CN100384969C - Process for preparing lubricant additives - Google Patents
Process for preparing lubricant additives Download PDFInfo
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- CN100384969C CN100384969C CNB2003801053167A CN200380105316A CN100384969C CN 100384969 C CN100384969 C CN 100384969C CN B2003801053167 A CNB2003801053167 A CN B2003801053167A CN 200380105316 A CN200380105316 A CN 200380105316A CN 100384969 C CN100384969 C CN 100384969C
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- 239000003879 lubricant additive Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 claims abstract description 18
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims abstract description 6
- 229940053198 antiepileptics succinimide derivative Drugs 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 239000005077 polysulfide Chemical group 0.000 claims abstract description 5
- 229920001021 polysulfide Chemical group 0.000 claims abstract description 5
- 150000008117 polysulfides Chemical group 0.000 claims abstract description 5
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000007669 thermal treatment Methods 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000007385 chemical modification Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001281 polyalkylene Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 Wherein M' is NH 4 Substances 0.000 abstract description 34
- 239000000654 additive Substances 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000005078 molybdenum compound Substances 0.000 abstract description 2
- 150000002752 molybdenum compounds Chemical class 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 5
- 229910013812 M2MoO4 Inorganic materials 0.000 abstract 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052945 inorganic sulfide Chemical group 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 22
- 229910052750 molybdenum Inorganic materials 0.000 description 22
- 239000011733 molybdenum Substances 0.000 description 22
- 229940010552 ammonium molybdate Drugs 0.000 description 20
- 235000018660 ammonium molybdate Nutrition 0.000 description 20
- 239000011609 ammonium molybdate Substances 0.000 description 20
- 229960002317 succinimide Drugs 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical group [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000235 small-angle X-ray scattering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- 229910003185 MoSx Inorganic materials 0.000 description 1
- 240000006474 Theobroma bicolor Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- GLBQVJGBPFPMMV-UHFFFAOYSA-N sulfilimine Chemical compound S=N GLBQVJGBPFPMMV-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Images
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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
- 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
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
-
- 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
- C10M2227/09—Complexes with metals
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
本发明涉及石油化工领域，更具体地说涉及含硫的钼化合物及其在减少摩擦系数的润滑材料中作为添加剂的应用。在第一实施方案中，三硫化钼及其衍生物的纳米颗粒在两种改性剂存在下由通式M2MoS4-xOx的硫代钼酸盐制备，其中M为NH4、Na，x为0-3，通式R1R2R3R4NX的四烷基铵盐或其混合物用作第一种改性剂，其中R1、R2、R3和R4为相同的或不同的并选自C1-C16烷基，X为Cl或Br，而下式的琥珀酰亚胺衍生物用作第二种改性剂，其中R5为直链的或支链的烷基或分子量为140至约1000的低聚亚烷基，R6选自H、-C(＝O)NH2、-(CH2CN2NH)nCH3，n为1-4，其中，所述的方法通过以下步骤进行：热处理在极性溶剂中均化的所述硫代钼酸盐和所述第一种改性剂或第二种改性剂的混合物，冷却制得的混合物，随后分别加入所述的第二种改性剂或第一种改性剂。在第二方案中，在两种改性剂存在下由通式M2MoO4的钼酸盐，其中M为NH4、Na和通式M′2Sn的无机硫化物或多硫化物，其中M′为NH4、Na，n为1-4或硫脲的硫供体制备三硫化钼及其衍生物的纳米颗粒，其下同第一方案。
The invention relates to the field of petrochemical industry, in particular to sulfur-containing molybdenum compounds and their application as additives in lubricating materials for reducing friction coefficients. In a first embodiment, nanoparticles of molybdenum trisulfide and its derivatives are prepared from thiomolybdates of general formula M 2 MoS 4-x O x , where M is NH 4 , Na, x is 0-3, the tetraalkylammonium salt of general formula R 1 R 2 R 3 R 4 NX or its mixture is used as the first modifier, wherein R 1 , R 2 , R 3 and R 4 are The same or different and selected from C 1 -C 16 alkyl, X is Cl or Br, and succinimide derivatives of the following formula are used as the second modifier, wherein R is linear or branched chain alkyl or oligoalkylene having a molecular weight of 140 to about 1000, R 6 is selected from H, -C(=O)NH 2 , -(CH 2 CN 2 NH) n CH 3 , n is 1-4 , wherein, the method is carried out by the following steps: heat-treating the mixture of the thiomolybdate and the first modifying agent or the second modifying agent homogenized in a polar solvent, cooling to obtain The mixture, and then add the second modifier or the first modifier respectively. In the second scheme, molybdates of the general formula M2MoO4 , wherein M is NH4 , Na and inorganic sulfides or polysulfides of the general formula M'2Sn , in the presence of two modifiers, Wherein M' is NH 4 , Na, n is 1-4 or sulfur donor of thiourea to prepare nanoparticles of molybdenum trisulfide and its derivatives, the following is the same as the first scheme.
