CN114381314A - Phosphate-sulfur-free lubricant additive molybdate complex and preparation method thereof - Google Patents
Phosphate-sulfur-free lubricant additive molybdate complex and preparation method thereof Download PDFInfo
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003879 lubricant additive Substances 0.000 title claims description 11
- 238000010668 complexation reaction Methods 0.000 title description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010687 lubricating oil Substances 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 239000011733 molybdenum Substances 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 13
- 229930195729 fatty acid Natural products 0.000 claims abstract description 13
- 239000000194 fatty acid Substances 0.000 claims abstract description 13
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 8
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 239000005078 molybdenum compound Substances 0.000 claims description 2
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 claims 3
- 238000005461 lubrication Methods 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 230000009467 reduction Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 235000013162 Cocos nucifera Nutrition 0.000 description 6
- 244000060011 Cocos nucifera Species 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- -1 molybdate compound Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 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
- 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
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
-
- 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
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- 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 relates to the technical field of lubricating oil, in particular to a phosphate-sulfur-free lubricating oil additive molybdate complex and a preparation method thereof, wherein the phosphate-sulfur-free lubricating oil additive molybdate complex comprises the following steps: adding fatty acid diethanolamide and fatty acid monoglyceride into a container, adding toluene and a DMF solvent to form a mixed solution, dropwise adding an inorganic molybdenum aqueous solution into the mixed solution, carrying out reflux reaction, removing water from reactants, cooling, carrying out suction filtration, collecting filtrate, and carrying out reduced pressure distillation to obtain a phosphorus-sulfur-free lubricating oil additive molybdate complex, wherein the mass fraction of molybdenum content in the phosphorus-sulfur-free lubricating oil additive molybdate complex is 7.5-8.5%; the molybdate complex provided by the invention does not contain elements such as phosphorus, sulfur and the like, has more excellent wear-resistant and antifriction properties, and plays a role in boundary lubrication and mixed lubrication states.
Description
Technical Field
The invention relates to the technical field of lubricating oil, in particular to a phosphate-sulfur-free lubricating oil additive molybdate complex and a preparation method thereof.
Background
With the improvement of environmental protection consciousness of various countries in the world and the active implementation of sustainable development strategy of China, the lubricating oil market places more importance on environmental protection, energy conservation and consumption reduction, and higher requirements on lubricating oil additives are put forward. If the silver alloy bearing requires to use zinc-free lubricating oil, the internal combustion engine provided with a tail gas treatment device requires to use phosphorus-free lubricating oil; phosphorus in the lubricating oil can shorten the service life of the three-way catalyst in the tail gas device, and sulfur in the lubricating oil can easily corrode the elastomer sealing element and cause great pollution to the environment. Therefore, a phosphorus-free and sulfur-free organic molybdenum additive is developed according to market demands, and the oil-soluble molybdate compound meets the requirements of environmental protection, energy conservation and consumption reduction.
However, the production level in China always stays in the primary organic molybdenum products of high-phosphorus-content MoDDP and short-chain MoDTC products, and the catalyst of the automobile exhaust converter is poisoned due to the phosphorus element contained in the dialkyl molybdenum dithiophosphate (MoDTP) additive; meanwhile, the production cost is high, and the application range of the lubricating grease in engine oil is limited; although the molybdenum dialkyl dithiocarbamate (MoDTC) additive has better antiwear performance, the additive contains sulfur element and has stronger corrosivity to metals; the sulfur-phosphorus-free organic molybdenum product has good abrasion resistance, but poor friction reduction, and has good friction reduction but poor abrasion resistance, wherein some products mainly act in a boundary lubrication state, and some products mainly act in a mixed lubrication state, and the performance is not comprehensive. Some sulfur-free and phosphorus-free products have better abrasion resistance but poor friction reduction, some have good friction reduction but poor abrasion resistance, some mainly act in a boundary lubrication state, and some mainly act in a mixed lubrication state, so that the invention provides a product which has the functions of abrasion resistance and friction reduction and acts in both boundary lubrication and mixed lubrication, which is the direction of effort of people in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a phosphate-sulfur-free lubricating oil additive molybdate complex and a preparation method thereof, so as to solve the problem of poor wear resistance and friction reduction of the conventional lubricating oil and realize the function under boundary lubrication and mixed lubrication.
In order to solve the problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a phosphate-sulfur-free lubricating oil additive molybdate complex, which comprises the following steps:
1) adding fatty acid diethanolamide and fatty acid monoglyceride into a container, and adding toluene and a DMF solvent to form a mixed solution;
2) dropwise adding an inorganic molybdenum aqueous solution into the mixed solution, and carrying out reflux reaction;
3) and removing moisture from the reactant obtained in the step 2), cooling, performing suction filtration, collecting filtrate, and performing reduced pressure distillation to obtain the phosphosulfate-free lubricating oil additive molybdate complex.
