CN1281727C - Extreme pressure wear resistance additive of double alkoxy monosulfur phosphorus triazine derivative and its preparing method - Google Patents
Extreme pressure wear resistance additive of double alkoxy monosulfur phosphorus triazine derivative and its preparing method Download PDFInfo
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- CN1281727C CN1281727C CN 200410099191 CN200410099191A CN1281727C CN 1281727 C CN1281727 C CN 1281727C CN 200410099191 CN200410099191 CN 200410099191 CN 200410099191 A CN200410099191 A CN 200410099191A CN 1281727 C CN1281727 C CN 1281727C
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- alkoxy
- triazine
- triazine derivative
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Abstract
The present invention relates to a dialkoxy monothio phosphotriazine derivative limit pressure antiwear additive and a preparation method thereof. The dialkoxy monothio phosphotriazine derivative limit pressure antiwear additive has the chemical structure of a general formula (I), wherein R1, R2, R3 and R4 are the same or different linear chains or alkyl groups of C1 to C 20. Dialkyl phosphorodithioate or dialkyl dithiophosphate and 2, 4-double-(dialkyl amidogroup)-6-chlorine-1, 3, 5-sym-triazine are used for a chemical reaction for synthesis. The synthesis technology of the present invention has mild conditions, and the cost of synthesis is low. Dialkoxy monothio phosphotriazine derivatives synthesized by the present invention can be compounded with other lubricant additives as well as singly used as multifunctional lubricant additives, and simultaneously have the performance of corrosion resistance, antioxidation, etc. as well as the favorable performance of abrasion resistance and limit pressure resistance.
Description
Technical field: the present invention relates to a kind of lubricating oil and grease additive and preparation method thereof, particularly a kind of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-wear lubricating grease additive and preparation method thereof.
Background technology: well-known, zinc dialkyl dithiophosphate (ZDDP) is a very effective multifunctional lubricant fat additives commonly used on a kind of modern industry, but the zinc salt that wherein contains is easy to generate galvanic corrosion, thereby has limited its use.
Element such as S, P is the excellent activity element that improves lubricant extreme pressure, wear-resistant, antifriction performance, but misapplication has the defective of excessive corrosion wearing and tearing.
Nitrogen heterocyclic ring and derivative thereof are the lubricating oil and grease additives of a class excellent property, have good anticorrosively, and anti-oxidation metal causes function such as blunt dose, and in general, heterocyclic moiety costs an arm and a leg, and has also limited its application.
Three chlorotriazines are industrial goods of a kind of cheapness, and three chlorotriazines contain three reactive chlorine, can introduce three identical or different activities functional groups, make it reach requirement.
EP320450 has introduced the pyrrolotriazine derivatives of a kind of S of containing, has good anti-oxidant, corrosion resistance.US5512189 has introduced a class and has contained compound and the derivative thereof that thiophosphatephosphorothioate and alcohol compound form, and has a good wear-resistant and resistance of oxidation.But its extreme pressure ability is not thoroughly discussed.
US1087029 has introduced the synthetic of a kind of pyrrolotriazine derivatives that contains amino short chain thiophosphatephosphorothioate, and products therefrom is applied to weedicide and sterilant, but its building-up process complexity.
Summary of the invention: the object of the present invention is to provide the triazine phosphate derivative of a kind of C-O-C-N of containing and P-S-C-N chemical bond, this compound has good extreme pressure and antiwear behavior and corrosion resistance.Another object of the present invention provides the method for simple synthetic above-claimed cpd, its processing condition gentleness, and synthetic cost is low.
The chemical name of a class bis-alkoxy list sulphur phosphorus triazine derivative of the present invention is 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3, and the 5-s-triazine, its chemical structure is as shown in the formula shown in (I):
R in the formula
1, R
2, R
3, R
4Be identical or different C
1～C
20The straight or branched alkyl.
The concrete preparation method of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive of the present invention is as follows:
In the three-necked bottle that agitator and prolong are housed, add 2,4-bis-alkoxy-6-chloro-1,3,5-s-triazine and reaction medium drip acid binding agent then, drip dialkyl dithiophosphate or salt at last; 2,4-bis-alkoxy-6-chloro-1,3, the mol ratio of 5-s-triazine and dialkyl dithiophosphate or salt is 1: 0.8～1.2; Dialkyl dithiophosphate or salt (mol): reaction medium (ml) is 1: 50～5000; Dialkyl dithiophosphate or salt (mol): acid binding agent (mol) is 1: 1.0～1.2; ℃ following reaction is 2～12 hours in normal temperature～150; Suction filtration removes and desalts, filtrate washing, anhydrous sodium sulfate drying; Filter, filtrate decompression is steamed and is desolventized, and gets light yellow viscous liquid, is bis-alkoxy list sulphur phosphorus triazine derivative.
