CN1184295C - Organic compound containing Mo, Zn and Cu used as additive of lubricating oil and its application - Google Patents
Organic compound containing Mo, Zn and Cu used as additive of lubricating oil and its application Download PDFInfo
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- CN1184295C CN1184295C CNB001343270A CN00134327A CN1184295C CN 1184295 C CN1184295 C CN 1184295C CN B001343270 A CNB001343270 A CN B001343270A CN 00134327 A CN00134327 A CN 00134327A CN 1184295 C CN1184295 C CN 1184295C
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- dithiophosphate
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Abstract
The present invention relates to a lubricating oil additive containing molybdenum organic compounds, zinc organic compounds and copper organic compounds, which mainly contains sulfurized molybdenum dialkyl bithiophosphate, zinc dialkyl bithiophosphate and copper dialkyl bithiophosphate as active components. The active components are obtained in the same synthesis reaction, and the yield can be enhanced by 3%; H2S generated in the sulfur phosphorizing reaction, and H2S generated by P2S5 residue reacting with water in the last sulfur phosphorizing reaction are introduced in the metallization reaction to used as a reducing agent; therefore, the lubricating oil additive has the advantages of energy saving, low product cost and reasonable technique. When 0.6 to 1.0% of lubricating oil additive of the present invention is added into internal combustion engine oil, the P<B> of the internal combustion engine oil is enhanced by one time, and D30 kg<60 min>(75DEG C) is reduced by 50 to 60%.
Description
Technical field
The present invention relates to a kind of lubricating oil additive and application thereof that contains molybdenum, copper, zinc organic compound.
Background technology
The lubricating oil antiwear and friction-reducing additive has experienced by inorganic antifriction and antiwear agents, ashless oil soluble low friction compound, develops into the antifriction and antiwear agents of present oil soluble organometallic compound, and it has both preceding two class antifriction and antiwear agents advantages.The molten molybdenum of oil is exactly a wherein noticeable big class antifriction and antiwear agents, obtained develop rapidly especially in developed country, and China in the last few years, and institution of higher learning and R﹠D institution also develop, developed series product, and the beginning industrialization.Some products and application thereof are all disclosed as CN88102769A, CN1147540A.In order to bring into play its anti-wear and wear-resistant performance better, and expectation has both antioxygen, performance such as antirust, again with some additives carry out composite, as ZL92100282.3 disclosed in machine oil, add oil-soluble organic molybdenum, tungsten after dynamic property improve, power averaging increases by 3.4%, average rate of economizing gasoline 4.4%.But, be used for each single-activity organometallics that mixed preparing has multiple performance, generally all synthetic one by one, certainly will influence the metal-organic yield of single-activity like this, make the products production cost higher etc.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, and provide a kind of in same building-up reactions, can obtain the active substance and the application of molybdenum, zinc, copper organic compound simultaneously.
The present invention also aims to provide a kind of rational synthesis technique, reduce the alkali consumption of 80% absorbing hydrogen sulphide and operating process thereof etc.
A kind of lubricating oil additive that contains molybdenum, zinc, copper organic compound is characterized in that this additive is made up of following compound:
A) sulfuration molybdenum dialkyl-dithiophosphate, its chemical formula is [(RO)
2P (S) S]
2Mo
2(S)
2S
2
B) sulfuration molybdenum dialkyl-dithiophosphate dimer, its chemical formula is [(RO)
2P (S) S]
4Mo
2(S)
2S;
C) zinc dialkyl dithiophosphate [(RO)
2P (S) S]
2Zn;
D) dialkyl dithiophosphoric acid copper [(RO)
2P (S) S]
2Cu;
E) dialkyl dithiophosphate [(RO)]
2P (S) SH.
R is C in the formula
2-C
16Positive alkyl, iso-alkyl are as ethyl, propyl group, butyl, amyl group, base, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl; Isobutyl-, isopentyl, different heptyl, iso-octyl, different nonyl, isodecyl, different undecyl, Permethyl 99A. base, isotridecyl, different tetradecyl, different pentadecyl, isocetyl.
Above-mentioned additive adopts following method to make:
(1) with 1.05 moles P
2S
5At N
2Protect monohydroxy (C following and 4.0 moles
2-C
16Positive alkyl, iso-alkyl) pure hybrid reaction, make dialkyl dithiophosphate.
