CN111892629A - Thiadiazole derivative containing molybdenum and preparation method and application thereof - Google Patents
Thiadiazole derivative containing molybdenum and preparation method and application thereof Download PDFInfo
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- CN111892629A CN111892629A CN202010828895.3A CN202010828895A CN111892629A CN 111892629 A CN111892629 A CN 111892629A CN 202010828895 A CN202010828895 A CN 202010828895A CN 111892629 A CN111892629 A CN 111892629A
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- molybdenum
- thiadiazole
- thiadiazole derivative
- derivative containing
- containing molybdenum
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000011733 molybdenum Substances 0.000 title claims abstract description 87
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 87
- 150000004867 thiadiazoles Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000010687 lubricating oil Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002199 base oil Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 125000005265 dialkylamine group Chemical group 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 24
- 125000000217 alkyl group Chemical group 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- -1 and the stability Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- FSZAJHPURMNBCO-UHFFFAOYSA-N molybdenum;thiadiazole Chemical compound [Mo].C1=CSN=N1 FSZAJHPURMNBCO-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- BUENGNLRZFMAFO-UHFFFAOYSA-N n-(2-ethylhexyl)tridecan-1-amine Chemical compound CCCCCCCCCCCCCNCC(CC)CCCC BUENGNLRZFMAFO-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YOFPVMWVLDSWKR-UHFFFAOYSA-N 11-methyl-n-(11-methyldodecyl)dodecan-1-amine Chemical compound CC(C)CCCCCCCCCCNCCCCCCCCCCC(C)C YOFPVMWVLDSWKR-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- GHZULRCRKIWYMD-UHFFFAOYSA-N 3-(8-methylnonoxy)-n-propan-2-ylpropan-1-amine Chemical compound CC(C)CCCCCCCOCCCNC(C)C GHZULRCRKIWYMD-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- XJUNRGGMKUAPAP-UHFFFAOYSA-N dioxido(dioxo)molybdenum;lead(2+) Chemical compound [Pb+2].[O-][Mo]([O-])(=O)=O XJUNRGGMKUAPAP-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- OWXJWNXGYIVLBV-UHFFFAOYSA-J molybdenum(4+) tetracarbamothioate Chemical compound C(N)([O-])=S.[Mo+4].C(N)([O-])=S.C(N)([O-])=S.C(N)([O-])=S OWXJWNXGYIVLBV-UHFFFAOYSA-J 0.000 description 1
- KMYDSFJEYTVXKR-UHFFFAOYSA-B molybdenum(4+) tetrathiophosphate Chemical compound P(=S)([O-])([O-])[O-].[Mo+4].P(=S)([O-])([O-])[O-].P(=S)([O-])([O-])[O-].P(=S)([O-])([O-])[O-].[Mo+4].[Mo+4] KMYDSFJEYTVXKR-UHFFFAOYSA-B 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
-
- 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
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
The invention provides a thiadiazole derivative containing molybdenum, belonging to the technical field of lubricating oil additives. The structural formula of the thiadiazole derivative containing molybdenum is as follows:wherein R1 and R2 are C4‑C13Linear or branched alkyl groups of (a). The invention also provides a preparation method of the thiadiazole derivative containing molybdenum. The molybdenum-containing thiadiazole derivative combines the advantages of molybdenum and thiadiazole derivatives as additives, has good lubricity and high extreme pressure performance, has low corrosion effect on friction pair materials, and is an excellent lubricating oil antifriction additive.
Description
Technical Field
The invention relates to the technical field of lubricating oil additives, in particular to a thiadiazole derivative containing molybdenum, and a preparation method and application thereof.
Background
The lubricating oil is used on various types of automobiles and mechanical equipment to reduce friction and protect machines and workpieces, and mainly plays roles in lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like. The base oil is the main component of the lubricating oil, and the additive can make up and improve the deficiency of the base oil in performance, endow certain new performance and is an important component of the lubricating oil. Research on lubricating oil additives is carried out, and the improvement of extreme pressure anti-wear property of the additives becomes one of hot spots of research on the lubricating oil additives.
