CA1127171A - Molybdenum compounds (iii) - Google Patents
Molybdenum compounds (iii)Info
- Publication number
- CA1127171A CA1127171A CA351,481A CA351481A CA1127171A CA 1127171 A CA1127171 A CA 1127171A CA 351481 A CA351481 A CA 351481A CA 1127171 A CA1127171 A CA 1127171A
- Authority
- CA
- Canada
- Prior art keywords
- oil
- molybdenum
- product
- prepared
- lubricating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 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 claims abstract description 62
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 31
- 239000011733 molybdenum Substances 0.000 claims abstract description 31
- 239000010687 lubricating oil Substances 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 12
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 230000001050 lubricating effect Effects 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 125000005541 phosphonamide group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 2
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 3
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 235000016768 molybdenum Nutrition 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000654 additive Substances 0.000 description 18
- -1 MoOC14 Chemical class 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229960002317 succinimide Drugs 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012990 dithiocarbamate Substances 0.000 description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- FCEWRLVEPKVKBU-UHFFFAOYSA-N 2-[2-(tert-butylamino)-1-hydroxyethyl]phenol Chemical compound CC(C)(C)NCC(O)C1=CC=CC=C1O FCEWRLVEPKVKBU-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000008039 phosphoramides Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- SZXCCXFNQHQRGF-UHFFFAOYSA-N di(propan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(S)(=S)OC(C)C SZXCCXFNQHQRGF-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- GCMDLPXRCVHIMG-UHFFFAOYSA-N dioxomolybdenum(2+) Chemical compound O=[Mo+2]=O GCMDLPXRCVHIMG-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical class C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/18—Complexes with metals
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
-
- 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
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Antioxidant additives for lubricating oil are prepared by combining an acidic molybdenum compound and certain basic nitrogen compounds to form a molybdenum-containing com-position preferably in the presence of a polar promoter.
Antioxidant additives for lubricating oil are prepared by combining an acidic molybdenum compound and certain basic nitrogen compounds to form a molybdenum-containing com-position preferably in the presence of a polar promoter.
Description
` 11~'~17~
003 This invention relates to new lubricating oil 004 compositions. More specifically, it relates to new lubricating 005 oil compositions containing antioxidant molybdenum compounds.
006 BACKGROUND O~ THE INVENTION
007 Molybdenum disulfide has long been known as a 008 desirable additive for use in lubricating oil compositions.
009 However, one of its major detriments is its lack of oil 010 solubility. ~olybdenum disulfide is ordinarily finely ground 011 and then dispersed in the lubricating oil composition to impart 012 friction modifying and antiwear properties. Finely ground 013 molybdenum disulfide is not an effective oxidation inhibitor in 01~ lubricating oils.
015 As an alternative to finely grinding the molybdenum 016 disulfide, a number of different approaches involving preparing 017 salts of molybdenum compounds have been tried. One type of 018 compound which has been prepared molybdenum dithiocarbamates.
019 R~e~/resentative compositions are described in U.S. patent 020 3,~12,539, which teaches molybdenum (VI) dioxide dialkyldithio-021 carbamates; U.S. 3,509,051, which teaches sulfurized oxymolyb-022 denum dithiocarbamates; and U.S. 4,098,705, which teaches 023 sulfur containing molybdenum dihydrocarbyl dithiocarbamate 024 compositions.
025 An alternative approach is to form dithiophospbates 026 instead of dithiocarbamates. Representative of this type of 027 molybdenum compound are the compositions described in U.S.
028 3,494,866, such as oxymolybdenum diisopropylphosphorodithioate.
029 U.S. 3,184,410 describes certain dithiomolybdenyl 030 acetylacetonates for use in lubricating oils.
031 Braithwaite and Greene in Wear, 46 tl978) 405-432 032 describe various molybdenum-containing compositions for use in 033 motor oils.
034 U.S. Patent 3,349,108 teaches a molybdenum trioxide 035 complex with diethylenetriamine for use as an additive for 036 molten ~teel.
037 ~ussian patent 533,625 teaches lube oil additives llZ'7171 prepared from ammonium molybdate and alkenylated polyamines.
Another way to incorporate molybdenum compounds in oil is to prepare a colloidal complex of molybdenum disulfide or oxysulfides dispersed using known dispersants. United States patent 3,223,625 describes a procedure in which an acidic aqueous solution of certain molybdenum compounds is prepared and then extracted with a hydrocarbon ether dispersed with an oil soluble dispersant and then freed of the ether. United States 3,281,355 teaches the preparation of a dispersion of molybdenum disulfide by preparing a mixture of lubricating oil, dispersant, and a molybdenum compound in water or Cl 4 aliphatic alcohol, contacting this with a sulfide ion generator and then removing the solvent. Dispersants noted to be effective in this procedure are petroleum sulfonates, phenates, alkylphenate sulfides, phosphosulfurized olefins and combinations thereof.
It has now been found that a lubricating oil additive can be prepared by combining an acidic molybdenum compound and certain basic nitrogen-containing compositions.
; According to the invention, there is provided a process for preparing a molybdenum-containing composition which comprises combining an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a carboxylic acid amide, Mannich base, phosphonamide, thiophosphonamide, phosphoramide, and dispersant viscosity index improvers to form a molybdenum containing complex. The process if preferably carried out in the presence of a polar promoter.
Lubricating oil compositions containing the additive disclosed herein are effective as either fluid and grease compositions (depending upon the specific additive or additives employed) for inhibiting oxidation, imparting antiwear and extreme pressure properties t and modifying the friction proper-ties of the oil which may, when used as a crankcase lubricant, llZ7171 lead to improved mileage for the vehicle being lubricated with a lubricating oil of this invention.
The precise molecular formula of the molybdenum com-positions prepared in the process of this invention is not known with certainty; however, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of oxygen or sulfur is either complexed by or the salt of one or more nitrogen atoms of the basic nitrogen containing composition used in the preparation of these additives.
-2a-!