(2) 0.4 mole Sodium orthomolybdate is dissolved in 500 ml waters, adds 0.62 mol sulfuric acid, add 0.22 mole of zinc powder, 0.4 mole of cupric oxide again, simultaneously with the hydrogen sulfide of step (1) sulfur phosphatization reaction, the P of reaction
2S
5The hydrogen sulfide that residue and water effect generate imports wherein, and controlled temperature 80-85 ℃ of reaction added the thiophosphatephosphorothioate that makes in (a) after 1.5 hours, heats up and in 90-95 ℃ of reaction 2 hours.The sherwood oil of weight such as cooling back and product mixes, and standing demix collection organic phase is used the salt water washing, abandons water, vacuum desolventizing, makes the purpose product.
Molybdenum, zinc, the shared parts by weight of copper organic compound are respectively in the above-mentioned additive:
A) the sulfuration molybdenum dialkyl-dithiophosphate is 5 parts
B) sulfuration molybdenum dialkyl-dithiophosphate dimer is 17 parts
C) zinc dialkyl dithiophosphate is 30 parts
D) dialkyl dithiophosphoric acid copper is 28 parts
E) dialkyl dithiophosphate is 20 parts
Aforesaid Application of Additives is characterized in that the weight percent that this additive adds in I. C. engine oil or the hydraulic efficiency oil is 0.6-1.0%.
The present invention has following advantage:
1, molybdenum, zinc, the copper organic compound lubricating oil additive of containing of the present invention owing to obtain containing aforementioned molybdenum, zinc, copper compound simultaneously in same building-up reactions, compared with single variety is synthetic, and yield can improve 3%, and use properties exceeds 5% approximately.
2, additive provided by the invention has excellent extreme pressure property, resistance to abrasion, antifriction quality, oxidation-resistance etc., and non-corrosiveness is applied in I. C. engine oil, the hydraulic efficiency oil simultaneously, with oxidation and corrosion inhibitor and the composite use of other oxidation inhibitor, also has the antioxygen synergism.
3, because simultaneously with the hydrogen sulfide of step (1) sulfur phosphatization reaction, the P of reaction
2S
5The hydrogen sulfide that residue and water effect generate imports metallization reaction directly as reductive agent, makes synthesis technique more reasonable.Thereby can save alkali and sulfuric acid consumption, anti-secondary pollution further reduces production costs in advance.
4, in I. C. engine oil, hydraulic pressure wet goods lubricating oil, only add the additive of the present invention that weight percent is 0.6-1.0%, significant extreme pressure, wear-resistant, antifriction, effect such as anti-oxidant can be arranged.
Now, further specify as follows with a kind of preparation process lubricant oil additive that contains molybdenum, zinc, copper organic compound of the present invention:
(1) 1.05 mole P
2S
5At N
2Join in 4.0 moles of isooctyl alcohol under the protection, reaction made two-iso-octyl-phosphorodithioate in 2 hours under 90-95 ℃.
(2) 0.4 mole Sodium orthomolybdate is dissolved in 500 ml waters, adds 0.62 mol sulfuric acid, 0.22 mole of zinc powder, 0.4 mole of cupric oxide, simultaneously with the hydrogen sulfide of step (1) sulfur phosphatization reaction, the P of reaction
2S
5The hydrogen sulfide that residue and water effect generate imports wherein,, after 1.5 hours the above-mentioned thiophosphatephosphorothioate that makes is added wherein in 80-85 ℃ of reaction, and controlled temperature is 90-95 ℃, reacts 2 hours.Sherwood oil thorough mixing with weight such as product cooling back and products, standing demix is collected organic phase, removes solvent under the vacuum, makes brown or green viscous liquid---purpose product of the present invention, that is: vulcanize molybdenum dialkyl-dithiophosphate, its chemical formula is [(RO)
2P (S) S]
2Mo
2(S)
2S
2, sulfuration molybdenum dialkyl-dithiophosphate dimer, its chemical formula is [(RO)
2P (S) S]
4Mo
2(S)
2S.The former structure formula is
Latter's structural formula is
With zinc dialkyl dithiophosphate, dialkyl dithiophosphoric acid copper, dialkyl dithiophosphate, they are in additive of the present invention, and shared parts by weight are respectively 5 parts, 17 parts, 30 parts, 28 parts and 20 parts.
