CN1219038C - BIthiophosphotriazine derivative limit pressure antiwear agent and its preparation method - Google Patents

BIthiophosphotriazine derivative limit pressure antiwear agent and its preparation method Download PDF

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CN1219038C
CN1219038C CN 03129697 CN03129697A CN1219038C CN 1219038 C CN1219038 C CN 1219038C CN 03129697 CN03129697 CN 03129697 CN 03129697 A CN03129697 A CN 03129697A CN 1219038 C CN1219038 C CN 1219038C
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temephos
preparation
pyrrolotriazine derivatives
base
pressure anti
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CN1513962A (en
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芦金良
何忠义
曾祥琼
任天辉
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The present invention provides a bithiophosphotriazine derivative limit pressure antiwear additive which has the chemical name of 2-di n-butylamine base-4 6-di (O, O'-di alkyl phosphorodithioate) base-1, 3, 5-triazine and the structure of a general formula (I), wherein R<1> and R<2> are the same or different linear chains or alkyl groups of C1 to C20. The present invention is synthesized by a chemical reaction between thiophosphate and the 2-di n-butylamine base-4 6-di (O, O'-di alkyl phosphorodithioate) base-1, 3, 5-triazine, the utilized technology is simple, the cost is low, and obtained bithiophosphotriazine derivatives can be used as multifunctional lubricant additives for single use or / and other lubricant additives for compound use; lubricants can have the performance of corrosion resistance, antioxidation, etc. as well as the favorable performance of abrasion resistance and limit pressure resistance and high bearing capacity.