~lZ717~
The molybdenum compounds used to prepare the additives for com-positions of this invention are acidic molybdenum compounds. By acidic is meant that the molybdenum compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure. Typically these molybdenum compounds are hexavalent and are represented by the following compositions: lybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts such as MoOC14, MoO2Br2, Mo203C16, molybdenum trioxide or similar acidic molybdenum compounds. Preferred acidic molybdenum compounds are molybdic acid, ammonium lybdate, and alkali metal molybdates. Particularly preferred are molybdic acid and ammonium molybdate.
The polar promoter which is preferably used in the process of this invention is one which facilitates the interaction between the acidic moly-bdenum compound and the basic nitrogen compound. A wide variety of such promoters may be used. Typical promoters are 1,3-propanediol, 1,4-butanediol, diethylene glycol, butyl cellosolve, propylene glycol, 1,4-butyleneglycol, methyl carbitol, ethanolamine, diethanolamine, N-methyl-diethanol-amine, dimethyl formamide, N-methyl acetamide, dimethyl acetamide, methanol, ethylene glycol, dimethyl sulfoxide, hexamethyl phosphoramide, tetrahydrofuran and water. Preferred are water and ethylene glycol. Particularly preferred is water.
While ordinarily the polar promoter is separately added to the reaction mixture, it may also be present, particularly in the case of water, as a component of non-anhydrous starting materials or as waters of hydration in the acidic molybdenum compound, such as (NH4)6Mo7O24.4 H2O. Water may also be added as ammonium hydroxide.
The basic nitrogen compounds are selected from those having a basic B nitrogen content as measured by ASTM D-664 or D-2896. It is preferred that they be oil-soluble. These compositions are selected from -WWiA~
carboxylic acid amides, Mannich bases, phosphonamides, thiophosphonamides, phosphoramides, dispersant 1~27171 viscosity index improvers, and mixtures thereof. These basic nitrogen containing compounds are described below (keeping in mind the reservation that each must have at least one basic nitrogen). Any of the nitrogen-containing compositions may be after-treated with e.g., boron, using procedures well known in the art so long as the after-treated product continues to contain basic nitrogen. These after- treatments are particularly applicable to succinimides and Mannich base compositions.
Carboxylic amide compositions that are suitable starting materials for preparing the products of this invention, are known in the art. Typical of such compounds are those disclosed in United States patent 3,405,064. These compositions are ordinarily prepared by reacting a carboxylic acid or anhydride ester thereof, having at least 12 to about 350 aliphatic carbon atoms in the principal aliphatic chain and, if desired, having pendant aliphatic groups to render the molecule oil soluble which is with an amine or a hydrocarbyl polyamine, such as an ethylene amine, to give a mono or polycarboxylic acid amide. Preferred are those amides prepared from (1) a carboxylic acid of the formula R2COOH, where R2 is C12 20 alkyl or a mixture of this acid with a polyisobutenyl carboxylic ac~d in which the polyisobutenyl group contains from 72 to 128 carbon atoms and (2) an ethylene amine, especially triethylene tetraamine or tetraethylene pentaamine or mixtures thereof.
~lZ~
Another class of compounds useful for supplying basic nitrogen are the Mannich base compositions. The Mannich base compositions are prepared from a phenol or Cg 200 alkylphenol, an aldehyde, such as formaldehyde or formaldehyde precursor such a para-formaldehyde, and an amine compound.
The amine may be a mono or polyamine and typical compositions are prepared from an alkylamine, such as methylamine, or an ethylene amine, such as diethylene triamine, or tetraethylene pentaamine and the like. The phenolic material may be sulfurized and preferably in dodecylphenol or a C80 100 alkylphenol. Typical Mannich bases which can be used in this invention are disclosed in United States patents 3,649,229, 3,368,972, 3,539,663 and 4,157,309. The last specification discloses Mannich bases prepared by reacting an alkylphenol having at least 50 carbon atoms, preferably 50 to 200 carbon atoms with formaldehyde and an alkylene polyamine HN(ANH)nH
where A is a saturated divalent alkyl hydrocarbon of 2 to 6 carbon atoms and n is 1-10 and where the condensation product of said alkylene polyamine may be further reacted with urea or thiourea. The utility of these Mannich bases as starting materials for preparing lubricating oil additives can often be significantly improved by treating the Mannich base using conventional techniques to introduce boron into the composition.
B
The phosphoramides and phosphonamides, such as those disclosed in United States patents 3,909,430 and 3,968,157, may be prepared by forming oil soluble phosphorus compound having at least one P-N bond~ They can be prepared, for example, by reacting phosphorus oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a mono-functional amine. Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing from
003 This invention relates to new lubricating oil 004 compositions. More specifically, it relates to new lubricating 005 oil compositions containing antioxidant molybdenum compounds.
006 BACKGROUND O~ THE INVENTION
007 Molybdenum disulfide has long been known as a 008 desirable additive for use in lubricating oil compositions.
009 However, one of its major detriments is its lack of oil 010 solubility. ~olybdenum disulfide is ordinarily finely ground 011 and then dispersed in the lubricating oil composition to impart 012 friction modifying and antiwear properties. Finely ground 013 molybdenum disulfide is not an effective oxidation inhibitor in 01~ lubricating oils.
015 As an alternative to finely grinding the molybdenum 016 disulfide, a number of different approaches involving preparing 017 salts of molybdenum compounds have been tried. One type of 018 compound which has been prepared molybdenum dithiocarbamates.
019 R~e~/resentative compositions are described in U.S. patent 020 3,~12,539, which teaches molybdenum (VI) dioxide dialkyldithio-021 carbamates; U.S. 3,509,051, which teaches sulfurized oxymolyb-022 denum dithiocarbamates; and U.S. 4,098,705, which teaches 023 sulfur containing molybdenum dihydrocarbyl dithiocarbamate 024 compositions.
025 An alternative approach is to form dithiophospbates 026 instead of dithiocarbamates. Representative of this type of 027 molybdenum compound are the compositions described in U.S.
