CN1219037C - Monothio phosphotriazine derivative limit pressure antiwear agent and its preparation method - Google Patents
Monothio phosphotriazine derivative limit pressure antiwear agent and its preparation method Download PDFInfo
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- CN1219037C CN1219037C CN 03129696 CN03129696A CN1219037C CN 1219037 C CN1219037 C CN 1219037C CN 03129696 CN03129696 CN 03129696 CN 03129696 A CN03129696 A CN 03129696A CN 1219037 C CN1219037 C CN 1219037C
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- extreme pressure
- triazine
- straight
- dialkyl
- branched alkyl
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Abstract
The present invention relates to a monothio phosphotriazine derivative limit pressure antiwear lubricating oil additive which 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, or the same H, or one of R1, R2, R3 and R4 is H, and the other is a linear chain or an alkyl group in the formula; R5 and R6 are linear chains or alkyl groups of C4 to C20. Dialkyl phosphorodithioate or dialkyl dithiophosphate and 2, 4-double-(dialkyl amidogroup)-6-chlorine-1, 3, 5-sym-triazine in the present invention are used for a chemical reaction to synthesize the monothio phosphotriazine derivative limit pressure antiwear lubricating oil additive, the utilized technology has mild conditions, and the cost of synthesis is low. Sulfur and phosphorus triazine derivatives synthesized by the present invention can be 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 the anti-oxidant lubricating oil additive of a kind of single sulphur phosphorus triazine derivative extreme-pressure anti-wear, as the multifunctional lubricating agent addition agent, have good wear-resistant, anti-extreme pressure and performance such as anticorrosive, anti-oxidant by a kind of novel method synthetic list sulphur phosphorus triazine derivative.
Background technology: well-known, zinc dialkyl dithiophosphate (ZDDP) is a very effective multifunctional lubricating agent addition agent 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 lubricant 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.US3158450 has introduced organophosphate and the derivative thereof that a class contains the P-N-C key, has a good supporting capacity.But its extreme-pressure anti-wear ability awaits further raising.
US1087029 has introduced a kind of pyrrolotriazine derivatives synthetic of short chain thiophosphatephosphorothioate, products therefrom is applied to weedicide and sterilant, but its synthetic method is from complicated 4-chloro-2-amido-6-thiophosphoric acid ester group-1,3,5-triazine and amine reaction, its building-up process complexity.
Summary of the invention: the object of the present invention is to provide a kind of triazine phosphate derivative of the P-S-C-N of containing 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 structure of single sulphur phosphorus triazine derivative extreme pressure anti-wear additives of the present invention is 2 of a general formula (I), 4-pair-(dialkyl amino)-6-(O, O '-dialkyl dithiophosphate)-s-base-1,3, and the 5-s-triazine:
R in the formula
1, R
2, R
3, R
4Straight or branched alkyl for identical or different C1～C20; Or be all H, or one be H, another is the straight or branched alkyl of C2～C8.R
5, R
6Straight or branched alkyl for C4～C20.
In the above-mentioned formula (I), R
1, R
2, R
3, R
4Be preferably the straight or branched alkyl of C2～C8 identical or inequality, perhaps one is hydrogen, and another is the straight or branched alkyl of C2～C8; R
5, R
6Straight or branched alkyl for C4～C12.
It is as follows that the present invention prepares the extreme pressure anti-wear additives concrete grammar of single sulphur phosphorus triazine derivative: 2 of use formula (II), 4-pair-(dialkyl amino)-6-chloro-1,3, the dialkyl dithiophosphate of 5-s-triazine and formula (III) or dialkyl dithiophosphate are raw material.
The M of formula (III) is Na
+, K
+, NH
4 +Or quaternary ammonium ion, wherein 2,4-is two-(dialkyl amino)-6-chloro-1,3, the mol ratio of 5-s-triazine and dialkyl dithiophosphate or dialkyl dithiophosphate is 1: 0.8～1.2.Carry out in reaction medium, wherein dialkyl dithiophosphate or dialkyl dithiophosphate (mol): reaction medium (ml) is 1: 300～1600.Have acid binding agent in the presence of react wherein dialkyl dithiophosphate or dialkyl dithiophosphate (mol): acid binding agent (mol) is 1: 1.0～1.2, ℃ down reaction 2～12 hours in normal temperature～150.
The reaction medium that the present invention uses is water, acetone, N, dinethylformamide, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO), the Fatty Alcohol(C12-C14 and C12-C18) of C1-C10.
The acid binding agent that the present invention uses is sodium bicarbonate, yellow soda ash, sodium hydroxide, potassium hydroxide, triethylamine, Trimethylamine 99, pyridine, 2,3-picoline, N, accelerine, N, N-Diethyl Aniline.