(3) application experiment (four-ball tester experiment)
Press the GB/T12583-90 standard, measure last non seizure load P
B, long term wear value D
60min 30kg(75 ℃).Base oil oil (HVI150 6,0%+,HV1,500 40%) (to call base oil in the following text) adds 0.8% molybdenum, zinc, the copper organic compound lubricating oil additive of containing of the present invention, through tetra-ball machine test, than former base oil (not adding additive of the present invention) P
BDouble many, D
60min 30kg(75 ℃) reduce 50-60%.
Below in conjunction with embodiment and application examples, the present invention is further described:
One, embodiment
1, sulfur phosphatization reaction:
In 1 liter four-hole boiling flask of a configuration agitator, thermometer, airway and reflux condensing tube, add isooctyl alcohol 520 grams (4mol), stir and feed N down
2, with the P of 233.4 grams (1.05mol)
2S
5Add wherein in batches, avoid temperature rise too fast, and be no more than 95 ℃, be warming up to 90-95 ℃ gradually, reacted 2 hours, after reaction finishes, continue to feed a large amount of N
2The hydrogen sulfide that is dissolved in the product is blown out; The hydrogen sulfide that produces in the reaction imports in the metallization reaction directly as the partial reduction agent through prolong; The P that last step sulfur phosphatization reaction leaches
2S
5Residue, with 100 ml waters in 60-70 ℃ of reaction 2 hours, the hydrogen sulfide of generation also imports in the metallization reaction, with aforesaid hydrogen sulfide as reductive agent.
2, metallization reaction
In 1 liter of there-necked flask of configuration agitator, thermometer and a reflux exchanger, add 500 ml waters, Sodium orthomolybdate, 60.76 gram (0.62mol) sulfuric acid, 14.3 gram (0.22mol) zinc powders of adding 96.78 grams (0.4mol) again, reacted 20 minutes, add 32 gram (0.4mol) cupric oxide, import the hydrogen sulfide of the sulfur phosphatization reaction of above-mentioned steps (1), the P of reaction simultaneously
2S
5The hydrogen sulfide that residue and water effect generate, controlled temperature is 80-85 ℃, reacts after 1.5 hours, adds the front sulfur phosphatization reaction and makes two-iso-octyl-phosphorodithioate, is warming up to 90 ℃, controlled temperature is 90-95 ℃ and reacted 2 hours down.With standing demix behind the sherwood oil thorough mixing of weight such as product cooling back and product, add equal-volume salt solution washed twice after removing lower floor's water, divide the phase of anhydrating, behind the vacuum desolventizing, just obtain brown or green viscous liquid, i.e. purpose product, in weight part:
5 parts of sulfuration two-iso-octyl-molybdenum dithiophosphate
17 parts of sulfuration two-iso-octyl-molybdenum dithiophosphate dimer
30 parts of two-iso-octyl-zinc dithiophosphate
28 parts of two-iso-octyl-monothio cupric phosphate
20 parts of two-iso-octyl-phosphorodithioate
The technical indicator of the above-mentioned additive of producing after the enforcement technical solution of the present invention is described as follows:
| Project | Index | Analytical procedure |
| Outward appearance | Brown or green viscous liquid | Range estimation |
| Molybdenum content (%) | 2.5 | The n-butyl acetate extraction spectrophotometry |
| Sulphur content (%) | 15 | SH/T0303 |
| Phosphorus content (%) | 7 | SH/T0296 |
| Zinc content (%) | 3 | Hot borane reagent colorimetry |
| Copper content (%) | 2.2 | Potassiumiodide-Sulfothiorine volumetry |
| Moisture content (%) | 0.08 | GB/T260 |
| Mechanical impurity (%) | 0.06 | GB/T511 |
| Flash-point (opening) ℃ | Be not less than 150 | SH/T0318 |
| Mineral content (%) | 10 |
3, application test
On the MRS-10 type four ball frictional testing machiness that trier factory in Jinan produces, be that the 12.7mm steel ball be the ball that rubs with the diameter of phi of Shanghai Steel Ball Plant, press the GB/T12583-90 standard, the speed of mainshaft is 1500r/min, normal temperature time mensuration last non seizure load P
BThe speed of mainshaft is 1200r/min, and axial load is 30kg, and 75 ℃ are moved 60min down, measure long term wear value D
60min 30kg(75 ℃) see the following form with the antioxygen experimental result.Base oil (HVI150 6,0%+,HVI,500 40%) (to call base oil in the following text)
| Project | Base oil+0.8% additive of the present invention | Base oil |
| Four-ball tester experiment PB (kg) D 60min 30kg(75℃)(mm) | 82 0.35 | 40 0.71 |
| Antioxygen experiment rotary oxygen bomb method (min) | 175 |
Additive of the present invention dissolves in mineral oil, synthetic oil but must be after the compatibleness of the solvability in confirming used base oil and other additives, the additive of the present invention that adds weight percent and be 0.6-1.0% in lubricating oil can demonstrate positively effect, but add-on was less than 0.6% o'clock, act on not obvious, when add-on surpassed 1.0%, then lubricity descended.
