CN102382142A - High-sulfur phosphorus-free trinuclear molybdenum compound, its preparation method and application - Google Patents
High-sulfur phosphorus-free trinuclear molybdenum compound, its preparation method and application Download PDFInfo
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- CN102382142A CN102382142A CN2011102710177A CN201110271017A CN102382142A CN 102382142 A CN102382142 A CN 102382142A CN 2011102710177 A CN2011102710177 A CN 2011102710177A CN 201110271017 A CN201110271017 A CN 201110271017A CN 102382142 A CN102382142 A CN 102382142A
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Abstract
The invention discloses a high-sulfur phosphorus-free trinuclear molybdenum compound, its preparation method and an application. The high-sulfur phosphorus-free trinuclear molybdenum compound is Mo3S4(R2NCS2)4, wherein R is C2-C13 straight-chain or branched alkyl groups, R is preferably C4-C8 straight-chain or branched alkyl groups. The two alkyl groups can be the same and also can be different. The preparation method is to perform a reaction among a molybdenum-containing substance, potassium dialkyl dithiocarbamate and potassium sulfite or potassium cyanide so as to obtain the above compound which can be used as a lubricating oil additive. On the basis of common binuclear organic molybdenum, the molybdenum content and the sulfur content can be raised, and the structure contains no phosphorus element. Used in the lubricating oil additive, the high-sulfur phosphorus-free trinuclear molybdenum compound has remarkable performance of reducing friction and enhancing antiwear performance, antioxidation performance of raising fuel economy and oil products and an advantage of prolonging the oil change period of oil products, has an anticorrosion effect, has good addition and cooperative effects with other functional additives, and has good environmental protection benefits and economic benefits.
Description
Technical field
The present invention relates to the without phosphorus type three nuclear molybdenum compounds of a kind of high-sulfur, and its preparation method and its application in oil dope.
Background technology
Organic molybdenum can be used as antioxygen, the antifriction additive of I. C. engine oil, gear oil, railway grease and some technical oilss, and they are " kings of antifriction ", " star of antioxygen ".In the North America, developed country and area widespread uses such as West Europe and Japan, excellent antifriction, the energy-saving and environmental protection performance of these products obtained lubricated industry extensive acclaim and spoken approvingly of.In view of organic-molybdenum in antifriction, wear-resistant, energy-conservation, the effect that reduces aspect such as atmospheric pollution, both at home and abroad the research and development of organic-molybdenum are attached great importance to.The U.S. and the research staff of Japan successively develop multiple organic-molybdenum, are widely used in the multifunction additive in I. C. engine lubricating oil, gear oil, hydraulicefficiency oil, metal processing and the railway grease.
Summary of the invention
One of the object of the invention is to provide a kind of high-sulfur without phosphorus type three nuclear molybdenum compounds, and it is a kind of novel oil-soluble organo-molybdenum compound, can be used as oil dope.
The without phosphorus type three nuclear molybdenum compounds of a kind of high-sulfur provided by the invention, shown in general formula (I): Mo
3S
4(R
2NCS
2)
4Wherein R is C
2-C
13Straight chained alkyl or branched-chain alkyl, two R can be identical, also can be different.Wherein, the preferred C of R
4-C
8Straight chained alkyl or branched-chain alkyl; More preferably C
4Or C
8Straight chained alkyl or branched-chain alkyl.
The structural formula of said formula (I) compound is following:
Wherein, each Mo atom all connects a R
2NCS
2Structure, intermediary S atom also connects this structure.The described qualification of R above.
Another object of the present invention is to provide the preparation method of the without phosphorus type three nuclear molybdenum compounds of a kind of above-mentioned high-sulfur, it is by molybdenum-containing material matter and dialkyldithiocarbamacompositions potassium, and potassium sulfite or Potssium Cyanide react and makes.
Above-mentioned steps obtains is the crude product of the without phosphorus type three nuclear molybdenum compounds of said high-sulfur, and it can be again makes finished product through after ester class oil and alcoholic solvent cleaning, the drying.Used alcoholic solvent particular methanol.
Wherein, said molybdenum-containing material matter is two water, ten trithio amine molybdates, i.e. (NH4)
2Mo
3S
132H
2O.
Wherein, the alkyl in the said dialkyldithiocarbamacompositions potassium is C
2-C
13Straight chained alkyl or branched-chain alkyl, preferred C
4-C
8Straight chained alkyl or branched-chain alkyl; More preferably C
4Or C
8Straight chained alkyl or branched-chain alkyl.