Description

Temephos pyrrolotriazine derivatives extreme pressure anti-wear additives and preparation method thereof
Technical field: the present invention relates to a kind of temephos pyrrolotriazine derivatives extreme-pressure anti-friction additive, synthetic by the method for cheap and simple, it has good extreme pressure and antiwear behavior as lubricant additive.
Background technology: well-known, O, O '-zinc dialkyl dithiophosphate (ZDDP) are the additives of very effective multifunctional lubricant commonly used on a kind of modern industry, but wherein contain zinc salt, are easy to generate electrocorrosion, and be also unfriendly to environment.The research worker is devoted to seek a kind of substitute products always, wishes that it has the identity function with ZDDP, but can not produce the side effect that metal-salt has.EP320450 has introduced the pyrrolotriazine derivatives of a kind of S of containing, has good anti-oxidant, corrosion resistance.Research in the past also finds, nitrogenous heterogeneous ring compound and derivative thereof have good extreme pressure, wear-resistant, antifriction performance, higher thermostability and good anti-oxidant and corrosion resistance as lubricant additive.
Summary of the invention: the object of the present invention is to provide a kind of s-triazine derivative that contains the P-S-C-N chemical bond of novelty, this compound has excellent extreme pressure and antiwear behavior and low-corrosiveness energy as lubricant additive.
Another object of the present invention provides a kind of preparation method of above-mentioned s-triazine derivative, and this method has the common cheap characteristics of raw material that technology is simple, reaction conditions is gentle, adopt.
Temephos pyrrolotriazine derivatives provided by the present invention has the structure of formula (I):
R in the formula (I) 1, R 2Be identical or different C1~C20 straight or branched alkyl, preferred C4-C8 straight or branched alkyl.
The concrete grammar of preparation temephos pyrrolotriazine derivatives is: with 1 mole of 2-Di-n-Butyl Amine base-4,6-two chloro-1,3, the 5-s-triazine joins in 100 moles of organic solvents, stir and slowly add 2 moles of acid binding agents and 1.8-2.2 mole O down successively, O '-di-n-butyl phosphorodithioate, room temperature~150 ℃ following reaction 0.5~12 hour, the preferred backflow 2~6 hours at room temperature filtered, and filter residue washs with a small amount of solvent, filtrate washing 3 times, anhydrous magnesium sulfate drying filters, and filtrate obtains product after steaming and desolventizing under normal pressure.
Above-mentioned synthetic method can be represented with following chemical equation:
The used organic solvent of the present invention is benzene, tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO), toluene, dimethyl formamide, preferred benzene, tetrahydrofuran (THF) and toluene.
The used acid binding agent of the present invention is triethylamine, pyridine, 2,4,6-collidine, N, accelerine, N, N-Diethyl Aniline, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, preferred organic amine.
The temephos pyrrolotriazine derivatives extreme-pressure anti-friction additive of Chinese style of the present invention (I) can use separately, add in mineral oil, crude vegetal, the synthetic lubricant, can obtain good wear-resistant, anti-extreme pressure can lubricating system, also have erosion resistance, antioxidant property simultaneously; Also can with the compound use of other lubricant additives, can reach synergy synergy.The addition of temephos pyrrolotriazine derivatives extreme pressure anti-wear additives provided by the invention is 0.1wt%-15wt%, preferred 0.5wt%-4wt%.
Description of drawings:
The 2-Di-n-Butyl Amine base-4 of Fig. 1: embodiment 1, the infrared spectra spectrogram of 6-two (O, O '-di-n-butyl phosphorodithioate) base-1,3,5-triazines
The 2-Di-n-Butyl Amine base-4 of Fig. 2: embodiment 1, the nmr spectrum of 6-two (O, O '-di-n-butyl phosphorodithioate) base-1,3,5-triazines
Embodiment: for a better understanding of the present invention, describe by the following examples.
Embodiment 1
With 2-Di-n-Butyl Amine base-4,6-two chloro-1,3,5-s-triazine 13.9g (about 0.05mol) joins in the 100ml benzene, stirs slowly to add 10.1g (about 0.1mol) triethylamine and 24.2g (about 0.1mol) O, O '-di-n-butyl phosphorodithioate down successively, 75 ℃ of isothermal reactions 4 hours, cooling is filtered, and filter residue washs with a small amount of benzene, filtrate washing 3 times (3 * 15ml), anhydrous magnesium sulfate drying filters, and obtains oyster thickness oily product after filtrate is steamed and desolventized under normal pressure: 2-Di-n-Butyl Amine base-4,6-two (O, O '-di-n-butyl phosphorodithioate) base-1,3,5-triazines.Obtain pure product through chromatographic separation, carry out Infrared spectroscopy (Fig. 1) and hydrogen nuclear magnetic resonance spectrum analysis (Fig. 2), analytical results is as follows: IR (cm -1): 2960,2933,2873 (CH 3, CH 2), 1565,1530 (C-N=C), 1340 (tertiary amines), 1230 (P-S), 1058 (P-O-C), 800 (P=S), 650 (S-C); 1HNM (δ, ppm): 0.93 (C-CH 3, 18H), 1.38 (N-C-CH 2-CH 2, 8H), 1.60 (O-C-CH 2-CH 2, 16H), 3.54 (N-CH 2, 4H), 4.20 (O-CH 2, 8H)
Embodiment two
With 2-Di-n-Butyl Amine base-4,6-two chloro-1,3,5-s-triazine 13.9g (about 0.05mol) joins in the 100ml benzene, stirs slowly to add 10.1g (about 0.1mol) triethylamine and 35.4g (about 0.1mol) O, O '-diisooctyl phosphorodithioate down successively, 75 ℃ of isothermal reactions 5 hours, cooling is filtered, and filter residue washs with a small amount of benzene, filtrate washing 3 times (3 * 15ml), anhydrous magnesium sulfate drying filters, and obtains oyster thickness oily product after filtrate is under reduced pressure steamed and desolventized: 2-Di-n-Butyl Amine base-4,6-two (O, O '-diisooctyl phosphorodithioate) base-1,3,5-triazines.
Embodiment three
With 2-Di-n-Butyl Amine base-4,6-two chloro-1,3,5-s-triazine 12.9g (about 0.1mol) joins in the 100ml benzene, stirs slowly to add 10.1g (about 0.2mol) triethylamine and 29.8g (about 0.1mol) O-normal-butyl, O-iso-octyl phosphorodithioate down successively, 75 ℃ of isothermal reactions 5 hours, cooling is filtered, and filter residue washs with a small amount of benzene, filtrate washing 3 times (3 * 15ml), anhydrous magnesium sulfate drying filters, and obtains oyster thickness oily product after filtrate is under reduced pressure steamed and desolventized: 2-Di-n-Butyl Amine base-4,6-two (O-normal-butyl, O-iso-octyl phosphorodithioate) base-1,3,5-triazines.
Embodiment four
Present embodiment is the ultimate analysis of sample.Table 1 has been listed the results of elemental analyses of embodiment 1-3 product.
Table 1, results of elemental analyses
Embodiment ?S% ?P% N% C% H%
Embodiment one embodiment two embodiment three ?18.98(18.60) ?14.31(14.04) ?15.88(16.00) ?8.34(9.01) ?7.01(6.80) ?7.23(7.75) 8.12(8.14) 6.059(6.14) 6.30(7.00) 47.53(47.09) 57.51(56.58) 53.28(52.50) 7.71(7.85) 10.04(9.43) 9.18(8.75)
Embodiment five
Present embodiment is to the extreme pressure and antiwear behavior of sample and corrosion resistance test.
According to the GB-3142-82 standard, to 1,3 of commodity ZDDP and embodiment 1-3 preparation, the last non seizure load that the 5-s-triazine derivative is dispersed in the rapeseed oil has carried out measuring (additive level all is weight percentage 1%).Testing used four-ball tester is that Britain Stanhope Engineering Co LTD produces, test used steel ball GGrl5 secondary standard steel ball (Φ 12.7mm, HRC is 59-61HRC), testing used rapeseed oil is the rape salad oil that oil prodution industry company limited produced in praised in Xi'an.Experiment is at room temperature carried out, and rotating speed is 1450rpm, and the results are shown in Table 2.
Table 2, four ball commentary valency result (last non seizure load, P BValue)
Additive Concentration (wt%) ?P BValue (N)
Base oil ZDDP embodiment one embodiment two embodiment three 100 1.0 1.0 1.0 1.0 ?686 ?980 ?1401 ?980 ?1323
The result shows that the synthetic compound can effectively improve the P of base oil among the embodiment BValue, and the effect of embodiment one and embodiment three is far above ZDDP.
Simultaneously the vertical omnipotent friction wear testing machine of producing with Shijin Group Co., Ltd., Jinan measured the 392N load down, experimental period is that 30min, additive level are that 1.0wt%, rotating speed are the wear scar diameter (WSD) of 1450rpm.It is the same to test used steel ball and base oil.The results are shown in table 3.
Table 3, four ball commentary valency results (wear scar diameter, WSD)
Additive Concentration (wt%) Wear scar diameter (mm)
Base oil ZDDP embodiment one embodiment two embodiment three 100 1.0 1.0 1.0 1.0 ?0.63 ?0.40 ?0.52 ?0.46 ?0.50
The result shows that the synthetic compound can effectively reduce the WSD value among the embodiment, and effect is near ZDDP.
In addition, measured the corrosion resistance of 3 kinds of products that prepare of embodiment 1-embodiment according to the GB5096-85 standard method.After measured as can be known, the oil sample of the 1wt% of each product is the 1A level in the corrosion to copper sheet in 3 hours of 100 ℃ of following constant temperature.