028 3,494,866, such as oxymolybdenum diisopropylphosphorodithioate.
029 U.S. 3,184,410 describes certain dithiomolybdenyl 030 acetylacetonates for use in lubricating oils.
031 Braithwaite and Greene in Wear, 46 tl978) 405-432 032 describe various molybdenum-containing compositions for use in 033 motor oils.
034 U.S. Patent 3,349,108 teaches a molybdenum trioxide 035 complex with diethylenetriamine for use as an additive for 036 molten ~teel.
037 ~ussian patent 533,625 teaches lube oil additives llZ'7171 prepared from ammonium molybdate and alkenylated polyamines.
Another way to incorporate molybdenum compounds in oil is to prepare a colloidal complex of molybdenum disulfide or oxysulfides dispersed using known dispersants. United States patent 3,223,625 describes a procedure in which an acidic aqueous solution of certain molybdenum compounds is prepared and then extracted with a hydrocarbon ether dispersed with an oil soluble dispersant and then freed of the ether. United States 3,281,355 teaches the preparation of a dispersion of molybdenum disulfide by preparing a mixture of lubricating oil, dispersant, and a molybdenum compound in water or Cl 4 aliphatic alcohol, contacting this with a sulfide ion generator and then removing the solvent. Dispersants noted to be effective in this procedure are petroleum sulfonates, phenates, alkylphenate sulfides, phosphosulfurized olefins and combinations thereof.
It has now been found that a lubricating oil additive can be prepared by combining an acidic molybdenum compound and certain basic nitrogen-containing compositions.
; According to the invention, there is provided a process for preparing a molybdenum-containing composition which comprises combining an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a carboxylic acid amide, Mannich base, phosphonamide, thiophosphonamide, phosphoramide, and dispersant viscosity index improvers to form a molybdenum containing complex. The process if preferably carried out in the presence of a polar promoter.
Lubricating oil compositions containing the additive disclosed herein are effective as either fluid and grease compositions (depending upon the specific additive or additives employed) for inhibiting oxidation, imparting antiwear and extreme pressure properties t and modifying the friction proper-ties of the oil which may, when used as a crankcase lubricant, llZ7171 lead to improved mileage for the vehicle being lubricated with a lubricating oil of this invention.
The precise molecular formula of the molybdenum com-positions prepared in the process of this invention is not known with certainty; however, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of oxygen or sulfur is either complexed by or the salt of one or more nitrogen atoms of the basic nitrogen containing composition used in the preparation of these additives.
-2a-!
~lZ717~
The molybdenum compounds used to prepare the additives for com-positions of this invention are acidic molybdenum compounds. By acidic is meant that the molybdenum compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure. Typically these molybdenum compounds are hexavalent and are represented by the following compositions: lybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts such as MoOC14, MoO2Br2, Mo203C16, molybdenum trioxide or similar acidic molybdenum compounds. Preferred acidic molybdenum compounds are molybdic acid, ammonium lybdate, and alkali metal molybdates. Particularly preferred are molybdic acid and ammonium molybdate.
The polar promoter which is preferably used in the process of this invention is one which facilitates the interaction between the acidic moly-bdenum compound and the basic nitrogen compound. A wide variety of such promoters may be used. Typical promoters are 1,3-propanediol, 1,4-butanediol, diethylene glycol, butyl cellosolve, propylene glycol, 1,4-butyleneglycol, methyl carbitol, ethanolamine, diethanolamine, N-methyl-diethanol-amine, dimethyl formamide, N-methyl acetamide, dimethyl acetamide, methanol, ethylene glycol, dimethyl sulfoxide, hexamethyl phosphoramide, tetrahydrofuran and water. Preferred are water and ethylene glycol. Particularly preferred is water.
While ordinarily the polar promoter is separately added to the reaction mixture, it may also be present, particularly in the case of water, as a component of non-anhydrous starting materials or as waters of hydration in the acidic molybdenum compound, such as (NH4)6Mo7O24.4 H2O. Water may also be added as ammonium hydroxide.
The basic nitrogen compounds are selected from those having a basic B nitrogen content as measured by ASTM D-664 or D-2896. It is preferred that they be oil-soluble. These compositions are selected from -WWiA~
carboxylic acid amides, Mannich bases, phosphonamides, thiophosphonamides, phosphoramides, dispersant 1~27171 viscosity index improvers, and mixtures thereof. These basic nitrogen containing compounds are described below (keeping in mind the reservation that each must have at least one basic nitrogen). Any of the nitrogen-containing compositions may be after-treated with e.g., boron, using procedures well known in the art so long as the after-treated product continues to contain basic nitrogen. These after- treatments are particularly applicable to succinimides and Mannich base compositions.
Carboxylic amide compositions that are suitable starting materials for preparing the products of this invention, are known in the art. Typical of such compounds are those disclosed in United States patent 3,405,064. These compositions are ordinarily prepared by reacting a carboxylic acid or anhydride ester thereof, having at least 12 to about 350 aliphatic carbon atoms in the principal aliphatic chain and, if desired, having pendant aliphatic groups to render the molecule oil soluble which is with an amine or a hydrocarbyl polyamine, such as an ethylene amine, to give a mono or polycarboxylic acid amide. Preferred are those amides prepared from (1) a carboxylic acid of the formula R2COOH, where R2 is C12 20 alkyl or a mixture of this acid with a polyisobutenyl carboxylic ac~d in which the polyisobutenyl group contains from 72 to 128 carbon atoms and (2) an ethylene amine, especially triethylene tetraamine or tetraethylene pentaamine or mixtures thereof.
~lZ~
Another class of compounds useful for supplying basic nitrogen are the Mannich base compositions. The Mannich base compositions are prepared from a phenol or Cg 200 alkylphenol, an aldehyde, such as formaldehyde or formaldehyde precursor such a para-formaldehyde, and an amine compound.