Wherein, the temperature of reaction of said reaction is normal temperature (10-30 a ℃), and the reaction times is 24 hours.
Above-mentioned preparation method more excellently is: said dialkyldithiocarbamacompositions potassium solution is slowly mixed with two water, ten trithio amine molybdate solution, slowly add potassium sulfite solution again, this mixture reacted 24 hours at normal temperatures; Reaction with ester class oil wash, behind the extracting ester class oil, is being used washed with methanol after accomplishing then under nitrogen protection, drying makes finished product under vacuum state at last.
The present invention continues to provide a kind of oil dope, and it contains the without phosphorus type three nuclear molybdenum compounds of the described high-sulfur of general formula (I).Can be used in I. C. engine oil, gear oil, railway grease and some technical oilss, use as antioxygen, antiwear and friction-reducing additive.
The present invention further provides a kind of lubricating oil composition, and it is added with above-mentioned oil dope in lubricating base oil.Described lubricating oil composition can also contain dispersion agent, purification agent, extreme pressure anti-wear additives, antioxidant preservative, friction improver, oxidation inhibitor, tackifier or kilfoam etc., can be one or more.
The without phosphorus type three nuclear molybdenum compounds of said high-sulfur can be used as a kind of additive and are used for the additive preparation compsn, also can be added directly in the lubricating oil product, and it is following that range of application and recommendation add dosage:
Add dosage: 0.2%-0.6% in the I. C. engine oil;
Add dosage: 1%-3% in the railway grease;
Add dosage: 0.2%-1% in automatic transmission fluid, the speed reduction unit oil;
Add dosage: 0.1%-1% in the gear oil (industry and vehicle);
Add dosage: 0.1%-0.2% in the compressor oil;
Add dosage: 0.1%-0.2% in the hydraulicefficiency oil;
Add dosage: 0.1%-0.5% in other oil products.
The present invention was changing the products molecule structure on the basis of comprehensive product performance in the past, most critical be in structure, to improve molybdenum and element sulphur content, and phosphorus element-containing not in the product makes it to have following outstanding performance characteristics:
The first, can improve the lubricating oil antioxidant property greatly.Sulphur (S) element suitable in base oil has natural antioxygen property; The molybdenum that contains in the additive (Mo) element also has good antioxygen property; When the content that in identical product, improves element sulphur and molybdenum element simultaneously, will more strengthen the high-temperature oxidation resistance of lubricating oil undoubtedly.
The second, the antifriction cooling is strengthened in this invention, prolongs the lubricating oil product oil draining period.This type of organic molybdenum additive can significantly reduce friction at surface of friction pair, obviously reduces the working temperature of lubricating oil product.
The 3rd, reduce friction, just mean save energy and improve fuel economy.Repeatedly simulation test and road test show that the without phosphorus type three nuclear molybdenum additives of this type of organic high-sulfur can reach the fuel oil saving effect of 1-5%.
The 4th, additive of the present invention has good corrosion-resisting function, can prevent that oil product from use causing corrosion to machine surface.
The 5th, examples of such additives becomes real environmentfriendly products.Because this type of organic molybdenum additive can improve fuel economy for a long time, thereby reduce the consumption of fuel oil, thereby reduce noxious gas emission; From another point of view, they can prolong the oil product oil draining period, also reduce consumption of petroleum resources; The most outstanding in addition a bit; These type of high-sulfur three nuclear organic molybdenums itself do not contain phosphoric; Their application can reduce in the lubricating oil product additive formulations that other are wear-resistant, the use of antioxygen, antifriction component; Phosphorus content reduces greatly in the lubricating oil product thereby make, and is highly beneficial to ternary catalyzing unit and exhaust emissions.
The 6th, this invention has good additive effect with other functional additive in lubricating oil, has guaranteed the balance in the oil product system.Auxiliary effects such as its dropping point, reduction noise also are improved largely in railway grease.