Claims (2)
1, a kind of molybdenum, copper, zinc organic compound lubricating oil additive of containing is characterized in that this additive is made up of following compound:
1) sulfuration molybdenum dialkyl-dithiophosphate, its chemical formula is [(RO)
2P (S) S]
2Mo
2(S)
2S
2
2) sulfuration molybdenum dialkyl-dithiophosphate dimer, its chemical formula is [(RO)
2P (S) S]
4Mo
2(S)
2S
3) zinc dialkyl dithiophosphate, its chemical formula are [(RO)
2P (S) S]
2Zn
4) dialkyl dithiophosphoric acid copper, its chemical formula are [(RO)
2P (S) S]
2Cu
5) dialkyl dithiophosphate, its chemical formula are [(RO)]
2P (S) SH
R is C in the formula
2-C
16The positive alkyl of g, iso-alkyl;
Above-mentioned additive adopts following method to make:
A) with 1.05 moles P
2S
5At N
2Protect monohydroxy (C following and 4.0 moles
2-C
16Positive alkyl, iso-alkyl) pure hybrid reaction, make dialkyl dithiophosphate,
B) 0.4 mole Sodium orthomolybdate is dissolved in 500 ml waters, adds 0.62 mol sulfuric acid, add 0.22 mole of zinc powder, 0.4 mole of cupric oxide again, simultaneously with the hydrogen sulfide of step (a) sulfur phosphatization reaction, the P of reaction
2S
5The hydrogen sulfide that residue and water effect generate imports wherein, and controlled temperature 80-85 ℃ of reaction added the thiophosphatephosphorothioate that makes in (a) after 1.5 hours, heats up and in 90-95 ℃ of reaction 2 hours.The sherwood oil of weight such as cooling back and product mixes, and standing demix collection organic phase is used the salt water washing, abandons water, vacuum desolventizing, makes the purpose product.
2, the described Application of Additives of a kind of claim 1 is characterized in that the weight percent that this additive adds in I. C. engine oil or the hydraulic efficiency oil is 0.6-1.0%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001343270A CN1184295C (en) | 2000-12-19 | 2000-12-19 | Organic compound containing Mo, Zn and Cu used as additive of lubricating oil and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001343270A CN1184295C (en) | 2000-12-19 | 2000-12-19 | Organic compound containing Mo, Zn and Cu used as additive of lubricating oil and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1360014A CN1360014A (en) | 2002-07-24 |
| CN1184295C true CN1184295C (en) | 2005-01-12 |
Family
ID=4596160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001343270A Expired - Fee Related CN1184295C (en) | 2000-12-19 | 2000-12-19 | Organic compound containing Mo, Zn and Cu used as additive of lubricating oil and its application |
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| Country | Link |
|---|---|
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| CN110257131B (en) * | 2019-07-10 | 2022-02-18 | 新乡市瑞丰新材料股份有限公司 | Additive for improving extreme pressure wear resistance of lubricating grease and preparation method thereof |
| CN112296345B (en) * | 2019-07-23 | 2022-02-18 | 富兰克科技（深圳）股份有限公司 | Preparation method of self-dispersible nano-copper with long organic carbon chain, nano-copper preparation and application thereof |
| CN110776976A (en) * | 2019-11-07 | 2020-02-11 | 重庆昆崧科技有限公司 | Preparation method of lubricating oil extreme pressure antiwear agent |
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| Publication number | Publication date |
|---|---|
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