CN108129517A - A kind of preparation method of organic three core molybdenum additives - Google Patents
A kind of preparation method of organic three core molybdenum additives Download PDFInfo
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- CN108129517A CN108129517A CN201711486108.6A CN201711486108A CN108129517A CN 108129517 A CN108129517 A CN 108129517A CN 201711486108 A CN201711486108 A CN 201711486108A CN 108129517 A CN108129517 A CN 108129517A
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- molybdenum additives
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- core molybdenum
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 95
- 239000011733 molybdenum Substances 0.000 title claims abstract description 93
- 239000000654 additive Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000005843 Thiram Substances 0.000 claims abstract description 24
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960002447 thiram Drugs 0.000 claims abstract description 24
- -1 thio ammonium molybdate Chemical compound 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 20
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 20
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012046 mixed solvent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 40
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 4
- 239000010687 lubricating oil Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000002574 poison Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 abstract 1
- 235000016768 molybdenum Nutrition 0.000 description 70
- 239000010705 motor oil Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 150000003335 secondary amines Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001972 liquid chromatography-electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/30—Dithiocarbamic acids; Derivatives thereof having sulfur atoms of dithiocarbamic groups bound to other sulfur atoms
- C07C333/32—Thiuramsulfides; Thiurampolysulfides
-
- 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
-
- 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
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 discloses a kind of preparation method of organic three core molybdenum additives, this method is：First, curing tetraalkyl thiram is prepared using dialkyl secondary amine, carbon disulfide, the ethanol water of sodium hydroxide and hydrogen peroxide；2nd, organic three core molybdenum additives crude product is prepared using 13 thio ammonium molybdate crystals, curing tetraalkyl thiram and mixed solvent；3rd, it post-processes organic three core molybdenum additives crude product and obtains organic three core molybdenum additives of oily.The present invention innovatively devises a kind of preparation method of organic three core molybdenum additives, organic three core molybdenum additives have been synthesized using 13 thio ammonium molybdate crystals and curing tetraalkyl thiram, molybdenum content compared to existing dinuclear molybdenum additives is more preferable, the additive amount being added under identical frictional behaviour in lubricating oil is less, anti-friction performance is also more excellent, and without using the raw material that poison is harmful in preparation process, also the discharge without toxic and harmful gas, method are environmentally protective.
Description
Technical field
The invention belongs to lube oil additive technical fields, and in particular to a kind of preparation side of organic three core molybdenum additives
Method.
Background technology
It is well known that the high soot in diesel oil can work with engine into machine oil, show the dynamic viscosity of machine oil
It writes and improves, yield stress is generated under low temperature and abrasion resistance is greatly reduced, acceleration motor abrasion, so as to which lubricants performance generates
Adverse effect.
Although traditional molybdenum disulfide, nano molybdenum disulfide and MoDTC, MoDDP and ZnDDP are improving antiwear and friction reduction property
On have an excellent performance, but still helpless to the harm of lubricants performance in face of diesel soot, at the same time, in soot
Harmful ion or atomic group intermediate can be wear-resistant to these in the wear-resistant layer for touching lubricated surface with low-energy electron
Additive generates fatal harm.It is pointed out in the research of Howard L.Fang, the organic compound with three core molybdenum structures can be with
Effectively reduce soot abrasion.Compared to traditional dispersant, organic three core molybdenum has higher absorption on these charged metal surfaces
Trend, and be subsequently formed MoS2Antiwear and antifriction film.Organic three core molybdenum Mo3S7R4Include two kinds of ligand, Yi Zhonglian
It is connected on individual molybdenum position and passes through Weak link and connect with molybdenum core, another (the 4th R) is then easy to detach and produce with molybdenum core
Raw electrophilic group, so as to be easily combined with the anion of metal surface.