Further, the structural formula of the fatty acid diethanolamide is shown in formula I, and the structural formula of the fatty acid monoglyceride is shown in formula II.
Specifically, the R group of the fatty acid diethanolamide is C6-C18, preferably C12, namely the fatty acid diethanolamide; the R group of the fatty acid monoglyceride is C8-C24, preferably C18, namely, oleic acid monoglyceride.
Further, the inorganic molybdenum compound is one of ammonium molybdate, sodium molybdate, molybdenum trioxide and ammonium heptamolybdate, and preferably ammonium heptamolybdate.
Specifically, the molar ratio of the coconut diethanolamide to the oleic acid monoglyceride is 1:1-9:1, and preferably 2:1-4: 1.
Specifically, the molar ratio of the coconut diethanolamide to the molybdenum element in the inorganic molybdenum aqueous solution is 1:1-5:1, and preferably 2:1-4: 1.
Specifically, the mass ratio of the toluene to the DMF is 1:1-7:1, preferably 3:1-4: 1.
Further, the reaction temperature of the reflux reaction in the step 2) is 110-170 ℃, preferably 120-150 ℃; the reaction time of the reflux reaction is 2 to 12 hours, preferably 4 to 6 hours.
Further, the temperature of the reduced pressure distillation in the step 3) is 130-170 ℃, preferably 150-160 ℃; the time of reduced pressure distillation is 1-3 hours.
The invention also provides a molybdate complex of the phosphorus-sulfur-free lubricating oil additive, which is prepared by the preparation method of the molybdate complex of the phosphorus-sulfur-free lubricating oil additive.
More preferably, the mass fraction of molybdenum in the molybdenate complex of the phosphorus-sulfur-free lubricating oil additive is 1-10%, preferably 7.5-8.5%
The invention has the beneficial effects that: compared with the prior art, the molybdate complex provided by the invention does not contain elements such as phosphorus, sulfur and the like, has more excellent wear-resistant and antifriction properties, and plays a role in boundary lubrication and mixed lubrication; the preparation method of the molybdate complex is simple and feasible and is suitable for large-scale production.
Drawings
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings, in which:
FIG. 1: stribeck curve chart of various oil samples in the seventh embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
It should be noted that these examples are only for illustrating the present invention, and not for limiting the present invention, and the simple modification of the method based on the idea of the present invention is within the protection scope of the present invention.
Example one
21.8g (0.075moL) of coconut diethanolamide, 8.9g (0.025moL) of oleic acid monoglyceride, 80g of toluene and 20g of DMF solvent are added into a 500mL four-neck flask with a mechanical stirring device, a thermometer and a reflux condensation water separator, and stirred for 10-20min at 90 ℃; and then dropwise adding an ammonium heptamolybdate aqueous solution (5.12g is dissolved in 15g of water), gradually heating to 120 ℃, preserving the temperature for 4h of reaction, cooling to room temperature after the reaction is finished, performing suction filtration, collecting filtrate, and performing reduced pressure distillation at 160 ℃ for 1h to obtain a brown oily object, which is recorded as M-01. Wherein the molybdenum content is 7.51% of the total weight of the molybdate complex,
example two
21.8g (0.075moL) of coconut diethanolamide, 8.9g (0.025moL) of oleic acid monoglyceride, 80g of toluene and 20g of DMF solvent are added into a 500mL four-neck flask with a mechanical stirring device, a thermometer and a reflux condensation water separator, and stirred for 10-20min at 90 ℃; and then adding an ammonium heptamolybdate aqueous solution (5.12g is dissolved in 15g of water), gradually heating to 125 ℃, preserving the temperature for 5h, cooling to room temperature after the reaction is finished, carrying out suction filtration, collecting filtrate, and carrying out reduced pressure distillation at 160 ℃ for 1h to obtain a brown oily object, which is recorded as M-02. Wherein the molybdenum content is 8.01% of the total weight of the molybdate complex,
EXAMPLE III
21.8g (0.075moL) of coconut diethanolamide, 8.9g (0.025moL) of oleic acid monoglyceride, 80g of toluene and 20g of DMF solvent are added into a 500mL four-neck flask with a mechanical stirring device, a thermometer and a reflux condensation water separator, and stirred for 10-20min at 90 ℃; and then adding an ammonium heptamolybdate aqueous solution (5.3g is dissolved in 15g of water), gradually heating to 125 ℃ under the protection of nitrogen, preserving the temperature for 6 hours for reaction, cooling to room temperature after the reaction is finished, carrying out suction filtration, collecting filtrate, and carrying out reduced pressure distillation at 160 ℃ for 2 hours to obtain a brown oily object, which is marked as M-03. Wherein the content of molybdenum is 8.23 percent of the total weight of the organic molybdenum lubricating oil additive.
