WO2008092945A1 - Organic molybdenum compounds and lubricating compositions comprising said compounds - Google Patents
Organic molybdenum compounds and lubricating compositions comprising said compounds Download PDFInfo
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- WO2008092945A1 WO2008092945A1 PCT/EP2008/051257 EP2008051257W WO2008092945A1 WO 2008092945 A1 WO2008092945 A1 WO 2008092945A1 EP 2008051257 W EP2008051257 W EP 2008051257W WO 2008092945 A1 WO2008092945 A1 WO 2008092945A1
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- complex
- dithio
- oxomolybdenum
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- 239000005078 molybdenum compound Substances 0.000 title claims abstract description 21
- 150000002752 molybdenum compounds Chemical class 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims description 24
- 230000001050 lubricating effect Effects 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 title description 36
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 8
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000003607 modifier Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000002199 base oil Substances 0.000 claims description 14
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 2
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 claims description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- SYQNCORZHMQJLS-UHFFFAOYSA-N piperazin-1-ylcarbamodithioic acid Chemical compound SC(=S)NN1CCNCC1 SYQNCORZHMQJLS-UHFFFAOYSA-N 0.000 description 18
- -1 n-octyl Chemical group 0.000 description 17
- WOAFYBKYNMKSID-UHFFFAOYSA-N S-carbamothioyl 1H-imidazole-2-carbothioate Chemical compound C(N)(SC(=O)C=1NC=CN=1)=S WOAFYBKYNMKSID-UHFFFAOYSA-N 0.000 description 16
- AMSVIQWYIRFEPN-UHFFFAOYSA-N morpholin-4-yl carbamodithioate Chemical compound C(N)(SN1CCOCC1)=S AMSVIQWYIRFEPN-UHFFFAOYSA-N 0.000 description 16
- JUPNMDQHEJJKSV-UHFFFAOYSA-N piperidin-1-yl carbamodithioate Chemical compound NC(=S)SN1CCCCC1 JUPNMDQHEJJKSV-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 239000010687 lubricating oil Substances 0.000 description 11
- 239000012990 dithiocarbamate Substances 0.000 description 10
- BHMARGUMXFEJHW-UHFFFAOYSA-N pyrrolidin-1-ylcarbamodithioic acid Chemical compound SC(=S)NN1CCCC1 BHMARGUMXFEJHW-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- KIGQKWMSXVLDLU-UHFFFAOYSA-N pyrazolidin-1-ylcarbamodithioic acid Chemical compound SC(=S)NN1CCCN1 KIGQKWMSXVLDLU-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZNIKVGNRRARPHS-UHFFFAOYSA-N 1,3-oxazol-2-ylcarbamodithioic acid Chemical compound SC(=S)NC1=NC=CO1 ZNIKVGNRRARPHS-UHFFFAOYSA-N 0.000 description 5
- JSSXTXUFCZYPOS-UHFFFAOYSA-N 2,3-dihydropyrrol-1-ylcarbamodithioic acid Chemical compound SC(=S)NN1CCC=C1 JSSXTXUFCZYPOS-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 0 *C1=SCCS1 Chemical compound *C1=SCCS1 0.000 description 4
- ZWZGXWWNEFZFIN-UHFFFAOYSA-N 1H-pyrrol-2-ylcarbamodithioic acid Chemical compound SC(=S)NC1=CC=CN1 ZWZGXWWNEFZFIN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011684 sodium molybdate Substances 0.000 description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 4
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- KYYCZEBROMVIBQ-UHFFFAOYSA-L O=[Mo+2].C(C)N(C([S-])=S)CC.C(C)N(C([S-])=S)CC Chemical compound O=[Mo+2].C(C)N(C([S-])=S)CC.C(C)N(C([S-])=S)CC KYYCZEBROMVIBQ-UHFFFAOYSA-L 0.000 description 2
- 102000001708 Protein Isoforms Human genes 0.000 description 2