Meanwhile, the five-membered heterocyclic substance with nitrogen and sulfur has a closely linked chemical structural formula, has excellent extreme pressure wear resistance and can play a good lubricating role. The thiadiazole derivative containing the sulfur and the nitrogen can meet the functions of a common lubricating oil additive in the aspect of being used as the lubricating oil additive, and is an excellent lubricating oil additive. The thiadiazole derivative can be used as an antioxidant, antiwear and metal deactivator of internal combustion engine oil, gear oil, lubricating grease and industrial oil, and is a lubricating oil additive with multiple functions. Jianglawei and the like (the thiadiazole derivatives are used as a performance research of a lubricating oil additive, the study of Hunan engineering academy, 2019,29(2): 55-59) synthesize two thiadiazole derivatives by using DMTD (2, 5-dimercapto-1, 3, 4-thiadiazole), n-octylamine, n-decylamine and chloroacetyl chloride as raw materials, dichloromethane as a solvent and triethylamine as an acid-binding agent, and the stability, oil solubility and tribological performance of the product are measured, so that the two products have good extreme pressure anti-wear performance.
The molybdenum additive has excellent tribological performance, can obviously improve the wear resistance and the antifriction performance of the lubricant, effectively reduce the friction on the surface of a friction pair, improve the mechanical efficiency of an engine and obviously improve the fuel economy of an automobile, and is called as the King of antifriction. The most commonly used molybdenum-containing compounds are: molybdenum disulfide (MoS 2), oil soluble molybdenum dialkyl dithiocarbamate sulfide oxide (MoDTC), and molybdenum dialkyl dithiophosphate sulfide oxide (MoDTP).
MoDTC (molybdenum thiocarbamate) has excellent wear resistance and friction reduction performance and is a very effective friction modifier. Since MoDTC contains polar atoms such as S, N, the MoDTC can be compatible with the metal surface and forms MoS-containing substances at high temperature and high pressure2And Fe, FeS, FeO and the like, thereby generating the effects of reducing friction, resisting wear and improving extreme pressure.
Molybdenum dialkyldithiocarbamates (MoDTC) developed by R T Vanderbilt (US 5,631,213) and have the following structural formula:
R1,R2,R3,R4the alkyl groups may be the same or different. The lower alkyl hydrocarbon organic molybdenum is solid, and the organic molybdenum of the alkane with more than 8 carbons is liquid. Kevin J Chase et al (US 200601997) from R T Vanderbilt, Inc. prepares solid MoDTC from triethylamine, a hexavalent molybdenum compound, carbon disulfide, water and dialkyl amine, and the product has poor oil solubility in mineral oil and is mainly used as a grease additive. Therefore, researchers make further improvement, and liquid MoDTC is obtained by using dialkyl amine with 8-19 carbon atoms, and the product is a reddish brown viscous liquid with the molybdenum content of 10.6%. Robert JTynik et al (WO 2006094011) research asymmetric MoDTC containing different alkyl groups, and the amine source adopted by the preparation method is 2-ethylhexyl tridecylamine, isodecyl oxypropyl isopropylamine or C-containing12~C15The alkoxypropylisopropylamine of (a) can be used to prepare MoDTCs with different alkyl characteristics by using different amine sources. Tanaka Noriyoshi et al (CA 2169312), adi, japan, dissolve hexavalent molybdenum in sodium hydrosulfide or sodium sulfide and mix carbon disulfide, diamine, acid, and a reducing agent to prepare a novel MoDTC.