The synthetic method report to three cores domestic at present is very few, has no the total synthesis technology of three core molybdenum additives, there is correlation
Report (10238214 A of CN) is reacted using molybdenum-containing material matter with dialkyl dithiocarbamate, in this way, due to
Dialkyl dithiocarbamate is dinuclear molybdenum, and molybdenum content is relatively low, is hardly formed three higher core molybdenum structures of molybdenum content.Directly
Purchase 13 thio ammonium molybdate crystal of external monopolization product is starting material, and the potassium cyanide for having added in catalytic action in the process holds
Hypertoxic cyanide gas has been also easy to produce, has been unfavorable for health and environmental protection, and raw material is limited, method is simultaneously infeasible.
Invention content
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, to provide a kind of organic three core
The preparation method of molybdenum additives.The preparation method is novel in design, using 13 thio ammonium molybdate crystals and curing tetraalkyl autumn
Blue nurse has synthesized organic three core molybdenum additives, and the molybdenum content compared to existing dinuclear molybdenum additives is more preferable, under identical frictional behaviour
The additive amount being added in lubricating oil is less, and anti-friction performance is also more excellent, and be harmful in preparation process without using poison
Raw material, also the discharge without toxic and harmful gas, method are environmentally protective.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of preparation of organic three core molybdenum additives
Method, which is characterized in that this method includes the following steps：
Step 1: the preparation of curing tetraalkyl thiram：The ethanol water for measuring the sodium hydroxide of 100mL is added to three
In mouth flask, dialkyl secondary amine is added, carbon disulfide then is slowly added dropwise under ice-water bath, after being added dropwise, is in temperature
Constant temperature stirs 2h under conditions of 30 DEG C, adds hydrogen peroxide, and isothermal reaction 1h after vacuum concentration is evaporated, obtains intermediate product two
Vulcanize tetraalkyl thiram；
Step 2: the preparation of organic three core molybdenum additives crude product：By what is obtained in 13 thio ammonium molybdate crystals, step 1
Curing tetraalkyl thiram and mixed solvent are placed in three-necked flask, obtain reaction solution, and the reaction solution is 60 in temperature
DEG C~70 DEG C under conditions of isothermal reaction 20h, the color of the reaction solution is gradually deepened during isothermal reaction, has been finally obtained
Three core molybdenum additives crude product of machine；The volume of the mixed solvent is 10 times of described 13 thio ammonium molybdate crystal moles, institute
The volume unit for stating mixed solvent is L, and the mole unit of 13 thio ammonium molybdate crystals is mol, and the mixed solvent is by first
Alcohol and tetrahydrofuran are according to 1:1 volume ratio is mixed；
Step 3: the post processing of organic three core molybdenum additives crude product：It is evaporated the organic three core molybdenum addition obtained in step 2
Mixed solvent in agent crude product obtains solids, and the solids is then repeatedly washed with methanol, and filter cake, institute are obtained after filtering
It states after filter cake is dissolved using tetrahydrofuran and continues to stir 2h~3h, after then filtering is evaporated tetrahydrofuran, obtain oily has
Three core molybdenum additives of machine.
A kind of preparation method of above-mentioned organic three core molybdenum additives, which is characterized in that sodium hydroxide described in step 1
The process for preparation of ethanol water be：Ethyl alcohol and distilled water are pressed into (3~1):1 volume ratio mixing, then adds in hydroxide
Sodium dissolves, and the ethanol water for the sodium hydroxide that mass concentration is 5% is obtained after dissolving.
A kind of preparation method of above-mentioned organic three core molybdenum additives, which is characterized in that the body of the ethyl alcohol and distilled water
Product is than being 2:1.
A kind of preparation method of above-mentioned organic three core molybdenum additives, which is characterized in that carbon disulfide described in step 1
Drop rate be 0.05mL/s.
The preparation method of above-mentioned a kind of organic three core molybdenum additives, which is characterized in that dialkyl described in step 1 is secondary
The alkyl of amine is C4~C18Straight chain saturated alkyl.