The amine may be a mono or polyamine and typical compositions are prepared from an alkylamine, such as methylamine, or an ethylene amine, such as diethylene triamine, or tetraethylene pentaamine and the like. The phenolic material may be sulfurized and preferably in dodecylphenol or a C80 100 alkylphenol. Typical Mannich bases which can be used in this invention are disclosed in United States patents 3,649,229, 3,368,972, 3,539,663 and 4,157,309. The last specification discloses Mannich bases prepared by reacting an alkylphenol having at least 50 carbon atoms, preferably 50 to 200 carbon atoms with formaldehyde and an alkylene polyamine HN(ANH)nH
where A is a saturated divalent alkyl hydrocarbon of 2 to 6 carbon atoms and n is 1-10 and where the condensation product of said alkylene polyamine may be further reacted with urea or thiourea. The utility of these Mannich bases as starting materials for preparing lubricating oil additives can often be significantly improved by treating the Mannich base using conventional techniques to introduce boron into the composition.
B
The phosphoramides and phosphonamides, such as those disclosed in United States patents 3,909,430 and 3,968,157, may be prepared by forming oil soluble phosphorus compound having at least one P-N bond~ They can be prepared, for example, by reacting phosphorus oxychloride with a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorus oxychloride with a difunctional secondary amine and a mono-functional amine. Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compound containing from
2 to 450 or more carbon atoms, such as polyethylene, poly-isobutylene, polypropylene, ethylene, l-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, and the like, with phosphorus pentasulfide and nitrogen-containing compound as defined above, particularly an alkylamine, alkyldiamine, alkylpolyamine, or an alkyleneamine, such as ethylene diamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, and the like.
Another class of nitrogen-containing compositions useful in preparing the molybdenum compositions of this invention includes the so-called dispersant viscosity index improvers (VI improvers). These VI improvers are commonly prepared by functionalizing a hydrocarbon polymer, especially a polymer derived from ethylene and/or propylene, optionally containing additional units derived from one or more co-monomers such as ~2'7171 oo 1 -7 -002 alicyclic or aliphatic olefins or diolefins. The functionaliza-003 tion may be carried out by a variety of processes which ù04 introduce a reactive site or sites which usually has at least 005 one oxygen atom on the polymer. The polymer is then contacted 006 with a nitrogen-containing source to introduce nitrogen-007 containing functional groups on the polymer backbone. Commonly 008 used nitrogen sources include any basic nitrogen compound, 009 especially those nitrogen-containing compounds and compositions 010 described herein. Preferred nitrogen sources are alkylene 011 amines, such as ethylene amines, alkyl amines, and Mannich 012 bases.
013 Preferred basic nitrogen compounds for use in this 014 invention are succinimides, carboxylic acid amides, and ~annich 015 bases.
016 The process of this invention may be carried out by 017 combining the acidic molybdenum precursor as described above, 018 with a basic nitrogen-containing composition as described above 019 preferably in the presence of a polar promoter. The reaction 020 is ordinarily carried out at atmospheric pressure; however, 021 higher or lower pressures may be used, if desired, using 022 methods that are well-known to those skilled in the art. A
023 diluent may be used to enable the reaction mixture to be 024 eficiently stirred. Typical diluents are lubricating oil and 025 liquid compounds containing only carbon and hydrogen. If the 026 mixture is sufficiently fluid to permit stirring, no diluent is 027 necessary. A diluent which does not react with the molybdenum 028 containing compound is desirable.
029 In the reaction mixture, the ratio of molybdenum 030 compound to basic nitrogen compound is not critical; however, 031 as the amount of molybdenum with respect to basic nitrogen, 032 increases, the filtration of the product becomes more diffi-033 cult. Since the molybdenum component probably oligomerizes, it 034 is ad~7antageous to add as much molybdenum as can easily be 035 maintained in the composition. Usually the reaction mixture 036 will have charged to it from 0.01 to 2.00 atoms of molybdenum 037 per basic nitrogen atom. Preferably from 0.4 to 1.0, and most 7~
001 ~-002 preferably from 0.4 to 0.7, atoms of molybdenum per atom of 003 basic nitrogen is added to the reaction mixture.
004 The polar promoter, which is preferably used, is 005 ordinarily present in the ratio of 0.1 to S0 mols of water per 006 mol of molybdenum. Preferably from 0.5 to 25 and most 007 preferably 1.0 to 15 mols of the promoter is present per mol of 008 molybdenum.
009 The lubricating oil compositions of this invention 010 can be prepared by admixing, by conventional techniques, the 011 appropriate amount of the molybdenum-containing composition 012 with a lubricating oil. The selection of the particular base 013 oil depends on the contemplated application of the lubricant 014 and the presence of other additives. Generally, the amount of 015 the molybdenum containing additive will vary from 0.l05 to 15%
016 by weight and preferably from 0.2 to 10~ by weight.
017 The lubricating oil which may be used in this 018 invention includes a wide variety of hydrocarbon oils, such as 019 naphthenic bases, paraffin bases and mixed base oils as well as 020 synthetic oils such as esters and the like. The lubricating 021 oils may be used individually or in combination and generally 022 have a viscosity which ranges from 50 to 5,000 SUS and usually 023 from 100 to 15,000 SUS at 38C.
024 In many instances, it may be advantageous to form 025 concentrates of the molybdenum containing additive within a 026 carrier liquid. These concentrates provide a convenient method 027 of handling and transporting the additives before their subse-028 quent dilution and use. The concentration of the molybdenum-029 containing additive within the concentrate may vary from 0.25 030 to 90% by weight although it is preferred to maintain a con-031 centration between 1 and 50% by weight. The final application 032 of the lubricating oil compositions of this invention may be in 033 marine cylinder lubricants as in crosshead diesel engines, 034 crankcase lubricants as in automobiles and railroads, lubri-035 cants for heavy machinery such as steel mills and the like, or 036 as greases or bearings and the like. Whether the lubricant is 037 fluid or a solid will ordinarily depend on whether a thickening 11~717~
001 ~9 ~
002 agent is present. Typical thickening agents include polyurea 003 acetates, lithium stearate and the like.