- 108010029485 Protein Isoforms Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002818 heptacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000002465 nonacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VNOQVTBXOMQMQO-UHFFFAOYSA-N C/S=C(/N)\SC=C Chemical compound C/S=C(/N)\SC=C VNOQVTBXOMQMQO-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VSWDORGPIHIGNW-UHFFFAOYSA-N Pyrrolidine dithiocarbamic acid Chemical compound SC(=S)N1CCCC1 VSWDORGPIHIGNW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- ACFADQPXOVUUAY-UHFFFAOYSA-N di(docosyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCCCCCCCCCC ACFADQPXOVUUAY-UHFFFAOYSA-N 0.000 description 1
- DFEUQQCFHUHPGL-UHFFFAOYSA-N di(heptadecyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCCCCC DFEUQQCFHUHPGL-UHFFFAOYSA-N 0.000 description 1
- RMPYKGQVCRZVSP-UHFFFAOYSA-N di(hexacosyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCCCCCCCCCC)C(=S)S RMPYKGQVCRZVSP-UHFFFAOYSA-N 0.000 description 1
- SIBDVWCIOMFMHJ-UHFFFAOYSA-N di(nonadecyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCCCCCCC SIBDVWCIOMFMHJ-UHFFFAOYSA-N 0.000 description 1
- ULPXPCXAHFNIJI-UHFFFAOYSA-N di(nonyl)carbamodithioic acid Chemical compound CCCCCCCCCN(C(S)=S)CCCCCCCCC ULPXPCXAHFNIJI-UHFFFAOYSA-N 0.000 description 1
- CLFVDWHZTGGDDL-UHFFFAOYSA-N di(octacosyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCCCCCCCCCCCC)C(=S)S CLFVDWHZTGGDDL-UHFFFAOYSA-N 0.000 description 1
- LTCXRINLEGIQFA-UHFFFAOYSA-N di(pentadecyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCCC LTCXRINLEGIQFA-UHFFFAOYSA-N 0.000 description 1
- GGHVYBKGTQPRPO-UHFFFAOYSA-N di(tetracosyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCCCCCCCC)C(=S)S GGHVYBKGTQPRPO-UHFFFAOYSA-N 0.000 description 1
- JAGITJQNFUUREO-UHFFFAOYSA-N di(tetradecyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCC JAGITJQNFUUREO-UHFFFAOYSA-N 0.000 description 1
- GKEVEJUAVWUHRF-UHFFFAOYSA-N di(tridecyl)carbamodithioic acid Chemical compound CCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCC GKEVEJUAVWUHRF-UHFFFAOYSA-N 0.000 description 1
- KNJNVVFOWBNNFI-UHFFFAOYSA-N di(undecyl)carbamodithioic acid Chemical compound CCCCCCCCCCCN(C(S)=S)CCCCCCCCCCC KNJNVVFOWBNNFI-UHFFFAOYSA-N 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- DJWLPDXKMXJIEW-UHFFFAOYSA-N didodecylcarbamodithioic acid Chemical compound CCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCC DJWLPDXKMXJIEW-UHFFFAOYSA-N 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- XZZIGJYRELIWIB-UHFFFAOYSA-N diheptylcarbamodithioic acid Chemical compound CCCCCCCN(C(S)=S)CCCCCCC XZZIGJYRELIWIB-UHFFFAOYSA-N 0.000 description 1
- SRUUTPTZTQAXOP-UHFFFAOYSA-N dihexadecylcarbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCCCC SRUUTPTZTQAXOP-UHFFFAOYSA-N 0.000 description 1
- VXZVULMCJMCXLK-UHFFFAOYSA-N dioctadecylcarbamodithioic acid Chemical compound CCCCCCCCCCCCCCCCCCN(C(S)=S)CCCCCCCCCCCCCCCCCC VXZVULMCJMCXLK-UHFFFAOYSA-N 0.000 description 1
- BQCRLWBELMWYQA-UHFFFAOYSA-N dipropylcarbamodithioic acid Chemical compound CCCN(C(S)=S)CCC BQCRLWBELMWYQA-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- MGJYZNJAQSLHOL-UHFFFAOYSA-M n,n-dioctylcarbamodithioate Chemical compound CCCCCCCCN(C([S-])=S)CCCCCCCC MGJYZNJAQSLHOL-UHFFFAOYSA-M 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- LGIWQUXJCCGZOC-UHFFFAOYSA-N pyrrolidin-1-yl carbamodithioate Chemical compound NC(=S)SN1CCCC1 LGIWQUXJCCGZOC-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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 .