Example four
21.8kg (75moL) of coconut diethanolamide, 8.9kg (25moL) of oleic acid monoglyceride, 80kg of toluene and 20kg of DMF solvent are added into a 500L reaction kettle which is provided with a mechanical stirring device, a thermometer and a reflux condensation water separator, and stirred for 10-20min at 90 ℃; and then adding an ammonium heptamolybdate aqueous solution (5.3kg is dissolved in 15kg of water), gradually heating to 125 ℃ under the protection of nitrogen, preserving the temperature for 6 hours for reaction, cooling to room temperature after the reaction is finished, carrying out suction filtration, collecting filtrate, and carrying out reduced pressure distillation at 160 ℃ for 2 hours to obtain a brown oily object, which is marked as M-04. Wherein the content of molybdenum is 8.17 percent of the total weight of the organic molybdenum lubricating oil additive.
EXAMPLE five
Comparative example 1
Commercially available MOLYVAN 855 with a molybdenum content of 7.92%.
Comparative example II
The preparation method is carried out according to the method of Chinese patent CN101029265A, and the brown oily liquid with the molybdenum content of 6.42 percent is obtained.
Comparative example III
The preparation method is carried out according to the method of Chinese patent CN103060059B, and the brown oily liquid with the molybdenum content of 5.90 percent is obtained.
Comparative example four
The preparation method is carried out according to the method of Chinese patent CN113004335A, and the green oily liquid with the molybdenum content of 7.10 percent is obtained.
EXAMPLE six
The molybdate complexes M-01, M-02, M-03 and M-04, the commercially available MOLYVAN 855, the second, third and fourth products were added to a commercially available SN5W-30 product oil at a molybdenum concentration of 700ppm, respectively. And (3) evaluating the six compounded oil samples and the SN5W-30 oil samples by using a four-ball friction tester respectively, and testing the antifriction and antiwear performances (the industry standard SH/T0189-92). The test conditions are as follows: GCr15 steel ball, 1200r/min of rotation speed, 75 ℃ of oil temperature, 60min of long grinding time and 392N of load. The data given by the test of the four-ball friction tester comprises the diameter of the friction marks and the friction coefficient, wherein the smaller the diameter of the friction marks, the higher the wear resistance, the smaller the friction coefficient and the better the friction reduction performance. The results are shown in Table 1.
Table 1 results of anti-wear and anti-friction tests on the compounded system of synthetic products and comparative examples
| Numbering | Scrub diameter (nm) | Coefficient of friction |
| SN5W-30 finished oil | 0.51 | 0.118 |
| SN5W-30 product oil + M-01 | 0.35 | 0.067 |
| SN5W-30 finished oil + M-02 | 0.34 | 0.065 |
| SN5W-30 oil + M-03 | 0.33 | 0.064 |
| SN5W-30 oil + M-04 | 0.33 | 0.064 |
| SN5W-30 finished oil + Molyvan 855 | 0.41 | 0.071 |
| SN5W-30 Final oil + comparative example II | 0.43 | 0.073 |
| SN5W-30 Final oil + COMPARATIVE EXAMPLE III | 0.46 | 0.085 |
| SN5W-30 Final oil + comparative example four | 0.44 | 0.079 |
As can be seen from the test results in Table 1, in the SN5W-30 finished oil, the diameter of the wear-scar and the friction coefficient of the oil sample were reduced regardless of whether the molybdate complex of the present invention or the products of the comparative examples were added, indicating that the molybdate complex of the present invention and the products of the comparative examples have anti-wear and anti-friction effects. However, the oil samples containing the molybdate ester complex of the invention have smaller wear-scar diameters and smaller friction coefficients than those of the comparative examples, which shows that the molybdate ester complex provided by the invention has better anti-wear and anti-friction properties than the prior art.
EXAMPLE seven
As a simple and effective method for judging the lubricating state and performance, the Stribeck lubricating curve has strong guiding significance for the investigation of the friction and wear resistance of the lubricating oil.