Description
Technical field
The present invention relates to petrochemical industry, more specifically to the molybdenum compound of sulfur-bearing and in the lubricant of coefficient of reducing friction as Application of Additives.
Background technology
As everyone knows, in order in friction process, to reduce the wearing and tearing of fuel consumption and machine part, anti-friction additive (friction improver) is used for lubricating oil.Everybody knows that also oil soluble contains molybdenum match as friction improver, and described compound contains sulphur, nitrogen or phosphorus atom as part.
For example, in United States Patent (USP) [1], the method for a kind of preparation based on the lubricating oil additive of tetraalkyl (alkenyl) ammonium thiomolybdate disclosed, so that improve the anti-friction performance of lubricating oil.The shortcoming of described method be to use by Vegetable oil lipoprotein for example theobroma oil or soybean oil produce be difficult to that obtain and more expensive alkyl or alkenyl relatively as a kind of initial component, i.e. quaternary alkylammonium halides.
A kind of like this method is known [2], and organic compounds containing sulfur and the molybdenum pentachloride of wherein lubricated oil additives by active hydrogen atom is arranged reacts and prepare.Isolating reaction product contains 3% molybdenum and about 1% chlorine, because ecological consideration and the possible corrosion activity of product, the latter is undesirable.
The molybdenum additives that contains of lubricating oil has anti-friction and antioxidant property, it is with the preparation of three steps, as disclosed in United States Patent (USP) [3], wherein in the first step, carry out the reaction of the triglyceride level and the nitrogenous compound of vegetables oil, then in second step with the product of the first step and molybdate compound reaction, in the 3rd step, the product in second step and sulphur or sulfocompound are reacted.The synthetic method of relative complex (multistep processes, the existence of inert atmosphere, the strictness restriction of temperature range) should be as the shortcoming of this method.
Method [4,5] is known, has wherein prepared the lubricating oil additive based on the Dithiocarbamyl title complex of molybdenum.These additives are multi-purpose (comprising the anti-friction performance), but synthesizing of theirs is very complicated, comprise and use deleterious reagent, for example dithiocarbonic anhydride.
A kind of like this method is known, according to this method, lubricating oil additive prepares [6] at friction improver (nitrogenous or oxygen containing organic compound) and the amino methylamino of a kind of dithio on the basis as the mixture of the molybdenum match of three nuclear sulfur-bearings of part.The complexity preparation of additive and the multistep of organic molybdenum are synthetic to be the shortcoming of this method.
The most similar with the present invention is method [7], and wherein the anti-friction additive is with the form preparation of the molybdenum trisulfide nano particle of chemical modification.In this method, the nano particle of molybdenum trisulfide prepares with following step: make the contrary microemulsion with tensio-active agent water-in-oil-type stable and contain water-soluble molybdate at aqueous phase, by reacting they are transformed into Thiomolybdate, and separate the MoS that handles with modified compound in advance subsequently with hydrogen sulfide
3Nano particle.Thereby make the molybdenum trisulfide nano particle, it is stable in comprising the hydrocarbon medium of oil product, and it has efficiently as the anti-friction additive.The low process efficiency of additive synthetic is considered to the shortcoming of this method, and it relates to implements this method and use hydrogen sulfide as reaction reagent in the organic solution of high dilution.
The objective of the invention is to provide a kind of easy processing method for preparing the lubricant additive based on the molybdenum trisulfide and the derivates nanometer particulate thereof of chemical modification.
Summary of the invention
In order to realize described purpose, the described method of preparation lubricant additive is provided, and has proposed two embodiments of implementing described method.