The synthetic of single sulphur phosphorus triazine derivative extreme pressure anti-wear additives involved in the present invention can be represented with following chemical equation:
2 of general formula (I), 4-pair-(dialkyl amino)-6-(O, O '-dialkyl dithiophosphate)-s-base-1,3, the 5-s-triazine uses as a kind of multifunctional lubricating agent addition agent.
Formula of the present invention (I) compound can use separately, also can add mineral oil, synthetic oil to, vegetables oil, synthetic ester, polyethers, hydrogenated oil, lithium saponify uses in the lubricants such as calcium grease, can obtain good wear-resistant, anti-extreme pressure can lubricating system, also have simultaneously anticorrosive, oxidation resistant ability.
The addition of formula of the present invention (I) compound is 0.1wt%～15.0wt%.
Formula of the present invention (I) compound also can with the compound use of other lubricant additive, can reach synergy synergy.
The processing condition gentleness that the present invention is designed, synthetic cost is low.Have good extreme-pressure anti-wear, antioxidant property in the compound interpolation lubricant that obtains.
Description of drawings:
Fig. 1 is a compound 2,4-pair-(dibutyl amino)-6-(O, O '-di-n-butyl phosphorodithioate)-s-base-1,3, and infrared (IR) of 5-s-triazine
Fig. 2 is a compound 2, and 4-is two-(dibutyl amino)-6-(O, O '-di-n-butyl phosphorodithioate)-s-base-1,3, the 5-s-triazine and nucleus magnetic resonance (
1H NMR)
Fig. 3 is a compound 2,4-pair-(dibutyl amino)-6-(O, O '-di-n-butyl phosphorodithioate)-s-base-1,3, and 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 37.0g, 4-pair-(Di-n-Butyl Amine base)-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 5h 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 2,4-pair-(dibutyl amino)-6-(O, O '-di-n-butyl phosphorodithioate)-s-base-1,3,5-s-triazine 38.9g, productive rate be 67.7% (with 2,4-is two-(Di-n-Butyl Amine base)-6-chloro-1,3, the 5-s-triazine is a benchmark).Through column chromatography purification, with infrared (IR) and nucleus magnetic resonance (
1H NMR) and thermogravimetric analysis, its analytical results is as follows: IR (KBr) υ
C-H: 2956.97,2859.68cm
-1, υ
C=N: 1594.81cm
-1, β
C-H: 1427.46,1372.97cm
-1, υ
P-O-C: 1178.38,976.00cm
-1, υ
P=S: 800.86cm
-1, υ
S-P-S: 730.81cm
-1, υ
P-S: 1295.14cm
-1, υ
C-S: 660.76cm
-1
1H NMR(CDCl
3，400MHz)6(CDCl
3)：0.877～0.943(m，18H，6CH
3)，1.300～1.429(m，12H，6CH
2)，1.599～1.711(m，12H，6CH
2)，3.448～3.595(m，8H，2NCH
2)，4.034～4.152(s，4H，2OCH
2)
Temperature of initial decomposition is 173.77 ℃, and second decomposition temperature is 293.61 ℃.
Embodiment 2:
With 2 of 25.8g, 4-pair-(diethylin)-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 '-di-n-octyl 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 2,4-pair-(diethylin)-6-(O, O '-di-n-octyl phosphorodithioate)-s-base-1,3,5-s-triazine 40.1g, productive rate be 69.6% (with 2,4-is two-(diethylin)-6-chloro-1,3, the 5-s-triazine is a benchmark).
Embodiment 3:
With 2 of 25.8g, 4-pair-(diethylin)-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 '-diisooctyl 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 2,4-pair-(diethylin)-6-(O, O '-diisooctyl phosphorodithioate)-s-base-1,3,5-s-triazine 35.8g, productive rate be 62.1% (with 2,4-is two-(diethylin)-6-chloro-1,3, the 5-s-triazine is a benchmark).
Embodiment 4:
With 2 of 37.0g, 4-pair-(Di-n-Butyl Amine base)-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-hexyl phosphorodithioate, behind the reaction 2h, be warming up to 80 ℃ of following backflow 6h, 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 2,4-pair-(Di-n-Butyl Amine base)-6-(O, O '-di-n-hexyl phosphorodithioate)-s-base-1,3,5-s-triazine 36.1g, productive rate be 60.1% (with 2,4-is two-(Di-n-Butyl Amine base)-6-chloro-1,3, the 5-s-triazine is a benchmark).
Embodiment 5: with 2 of 37.0g, 4-pair-(Di-n-Butyl Amine base)-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-octyl phosphorodithioate, behind the reaction 2h, be warming up to 80 ℃ of following backflow 8h, 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 2,4-pair-(Di-n-Butyl Amine base)-6-(O, O '-di-n-octyl phosphorodithioate)-s-base-1,3,5-Strinoline 2.2g, productive rate be 75.9% (with 2,4-is two-(Di-n-Butyl Amine base)-6-chloro-1,3, the 5-s-triazine is a benchmark).