- a 1 and A 2 are groups each selected individually from the group comprising heterocyclic rings, which may have substituent groups, and dialkylamino groups .
- 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 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.
- 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.
- 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
- 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.
- 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 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.
- 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 VI . (D Type I
- a 1 is a five-membered ring and A 2 is:
- 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.
- a 1 is six-membered ring and A 2 is:
- Type III The case where A 1 and A 2 are both five-membered rings .
- Type V The case where A 1 is a six-membered ring and A 2 is a five-membered ring.
- Type VI The case where A 1 is a six-membered ring and A 2 is a five-membered ring.
- a 1 is -N(R 1 ⁇ R 11 ) and A 2 is -N(R l ⁇ ' ,R n' )
- the group of compounds indicated below can be shown as compounds of Type I.
- 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
- 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
- R 5 to R 9 and R 5' to R 9' , and R 10 and R 11 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 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 -,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.
- 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 dithi
- 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.
- 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
- 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.
- Tetrazoyldithiocarbamate/tetrazolyldithiocarbamate di-oxymolybdenum Tetrazoyldithiocarbamate/tetrazolyldithiocarbamate di-oxymolybdenum, tetrazoylditiocarbamate/ triazoyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/pyrazoyldithiocarbamate dithio- oxomolybdenum complex, tetrazoyldithiocarbamate/- pyrazolidyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarbamate/imidazoyldithiocarbamate dithio-oxomolybdenum complex, tetrazoyldithiocarba
- 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
- 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/
- 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, diund
- 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 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.
- Example 1 Comparative Examples but the invention is not limited in any way by these examples .
- Example 1 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 .
- Example 2 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
- Example 2 exhibited a lower friction coefficient than that of Comparative Example 1.
- 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.
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Abstract
The present inventon provides organic molybdenum compounds which can be represented by the general formula (1) which is indicated below. General Formula (1) In this formula A1 and A2 are groups each selected individually from the group comprising heterocyclic rings, which may have substituent groups, and the dialkylamino groups.
Description
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 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)
(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 A1 and A2 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 A1 and A2 are dialkylamino groups and A1 is -N(R1^R11) and A2 is -N(R10',Rn'), and R10, R11, R10' and R11' 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 A1 and A2 are groups each selected individually from the group comprising -N (CH3) 2, -N(C2Hs)2, -N(C3H7),, -N(C4Hg)2, -N(C5Hn)2, -N(C6H13),, -N(C7H15), and -N (C8H17),. It is especially preferred that A1 and A2 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 A1 and A2 are the same:
(b) Synthesis of a compound of this invention from the intermediate. In the formulae indicated below PPh3 signifies triphenylphosphine .
:i]
In a case where the aforementioned A1 or A2 is a five-membered ring, then A1 or A2 can be represented by:
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 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 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:
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
Table 2 In the case of a six-membered ring
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 VI . (D Type I
The case where A1 is a five-membered ring and A2 is:
Moreover, R10 and R11 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 A1 is six-membered ring and A2 is:
(3) Type III 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. (6) Type VI
The case where A1 is -N(R1^R11) and A2 is -N(Rlϋ',Rn') 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 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, R10 and R11 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 .
Moreover, R5 to R9 and R5' to R9', and R10 and R11, 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.
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.
Moreover , Rb to R , R to R R16 to R20 and R16' to
R -,2z0u' 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.
Moreover, R5 to R9, R5' to R9', 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. 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]
Na2MoO4 + 2 NaS2CNEt2 + 4 HCl
→ MoO2(Et2NCSz)2 + 2 H2O + 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)
Example 2
Synthesis of the Pyrrolidinyldithiocarbamate/Dithio- oxomolybdenum Complex:
Formula [ I ]
( Proces s 1 )
Synthesis of the Pyrrolidinyldithiocarbamate/Dithio- oxomolybdenum Complex Intermediate
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 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. 1H NMR (CDCl3) 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 CI0HI6N2S6OMO: 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 1000C 4.23 mm2/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.