According to first embodiment, a kind of preparation is included in two kinds of properties-correcting agent existence down by formula M based on the molybdenum trisulfide of chemical modification and/or the method for its derivates nanometer particulate lubricant additive
2MoS
4-xO
xThiomolybdate prepare the nano particle of molybdenum trisulfide and/or its derivative, wherein M is NH
4, Na, x is 0-3, general formula R
1R
2R
3R
4The tetraalkylammonium salt of NX or its mixture are as first kind of properties-correcting agent, wherein R
1, R
2, R
3And R
4For identical or different and independently be selected from C
1-C
16Alkyl, X are Cl or Br, and the succinimide derivatives of following formula is as second kind of properties-correcting agent
R wherein
5For alkyl straight chain or side chain or molecular weight are 140 to about 1000 low polyalkylene, R
6Be selected from H ,-C (=O) NH
2,-(CH
2CN
2NH)
nCH
3, n is 1-4.
Wherein, described method is undertaken by following steps: the described Thiomolybdate of thermal treatment homogenizing in polar solvent and the mixture of described first kind of properties-correcting agent or second kind of properties-correcting agent, the mixture that cooling makes adds described second kind of properties-correcting agent or first kind of properties-correcting agent subsequently respectively.
Second embodiment implementing the inventive method be, in the presence of two kinds of properties-correcting agent by formula M
2MoO
4Molybdate (wherein M is NH
4, Na) and formula M '
2S
nInorganic sulphide or polysulfide (wherein M ' is NH
4, Na, n is 1-4) or the sulphur donor of thiocarbamide prepare the nano particle of molybdenum trisulfide and/or its derivative, general formula R
1R
2R
3R
4The tetraalkylammonium salt of NX or its mixture are as first kind of properties-correcting agent, wherein R
1, R
2, R
3And R
4For identical or different and independently be selected from C
1-C
16Alkyl, X are Cl or Br, and the succinimide derivatives of general formula is as second kind of properties-correcting agent
R wherein
5For alkyl straight chain or side chain or molecular weight are 140 to about 1000 low polyalkylene, R
6Be selected from H ,-C (=O) NH
2,-(CH
2CN
2NH)
nCH
3, n is 1-4,
Wherein, described method is undertaken by following steps: the sulphur donor of the described molybdate of thermal treatment homogenizing in polar solvent, described use inorganic sulphide, polysulfide or thiocarbamide and the mixture of described first kind of properties-correcting agent or second kind of properties-correcting agent, the mixture that cooling makes adds described second kind of properties-correcting agent or first kind of properties-correcting agent subsequently respectively.
In described method, according in the above-mentioned embodiment any one, thermal treatment was carried out under 150-220 ℃ 1-2 hour, and methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-butanols, acetone or benzene are as solvent.
Tetraalkylammonium salt is selected from tri-n-octyl methyl ammonium chloride (Alikvat
336), methyl trialkyl (C
8-C
10) ammonium chloride (Adogen
464), cetyl trimethylammonium bromide (CTAB).
By the product of any work-around solution preparation of implementing present method after filtration so that the separate solid mixture, and the residue of under vacuum, removing volatile organic solvent.Whole preparation method can be carried out in a jar, does not have intermediary to separate and/or purification step, does not also relate to a large amount of organic solvents.
The product that makes is the chocolate thick liquid, is easy to hydro carbons and petroleum oil product misciblely, generates transparent solution or composition, and its color is pale red brown or brown.The content of molybdenum is generally 0.5-2.0% (weight) in the product.The solution that makes product is the stable dispersions of the molybdenum trisulfide nano particle of surface modification, and this point is by electronic spectrum of ultraviolet and visible-range (Fig. 1) and small angle X ray scattering (SAXS) data acknowledgement (Fig. 2).The SAXS method makes the size of the inorganic core of measuring nano particle become possibility, and it is different with disclosed surface-modified nano particles in [7] in the 1-6 nanometer range, it is characterized by single dispersion size and distributes.Back one situation makes the synthetic reproduction degree of higher degree become possibility.
With following embodiment the present invention is described, but limits the scope of the invention never in any form.
Embodiment 1
Under 60 ℃, with 0.12 gram four thio ammonium molybdate, 3.0 gram methyl trialkyl (C
8-C
10) ammonium chloride (Adogen
464) and 5 ml methanol mixed uniform mixture 200 ℃ of following thermal treatments 2 hours, the product residue is 30% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate by " blue zone " strainer with magnetic stirrer.The content of molybdenum is 1.22% in the product.In making the UV spectrum of product, there is not absorption band corresponding to four thio ammonium molybdate.