004 If desired, other additives may be included in the lubri-005 cating oil compositions of this invention. These additives 006 include antioxidants or oxidation inhibitors, dispersants, rust 007 inhibitors, anticorrosion agents and so forth. Also anti-foam 008 agents stabilizers, anti-stain agents, tackiness agents, anti-009 chatter agents, dropping point improvers, anti-squawk agents, 010 extreme pressure agents, odor control agents and the like may 011 be included.
012 Certain molybdenum products that can be prepared by 013 the process of invention also find utility in making brake 014 lining materials, in high-temperature structural materials, in 015 iron and steel alloys, in cladding materials, in electroplating 016 solutions, as components for electrical discharge machine 017 electrodes, as fuel additives, in making self-lubricating or 018 wear-resistant structures, as mold release agents, in composi-019 tions for phosphatizing steel, in brazing fluxes, in nutrient 020 media for microorganisms, in making electrosensitive recording 021 material, in catalysts for refining coal, oil, shale, tar 022 sands, and the like or as stabilizers or curing agents for 023 natural rubber or polymers.
024 The following examples are presented to illustrate 025 the operation of the invention and are not intended to be a 026 limitation upon the scope of the claims.
027 Example 1 028 To a 1 liter flask was added 290 grams of a solution 029 of 45% concentrate in oil of the succinimide prepared from 030 polyisobutenyl succinic anhydride and tetraethylene pentaamine 031 and having a number average molecular weight for the polyiso-032 butenyl group of about 980, 28.8 grams of molybdenum trioxide 033 as a dry powder, 9.6 ml of water and 150 ml of hydrocarbon 034 thinner. The reaction mixture, which was a murky yellow-green 035 suspension, was heated to 65C and held at this temperature for 036 3-1/2 hours. The temperature was then raised to 150C to 037 remove water and held at this temperature for one hour. Then llZ7171 002 50 ml of hot hydrocarbon thinner was added and the reaction 003 mixture was filtered through diatomaceous earth. The filter 004 cake was washed with 100 ml of hot hydrocarbon thinner and a 005 light blue residue remained on the filter cake. The reaction 006 mixture was then stripped to 160C at 20 mm Hg to yield a 007 product containing 4.16~ molybdenum, 3.4896 oxygen, and 1.97%
008 nitrogen.
009 Example 2 010 To a l-liter flask was added 290 grams of the 011 succinimide described in Example 1 and 150 ml of hydrocarbon 012 thinner. The mixture was heated to 65C and then 28.8 grams of 013 molybdenum trioxide and 50 ml of water was added. The tempera-014 ture of the mixture was maintained at 65C for 1/2 hour and 015 then increased to 155C over a period of one hour and main-016 tained at 155 to 160C for one hour. To this mixture was 017 added 50 ml hydrocarbon thinner and the product was filtered 018 through diatomaceous earth. The filtrate was stripped to 160C
019 at 20 mm Hg to yield 311 grams of product containing 6.18%
020 molybdenum, 4.17% oxygen and 1.94% nitrogen.
021 Example 3 022 To a 3-liter flask was added 1160 9 o~ the succini-023 mide described in Example 1 and 800 ml hydrocarbon thinner.
024 The temperature of the mixture was increased to 75C and 200 ml 025 water and 116 g MoO3 were added and the mixture was stirred at 026 97C for 3 hours. It was then stripped at 188C. After 027 cooling to 130C, 100 ml hydrocarbon thinner and 25 g diatoma-028 ceous earth were added and the mixture was filtered through 029 diatomaceous earth and then stripped at 180C and 20 mm Hg.
030 The product contained 5.84% molybdenum and 1.92~ nitrogen.
031 Example 4 032 To a l-liter flask containing 290 g of the succini-033 mide described in Example 1 and 200 ml hydrocarbon thinner at 034 65C was added 50 ml water and 589 MoO3. The mixture was 035 stirred at reflux for 4.5 hours and then stripped at 198-209C.
03~ The product was diluted with hydrocarbon thinner and then 037 filtered through diatomaceous earth to yield 332 9 of product llz7ln containing 10.1% molybdenum (by X-ray fluorescence), 9.71% molybdenum ~by neutron activation) and 5.97% oxygen ~by neutron activation).
Example 5 Lubricating oil compositions containing the additives prepared according to this invention have been tested in a variety of tests. Reported below are results from certain of these tests which are described as follows.
In the Oxidator B test the stability of the oil is measured by the time required for the consumption of 1 liter of oxygen by 100 grams of the test oil at 340F. In the actual test, 25 grams of oil is used and the results are corrected to 100-gram samples. The catalyst which is used at a rate of 1.38 cc per 100 cc oil contains a mixture of soluble salts pToviding 95 ppm copper, 80 ppm iron, 4.8 ppm manganese, 1100 ppm lead, and 49 ppm tin.
The results of this test are reported as hours to consumption of 1 liter of oxygen and our measure of the oxidative stability of the oil.
The anti-corrosion properties of compositions can be tested by their performance in the CRC L-38 bearing corrosion test. In this test, separate strips of copper and lead are immersed in the test lubricant and the lubricant is heated for 20 hours at a temperature of 295F. The copper strip is weighed and then washed with potassium cyanide solution to remove copper compound deposits. It is then re-weighed. The weight losses of the two strips are reported as a measure of the degree of corrosion caused by the oil.
The copper strip test is a measure of corrosivity toward non-ferrous metals and is described as ASTM Test Method D-130. Anti-wear properties are measured by the 4-ball wear and the 4-ball weld tests. The 4-ball wear test is described in ASTM D-2266 and the 4-ball weld test is ASTM D-2783. The data for some of the tests run on compositions of this in~ention is reported in the Table below.
p~'' 1127~.71.