Claims
1. An organic molybdenum compound having the general formula (1) below General Formula (1)
wherein A1 and A2 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, A1 is -N(R10,Rn) and A2 is -N (R10' , R11' ) , and R10, R11, R10' and R11' 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 A1 and A2 are groups each selected individually from among the group comprising -N (CH3) 2, -N(C2Hs)2, -N(C3H7),, -N(C4Hg)2, -N(C5Hn)2, -N(C6H13),, -N(C7HiS)2 and -N (C8Hi7) 2.
7. An organic molybdenum compound according to any of Claims 1-6, wherein A1 and A2 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.
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| JP2007023211A JP5108316B2 (en) | 2007-02-01 | 2007-02-01 | Friction modifier comprising organomolybdenum compound and lubricating composition containing the same |
| JP2007-023211 | 2007-02-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2233554A1 (en) | 2009-03-27 | 2010-09-29 | Infineum International Limited | Lubricating oil compositions |
| WO2014207176A1 (en) * | 2013-06-28 | 2014-12-31 | Shell Internationale Research Maatschappij B.V. | Lubricating oil additive and lubricating oil composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015010176A (en) * | 2013-06-28 | 2015-01-19 | 昭和シェル石油株式会社 | Lubricant oil additive and lubricant oil composition |
| JP7206710B2 (en) * | 2018-09-04 | 2023-01-18 | 東ソー株式会社 | Dithiocarbamic acid compound, organic molybdenum complex, and lubricating oil composition |
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| EP1041135A1 (en) * | 1999-03-29 | 2000-10-04 | Asahi Denka Kogyo Kabushiki Kaisha | Lubricating composition for diesel engines |
| JP2000303088A (en) * | 1999-04-16 | 2000-10-31 | Koyo Seiko Co Ltd | Lubricant composition and rolling bearing using the same |
| US20060199745A1 (en) * | 2005-03-01 | 2006-09-07 | R.T. Vanderbilt Company, Inc. | Molybdenum dialkyldithiocarbamate compositions and lubricating compositions containing the same |
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| JP3554757B2 (en) * | 1992-12-21 | 2004-08-18 | シェブロンテキサコジャパン株式会社 | Engine oil composition |
| JP2003321692A (en) * | 2002-04-26 | 2003-11-14 | Nippon Oil Corp | Grease composition |
| JP2005247995A (en) * | 2004-03-03 | 2005-09-15 | Cosmo Sekiyu Lubricants Kk | Engine oil composition |
-
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| EP1041135A1 (en) * | 1999-03-29 | 2000-10-04 | Asahi Denka Kogyo Kabushiki Kaisha | Lubricating composition for diesel engines |
| JP2000303088A (en) * | 1999-04-16 | 2000-10-31 | Koyo Seiko Co Ltd | Lubricant composition and rolling bearing using the same |
| US20060199745A1 (en) * | 2005-03-01 | 2006-09-07 | R.T. Vanderbilt Company, Inc. | Molybdenum dialkyldithiocarbamate compositions and lubricating compositions containing the same |
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| 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 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2233554A1 (en) | 2009-03-27 | 2010-09-29 | Infineum International Limited | Lubricating oil compositions |
| WO2014207176A1 (en) * | 2013-06-28 | 2014-12-31 | Shell Internationale Research Maatschappij B.V. | Lubricating oil additive and lubricating oil composition |
| CN105339474A (en) * | 2013-06-28 | 2016-02-17 | 国际壳牌研究有限公司 | Lubricating oil additive and lubricating oil composition |
| US20160152917A1 (en) * | 2013-06-28 | 2016-06-02 | Shell Oil Company | Lubricating oil additive and lubricating oil composition |
| RU2669925C2 (en) * | 2013-06-28 | 2018-10-17 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Lubricating oil additive and lubricating oil composition |
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| JP5108316B2 (en) | 2012-12-26 |
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