The preparation method of above-mentioned a kind of organic three core molybdenum additives, which is characterized in that constant temperature described in step 1 stirs
Temperature for 30 DEG C, the time of constant temperature stirring is 2h.
A kind of preparation method of above-mentioned organic three core molybdenum additives, which is characterized in that hydrogen peroxide described in step 1
The mole ratio for adding in volume and dialkyl secondary amine is (0.8~1.2):1, the unit of the addition volume of the hydrogen peroxide is mL,
The mole unit of the dialkyl secondary amine is mol.
The preparation method of above-mentioned a kind of organic three core molybdenum additives, which is characterized in that 13 is thio described in step 2
The molar ratio of ammonium molybdate crystal and curing tetraalkyl thiram is 1:2.5.
A kind of preparation method of above-mentioned organic three core molybdenum additives, which is characterized in that reaction solution described in step 2
Reaction temperature is 65 DEG C.
The preparation method of above-mentioned a kind of organic three core molybdenum additives, which is characterized in that the reaction is evaporated in step 3
The pressure of liquid is 0.08MPa~0.10MPa.
Compared with the prior art, the present invention has the following advantages：
1st, the present invention is had certain using ethanol water as the reaction dissolvent for preparing curing tetraalkyl thiram
Catalytic action changes the conventional method that potassium cyanide etc. is added in existing method, avoids the generation of toxic cyanide gas, both protected
It has protected environment and has saved cost again.
2nd, the present invention devises a kind of completely new approach and is prepared for curing tetraalkyl thiram, curing tetraalkyl thiram
Organic three core molybdenum additives are obtained after isothermal reaction 20h under conditions of 60 DEG C~70 DEG C with 13 thio ammonium molybdate crystals, are
The Recent Progresses In The Development of organic three core and follow-up process of industrialization provide theoretical foundation, and the molybdenum content of organic three core molybdenum additives is more
Height has more preferably abrasion resistance as lube base oil.
3rd, profit is recycled using extraction filtering technique, filtrate again in the last handling process of three core molybdenum additives crude products of the invention
With technological operation is simple, and cost is relatively low, is conducive to later stage research and development and marketing.
Technical scheme of the present invention is described in further detail below by drawings and examples.
Description of the drawings
Fig. 1 is the energy spectrum diagram of organic three core molybdenum additives prepared by the embodiment of the present invention 1.
Specific embodiment
The 13 thio ammonium molybdate crystals used in 1~embodiment of the embodiment of the present invention 3 are CN for Authorization Notice No.
13 thio ammonium molybdate crystals being prepared in 105133002 B.
Embodiment 1
The preparation method of the present embodiment includes the following steps：
Step 1: the preparation of curing tetraalkyl thiram：Ethyl alcohol and distilled water are pressed 2:1 volume ratio mixing, then
Sodium hydroxide dissolving is added in, the ethanol water for the sodium hydroxide that mass concentration is 5% is obtained after dissolving, measures the hydrogen of 100mL
The ethanol water of sodium oxide molybdena is added in the three-necked flask of 250mL, the dibutyl secondary amine of 5mol is added, then under ice-water bath
Carbon disulfide is slowly added dropwise with the drop rate of 0.05mL/s, the wherein molar ratio of dibutyl secondary amine and carbon disulfide is 1.35:
1, after being added dropwise, constant temperature stirs 2h under conditions of being 30 DEG C in temperature, adds the hydrogen peroxide (analysis is pure) of 5mL, constant temperature is anti-
After 1h, vacuum concentration is answered to be evaporated, intermediate product curing tetraalkyl thiram is obtained；
Step 2: the preparation of organic three core molybdenum additives crude product：By the 13 of 0.002mol thio ammonium molybdate crystals,
The curing tetraalkyl thiram and the mixed solvent of 20mL obtained in the step of 0.005mol one is placed in three mouthfuls of burnings of 200mL
In bottle, the molar ratio of the 13 thio ammonium molybdate crystal and curing tetraalkyl thiram is 1:2.5, reaction solution is obtained,
Isothermal reaction 20h under conditions of the reaction solution is 65 DEG C in temperature, the color of the reaction solution is gradual during isothermal reaction
Deepen, finally obtain organic three core molybdenum additives crude product；The mixed solvent is by methanol and tetrahydrofuran according to 1:1 volume ratio
It is mixed；
Step 3: the post processing of organic three core molybdenum additives crude product：In pressure 0.09MPa, reacting liquid temperature is 65 DEG C of items
Under part, negative pressure is evaporated the mixed solvent in the organic three core molybdenum additives crude product obtained in step 2, obtains solids, Ran Houyong
Methanol washs the solids 2 times, obtains filter cake after filtering, the filter cake using after tetrahydrofuran dissolving and continue to stir 2h~
3h after then filtering is evaporated tetrahydrofuran, obtains organic three core molybdenum additives of oily.