In a word; The invention has the beneficial effects as follows: on the basis of common double-core organic-molybdenum; Success improves the content of element sulphur and molybdenum element from structure; Making product when improving the antifriction antiwear effect, strengthen antioxygenation again, and have good synergy with other wear-resistant friction reducer and oxidation inhibitor, is a kind of multi-functional lubricating oil product additive.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
In the flask that electronic stirring is installed, drop into dioctyl dithiocarbamic acid potassium (2.12g) and in 50 ml waters and fully, dissolve, slowly add two water, ten trithio ammonium molybdates (0.78g) then, and fully dissolving; In another beaker, with the potassium sulfite formation solution of 50 ml waters dilution, 0.95 gram.Dropwise be added to this potassium sulfite solution the ammonium molybdate/carboxylamine potassium solution of above-mentioned outfit then.This reaction mixture reacted 24 hours at normal temperatures, and the product that obtains filters and extracting ester class oil with the dilution of ester class oil then; Use washed with methanol again three times; Dry and obtain finished product under vacuum state product at last, through this product of RIPP atomic absorption spectrometry, the mass content of each element is following, and: Mo% is 16.0%; S% is 21.1%, and N% is 3.0%; C% is 14.2%, and H% is 4.02%; Through inferring this product structure be: Mo
3S
4[(C
8H
17)
2NCS
2]
4, molecular weight is 1682.4.
Embodiment 2
In the flask that electronic stirring is installed, drop into two (2-ethylhexyl) dithiocarbamic acid potassium (2.12g) and in 50 ml waters and fully, dissolve, slowly add two water, ten trithio ammonium molybdates (0.78g) then, and fully dissolving; In another beaker, with the Potssium Cyanide formation solution of 50 ml waters dilution, 0.40 gram.Dropwise be added to this potassium cyanide solution the ammonium molybdate/carboxylamine potassium solution of above-mentioned outfit then.This reaction mixture reacted 24 hours at normal temperatures, obtained product with the dilution of ester class oil, filtered then and extracting ester class oil; Use washed with methanol again three times, dry and obtain finished product under vacuum state product at last, through this product of RIPP atomic absorption spectrometry; Each element mass content is following: Mo% is 16.0%, and S% is 21.2%, and N% is 3.1%; C% is 14.2%, and H% is 4.02%; Through inferring this product structure is Mo
3S
4[(C
8H
17)
2NCS
2]
4, molecular weight is 1682.4.
Embodiment 3
Basically with embodiment 1, different is that used dialkyldithiocarbamacompositions potassium is potassium dibutyldithiocarbamate (weight: 1.50 grams).Finally obtain product and be (2.12g).Through this product of RIPP atomic absorption spectrometry, each element mass content is following: Mo% is 22.5%, and S% is 30.8%, and N% is 4.52%, and C% is 11.2%, and H% is 5.82%; Through inferring this product structure is Mo
3S
4[(C
4H
9)
2NCS
2]
4, molecular weight is 1233.6.
Following product data and test the without phosphorus type of used high-sulfur three nuclear molybdenum compounds and made by embodiment 1 are represented with POUPC8002.
The materialization data see the following form:
Wherein, RIPP is a petroleum science research institute measured center use test method; GB/T2540 is the petroleum products densitometry, and GB/T265 is a petroleum products kinematic viscosity assay method, and GB/T3536 is a petroleum products flashing test method.
Without phosphorus type three tests of nuclear molybdenum compound in the full formula I. C. engine oil of Test Example 1 high-sulfur
Four-ball tester frictional behaviour (the long mill experiment of 60min, rotating speed: 1450rpm)
Test oil CF-415W/40 full formula: 400SN 20%; 150SN 50%; 150BS10%; PPT148 0.5%; HITEC1275 8.2%; SV260 11.3%.
Test-results sees the following form:
See that from above data antifriction, the abrasion resistance of oil product can be significantly improved behind the adding POUPC8002.
The antiwear and friction reduction property simultaneous test of Test Example 2 and double-core organic-molybdenum MoDTC
Test oil: Dalian 150SN base oil, four-ball tester frictional behaviour (load: 40kg, rotating speed: 1450rpm, the long mill experiment of duration: 60min); Product of the present invention calculates with identical molybdenum content (Mo% is 0.05w%) with the dosage that adds of double-core organic-molybdenum MoDTC.
Wherein, double-core organic-molybdenum MoDTC is a molybdenum dithiocarbamate.
Test-results sees the following form:
Find out that from test under the condition of identical molybdenum content, three nuclear organic molybdenums have more excellent anti-wear and wear-resistant performance than double-core organic molybdenum.
Test Example 3 anticorrosive, corrosion performance tests
Test oil: Dalian 150SN base oil, test-results sees the following form:
Can find out that from last table this product has good preservative property, corrosion function.