The formulations tested contained, in neutral oil, 3.5% of a 50%
in oil solution of succinimide, 22 mmols/kg of the molybdenum product being tested, 20 mmols/kg sulfuri~ed calcium phenate, 30 mmols/kg overbased magnesium sulfonate, 5.5% viscosity index improver and, if necessary, additional succinimide to bring the total nitTogen content of the finished oil to 2.14%.
~27~71 TABLE
Product Oxidator ASTM ASTM L-38 D-130 of B, hrs. D-2266, D-2783 Cu, mg Pb, mg Example mm kg 1 7.7 .39 165 16.3 10.1 ; 2 8.0 ~ 3 8.5 lA
: 4 I Fortulation tested was 4~ ~t. = Iybdenum oo Found in neutral oil.
~- .
' :
. -13-
Another class of nitrogen-containing compositions useful in preparing the molybdenum compositions of this invention includes the so-called dispersant viscosity index improvers (VI improvers). These VI improvers are commonly prepared by functionalizing a hydrocarbon polymer, especially a polymer derived from ethylene and/or propylene, optionally containing additional units derived from one or more co-monomers such as ~2'7171 oo 1 -7 -002 alicyclic or aliphatic olefins or diolefins. The functionaliza-003 tion may be carried out by a variety of processes which ù04 introduce a reactive site or sites which usually has at least 005 one oxygen atom on the polymer. The polymer is then contacted 006 with a nitrogen-containing source to introduce nitrogen-007 containing functional groups on the polymer backbone. Commonly 008 used nitrogen sources include any basic nitrogen compound, 009 especially those nitrogen-containing compounds and compositions 010 described herein. Preferred nitrogen sources are alkylene 011 amines, such as ethylene amines, alkyl amines, and Mannich 012 bases.
013 Preferred basic nitrogen compounds for use in this 014 invention are succinimides, carboxylic acid amides, and ~annich 015 bases.
016 The process of this invention may be carried out by 017 combining the acidic molybdenum precursor as described above, 018 with a basic nitrogen-containing composition as described above 019 preferably in the presence of a polar promoter. The reaction 020 is ordinarily carried out at atmospheric pressure; however, 021 higher or lower pressures may be used, if desired, using 022 methods that are well-known to those skilled in the art. A
023 diluent may be used to enable the reaction mixture to be 024 eficiently stirred. Typical diluents are lubricating oil and 025 liquid compounds containing only carbon and hydrogen. If the 026 mixture is sufficiently fluid to permit stirring, no diluent is 027 necessary. A diluent which does not react with the molybdenum 028 containing compound is desirable.
029 In the reaction mixture, the ratio of molybdenum 030 compound to basic nitrogen compound is not critical; however, 031 as the amount of molybdenum with respect to basic nitrogen, 032 increases, the filtration of the product becomes more diffi-033 cult. Since the molybdenum component probably oligomerizes, it 034 is ad~7antageous to add as much molybdenum as can easily be 035 maintained in the composition. Usually the reaction mixture 036 will have charged to it from 0.01 to 2.00 atoms of molybdenum 037 per basic nitrogen atom. Preferably from 0.4 to 1.0, and most 7~
001 ~-002 preferably from 0.4 to 0.7, atoms of molybdenum per atom of 003 basic nitrogen is added to the reaction mixture.
004 The polar promoter, which is preferably used, is 005 ordinarily present in the ratio of 0.1 to S0 mols of water per 006 mol of molybdenum. Preferably from 0.5 to 25 and most 007 preferably 1.0 to 15 mols of the promoter is present per mol of 008 molybdenum.
009 The lubricating oil compositions of this invention 010 can be prepared by admixing, by conventional techniques, the 011 appropriate amount of the molybdenum-containing composition 012 with a lubricating oil. The selection of the particular base 013 oil depends on the contemplated application of the lubricant 014 and the presence of other additives. Generally, the amount of 015 the molybdenum containing additive will vary from 0.l05 to 15%
016 by weight and preferably from 0.2 to 10~ by weight.
017 The lubricating oil which may be used in this 018 invention includes a wide variety of hydrocarbon oils, such as 019 naphthenic bases, paraffin bases and mixed base oils as well as 020 synthetic oils such as esters and the like. The lubricating 021 oils may be used individually or in combination and generally 022 have a viscosity which ranges from 50 to 5,000 SUS and usually 023 from 100 to 15,000 SUS at 38C.
024 In many instances, it may be advantageous to form 025 concentrates of the molybdenum containing additive within a 026 carrier liquid. These concentrates provide a convenient method 027 of handling and transporting the additives before their subse-028 quent dilution and use. The concentration of the molybdenum-029 containing additive within the concentrate may vary from 0.25 030 to 90% by weight although it is preferred to maintain a con-031 centration between 1 and 50% by weight. The final application 032 of the lubricating oil compositions of this invention may be in 033 marine cylinder lubricants as in crosshead diesel engines, 034 crankcase lubricants as in automobiles and railroads, lubri-035 cants for heavy machinery such as steel mills and the like, or 036 as greases or bearings and the like. Whether the lubricant is 037 fluid or a solid will ordinarily depend on whether a thickening 11~717~
001 ~9 ~
002 agent is present. Typical thickening agents include polyurea 003 acetates, lithium stearate and the like.
004 If desired, other additives may be included in the lubri-005 cating oil compositions of this invention. These additives 006 include antioxidants or oxidation inhibitors, dispersants, rust 007 inhibitors, anticorrosion agents and so forth. Also anti-foam 008 agents stabilizers, anti-stain agents, tackiness agents, anti-009 chatter agents, dropping point improvers, anti-squawk agents, 010 extreme pressure agents, odor control agents and the like may 011 be included.
012 Certain molybdenum products that can be prepared by 013 the process of invention also find utility in making brake 014 lining materials, in high-temperature structural materials, in 015 iron and steel alloys, in cladding materials, in electroplating 016 solutions, as components for electrical discharge machine 017 electrodes, as fuel additives, in making self-lubricating or 018 wear-resistant structures, as mold release agents, in composi-019 tions for phosphatizing steel, in brazing fluxes, in nutrient 020 media for microorganisms, in making electrosensitive recording 021 material, in catalysts for refining coal, oil, shale, tar 022 sands, and the like or as stabilizers or curing agents for 023 natural rubber or polymers.