Fig. 1 is the energy spectrum diagram of organic three core molybdenum additives manufactured in the present embodiment, due to four in organic three core molybdenum additives
A alkane group is moved freely there are one alkane group in 13 thio ammonium molybdate crystal stereoeffects, and organic structure is not
Disconnected variation, belongs to mixture, therefore cannot determine structure using the organic chemical analysis means such as NMR, LC-ESI-MS, can only adopt
It is analyzed with power spectrum by element ratio, power spectrum result is shown：C, the weight ratio of S, Mo are 58.59:24.33:16.41 atom
Number is than being 83.89:13.05:2.94, meet product requirement Mo:S=3:13, remaining is carbon, hydrogen atom, illustrates that alkyl is fine
Be linked on three core molybdenum skeletons.The atomic ratio of Mo, S and three core molybdenum basic frameworks one disclosed in patent CN105133002B
It causes, it was demonstrated that basic framework is unchanged in reaction process, ensure that the high spatial symmetry of organic three core molybdenum additives and high
Molybdenum content.
The three core molybdenum additives prepared in embodiment 1 are added in full formula I. C. engine oil and are tested, the addition of three core molybdenums
The additive amount of agent is respectively 0wt%, 0.1wt%, 0.3wt% and 0.5wt%, and foreign brand name is used in experiment
The full formula I. C. engine oil of MFSB1000SN10W/40, use four-ball tester testing friction performance (condition of friction test for：
60min long mill experiments, rotating speed：1450rpm), experimental result is as shown in table 1.
Table 1
| Test sample | Maximal friction (N) | Friction coefficient | Wear scar diameter (mm) |
| MFSB 1000 | 4.26 | 0.106 | 0.42 |
| 0.1wt% | 3.119 | 0.073 | 0.316 |
| 0.3wt% | 2.975 | 0.058 | 0.290 |
| 0.5wt% | 2.72 | 0.049 | 0.258 |
From the data in table 1 can be seen that add in embodiment 1 prepare three core molybdenum additives after foreign brand name
The anti-attrition of MFSB1000SN10W/40 I. C. engine oils, abrasion resistance are significantly increased.