2 of the present invention's use, 4-bis-alkoxy-6-chloro-1,3, the 5-s-triazine has the chemical structure of following general formula (II),
R in the formula
1, R
2Be identical or different C
1～C
20The straight or branched alkyl.
Dialkyl dithiophosphate or salt that the present invention uses have the chemical structure of following general formula (III),
R in the formula
3, R
4Be identical or different C
1～C
20The straight or branched alkyl, M is alkalimetal ion, NH
4 +Or quaternary ammonium ion.
The reaction medium that the present invention uses is water, acetone, benzene, toluene, chloroform, ethyl acetate, N, dinethylformamide, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO) or C
1-C
8Fatty Alcohol(C12-C14 and C12-C18).
The acid binding agent that the present invention uses is sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, triethylamine, Trimethylamine 99, pyridine, 2,4,6-trimethylpyridine, 3-picoline, N, accelerine or N, N-Diethyl Aniline.
Of the present invention 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3, the 5-s-triazine can use separately, also can add in the lubricating greases such as mineral oil, synthetic oil, vegetables oil, lithium saponify, calcium grease and use, and can obtain the lubricating system of good wear-resistant, extreme pressure property, also have simultaneously anticorrosive, oxidation resistant ability.
Of the present invention 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3, the addition of 5-s-triazine in lubricating grease is 0.1wt%～15.0wt%.
Of the present invention 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3,5-s-triazine also can with the compound use of other lubricating oil and grease additive, can reach the synergy synergy.
Of the present invention 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3, the synthetic technological condition gentleness of 5-s-triazine, synthetic cost is low.Obtain 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3,5-s-triazine add to and have good extreme-pressure anti-wear, antioxidant property in the lubricating grease.
Description of drawings:
Accompanying drawing 1 is a compound 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1,3 of 4-, infrared (IR) spectrogram of 5-s-triazine
Accompanying drawing 2 is a compound 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1,3 of 4-, the nucleus magnetic resonance of 5-s-triazine (
1H NMR) spectrogram
Accompanying drawing 3 is a compound 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1,3 of 4-, the thermogravimetric analysis figure (TGA) of 5-s-triazine
Embodiment:
In order to understand technical scheme of the present invention better, below describe in further detail by specific embodiment.
Embodiment 1:
With 2 of 26.0g, the two n-butoxies of 4--6-chloro-1,3, join in the 300ml benzole soln under 5-s-triazine (0.1mol) room temperature, add the 15ml triethylamine under the room temperature again, stir and drip 0.1mol O down lentamente, O '-di-n-butyl phosphorodithioate, behind the reaction 2h, be warming up to 80 ℃ of following backflow 4h again under the room temperature, be cooled to room temperature.Suction filtration washes that three times (3 * 100ml), benzene is washed secondary (2 * 50ml), anhydrous sodium sulfate drying filters, and filtrate decompression is steamed and desolventized, promptly get faint yellow thickness oily matter 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1 of 4-, 3,5-s-triazine 26.4g, productive rate be 56.8% (with 2, the two n-butoxies of 4--6-chloro-1,3, the 5-s-triazine is a benchmark).With infrared (IR) and nucleus magnetic resonance (
1H NMR) and thermogravimetric analysis, its analytical results is as follows:
Accompanying drawing is 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1,3 of 4-, and infrared (IR) spectrogram of 5-s-triazine can draw: IR (KBr) 2960.86,2929.73, the strong absorption peak at 2875.24cm-1 place is alkyl (CH
3,-CH
2-) absorption peak, strong absorption peak at the 1563.68cm-1 place is the charateristic avsorption band of the two keys of triazine ring C=N, 968.22cm-1 strong absorption peak be the vibration peak of P-O-C, 824.22cm-1 the strong absorption peak of locating is the vibration peak of P=S, 528.43cm-1 the absorption peak of locating is the vibration peak of S-P, absorption peak at 1415.78cm-1 is the vibration peak of C-O-C, is the vibration peak of N-C-S at the absorption peak of 660.76cm-1.