024 The following examples are presented to illustrate 025 the operation of the invention and are not intended to be a 026 limitation upon the scope of the claims.
027 Example 1 028 To a 1 liter flask was added 290 grams of a solution 029 of 45% concentrate in oil of the succinimide prepared from 030 polyisobutenyl succinic anhydride and tetraethylene pentaamine 031 and having a number average molecular weight for the polyiso-032 butenyl group of about 980, 28.8 grams of molybdenum trioxide 033 as a dry powder, 9.6 ml of water and 150 ml of hydrocarbon 034 thinner. The reaction mixture, which was a murky yellow-green 035 suspension, was heated to 65C and held at this temperature for 036 3-1/2 hours. The temperature was then raised to 150C to 037 remove water and held at this temperature for one hour. Then llZ7171 002 50 ml of hot hydrocarbon thinner was added and the reaction 003 mixture was filtered through diatomaceous earth. The filter 004 cake was washed with 100 ml of hot hydrocarbon thinner and a 005 light blue residue remained on the filter cake. The reaction 006 mixture was then stripped to 160C at 20 mm Hg to yield a 007 product containing 4.16~ molybdenum, 3.4896 oxygen, and 1.97%
008 nitrogen.
009 Example 2 010 To a l-liter flask was added 290 grams of the 011 succinimide described in Example 1 and 150 ml of hydrocarbon 012 thinner. The mixture was heated to 65C and then 28.8 grams of 013 molybdenum trioxide and 50 ml of water was added. The tempera-014 ture of the mixture was maintained at 65C for 1/2 hour and 015 then increased to 155C over a period of one hour and main-016 tained at 155 to 160C for one hour. To this mixture was 017 added 50 ml hydrocarbon thinner and the product was filtered 018 through diatomaceous earth. The filtrate was stripped to 160C
019 at 20 mm Hg to yield 311 grams of product containing 6.18%
020 molybdenum, 4.17% oxygen and 1.94% nitrogen.
021 Example 3 022 To a 3-liter flask was added 1160 9 o~ the succini-023 mide described in Example 1 and 800 ml hydrocarbon thinner.
024 The temperature of the mixture was increased to 75C and 200 ml 025 water and 116 g MoO3 were added and the mixture was stirred at 026 97C for 3 hours. It was then stripped at 188C. After 027 cooling to 130C, 100 ml hydrocarbon thinner and 25 g diatoma-028 ceous earth were added and the mixture was filtered through 029 diatomaceous earth and then stripped at 180C and 20 mm Hg.
030 The product contained 5.84% molybdenum and 1.92~ nitrogen.
031 Example 4 032 To a l-liter flask containing 290 g of the succini-033 mide described in Example 1 and 200 ml hydrocarbon thinner at 034 65C was added 50 ml water and 589 MoO3. The mixture was 035 stirred at reflux for 4.5 hours and then stripped at 198-209C.
03~ The product was diluted with hydrocarbon thinner and then 037 filtered through diatomaceous earth to yield 332 9 of product llz7ln containing 10.1% molybdenum (by X-ray fluorescence), 9.71% molybdenum ~by neutron activation) and 5.97% oxygen ~by neutron activation).
Example 5 Lubricating oil compositions containing the additives prepared according to this invention have been tested in a variety of tests. Reported below are results from certain of these tests which are described as follows.
In the Oxidator B test the stability of the oil is measured by the time required for the consumption of 1 liter of oxygen by 100 grams of the test oil at 340F. In the actual test, 25 grams of oil is used and the results are corrected to 100-gram samples. The catalyst which is used at a rate of 1.38 cc per 100 cc oil contains a mixture of soluble salts pToviding 95 ppm copper, 80 ppm iron, 4.8 ppm manganese, 1100 ppm lead, and 49 ppm tin.
The results of this test are reported as hours to consumption of 1 liter of oxygen and our measure of the oxidative stability of the oil.
The anti-corrosion properties of compositions can be tested by their performance in the CRC L-38 bearing corrosion test. In this test, separate strips of copper and lead are immersed in the test lubricant and the lubricant is heated for 20 hours at a temperature of 295F. The copper strip is weighed and then washed with potassium cyanide solution to remove copper compound deposits. It is then re-weighed. The weight losses of the two strips are reported as a measure of the degree of corrosion caused by the oil.
The copper strip test is a measure of corrosivity toward non-ferrous metals and is described as ASTM Test Method D-130. Anti-wear properties are measured by the 4-ball wear and the 4-ball weld tests. The 4-ball wear test is described in ASTM D-2266 and the 4-ball weld test is ASTM D-2783. The data for some of the tests run on compositions of this in~ention is reported in the Table below.
p~'' 1127~.71.
The formulations tested contained, in neutral oil, 3.5% of a 50%
in oil solution of succinimide, 22 mmols/kg of the molybdenum product being tested, 20 mmols/kg sulfuri~ed calcium phenate, 30 mmols/kg overbased magnesium sulfonate, 5.5% viscosity index improver and, if necessary, additional succinimide to bring the total nitTogen content of the finished oil to 2.14%.
~27~71 TABLE
Product Oxidator ASTM ASTM L-38 D-130 of B, hrs. D-2266, D-2783 Cu, mg Pb, mg Example mm kg 1 7.7 .39 165 16.3 10.1 ; 2 8.0 ~ 3 8.5 lA
: 4 I Fortulation tested was 4~ ~t. = Iybdenum oo Found in neutral oil.
~- .
' :
. -13-
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a molybdenum-containing com-position which comprises combining an acidic molybdenum compound and a basic nitrogen compound selected from the group consisting of a carboxylic acid amide, Mannich base, phosphonamide, thio-phosphonamide, phosphoramide, and dispersant viscosity index improvers to form a molybdenum containing complex.