Embodiment 2
The preparation method of the present embodiment includes the following steps：
Step 1: the preparation of curing tetraalkyl thiram：Ethyl alcohol and distilled water are pressed 3:1 volume ratio mixing, then
Sodium hydroxide dissolving is added in, the ethanol water for the sodium hydroxide that mass concentration is 5% is obtained after dissolving, measures the hydrogen of 100mL
The ethanol water of sodium oxide molybdena is added in three-necked flask, adds the dioctyl secondary amine of 5mol, then under ice-water bath with
Carbon disulfide is slowly added dropwise in the drop rate of 0.05mL/s, and the wherein molar ratio of dioctyl secondary amine and carbon disulfide is 1.2:1, drop
After adding, constant temperature stirs 2h under conditions of being 30 DEG C in temperature, adds the hydrogen peroxide of 4mL, and isothermal reaction 1h is concentrated in vacuo
After being evaporated, intermediate product curing tetraalkyl thiram is obtained；
Step 2: the preparation of organic three core molybdenum additives crude product：By the 13 of 0.002mol thio ammonium molybdate crystals,
The curing tetraalkyl thiram and the mixed solvent of 20mL obtained in the step of 0.005mol one is placed in three mouthfuls of burnings of 200mL
In bottle, reaction solution is obtained, isothermal reaction 20h under conditions of the reaction solution is 60 DEG C in temperature is described during isothermal reaction
The color of reaction solution is gradually deepened, and finally obtains organic three core molybdenum additives crude product；The mixed solvent is by methanol and tetrahydrochysene furan
It mutters according to 1:1 volume ratio is mixed；
Step 3: the post processing of organic three core molybdenum additives crude product：It is evaporated the organic three core molybdenum addition obtained in step 2
Mixed solvent in agent crude product obtains solids, and the solids is then repeatedly washed with methanol, and filter cake, institute are obtained after filtering
It states after filter cake is dissolved using tetrahydrofuran and continues to stir 2h~3h, after then filtering is evaporated tetrahydrofuran, obtain oily has
Three core molybdenum additives of machine；The pressure for being evaporated the reaction solution is 0.08MPa.
Three core molybdenum additives prepared by embodiment 2 are added in full formula I. C. engine oil and are tested, three core molybdenum additives
Additive amount be respectively 0wt%, 0.1wt%, 0.3wt% and 0.5wt%, in experiment use foreign brand name MFSB1000SN10W/
40 full formula I. C. engine oil, use four-ball tester testing friction performance (condition of friction test for：60min long mill experiments, turn
Speed：1450rpm), experimental result is as shown in table 2：
Table 2
| Test sample | Maximal friction (N) | Friction coefficient | Wear scar diameter (mm) |
| MFSB 1000 | 4.26 | 0.106 | 0.42 |
| 0.1wt% | 3.101 | 0.071 | 0.312 |
| 0.3wt% | 2.987 | 0.057 | 0.289 |
| 0.5wt% | 2.712 | 0.048 | 0.253 |
From the data in table 2 can be seen that add in the present embodiment 2 prepare three core molybdenum additives after foreign brand name
The anti-attrition of MFSB1000SN10W/40 I. C. engine oils, abrasion resistance are significantly increased.
Embodiment 3
The preparation method of the present embodiment includes the following steps：
Step 1: the preparation of curing tetraalkyl thiram：Ethyl alcohol and distilled water are pressed 1:1 volume ratio mixing, then
Sodium hydroxide dissolving is added in, the ethanol water for the sodium hydroxide that mass concentration is 5% is obtained after dissolving, measures the hydrogen of 100mL
The ethanol water of sodium oxide molybdena is added in three-necked flask, double tridecyl amines of 5mol is added, then with 0.05mL/ under ice-water bath
Carbon disulfide is slowly added dropwise in the drop rate of s, wherein the molar ratio of double tridecyl amines and carbon disulfide is 1.5:1, after being added dropwise,
Constant temperature stirs 2h under conditions of being 30 DEG C in temperature, adds the hydrogen peroxide of 6mL, and isothermal reaction 1h after vacuum concentration is evaporated, is obtained
To intermediate product curing tetraalkyl thiram；
Step 2: the preparation of organic three core molybdenum additives crude product：By the 13 of 0.002mol thio ammonium molybdate crystals,
The curing tetraalkyl thiram and the mixed solvent of 20mL obtained in the step of 0.005mol one is placed in three mouthfuls of burnings of 200mL
In bottle, reaction solution is obtained, isothermal reaction 20h under conditions of the reaction solution is 70 DEG C in temperature is described during isothermal reaction
The color of reaction solution is gradually deepened, and finally obtains organic three core molybdenum additives crude product；The mixed solvent is by methanol and tetrahydrochysene furan
It mutters according to 1:1 volume ratio is mixed；
Step 3: the post processing of organic three core molybdenum additives crude product：It is evaporated the organic three core molybdenum addition obtained in step 2
Mixed solvent in agent crude product obtains solids, then washs the solids 3 times with methanol, filter cake is obtained after filtering, described
After filter cake is dissolved using tetrahydrofuran and continue to stir 2h~3h, after then filtering is evaporated tetrahydrofuran, obtain the organic of oily
Three core molybdenum additives；The pressure for being evaporated the reaction solution is 0.09MPa.
