexane and the diethyldithiocarbamate oxo-molybdenum complex was obtained in an 85% yield. This compound is a yellow-brown coloured powder. (Process 2)
The aforementioned diethyldithiocarbamate oxomolybdenum complex (1.0 g, 2.3 mmol) and triphenylphosphine (1.0 g, 3.8 mmol) were added, under Ar, to a pear-shaped flask which had been fitted with a reflux tube and heated under reflux in 10 ml of 1,2- dichloroethane for from 10 to 15 minutes at about 90 0 C. The S 8 or propylene sulphide (3.2 mmol) was added to the mixture which had changed to a red colour and the mixture was heated under reflux for 30 minutes in the case of S 8 or for 1.5 hours in the case of propylene sulphide. The reaction mixture obtained was refined using a silica gel column and the crystals obtained were recrystallized and refined. Complex: Dark green crystals, yield 37% (synthesized with S 8 ), and verification of the production of the intended material was carried out with NMR and IR. 1 H NMR (CDCl 3 ) δ = 1.09, 1.38, 1.40 and 1.45 (4t, 4x3H) , 3.48 and 3.57 (m, 2H), 3.8-4.0 (m, 3x2H) IR (KBr) : v (CN) 1529s, 1497s; v (Mo=O) 299s; v (S-S) 554 cm "1
Example 2
Synthesis of the Pyrrolidinyldithiocarbamate/Dithio- oxomolybdenum Complex:
Formula [ I ]
( Proces s 1 )
Synthesis of the Pyrrolidinyldithiocarbamate/Dithio- oxomolybdenum Complex Intermediate
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 and 300 ml of 0.12 mol dilute hydrochloric acid were 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 and pyrrolidinyldithiocarbmate/dithio-oxomolybdenum complex represented by the formula [I] above was obtained. Complex: Yellow coloured powder; Yield 72%.
(Process 2 )
The aforementioned complex represented by formula [I] above (1.0 g, 2.3 mmol) and triphenylphosphine (1.0 g, 3.8 mmol) were super-heated under reflux in
10 ml of 1,2-dichloroethane for 10 minutes and then propylene sulphide (0.77 ml, 9.9 mmol) were added and super-heating under reflux was carried out for from 1 to 2 hours. The reaction mixture obtained was separated and refined using column chromatography and the pyrrolidinyldithiocarbmate/dithio-oxomolybdenum complex was obtained.
Complex: Blue-green coloured crystals; Yield 82% Production of the intended compound was verified by NMR and elemental analysis. 1 H NMR (CDCl 3 ) δ = 1.95-2.00 (m, 2HxI), 2.04-2.16 (m, 2Hx2), 3.36-3.50 (m, 2HxI), 3.77-4.02 (m, 2Hx4)
Elemental Analysis: Calculated (%) for C I0 H I6 N 2 S 6 OMO: C, 25.63; H, 3.44; N, 5.98; S, 41.06; 0, 3.41; Mo, 20.47. Found (%) : C, 25.60; H, 3.27; N, 5.75.
The aforementioned pyrolidinyldithiocarbamate/di- thio-oxomolybdenum complex was added to provide a molybdenum content of 500 ppm in API Group III mineral
011 (viscosity at 100 0 C 4.23 mm 2 /s) to which 5% of a dispersing agent (alkenyl succinic acid polyalkylene
SUBSTITUTE SHEET (RULE 26ϊ
polyimide, trade name Infineum C9266) had been added, and a lubricating oil composition was obtained. Comparative Example 1
A lubricating oil composition was prepared in the same way as before except that the compound indicated below was used instead of the aforementioned pyrrolidinyldithiocarbamate/dithio-oxomolybdenum complex .
The Chemical Formula of Naugalube MoIy FM2543, produced by the Crompton Co.
The lubricating oil composition of Example 2 in which the pyrrolidinyldithiocarbamate/dithio-oxo- molybdenum complex of this invention was used as a friction-modifier and the lubricating oil composition of Comparative Example 2 in which a commercial friction- modifier was used 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
As shown in Figure 1, the composition of Example 2 exhibited a lower friction coefficient than that of Comparative Example 1. Brief Explanation of the Drawings
Figure 1 is a graph which shows how the friction coefficient changed with the passage of time with the lubricating oil in which the compound of the present invention had been used as the lubrication-modifier and
the lubricating oil in which the conventional product had been used as a lubrication-modifier.
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.