2. The process of Claim 1 wherein the acidic molybdenum compound is selected from molybdic acid, ammonium molybdate, and alkali metal molybdates.
3. The process of Claim 2 wherein said acidic molybdenum compound is molybdic acid or ammonium molybdate, and said basic nitrogen compound is a carboxylic acid amide, or a Mannich base prepared from a C9-200 alkylphenol, formaldehyde, and an amine.
4. The process of Claim 3 wherein said basic nitrogen compound is a carboxylic acid amide prepared from one or more carboxylic acids of the formula R2-COOH, wherein R2 is C12-350 alkyl or C12-350 alkenyl and a hydrocarbyl polyamine.
5. The process of Claim 4 wherein R2 is C12-20 alkyl or C12-20 alkenyl and the hydrocarbyl polyamine is tetraethylene pentaamine or triethylene tetraamine.
6. The process of Claim 3 wherein said basic nitrogen compound is the Mannich base prepared from dodecyl phenol, formaldehyde, and methylamine.
7. The process of Claim 3 wherein said Mannich base is prepared from a C80-100 alkylphenol, formaldehyde, and triethylene tetraamine or tetraethylene pentaamine, or mixtures thereof.
8. The process of Claim 1 wherein said reaction is carried out in the presence of a polar promoter.
9. The process of Claim 8 wherein said polar promoter is water.
10. The product prepared by the process of Claim 1.
11. The product prepared by the process of claim 8.
12. The product prepared by the process of claim 9.
13. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.05 to 15% by weight of the product of Claim 10.
14. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15 to 90% by weight of the product of Claim 10.
15. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.05 to 15% by weight of the product of Claim 11.
16. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.05 to 15% by weight of the product of Claim 12.
17. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15 to 90% by weight of the product of Claim 11.
18. A lubricating oil concentrate composition comprising an oil of lubricating viscosity and from 15 to 90% by weight of the product of Claim 12.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/053,014 US4259195A (en) | 1979-06-28 | 1979-06-28 | Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same |
US53,014 | 1979-06-28 | ||
US06/052,698 US4261843A (en) | 1979-06-28 | 1979-06-28 | Reaction product of acidic molybdenum compound with basic nitrogen compound and lubricants containing same |
US52,698 | 1987-05-20 |
Publications (1)
Publication Number | Publication Date |
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CA1127171A true CA1127171A (en) | 1982-07-06 |
Family
ID=26730962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA351,481A Expired CA1127171A (en) | 1979-06-28 | 1980-05-08 | Molybdenum compounds (iii) |
Country Status (9)
Country | Link |
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AU (1) | AU5871580A (en) |
BR (1) | BR8003988A (en) |
CA (1) | CA1127171A (en) |
DE (1) | DE3021651A1 (en) |
FR (1) | FR2460321B1 (en) |
GB (1) | GB2053268B (en) |
IT (1) | IT1174677B (en) |
NL (1) | NL8003283A (en) |
SE (1) | SE8004421L (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US4673412A (en) * | 1985-09-24 | 1987-06-16 | The Lubrizol Corporation | Fuel additive comprising a metal compound and an oxime and fuel compositions containing same |
CA1260005A (en) * | 1985-09-24 | 1989-09-26 | Frederick W. Koch | Metal complexes of mannich bases |
US6528463B1 (en) | 2000-03-23 | 2003-03-04 | Ethyl Corporation | Oil soluble molybdenum compositions |
US6645921B2 (en) | 2002-02-08 | 2003-11-11 | Ethyl Corporation | Molybdenum-containing lubricant additive compositions, and processes for making and using same |
US7884059B2 (en) | 2004-10-20 | 2011-02-08 | Afton Chemical Corporation | Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases |
CN111785407B (en) * | 2020-07-13 | 2022-08-16 | 中国科学院上海应用物理研究所 | Treatment method of molybdenum-containing substance |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US3223625A (en) * | 1963-11-12 | 1965-12-14 | Exxon Research Engineering Co | Colloidal molybdenum complexes and their preparation |
FR1497465A (en) * | 1964-11-19 | 1967-10-06 | Castrol Ltd | Additives for lubricating compositions and lubricating compositions containing these additives |
GB1085903A (en) * | 1964-11-19 | 1967-10-04 | Castrol Ltd | Additives for lubricating compositions |
US3652616A (en) * | 1969-08-14 | 1972-03-28 | Standard Oil Co | Additives for fuels and lubricants |
SU633625A1 (en) * | 1977-06-15 | 1978-11-25 | Предприятие П/Я М-5143 | Article-washing device |
-
1980
- 1980-05-08 CA CA351,481A patent/CA1127171A/en not_active Expired
- 1980-05-23 AU AU58715/80A patent/AU5871580A/en not_active Abandoned
- 1980-06-05 NL NL8003283A patent/NL8003283A/en not_active Application Discontinuation
- 1980-06-10 DE DE19803021651 patent/DE3021651A1/en not_active Withdrawn
- 1980-06-13 SE SE8004421A patent/SE8004421L/en not_active Application Discontinuation
- 1980-06-20 FR FR8013736A patent/FR2460321B1/en not_active Expired
- 1980-06-25 GB GB8020783A patent/GB2053268B/en not_active Expired
- 1980-06-26 BR BR8003988A patent/BR8003988A/en unknown
- 1980-06-26 IT IT23091/80A patent/IT1174677B/en active
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Publication number | Publication date |
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NL8003283A (en) | 1980-12-30 |
AU5871580A (en) | 1981-01-08 |
GB2053268A (en) | 1981-02-04 |
FR2460321A1 (en) | 1981-01-23 |
SE8004421L (en) | 1980-12-29 |
FR2460321B1 (en) | 1985-07-19 |
GB2053268B (en) | 1983-05-18 |
DE3021651A1 (en) | 1981-01-22 |
BR8003988A (en) | 1981-01-13 |
IT1174677B (en) | 1987-07-01 |
IT8023091A0 (en) | 1980-06-26 |
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