Embodiment 2
Under 60 ℃, with 0.12 gram four thio ammonium molybdate, 3.0 gram tri-n-octyl methyl ammonium chloride (Alikvat
336) and 5 ml methanol mixed uniform mixture 200 ℃ of following thermal treatments 2 hours, the product residue is 29% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter resembling among the embodiment 1, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.25% in the product.
Embodiment 3
Under 60 ℃, with 1: 1 mixture of 0.12 gram four thio ammonium molybdate, 3.0 gram cetyl trimethylammonium bromides (CTAB) and 10 ml methanol-chloroform mixed must uniform mixture 200 ℃ of following thermal treatments 2 hours, the product residue is 55% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.36% in the product.
Embodiment 4
Under 60 ℃, with 0.12 gram four thio ammonium molybdate, 1.5 gram CTAB, 1.5 gram Adogen
With 10 ml methanol-1: 1 mixed uniform mixture that gets of mixture of chloroform was 200 ℃ of following thermal treatments 2 hours, the product residue is 42% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.38% in the product.
Embodiment 5
Under 60 ℃, with 0.12 gram four thio ammonium molybdate, 3.0 gram Adogen
With 5 ml methanol mixed uniform mixture 180 ℃ of following thermal treatments 2 hours, the product residue is 29% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.19% in the product.
Embodiment 6
Under 60 ℃, with 0.12 gram four thio ammonium molybdate, 3.0 gram Adogen
With 5 ml methanol mixed uniform mixture 210 ℃ of following thermal treatments 2 hours, the product residue is 27.5% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.25% in the product.
Embodiment 7
Under 60 ℃, with 0.24 gram four thio ammonium molybdate, 3.0 gram Adogen
With 5 ml methanol mixed uniform mixture 200 ℃ of following thermal treatments 2 hours, the product residue is 26.2% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 2.92% in the product.
Embodiment 8
Under 60 ℃, with 0.12 gram four thio ammonium molybdate, 3.0 gram Adogen
With 5 ml methanol mixed uniform mixture 200 ℃ of following thermal treatments 2 hours, the product residue is 28.2% of the initial gross weight of each component.4.2 gram alkenyl succinimide and 5 milliliters of chloroforms are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.22% in the product.
Embodiment 9
Under 60 ℃, with 0.24 gram four thio ammonium molybdate, 3.0 gram Adogen
With 5 ml methanol mixed uniform mixture 200 ℃ of following thermal treatments 2 hours, product is residual-thing is 30.1% of the initial gross weight of each component.N-alkylidene amino derivative and 5 milliliters of chloroforms of 4.2 gram alkenyl succinimide are added in the product residue, stir the mixture, filter, under vacuum, remove and desolvate with magnetic stirrer.The content of molybdenum is 1.19% in the product.
Embodiment 10
The preparation method of embodiment 1, different is to replace methyl alcohol with ethanol.
Embodiment 11
The preparation method of embodiment 1, different is to replace methyl alcohol with propyl alcohol.
Embodiment 12
The preparation method of embodiment 1, different is to replace methyl alcohol with Virahol.
Embodiment 13
The preparation method of embodiment 1, different is to replace methyl alcohol with propyl carbinol.
Embodiment 14
The preparation method of embodiment 1, different is to replace methyl alcohol with isopropylcarbinol.
Embodiment 15
The preparation method of embodiment 1, different is to replace methyl alcohol with the 2-butanols.
Embodiment 16
The preparation method of embodiment 9, different is to replace four thio ammonium molybdate with the trithio ammonium molybdate.
Embodiment 17
The preparation method of embodiment 9, different is to replace four thio ammonium molybdate with the dithio ammonium molybdate.
Embodiment 18
The preparation method of embodiment 9, different is to replace four thio ammonium molybdate with the monothio ammonium molybdate.