Compared with the existing molybdenum thiophosphate (MoDTP) in the market, the MoDTC does not contain phosphorus element, can reduce the poisoning of the automobile exhaust purifier, and the dosage of the MoDTC in the lubricating oil additive is increased year by year; however, in the MoDTC production process, a reducing agent is often used to reduce a high valence molybdenum compound to prepare a 5 valence molybdenum product containing a Mo-S-Mo bridge bond, although the S content is increased, the 5 valence molybdenum is unstable and is subject to valence change under the influence of illumination, temperature and pressure, so that the product is discolored, sulfur is separated, and the tribological properties of the product are reduced; meanwhile, the sulfur precipitation phenomenon can also cause corrosion of metal and influence the application of the metal.
Disclosure of Invention
The invention aims to provide a molybdenum-containing thiadiazole derivative and a preparation method thereof on the basis of the prior art, the molybdenum-containing thiadiazole derivative combines the advantages of molybdenum and thiadiazole derivatives as additives, has good lubricity and high extreme pressure performance, has low corrosion effect on friction pair materials, and is an excellent lubricating oil antifriction additive.
The structural formula of the thiadiazole derivative containing molybdenum is as follows:
wherein R1 and R2 are C4-C13And R1 and R2 are the same or different.
The invention also provides a preparation method of the thiadiazole derivative containing molybdenum, which comprises the following preparation steps:
(1) adding DMF (N, N-dimethylformamide), molybdenum trioxide and 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding a catalyst triethylamine, heating to 150-160 ℃, and reacting for 5-10 h (h);
(2) cooling to room temperature, washing with water, and filtering to obtain green yellow intermediate containing molybdenum thiadiazole with structural formula
(3) Dispersing the intermediate obtained in the step (2) in alkyl alcohol, adding dialkyl amine, mixing, dropwise adding carbon disulfide, and controlling the temperature of a reaction system to be below 40 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at the temperature of below 40 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 3-8 h;
(4) after the reaction is finished, the solvent is evaporated to obtain the product of the thiadiazole derivative containing molybdenum.
In the preparation method of the thiadiazole derivative containing molybdenum, in the step (1), the addition amount of the catalyst is 2-5% of the mass of molybdenum trioxide.
In the above preparation method of the molybdenum-containing thiadiazole derivative, in the step (1), the alkyl alcohol is n-propanol, isopropanol, n-butanol or isobutanol.
In the above preparation method of the molybdenum-containing thiadiazole derivative, in the step (3), the structural formula of the dialkylamine is as follows:
wherein 1 and R2 are C4-C13And R1 and R2 are the same or different.
In the preparation method of the molybdenum-containing thiadiazole derivative, the molar ratio of molybdenum trioxide, 2, 5-dimercapto-1, 3, 4-thiadiazole, carbon disulfide and dialkylamine is as follows: 1: 0.52-0.55: 1.1-1.5: 1.1 to 1.5.
The invention also provides an application method of the molybdenum-containing thiadiazole derivative, and the molybdenum-containing thiadiazole derivative is added into base oil and used as a lubricating oil additive.
The preparation method of the thiadiazole derivative containing molybdenum comprises the following reaction processes:
the molybdenum-containing thiadiazole derivative prepared by the invention is added into base oil to be applied to a lubricating oil additive, and has the following beneficial effects: the thiadiazole derivative containing molybdenum combines the advantages of molybdenum and thiadiazole derivatives as additives, molybdenum in the product exists in a stable state of hexavalent molybdenum, valence state change is not easy to occur even under the conditions of illumination, high temperature and high pressure, and the product can be stored and applied for a long time without color change; the thiadiazole five-membered heterocycle containing the sulfur and the nitrogen has a closely linked chemical structure, ring opening is not easy to occur, and the stable valence state of molybdenum also ensures that a molybdenum-sulfur bond is not easy to break, so that the high extreme pressure property of a product is ensured, and the molybdenum-containing thiadiazole derivative has good lubricity and high extreme pressure property; meanwhile, the product is stable, and the phenomenon of sulfur precipitation easily caused by the existing organic molybdenum additive such as MoDTC is not easy to occur, so that the additive has small corrosion effect on friction pair materials and is an excellent lubricating oil antifriction additive.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the present invention is not limited to the following embodiments.