Accompanying drawing is 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1,3 of 4-, the nucleus magnetic resonance of 5-s-triazine (
1H NMR) spectrogram can draw:
1H NMR (CDCl
3, 400MHz) δ (CDCl
3): 0.833～1.135 (m, 12H, 4CH
3), 1.421～1.182 (m, 8H, 4CH
2), 1.732～1.543 (m, 8H, 4CH
2), 2.796,3.462 (m, 2H, 2SPSOCH
2), 3.940～4.241 (m, 4H, 20CH
2)
Accompanying drawing is 2, the two n-butoxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1 of 4-, 3, the thermogravimetric analysis figure (TGA) of 5-s-triazine can draw: the temperature of initial decomposition of compound is 204.62 ℃, illustrate that product has thermal stability preferably, can be used as lubricating oil and grease additive.
Embodiment 2:
With 2 of 26.0g, the two isobutoxies of 4--6-chloro-1,3, join in the 300ml benzole soln under 5-s-triazine (0.1mol) room temperature, add the 15ml triethylamine under the room temperature again, under agitation drip 0.1mol O lentamente, O '-diisobutyl phosphorodithioate, behind the reaction 2h, be warming up to 80 ℃ of following backflow 6h under the room temperature, be cooled to room temperature.Suction filtration washes that three times (3 * 100ml), benzene is washed secondary (2 * 50ml), anhydrous sodium sulfate drying filters, and filtrate decompression is steamed and desolventized, promptly get faint yellow thickness oily matter 2, the two isobutoxy-6-(O, O '-diisobutyl phosphorodithioic acid ester group)-1 of 4-, 3,5-s-triazine 20.1g, productive rate be 43.2% (with 2, the two isobutoxies of 4--6-chloro-1,3, the 5-s-triazine is a benchmark).
Embodiment 3:
With 2 of 25.8g, 4-pair-n-octyloxy-6-chloro-1,3, join in the benzole soln of 300ml under 5-s-triazine (0.1mol) room temperature, add the 15ml triethylamine under the stirring at room, drip 0.1mol O then lentamente, O '-di-n-butyl phosphorodithioate, behind the reaction 2h, be warming up to 80 ℃ of following backflow 5h under the room temperature, be cooled to room temperature.Suction filtration washes that three times (3 * 100ml), benzene is washed secondary (2 * 50ml), anhydrous sodium sulfate drying filters, and filtrate decompression is steamed and desolventized, promptly get faint yellow thickness oily matter 2, the two n-octyloxy-6-(O, O '-di-n-butyl phosphorodithioic acid ester group)-1 of 4-, 3,5-s-triazine 18.6g, productive rate be 32.1% (with 2, the two n-octyloxies of 4--6-chloro-1,3, the 5-s-triazine is a benchmark).
The C of the compound that obtains in the above-mentioned example, H, N, S results of elemental analyses are as shown in table 1, results of elemental analyses as can be known from table 1, the measured value of the C of all target compounds, H, N element and the theoretical value of calculating by molecular formula meet the requirement of lubricating oil additive basically, and absolute error is in allowed band.Can determine that the gained compound is a target compound.
Table 1: the results of elemental analyses of various examples (in the bracket is calculated value)
| Embodiment | ％C | ％H | ％N | ％S | ％ |
| 1 2 3 | 49.98(49.01) 50.45(49.01) 57.05(56.15) | 8.34(7.80) 8.14(7.80) 9.27(9.01) | 9.75(9.03) 8.61(9.03) 6.15(7.28) | 12.87(13.75) 13.72(13.75) 11.38(11.92) | 6.47(6.66) 7.07(6.66) 5.66(5.37) |
The performance evaluation of target compound:
According to the GB3142-82 standard, to commodity ZDDP and by the bis-alkoxy list sulphur phosphorus triazine derivative of example 1～3 preparation be dispersed in commercially available refining rapeseed oil (rapeseed oil be Xi'an good in the rapeseed oil produced of oil prodution industry company limited) in last non seizure load (P
BValue) carried out measuring (addition is 1.0wt%).The four-ball tester that experiment is used is the EP lubricant tester of English home-made Seta-Shell type, and the steel ball that uses is secondary standard steel ball (Φ 12.7mm, GCr15 bearing steel, HRc are 59-61).At room temperature carry out, rotating speed is 1450rpm.Measured the 392N load down with above-mentioned four-ball tester simultaneously, experimental period is 30min, additive level is 1.0wt%, rotating speed is the wear scar diameter (WSD) of 1450rpm, the results are shown in Table 2 for it, and table 2 result shows that such bis-alkoxy list sulphur phosphorus triazine derivative adds to and has good extreme pressure property and good abrasion resistance in the lubricating oil.