Embodiment 19
Under 60 ℃, with 0.0095 gram ammonium molybdate, 0.0113 gram Na
2S9H
2O and 0.0360 gram Adogen in 1 milliliter of benzene
The mixed uniform mixture that gets was 200 ℃ of following thermal treatments 30 minutes, and the product residue is 48% of the initial gross weight of each component.0.0420 gram alkenyl succinimide and 1 milliliter of chloroform are added in the product residue, stir the mixture, filter, under vacuum, remove then and desolvate by " blue zone " strainer with magnetic stirrer.The content of molybdenum is 1.35% in the product.
Embodiment 20
The preparation method of embodiment 1, wherein at first with 0.12 the gram four thio ammonium molybdate and 4.2 the gram alkenyl succinimide homogenize, then with mixture 180-200 ℃ of following thermal treatment 1 hour, with 3.0 the gram Adogen
Be added in the residue, homogenize and 180-200 ℃ of following thermal treatment 1 hour.Residue is dissolved in chloroform, filters, under vacuum, remove and desolvate.Thereby make molybdenum content and be 0.66% product.
Embodiment 21
Under 60 ℃, with 0.0102 gram ammonium molybdate, 0.0320 gram Adogen
0.0101 gram thiocarbamide and 5 milliliters of mixed uniform mixtures that get of benzene were 200 ℃ of following thermal treatments 2 hours.After the thermal treatment, the product residue is 43.0% of the initial gross weight of each component.5 milliliters of chloroforms and 0.042 gram alkenyl succinimide are added in the product residue, stir the mixture, filter, then the vaporising under vacuum solvent with magnetic stirrer.The content of molybdenum is 2.35% in the product.
Embodiment 22
Under 60 ℃, with 0.0101 gram ammonium molybdate, 0.0315 gram Adogen
0.0145 gram Na
2S
2O
35H
2O and 5 milliliters of mixed uniform mixtures that get of benzene were 200 ℃ of following thermal treatments 2 hours.After the thermal treatment, the product residue is 39.0% of the initial gross weight of each component.5 milliliters of chloroforms and 0.042 gram alkenyl succinimide are added in the product residue, stir the mixture, filter, then the vaporising under vacuum solvent with magnetic stirrer.The content of molybdenum is 1.31% in the product.
All results list table 1 in.
The characteristic based on the anti-friction additive samples of the molybdenum trisulfide nano particle of surface modification for preparing among the embodiment 1-22 is expressed as follows
| Embodiment No, | Productive rate, % (weight) | Molybdenum concentration, % (weight) | Mo: S ratio, moles/mole | Average particle size, dust |
| O-1 | 26.1 | 1.22 | 1∶2.5 | 27.3 |
| O-2 | 31.3 | 1.25 | 1∶2.7 | 32.4 |
| O-3 | 20.3 | 1.36 | 1∶3.1 | 28.1 |
| O-4 | 22.0 | 1.38 | 1∶2.8 | 28.4 |
| O-5 | 22.4 | 1.19 | 1∶2.9 | 26.7 |
| O-6 | 27.5 | 1.25 | 1∶2.7 | 33.3 |
| O-7 | 33.8 | 2.92 | 1∶2.9 | 30.5 |
| O-8 | 31.2 | 1.22 | 1∶2.6 | 29.0 |
| O-9 | 35.9 | 1.19 | 1∶2.5 | 29.6 |
| O-10 | 37.4 | 1.08 | 1∶3.2 | 28.9 |
| O-11 | 27.6 | 1.32 | 1∶2.7 | 29.4 |
| O-12 | 21.1 | 1.40 | 1∶2.7 | 27.9 |
| O-13 | 25.8 | 1.11 | 1∶2.5 | 26.9 |
| O-14 | 19.7 | 2.03 | 1∶2.8 | 26.8 |
| O-15 | 26.1 | 1.56 | 1∶2.1 | 24.7 |
| O-16 | 22.6 | 1.34 | 1∶1.8 | 31.4 |
| O-17 | 35.2 | 0.98 | 1∶1.1 | 34.3 |
| O-18 | 20.3. | 2.56 | 1∶2.3 | 28.1 |
| O-19 | 15.9 | 1.35 | 1∶2.6 | 28.2 |
| O-20 | 30.5 | 0.66 | 1∶2.7 | 27.2 |
| O-21 | 27.0 | 2.35 | 1∶3.0 | 26.7 |
| O-22 | 20.6 | 1.31 | 1∶3.1 | 29.6 |
The frictional behaviour of the nano particle of preparation
(Optimol firm Germany), with regard to its composition in turbine oil T46, has studied the frictional behaviour based on the anti-friction additive samples of the molybdenum trisulfide nano particle of surface modification of preparation to use vibration tribometer SRV.Test conditions: right-ball-plane rubs; Oscillation Amplitude-1 millimeter, 50 hertz of frequencies; Axial load changes from 20 Ns and steps to 600 Ns, and in 1 minute per step, per step is 50 Ns.Measured the numerical value of frictional coefficient, thought that under these circumstances test finishes, wherein the numerical value of frictional coefficient surpasses 0.22 or cut (stopping automatically) arranged.By being mixed, T46 and 5% (weight) sample 0-1 to 0-22 prepares oil composition.The molybdenum trisulfide nano particle (sample [MoS of surface modification according to [7] preparation
x]) and the molybdenum dithiocarbamate sample as a comparison of formula III.