Test Example 4 oxidation resistance tests
Use DSC: the differential scanning method
Test oil: Dalian 150SN base oil, test-results such as following table:
Can find out that from last table this three nuclear molybdenum compound can effectively improve the antioxidant property of oil product.
The Synergism Testing of Test Example 5 and zinc dialkyl dithiophosphate (ZDDP)
Test oil: Dalian 150SN base oil, four ball frictional testing machiness (load: 35kg, rotating speed: 1450rpm; The long mill experiment of duration: 60min), test-results sees the following form:
Find out that from last table this three nuclear molybdenum compound has good synergy with conventional wear-resistant oxidation inhibitor ZDDP.
Can draw from above test: the lubricating oil product working temperature can effectively be reduced friction, reduced to the without phosphorus three nuclear molybdenum compounds of the organic high-sulfur of oil soluble of the present invention the use of lubricating oil product; Improve fuel economy; Strengthen wear-resistant protection, reduce mechanical wear and maintenance; Strengthen the oil product oxidation-resistance simultaneously, reduce and suppress acidic substance producing, thereby prolonged the oil draining period.And the without phosphorus three nuclear molybdenum compounds of the organic high-sulfur of this oil soluble are not phosphorous, and are more favourable to exhaust emissions, thereby are a kind of outstanding energy-saving and environmental protection products.
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. the without phosphorus type three nuclear molybdenum compounds of high-sulfur is characterized in that, shown in general formula (I): Mo
3S
4(R
2NCS
2)
4Wherein R is C
2-C
13Straight chained alkyl or branched-chain alkyl.
2. the without phosphorus type three nuclear molybdenum compounds of high-sulfur as claimed in claim 1 is characterized in that said R is C
4-C
8Straight chained alkyl or branched-chain alkyl.
3. the preparation method of the without phosphorus type of claim 1 or 2 described high-sulfurs three nuclear molybdenum compounds is characterized in that it is by molybdenum-containing material matter and dialkyldithiocarbamacompositions potassium, and potassium sulfite or Potssium Cyanide react and makes.
4. preparation method as claimed in claim 3 is characterized in that, said molybdenum-containing material matter is two water, ten trithio amine molybdates; Alkyl in the said dialkyldithiocarbamacompositions potassium is straight chained alkyl or the branched-chain alkyl of C2-C13.
5. preparation method as claimed in claim 4 is characterized in that, the dialkyldithiocarbamacompositions potassium solution is mixed with two water, ten trithio amine molybdate solution, adds potassium sulfite solution again, and this mixture reacted 24 hours down at 10-30 ℃; Reaction with ester class oil wash, behind the extracting ester class oil, is used washed with methanol after accomplishing then again under nitrogen protection, final drying makes finished product; Alkyl in the said dialkyldithiocarbamacompositions potassium is C
2-C
13Straight chained alkyl or branched-chain alkyl.
6. preparation method as claimed in claim 5 is characterized in that, the alkyl in the said dialkyldithiocarbamacompositions potassium is C
4-C
8Straight chained alkyl or branched-chain alkyl.
7. an oil dope is characterized in that, contains the without phosphorus type three nuclear molybdenum compounds of claim 1 or 2 described high-sulfurs.
8. a lubricating oil composition is characterized in that, in lubricating base oil, is added with the described oil dope of claim 7.
9. lubricating oil composition as claimed in claim 8 is characterized in that, also contains in dispersion agent, purification agent, extreme pressure anti-wear additives, antioxidant preservative, friction improver, oxidation inhibitor, tackifier or the kilfoam one or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523377A (en) * | 2017-08-17 | 2017-12-29 | 广州玮弘祺生物科技有限公司 | A kind of environment-friendly water-based cutting fluid and preparation method thereof of floorboard with high oil content, high anti-friction performance |
| CN112175690A (en) * | 2020-09-01 | 2021-01-05 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107523377A (en) * | 2017-08-17 | 2017-12-29 | 广州玮弘祺生物科技有限公司 | A kind of environment-friendly water-based cutting fluid and preparation method thereof of floorboard with high oil content, high anti-friction performance |
| CN112175690A (en) * | 2020-09-01 | 2021-01-05 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
| CN112175690B (en) * | 2020-09-01 | 2022-04-12 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
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Application publication date: 20120321 |