Example 1
A thiadiazole derivative containing molybdenum is prepared by the following steps:
(1) adding 200mL (milliliter) of DMF, 72g (gram) of molybdenum trioxide and 39g of 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding 2mL of triethylamine, heating to 150 ℃, and reacting for 5 hours;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in 100mL of n-propanol, adding 71g of diisobutylamine, mixing, dropwise adding 33mL of carbon disulfide, and controlling the temperature of a reaction system to be below 40 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at the temperature of below 40 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 3 h;
(4) after the reaction is finished, the solvent is evaporated to obtain the product of the thiadiazole derivative A containing molybdenum, wherein R1 and R2 are both isobutyl (C)4Branched alkyl group of (a), theoretical molybdenum content 23.6%; finally, 169g of product were weighed out, the calculated yield was 83.0%, and the molybdenum content was found to be 23.1%.
Example 2
A thiadiazole derivative containing molybdenum is prepared by the following steps:
(1) adding 200mL of DMF, 72g of molybdenum trioxide and 41g of 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding 5mL of triethylamine, heating to 160 ℃, and reacting for 5 h;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in 100mL of isopropanol, adding 139g of dihexylamine, mixing, dropwise adding 45mL of carbon disulfide, and controlling the temperature of a reaction system at 30 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at 30 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 5 h;
(4) after the reaction is finished, evaporating the solvent to obtain a product of the molybdenum-containing thiadiazole derivative B, wherein R1 and R2 are both n-hexyl (C)6Straight chain alkyl group of (d), theoretical molybdenum content 20.8%; finally, 201g of the product was weighed out, the calculated yield was 87.0%, and the molybdenum content was found to be 20.2%.
Example 3
A thiadiazole derivative containing molybdenum is prepared by the following steps:
(1) adding 200mL of DMF, 72g of molybdenum trioxide and 39g of 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding 3mL of triethylamine, heating to 160 ℃, and reacting for 10 hours;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in 100mL of n-butanol, adding 133g of diisooctylamine, mixing, dropwise adding 33mL of carbon disulfide, and controlling the temperature of a reaction system at 40 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at 40 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 4 h;
(4) after the reaction is finished, evaporating the solvent to obtain a product of the thiadiazole derivative C containing molybdenum, wherein R1 and R2 are both isooctyl (C)8Branched alkyl group of (a), theoretical molybdenum content 18.5%; finally, it was weighed to obtain 209g of product, the calculated yield was 80.6%, and the molybdenum content was found to be 18.5%.
Example 4
A thiadiazole derivative containing molybdenum is prepared by the following steps:
(1) adding 200mL of DMF, 72g of molybdenum trioxide and 41g of 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding 5mL of triethylamine, heating to 150 ℃, and reacting for 8 h;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in 100mL of isobutanol, adding 223g of didecylamine, mixing, dropwise adding 45mL of carbon disulfide, and controlling the temperature of a reaction system to be below 30 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at the temperature of below 30 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 5 h;
(4) after the reaction is finished, the solvent is evaporated to obtain the product of the thiadiazole derivative D containing molybdenum, wherein R1 and R2 are both decaalkyl (C)10Alkyl group of (d) theoretical molybdenum content 16.7%; finally, 256g of the product was weighed, the calculated yield was 89.2%, and the molybdenum content was found to be 16.4%.
Example 5
A thiadiazole derivative containing molybdenum is prepared by the following steps:
(1) adding 200mL of DMF, 72g of molybdenum trioxide and 41g of 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding 4mL of triethylamine, heating to 160 ℃, and reacting for 10 hours;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in 100mL of isopropanol, adding 219g of 2-ethylhexyl tridecylamine, mixing, dropwise adding 42mL of carbon disulfide, and controlling the temperature of a reaction system at 30 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at 30 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 5 h;
(4) after the reaction is finished, evaporating the solvent to obtain a product of the thiadiazole derivative E containing molybdenum, wherein R1 is isooctyl (C)8With branched alkyl group) R2 is n-tridecyl (C)13Linear alkyl group of (d), theoretical molybdenum content 16.3%; finally, weighing was carried out to obtain 258g of product, the calculated yield was 87.4%, and the molybdenum content was found to be 16.1%.