Last non seizure load (the P of table 2 base oil and various additives
BBe worth) and the wear scar diameter WSD under 392N
| Additive | Concentration (wt%) | P BValue (N) | WSD(mm) |
| Rapeseed oil ZDDP example 1 example 2 examples 3 | 100 1.0 1.0 1.0 1.0 | 686 980 1048 1186 1000 | 0.631 0.459 0.395 0.388 0.337 |
In addition, measured the corrosion resistance of the product of preparation in the example 1～3 by the GB5096-85 standard method.After measured as can be known, various production concentrations are that the oil sample of 1.0wt% is the 1A level at 100 ℃ of following constant temperature 3h to the corrosion of copper sheet.
The decomposition temperature of compound is 204.62 ℃, has higher thermostability, is suitable as lubricating oil and grease additive.
Claims (7)
1, a kind of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive is characterized in that this material has the chemical structure of general formula (I), and its chemical name is 2,4-bis-alkoxy-6-(O, O '-dialkyl dithiophosphate base)-1,3, and the 5-s-triazine,
R in the formula
1, R
2, R
3, R
4Be identical or different C
1～C
20The straight or branched alkyl.
2, bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive according to claim 1, extreme pressure, the wear preventive additive that it is characterized in that can be used as lubricating grease use separately or and the compound use of other lubricating oil and grease additive, its addition is 0.1wt%～15wt%.
3, the preparation method of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive as claimed in claim 1 is characterized in that its preparation method is as follows:
In the three-necked bottle that agitator and prolong are housed, add 2,4-bis-alkoxy-6-chloro-1,3,5-s-triazine and reaction medium drip acid binding agent then, drip dialkyl dithiophosphate or salt at last; 2,4-bis-alkoxy-6-chloro-1,3, the mol ratio of 5-s-triazine and dialkyl dithiophosphate or salt is 1: 0.8～1.2; Dialkyl dithiophosphate or salt (mol): reaction medium (ml) is 1: 50～5000; Dialkyl dithiophosphate or salt (mol): acid binding agent (mol) is 1: 1.0～1.2; ℃ following reaction is 2～12 hours in normal temperature～150; Suction filtration removes and desalts, filtrate washing, anhydrous sodium sulfate drying; Filter, filtrate decompression is steamed and is desolventized, and gets light yellow viscous liquid, is bis-alkoxy list sulphur phosphorus triazine derivative.
4, the preparation method of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive according to claim 3 is characterized in that 2,4-bis-alkoxy-6-chloro-1,3, and the 5-s-triazine has the chemical structure of following general formula (II),
R in the formula
1, R
2Be identical or different C
1～C
20The straight or branched alkyl.
5, the preparation method of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive according to claim 3 is characterized in that dialkyl dithiophosphate or salt have the chemical structure of following general formula (III),
R in the formula
3, R
4Be identical or different C
1～C
20The straight or branched alkyl, M is alkalimetal ion, NH
4 +Or quaternary ammonium ion.
6, the preparation method of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive according to claim 3, it is characterized in that reaction medium is water, acetone, benzene, toluene, chloroform, ethyl acetate, N, dinethylformamide, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO) or C
1-C
8Fatty Alcohol(C12-C14 and C12-C18).
7, the preparation method of bis-alkoxy list sulphur phosphorus triazine derivative extreme-pressure anti-friction additive according to claim 3, it is characterized in that acid binding agent is sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, triethylamine, Trimethylamine 99, pyridine, 2,4,6-trimethylpyridine, 3-picoline, N, accelerine or N, the N-Diethyl Aniline.
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|---|---|---|---|
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|---|---|---|---|
| CN 200410099191 CN1281727C (en) | 2004-12-29 | 2004-12-29 | Extreme pressure wear resistance additive of double alkoxy monosulfur phosphorus triazine derivative and its preparing method |
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|---|---|
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| CN1281727C true CN1281727C (en) | 2006-10-25 |
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