The data representation of the rub(bing)test of carrying out with regard to some samples is as follows.
| Sample | The quantity of molybdenum in oil, ppm | The minimized friction coefficient | Critical loading, ox |
| 0-1 | 670 | 0.065 | Do not have |
| 0-2 | 625 | 0.065 | Do not have |
| 0-4 | 690 | 0.065 | Do not have |
| 0-19 | 675 | 0.066 | 600 |
| 0-21 | 1175 | 0.060 | Do not have |
| Sample [MoSx] | 650 | 0.065 | 600 |
| Dithiocarbamic acid Mo (III) | 1000 | 0.067 | 550 |
Therefore, described method makes the molybdenum trisulfide nano particle based on surface modification prepare the anti-friction additive becomes possibility, this additive generates transparent stable dispersions in hydro carbons and petroleum oil product, and reduces the frictional coefficient between the metallic surface effectively and improve critical loading.Entire method can be carried out in a jar, does not have the intermediate steps of separation and/or purifying, does not relate to a large amount of organic solvents.
Information source:
1.US 4400282 (Augusts 23 nineteen eighty-three)
2.US 4474673 (on October 2nd, 1984)
3.US 4765918 (on Augusts 23rd, 1988)
4.US 6117826 (on September 12nd, 2000)
5.US 6245725 (June 12 calendar year 2001)
6.BP 2359092 (Augusts 15 calendar year 2001)
7.US WO01/94504A2 (December 13 calendar year 2001)
Claims (4)
1. a method for preparing based on the lubricant additive of the nano particle of the molybdenum trisulfide of chemical modification and/or its derivative is characterized in that, the nano particle of molybdenum trisulfide and/or its derivative in the presence of two kinds of properties-correcting agent by formula M
2MoS
4-xO
xThiomolybdate preparation, wherein M is NH
4, Na, x is 0-3, general formula R
1R
2R
3R
4The tetraalkylammonium salt of NX or its mixture are as first kind of properties-correcting agent, wherein R
1, R
2, R
3And R
4For identical or different and be selected from C
1-C
16Alkyl, X are Cl or Br, and the succinimide derivatives of following formula is as second kind of properties-correcting agent
R wherein
5For alkyl straight chain or side chain or molecular weight are 140 to about 1000 low polyalkylene, R
6Be selected from H ,-C (=O) NH
2,-(CH
2CN
2NH)
nCH
3, n is 1-4,
Wherein, described method is undertaken by following steps: the described Thiomolybdate of thermal treatment homogenizing in polar solvent and the mixture of described first kind of properties-correcting agent or second kind of properties-correcting agent, the mixture that cooling makes adds described second kind of properties-correcting agent or first kind of properties-correcting agent subsequently respectively.
2. a method for preparing based on the lubricant additive of the nano particle of the molybdenum trisulfide of chemical modification and/or its derivative is characterized in that, in the presence of two kinds of properties-correcting agent by formula M
2MoO
4Molybdate, wherein M is NH
4, Na and formula M '
2S
nInorganic sulphide or polysulfide, wherein M ' is NH
4, Na, n is the nano particle that the sulphur donor of 1-4 or thiocarbamide prepares molybdenum trisulfide and/or its derivative, general formula R
1R
2R
3R
4The tetraalkylammonium salt of NX or its mixture are as first kind of properties-correcting agent, wherein R
1, R
2, R
3And R
4For identical or different and be selected from C
1-C
16Alkyl, X are Cl or Br, and the succinimide derivatives of following formula is as second kind of properties-correcting agent
R wherein
5For alkyl straight chain or side chain or molecular weight are 140 to about 1000 low polyalkylene, R
6Be selected from H ,-C (=O) NH
2,-(CH
2CN
2NH)
nCH
3, n is 1-4,
Wherein, described method is undertaken by following steps: the sulphur donor of the described molybdate of thermal treatment homogenizing in polar solvent, described use inorganic sulphide, polysulfide or thiocarbamide and the mixture of described first kind of properties-correcting agent and/or second kind of properties-correcting agent, the mixture that cooling makes adds described second kind of properties-correcting agent and/or first kind of properties-correcting agent subsequently respectively.