Example 6
A thiadiazole derivative containing molybdenum is prepared by the following steps:
(1) adding 200mL of DMF, 72g of molybdenum trioxide and 41g of 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding 2mL of triethylamine, heating to 160 ℃, and reacting for 5 hours;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in 100mL of isobutanol, adding 286g of diisotridecylamine, mixing, dropwise adding 45mL of carbon disulfide, and controlling the temperature of a reaction system to be below 30 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at the temperature of below 30 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 8 h;
(4) after the reaction is finished, the solvent is evaporated to obtain the product of the molybdenum-containing thiadiazole derivative F, wherein R1 and R2 are isotridecyl (C)13Branched alkyl group of (a), theoretical molybdenum content 14.6%; finally, weighing was carried out to obtain 297g of product, which was calculated to have a yield of 90.2% and a molybdenum content of 13.7%.
In the above examples, the molybdenum content of the product was determined by gravimetric analysis of lead molybdate in GB/T5059.1-2014.
The products of the above examples were subjected to application examples and, at the same time, comparative examples using a commercially available organomolybdc additive, MoDTC (supplied by ADEKA, japan, trade mark Sakura-lube 525, molybdenum content 9.8%);
the base oil selected for the experiment is the HVI150SN I base oil of the Dalian petrochemical industry, the base oil is adopted to prepare the products of the embodiments and the commercial MoDTC into the additive with the same molybdenum content (9.8 percent), and then the experiment is carried out;
the experimental procedures and results are as follows.
Tribology performance experiments:
the additives of the products of the examples and the comparative examples were added to the base oil in mass fractions of 0.5%, 1.0%, 1.5%, 2..0%, 2.5%, respectively, and the load-bearing properties were tested with a four-ball friction tester (MQ-12-EP type manufactured by the junan tester works) according to GB 3142-82; the frictional wear test was performed on a mechanical long-time wear tester (MRS-1J model manufactured by Jinan tester Co., Ltd.). The results of the experiment are shown in table 1.
Table 1 results of experimental tribological properties of the products of the examples and of the additives of the comparative example in rapeseed oil
The friction coefficients of table 1 are measured by the test oil under a load of 20kg, and it can be seen from the values of the wear scar diameter WSD and the friction coefficient of table 1 that the friction coefficient of each test oil is reduced after adding each additive prepared in the examples and the MoDTC of the comparative example, wherein the wear scar diameter of the commercial MoDTC is reduced from 0.67mm to 0.41mm and the friction coefficient is reduced from 0.18 to 0.057 as the adding concentration is increased, while the friction coefficient is reduced from 0.18 to 0.05 by adding each additive prepared in the examples, so that the additive containing molybdenum thiadiazole derivative prepared by the present invention has better lubricity than that of the commercial lubricating oil additive MoDTC, and is an excellent lubricant under the same molybdenum content condition.
Seizure resistance load for bearing capacity of test oilP B Value and sintering load resistanceP D The values are represented. From the experimental results in Table 1, it can be seen that the additive containing molybdenum thiadiazole derivatives prepared according to the present invention has been compared with the conventional organic molybdenum additive of commercial MoDTCP B Value sumP D All have obvious improvement and have excellent extreme pressure performance.
As can be seen from the data in Table 1, the additive containing the molybdenum thiadiazole derivative provided by the invention is a friction modifier with high extreme pressure performance.
Copper sheet corrosion test:
the copper sheet corrosion test was performed according to ASTM D130: a polished copper sheet is hung by a glass hook and is immersed in sample oil (mass concentration is 2.0 percent), the experiment temperature is 121 ℃, the experiment time is 3 hours, the copper sheet is taken out after the experiment is finished, the copper sheet is wiped dry after being cleaned by a solvent (ethanol-benzene, 1: 4) (volume ratio), the color of the copper sheet is observed, and the color is compared with an ASTM corrosion standard color plate to determine the corrosion grade of the copper sheet. The results of the experiment are shown in table 2.