Three core molybdenum additives prepared by embodiment 3 are added in full formula I. C. engine oil and are tested, three core molybdenum additives
Additive amount in I. C. engine oil is respectively 0wt%, 0.1wt%, 0.3wt% and 0.5wt%, and foreign brand name is used in experiment
The full formula I. C. engine oil of MFSB1000SN10W/40, use four-ball tester testing friction performance (condition of friction test for：
60min long mill experiments, rotating speed：1450rpm), experimental result is as shown in table 3：
Table 3
| Test sample | Maximal friction (N) | Friction coefficient | Wear scar diameter (mm) |
| MFSB 1000 | 4.26 | 0.106 | 0.42 |
| 0.1wt% | 3.12 | 0.069 | 0.308 |
| 0.3wt% | 3.01 | 0.059 | 0.291 |
| 0.5wt% | 2.73 | 0.050 | 0.255 |
From the data in table 3 can be seen that add in embodiment 3 prepare three core molybdenum additives after foreign brand name
The anti-attrition of MFSB1000SN10W/40 I. C. engine oils, abrasion resistance are significantly increased.
The three core molybdenum additives prepared in 1~embodiment of embodiment 3 and existing double-core organic molybdenum additive MoDTC are produced
The antiwear and reducing friction performance of product is compared, and experiment is with oil using Kelamayi 150SN base oils, four-ball tester frictional behaviour (load：
40kg, rotating speed：145rpm, duration：60min), the three core organic-molybdenums and existing double-core that prepared by 1~embodiment of embodiment 3 are organic
The dosage that molybdenum additives MoDTC products add in 150SN base oils is calculated with identical molybdenum content (0.05wt%), as a result such as
Shown in table 4.
Table 4
It can be seen that in the case of identical molybdenum content from the data in table 4, three core molybdenum additives ratios prepared by the present invention
The anti-attrition of double-core molybdenum additives, abrasion resistance are more superior.
The above is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art substantially makees above example, still fall within technical solution of the present invention
Protection domain in.
Claims (10)
1. a kind of preparation method of organic three core molybdenum additives, which is characterized in that this method includes the following steps：
Step 1: the preparation of curing tetraalkyl thiram：The ethanol water for measuring the sodium hydroxide of 100mL is added to three mouthfuls of burnings
In bottle, dialkyl secondary amine is added, carbon disulfide then is slowly added dropwise under ice-water bath, be 30 DEG C in temperature after being added dropwise
Under conditions of constant temperature stirring 2h, add hydrogen peroxide, isothermal reaction 1h after vacuum concentration is evaporated, obtains intermediate product curing
Tetraalkyl thiram；
Step 2: the preparation of organic three core molybdenum additives crude product：Two sulphur that will be obtained in 13 thio ammonium molybdate crystals, step 1
Change tetraalkyl thiram and mixed solvent to be placed in three-necked flask, obtain reaction solution, the reaction solution temperature for 60 DEG C~
Isothermal reaction 20h under conditions of 70 DEG C, the color of the reaction solution is gradually deepened during isothermal reaction, finally obtains organic three
Core molybdenum additives crude product；The volume of the mixed solvent is 10 times of described 13 thio ammonium molybdate crystal moles, described mixed
The volume unit of bonding solvent is L, and the mole units of 13 thio ammonium molybdate crystals is mol, the mixed solvent by methanol and
Tetrahydrofuran is according to 1:1 volume ratio is mixed；
Step 3: the post processing of organic three core molybdenum additives crude product：It is thick to be evaporated the organic three core molybdenum additives obtained in step 2
Mixed solvent in product obtains solids, and the solids is then repeatedly washed with methanol, and filter cake, the filter are obtained after filtering
After cake is dissolved using tetrahydrofuran and continue to stir 2h~3h, after then filtering is evaporated tetrahydrofuran, obtain organic the three of oily
Core molybdenum additives.