The compound that obtains in the foregoing description is through column chromatography purification, the C of compound, 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 conforms to substantially with the theoretical value of calculating by molecular formula, 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 embodiment (in the bracket is calculated value)
| Embodiment | ％C | ％H | ％N | ％S |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 | 55.93(56.35) 55.83(56.35) 55.63(56.35) 58.56(58.95) 60.72(61.14) | 9.78(9.39) 9.47(9.39) 9.48(9.39) 10.22(9.51) 10.56(10.19) | 11.78(12.17) 11.92(12.17) 12.11(12.17) 10.51(11.09) 10.14(10.19) | 11.58(11.13) 10.63(11.13) 10.72(11.13) 9.71(10.14) 9.66(9.32) |
The performance evaluation of target compound:
According to the GB3142-82 standard, to commodity ZDDP and by the pyrrolotriazine derivatives of embodiment 1～5 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 single 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 (mm) under 392N
| Additive | Concentration (wt%) | P BValue (N) | WSD(mm) |
| Rapeseed oil ZDDP embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 | 100 1.0 1.0 1.0 1.0 1.0 1.0 | 686 1049 921 1254 1578 1490 1578 | 0.631 0.400 0.485 0.503 0.478 0.445 0.447 |
In addition, measured the corrosion resistance of the product of preparation among the embodiment 1～5 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 temperature of initial decomposition of compound is 173.77 ℃, and second decomposition temperature is 293.61 ℃.Have higher thermostability, be suitable as the lubricant antioxidant addn.
Claims (6)
1, a kind of single sulphur phosphorus triazine derivative extreme pressure anti-wear additives is characterized in that this material has the chemical structure of general formula (I), and its chemical name is 2,4-pair-(dialkyl amino)-6-(O, O '-dialkyl dithiophosphate)-s-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; R
5, R
6Be C
4～C
20The straight or branched alkyl.
2, single sulphur phosphorus triazine derivative extreme pressure anti-wear additives according to claim 1 is characterized in that R
1, R
2, R
3, R
4Be C
2～C
8The straight or branched alkyl, R
5, R
6Be C
4～C
12The straight or branched alkyl.
3, single sulphur phosphorus triazine derivative extreme pressure anti-wear additives according to claim 1, extreme pressure, the wear preventive additive that it is characterized in that can be used as lubricant use separately or and the compound use of other lubricant additive, its addition is the 0.1wt%～15wt% of lubricant.
4, a kind of preparation method of single sulphur phosphorus triazine derivative extreme pressure anti-wear additives is characterized in that concrete preparation method is as follows:
2 of use formula (II), 4-pair-(dialkyl amino)-6-chloro-1,3, the dialkyl dithiophosphate of 5-s-triazine and formula (III) is a raw material,
R in the formula
1, R
2, R
3, R
4Be identical or different C
1～C
20The straight or branched alkyl; R
5, R
6Be C
4～C
20The straight or branched alkyl;
2,4-pair-(dialkyl amino)-6-chloro-1,3, the mol ratio of 5-s-triazine and dialkyl dithiophosphate is 1: 0.8～1.2; Carry out in reaction medium, wherein dialkyl dithiophosphate (mol): reaction medium (ml) is 1: 300～1600; Have acid binding agent in the presence of react dialkyl dithiophosphate (mol) wherein: acid binding agent (mol) is 1: 1.0～1.2; Reaction was cooled to room temperature after 2～12 hours down in normal temperature～150 ℃, and suction filtration, filtrate water are given a baby a bath on the third day after its birth time, and benzene is washed secondary, and anhydrous sodium sulfate drying filters, and filtrate decompression is steamed and removed benzene, obtains single sulphur phosphorus triazine derivative extreme pressure anti-wear additives.
5, the synthetic method of single sulphur phosphorus triazine derivative extreme pressure anti-wear additives according to claim 4 is characterized in that reaction medium has benzene or toluene.
6, the synthetic method of single sulphur phosphorus triazine derivative extreme pressure anti-wear additives according to claim 4 is characterized in that acid binding agent has triethylamine, Trimethylamine 99, pyridine, 2,3-picoline, N, accelerine or N, N-Diethyl Aniline.
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|---|---|---|---|
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|---|---|---|---|
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| CN1219037C true CN1219037C (en) | 2005-09-14 |
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| CN103145634B (en) * | 2012-05-08 | 2015-01-21 | 上海交通大学 | Coupled dimercaptotriazine derivative, and preparation method and use thereof |
| CN111303061B (en) * | 2020-04-08 | 2021-05-11 | 玛可索(苏州)石化有限公司 | Arylamine compound and preparation method and application thereof |
| CN113563959B (en) * | 2021-07-27 | 2022-08-09 | 嘉兴顺诚精细化工有限公司 | High-abrasion-resistance water-based cutting fluid and preparation method thereof |
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