3. according to the method for claim 1 or 2, it is characterized in that thermal treatment was carried out 1-2 hour under 150-220 ℃.
4. according to the method for claim 1 or 2, it is characterized in that methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-butanols, acetone or benzene are as solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2002128364 | 2002-10-23 | ||
| RU2002128364/04A RU2002128364A (en) | 2002-10-23 | 2002-10-23 | METHOD FOR PRODUCING ADDITIVE TO LUBRICANTS (OPTIONS) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1723269A CN1723269A (en) | 2006-01-18 |
| CN100384969C true CN100384969C (en) | 2008-04-30 |
Family
ID=32173384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801053167A Expired - Fee Related CN100384969C (en) | 2002-10-23 | 2003-10-16 | Process for preparing lubricant additives |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20060094605A1 (en) |
| JP (1) | JP2006503954A (en) |
| CN (1) | CN100384969C (en) |
| AU (1) | AU2003277760A1 (en) |
| DE (1) | DE10393575T5 (en) |
| EA (1) | EA008515B1 (en) |
| GB (1) | GB2411660B (en) |
| RU (1) | RU2002128364A (en) |
| UA (1) | UA80727C2 (en) |
| WO (1) | WO2004037957A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4410159B2 (en) * | 2005-06-24 | 2010-02-03 | 三菱電機株式会社 | AC rotating electric machine |
| US8741821B2 (en) * | 2007-01-03 | 2014-06-03 | Afton Chemical Corporation | Nanoparticle additives and lubricant formulations containing the nanoparticle additives |
| US20080269086A1 (en) * | 2007-04-30 | 2008-10-30 | Atanu Adhvaryu | Functionalized nanosphere lubricants |
| BRPI0703141B1 (en) | 2007-08-02 | 2018-10-16 | Petroleo Brasileiro S/A Petrobras | process of obtaining an intermetallic compound. |
| US7994105B2 (en) * | 2007-08-11 | 2011-08-09 | Jagdish Narayan | Lubricant having nanoparticles and microparticles to enhance fuel efficiency, and a laser synthesis method to create dispersed nanoparticles |
| KR101083306B1 (en) | 2009-08-18 | 2011-11-15 | 한국전력공사 | Preparetion method of lubricating oil and lubricating oil produced thereby |
| IT1402163B1 (en) * | 2010-10-01 | 2013-08-28 | Univ Degli Studi Salerno | "ONE-POT" SYNTHESIS OF NANO CRISTALLI 1D, 2D, AND 0D OF TUNGSTEN AND MOLYBDENUM CALCOGENURES (WS2, MOS2) FUNCTIONALIZED WITH LONG-CHAIN AND / OR TIOL-AMMINE ACIDS AND / OR TIOLS |
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|---|---|---|---|---|
| US3223625A (en) * | 1963-11-12 | 1965-12-14 | Exxon Research Engineering Co | Colloidal molybdenum complexes and their preparation |
| US4263152A (en) * | 1979-06-28 | 1981-04-21 | Chevron Research Company | Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same |
| US4283295A (en) * | 1979-06-28 | 1981-08-11 | Chevron Research Company | Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing said composition |
| US4324672A (en) * | 1980-06-25 | 1982-04-13 | Texaco, Inc. | Dispersant alkenylsuccinimides containing oxy-reduced molybdenum and lubricants containing same |
| US4343746A (en) * | 1980-12-10 | 1982-08-10 | Gulf Research & Development Company | Quaternary ammonium thiomolybdates |
| SU1384612A1 (en) * | 1986-02-20 | 1988-03-30 | 29 Конструкторско-технологический центр | Method of producing lubricant composition |