TABLE 2 copper sheet Corrosion Performance test results for several test oils
Surface state of copper sheet | State of corrosion | Grade | |
Base oil | Light orange | Slight corrosion | 1a |
MoDTC | Deep purple color | Moderate corrosion | 2b |
Example 1 test oil | Purplish red color | Slight corrosion | 2a |
Example 2 test oil | Light orange | Slight corrosion | 1a |
Example 3 test oil | Dark orange | Slight corrosion | 1b |
Example 4 test oil | Dark orange | Slight corrosion | 1b |
Example 5 test oil | Light orange | Slight corrosion | 1a |
Example 6 test oil | Light orange | Slight corrosion | 1a |
As can be seen from Table 2, the copper corrosion grade of the commercially available MoDTC is 2b, in the test oil of the products of six examples, except the corrosion grade of the test oil of example 1 is 2a, the corrosion grade of the test oil of the products of the other five examples is 1b or 1a, and as a whole, the copper sheet corrosion effect of the products of the six examples is not obvious, so that the additive provided by the invention has low corrosion to the friction pair material.
The experimental results show that the additive provided by the invention combines the advantages of molybdenum and thiadiazole as additives, has good friction capacity and high extreme pressure performance, does not contain elements such as phosphorus, chlorine and the like, has low corrosion effect on friction pair materials, and is a lubricating oil additive with excellent performance.
The present invention is not described in detail in the prior art. % represents mass percentage content.
Claims (7)
2. A method for preparing the molybdenum-containing thiadiazole derivative according to claim 1, wherein: the preparation method comprises the following preparation steps:
(1) adding DMF, molybdenum trioxide and 2, 5-dimercapto-1, 3, 4-thiadiazole into a reaction bottle, fully mixing, adding triethylamine serving as a catalyst, heating to 150-160 ℃, and reacting for 5-10 hours;
(2) cooling to room temperature, washing with water, and filtering to obtain a green-yellow molybdenum-containing thiadiazole intermediate;
(3) dispersing the intermediate obtained in the step (2) in alkyl alcohol, adding dialkyl amine, mixing, dropwise adding carbon disulfide, and controlling the temperature of a reaction system to be below 40 ℃ in the dropwise adding process; after the dropwise addition is finished, continuously reacting for 1h at the temperature of below 40 ℃; heating the reaction system to 60 ℃, and heating and refluxing for 3-8 h;
(4) after the reaction is finished, the solvent is evaporated to obtain the product of the thiadiazole derivative containing molybdenum.
3. The process for preparing a thiadiazole derivative containing molybdenum according to claim 2, wherein: in the step (1), the adding amount of the catalyst is 2-5% of the mass of the molybdenum trioxide.
4. The process for preparing a thiadiazole derivative containing molybdenum according to claim 2, wherein: in the step (3), the alkyl alcohol is n-propanol, isopropanol, n-butanol or isobutanol.
6. The process for preparing a thiadiazole derivative containing molybdenum according to claim 2, wherein: in the preparation method, the molar ratio of the molybdenum trioxide, the 2, 5-dimercapto-1, 3, 4-thiadiazole, the carbon disulfide and the dialkyl amine is as follows: 1: 0.52-0.55: 1.1-1.5: 1.1 to 1.5.
7. The molybdenum-containing thiadiazole derivative according to claim 1, wherein: and adding the thiadiazole derivative containing molybdenum into base oil to be used as a lubricating oil additive.