A kind of 2. preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that institute in step 1
The process for preparation for stating the ethanol water of sodium hydroxide is：Ethyl alcohol and distilled water are pressed into (3~1):1 volume ratio mixing, then
Sodium hydroxide dissolving is added in, the ethanol water for the sodium hydroxide that mass concentration is 5% is obtained after dissolving.
3. a kind of preparation method of organic three core molybdenum additives according to claim 2, which is characterized in that the ethyl alcohol with
The volume ratio of distilled water is 2:1.
A kind of 4. preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that institute in step 1
The drop rate for stating carbon disulfide is 0.05mL/s.
A kind of 5. preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that institute in step 1
The alkyl for stating dialkyl secondary amine is C4~C18Straight chain saturated alkyl.
A kind of 6. preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that institute in step 1
The temperature for stating constant temperature stirring is 30 DEG C, and the time of constant temperature stirring is 2h.
A kind of 7. preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that institute in step 1
It is (0.8~1.2) that the addition volume of hydrogen peroxide, which is stated, with the mole ratio of dialkyl secondary amine:1, the addition volume of the hydrogen peroxide
Unit is mL, and the mole unit of the dialkyl secondary amine is mol.
8. a kind of preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that described in step 2
The molar ratio of 13 thio ammonium molybdate crystals and curing tetraalkyl thiram is 1:2.5.
A kind of 9. preparation method of organic three core molybdenum additives according to claim 1, which is characterized in that institute in step 2
The reaction temperature for stating reaction solution is 65 DEG C.
10. the preparation method of a kind of organic three core molybdenum additives according to claim 1, which is characterized in that in step 3
The pressure for being evaporated the reaction solution is 0.08MPa~0.10MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110878A (en) * | 1997-12-12 | 2000-08-29 | Exxon Chemical Patents Inc | Lubricant additives |
| CN1962627A (en) * | 2006-11-21 | 2007-05-16 | 陕西科技大学 | Process for preparing tetraalkyl thiram |
| CN101108819A (en) * | 2007-08-15 | 2008-01-23 | 濮阳市蔚林化工有限公司 | Process for producing vulcanization of rubber accelerant disulfide diisobutyl thiuram |
| CN102812111A (en) * | 2010-03-25 | 2012-12-05 | R.T.范德比尔特公司 | Ultra Low Phosphorus Lubricant Compositions |
-
2017
- 2017-12-30 CN CN201711486108.6A patent/CN108129517A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110878A (en) * | 1997-12-12 | 2000-08-29 | Exxon Chemical Patents Inc | Lubricant additives |
| CN1962627A (en) * | 2006-11-21 | 2007-05-16 | 陕西科技大学 | Process for preparing tetraalkyl thiram |
| CN101108819A (en) * | 2007-08-15 | 2008-01-23 | 濮阳市蔚林化工有限公司 | Process for producing vulcanization of rubber accelerant disulfide diisobutyl thiuram |
| CN102812111A (en) * | 2010-03-25 | 2012-12-05 | R.T.范德比尔特公司 | Ultra Low Phosphorus Lubricant Compositions |
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Application publication date: 20180608 |