| WO2001094504A2 (en) * | 2000-06-02 | 2001-12-13 | Crompton Corporation | Nanosized particles of molybdenum sulfide and derivatives, method for its preparation and uses thereof as lubricant additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400282A (en) * | 1980-12-05 | 1983-08-23 | Gulf Research & Development Company | Lubricating oils containing quaternary ammonium thiomolybdates |
| US4474673A (en) * | 1982-06-11 | 1984-10-02 | Standard Oil Company (Indiana) | Molybdenum-containing friction modifying additive for lubricating oils |
| US4588829A (en) * | 1984-07-27 | 1986-05-13 | Exxon Research & Engineering Company | (Disulfido)tris(N,N-substituted dithiocarbamato)Mo(V) complexes |
| US4765918A (en) * | 1986-11-28 | 1988-08-23 | Texaco Inc. | Lubricant additive |
| US6117826A (en) * | 1998-09-08 | 2000-09-12 | Uniroyal Chemical Company, Inc. | Dithiocarbamyl derivatives useful as lubricant additives |
| JP4201902B2 (en) * | 1998-12-24 | 2008-12-24 | 株式会社Ａｄｅｋａ | Lubricating composition |
| NZ537896A (en) * | 2002-07-23 | 2007-12-21 | Univ Michigan | Tetrapropylammonium tetrathiomolybdate and related compounds for anti-angiogenic therapies |
-
2002
- 2002-10-23 RU RU2002128364/04A patent/RU2002128364A/en not_active Application Discontinuation
-
2003
- 2003-10-16 JP JP2004546580A patent/JP2006503954A/en active Pending
- 2003-10-16 UA UAA200504796A patent/UA80727C2/en unknown
- 2003-10-16 GB GB0510381A patent/GB2411660B/en not_active Expired - Fee Related
- 2003-10-16 US US10/532,416 patent/US20060094605A1/en not_active Abandoned
- 2003-10-16 WO PCT/RU2003/000440 patent/WO2004037957A1/en active Application Filing
- 2003-10-16 DE DE10393575T patent/DE10393575T5/en not_active Withdrawn
- 2003-10-16 CN CNB2003801053167A patent/CN100384969C/en not_active Expired - Fee Related
- 2003-10-16 AU AU2003277760A patent/AU2003277760A1/en not_active Abandoned
- 2003-10-16 EA EA200500556A patent/EA008515B1/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223625A (en) * | 1963-11-12 | 1965-12-14 | Exxon Research Engineering Co | Colloidal molybdenum complexes and their preparation |
| US4263152A (en) * | 1979-06-28 | 1981-04-21 | Chevron Research Company | Process of preparing molybdenum complexes, the complexes so-produced and lubricants containing same |
| US4283295A (en) * | 1979-06-28 | 1981-08-11 | Chevron Research Company | Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing said composition |
| US4324672A (en) * | 1980-06-25 | 1982-04-13 | Texaco, Inc. | Dispersant alkenylsuccinimides containing oxy-reduced molybdenum and lubricants containing same |
| US4343746A (en) * | 1980-12-10 | 1982-08-10 | Gulf Research & Development Company | Quaternary ammonium thiomolybdates |
| SU1384612A1 (en) * | 1986-02-20 | 1988-03-30 | 29 Конструкторско-технологический центр | Method of producing lubricant composition |
| WO2001094504A2 (en) * | 2000-06-02 | 2001-12-13 | Crompton Corporation | Nanosized particles of molybdenum sulfide and derivatives, method for its preparation and uses thereof as lubricant additive |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2411660A (en) | 2005-09-07 |
| EA200500556A1 (en) | 2005-10-27 |
| UA80727C2 (en) | 2007-10-25 |
| AU2003277760A1 (en) | 2004-05-13 |
| RU2002128364A (en) | 2004-04-27 |
| GB2411660B (en) | 2006-07-12 |
| US20060094605A1 (en) | 2006-05-04 |
| WO2004037957A1 (en) | 2004-05-06 |
| JP2006503954A (en) | 2006-02-02 |
| CN1723269A (en) | 2006-01-18 |
| DE10393575T5 (en) | 2005-09-29 |
| EA008515B1 (en) | 2007-06-29 |
| GB0510381D0 (en) | 2005-06-29 |
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