The friction coefficient of the oil product is measured by using an MTM micro traction tester. The friction pair of the MTM is a steel ball and a steel disc, the friction pair is immersed in lubricating oil, the test ball and the test disc are respectively driven by a direct current motor independently, not only slide but also roll, and the sliding-rolling ratio can be adjusted, so that the traction coefficient at different speeds is obtained, the traction coefficient is similar to the friction coefficient, the Stribeck curve of an oil product can be conveniently obtained, and particularly the friction curve of the oil product in boundary lubrication, mixed lubrication and elastohydrodynamic lubrication areas is obtained. The lower the friction coefficient of the oil in each area, the better the antifriction and antiwear performance.
The molybdate complex M-04, the commercially available MOLYVAN 855, and the product of comparative example II were added to a commercially available SN5W-30 finished oil at a molybdenum concentration of 700ppm, respectively. And (3) evaluating the three compounded oil samples and the SN5W-30 oil sample by using an MTM micro traction tester respectively to obtain the Stribeck curve of each oil sample. And (3) testing conditions are as follows: 120 ℃, 5-3000mm/s of rotating speed, 35N of load and 50 percent of rolling-sliding ratio. The test results are shown in fig. 1.
As can be seen from the test results shown in FIG. 1, in the SN5W-30 finished oil, the friction coefficient of the oil sample in the boundary lubrication, mixed lubrication and elastohydrodynamic lubrication areas is reduced no matter the molybdate complex of the invention or the product of the comparative example is added, which indicates that the molybdate complex of the invention and the product of the comparative example have the functions of friction reduction and wear resistance. However, the friction coefficient of the oil sample containing the molybdate complex disclosed by the invention is smaller than that of the comparative example in boundary lubrication and mixed lubrication areas, so that the molybdate complex disclosed by the invention has better antifriction and antiwear performances than those of the molybdate complex in the prior art.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that, while the invention has been described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a phosphate-sulfur-free lubricant additive molybdate complex is characterized by comprising the following steps:
1) adding fatty acid diethanolamide and fatty acid monoglyceride into a container, and adding toluene and a DMF solvent to form a mixed solution;
2) dropwise adding an inorganic molybdenum aqueous solution into the mixed solution, and carrying out reflux reaction;
3) and removing moisture from the reactant obtained in the step 2), cooling, performing suction filtration, collecting filtrate, and performing reduced pressure distillation to obtain the phosphosulfate-free lubricating oil additive molybdate complex.
2. The method for preparing the phosphosulfate-free lubricant additive molybdate complex according to claim 1, wherein the R group of the fatty acid diethanolamide is C6-C18, preferably C12, i.e., coco diethanolamide; the R group of the fatty acid monoglyceride is C8-C24, preferably C18, namely, oleic acid monoglyceride.
3. The method of claim 1, wherein the inorganic molybdenum compound is one of ammonium molybdate, sodium molybdate, molybdenum trioxide and ammonium heptamolybdate, preferably ammonium heptamolybdate.
4. The method of preparing the phospho-sulfur-free lubricating oil additive molybdate complex according to claim 2, characterized in that the molar ratio of cocodiethanolamide to oleic acid monoglyceride is 1:1 to 9:1, preferably 2:1 to 4: 1.
5. The method of preparing the phospho-sulfur-free lubricant additive molybdate complex according to claim 2, characterized in that the molar ratio of the cocodiethanolamide to the molybdenum element in the aqueous inorganic molybdenum solution is 1:1 to 5:1, preferably 2:1 to 4: 1.
6. The method of claim 1, wherein the mass ratio of the toluene to the DMF is 1:1 to 7:1, preferably 3:1 to 4: 1.
7. The method for preparing the molybdate complex of the phosphorus-free and sulfur-free lubricant additive according to claim 1, wherein the reflux reaction in step 2) is carried out at a temperature of 110-170 ℃, preferably at a temperature of 120-150 ℃; the reaction time of the reflux reaction is 2 to 12 hours, preferably 4 to 6 hours.
8. The method for preparing the molybdate complex of the phosphorus-free and sulfur-free lubricant additive according to claim 1, wherein the temperature of the reduced pressure distillation in the step 3) is 130-170 ℃, preferably 150-160 ℃; the time of reduced pressure distillation is 1-3 hours.
9. The molybdate complex of a phosphorus-and-sulfur-free lubricant additive prepared by the method of any one of claims 1 to 8.
10. The molybdate complex of the phosphorus-and-sulfur-free lubricant additive, which is prepared according to the preparation method of the molybdate complex of the phosphorus-and-sulfur-free lubricant additive according to claim 9, is characterized in that the mass fraction of molybdenum in the molybdate complex of the phosphorus-and-sulfur-free lubricant additive is 1 to 10 percent, preferably 7.5 to 8.5 percent.
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