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1987002358A1 (en) * | 1985-10-15 | 1987-04-23 | Pennwalt Corporation | Thiadiazole compounds and lubricant additives thereof |
US4990273A (en) * | 1985-09-30 | 1991-02-05 | Union Oil Company Of California | Lubrication anti-wear additive |
US5177213A (en) * | 1989-07-20 | 1993-01-05 | R. T. Vanderbilt Company, Inc. | Succinate derivatives of 2,5-dimercapto-1,3,4-thiadiazoles |
US5631213A (en) * | 1995-02-15 | 1997-05-20 | Asahi Denka Kogyo K. K. | Process for producing molybdenum oxysulfide dithiocarbamate |
CN103509057A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | Oil-soluble molybdenum dialkyldithiocarbamate additive preparation method |
CN103965139A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Thiocarbamate-containing thiadiazole derivative, and preparation method and use thereof |
CN105859784A (en) * | 2016-05-06 | 2016-08-17 | 文万军 | High-activity organic molybdenum compound and preparation and application method thereof |
CN105886002A (en) * | 2016-04-21 | 2016-08-24 | 济宁利特纳米技术有限责任公司 | Lubricating oil additive containing thiadiazole derivatives and nano copper, preparation method of additive and lubricating oil containing additive |
CN105924476A (en) * | 2016-05-30 | 2016-09-07 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN105924475A (en) * | 2016-05-06 | 2016-09-07 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN105924473A (en) * | 2016-05-06 | 2016-09-07 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN105968139A (en) * | 2016-05-30 | 2016-09-28 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN106281578A (en) * | 2016-05-06 | 2017-01-04 | 文万军 | Activity organic-molybdenum is utilized to improve method and the compound of oil lubrication performance |
-
2020
- 2020-08-18 CN CN202010828895.3A patent/CN111892629B/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4990273A (en) * | 1985-09-30 | 1991-02-05 | Union Oil Company Of California | Lubrication anti-wear additive |
WO1987002358A1 (en) * | 1985-10-15 | 1987-04-23 | Pennwalt Corporation | Thiadiazole compounds and lubricant additives thereof |
US5177213A (en) * | 1989-07-20 | 1993-01-05 | R. T. Vanderbilt Company, Inc. | Succinate derivatives of 2,5-dimercapto-1,3,4-thiadiazoles |
US5631213A (en) * | 1995-02-15 | 1997-05-20 | Asahi Denka Kogyo K. K. | Process for producing molybdenum oxysulfide dithiocarbamate |
CN103509057A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | Oil-soluble molybdenum dialkyldithiocarbamate additive preparation method |
CN103965139A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Thiocarbamate-containing thiadiazole derivative, and preparation method and use thereof |
CN105886002A (en) * | 2016-04-21 | 2016-08-24 | 济宁利特纳米技术有限责任公司 | Lubricating oil additive containing thiadiazole derivatives and nano copper, preparation method of additive and lubricating oil containing additive |
CN105859784A (en) * | 2016-05-06 | 2016-08-17 | 文万军 | High-activity organic molybdenum compound and preparation and application method thereof |
CN105924475A (en) * | 2016-05-06 | 2016-09-07 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN105924473A (en) * | 2016-05-06 | 2016-09-07 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN106281578A (en) * | 2016-05-06 | 2017-01-04 | 文万军 | Activity organic-molybdenum is utilized to improve method and the compound of oil lubrication performance |
CN105924476A (en) * | 2016-05-30 | 2016-09-07 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
CN105968139A (en) * | 2016-05-30 | 2016-09-28 | 文万军 | High-activity organic molybdenum compound and preparation and use method thereof |
Non-Patent Citations (3)
Title |
---|
HU JIANQIANG 等: "Study on tribological and corrosion inhibiting properties of thiadiazole derivative as lubricant grease additive", 《INDUSTRIAL LUBRICATION AND TRIBOLOGY》 * |
XUE WEIGUO 等: "Synthesis and properties of thiadiazole lubricant additives", 《INDUSTRIAL LUBRICATION AND TRIBOLOGY》 * |
姚俊兵: "润滑油脂抗磨极压添加剂研究进展", 《润滑油》 * |
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