Claims (5)

1, a kind of temephos pyrrolotriazine derivatives extreme-pressure anti-friction additive, its chemistry 2-Di-n-Butyl Amine base-4 by name, 6-two (O, O '-dialkyl dithiophosphate) base-1,3,5-triazines has following structure:
Figure C031296970002C1
R in the formula 1, R 2Be C identical or inequality 1~C 20The straight or branched alkyl; (n-C 4H 9) 2N-is the Di-n-Butyl Amine base.
2, temephos pyrrolotriazine derivatives extreme-pressure anti-friction additive as claimed in claim 1, it is characterized in that as the multifunctional lubricating agent addition agent use separately or and the compound use of other lubricant additives, its additive capacity is the 0.1wt%~15wt% of lubricant.
3, the preparation method of a kind of temephos pyrrolotriazine derivatives extreme pressure anti-wear additives as claimed in claim 1, it is characterized in that concrete preparation method is as follows: with 1 mole of 2-Di-n-Butyl Amine base-4,6-two chloro-1,3, the 5-s-triazine joins in 100 moles of organic solvents, stir and slowly add 2 moles of acid binding agents and 1.8-2.2 mole O down successively, O '-di-n-butyl phosphorodithioate, the a small amount of organic solvent washing of filter residue is at room temperature filtered in room temperature~150 ℃ following reaction 0.5~12 hour, filtrate washing 3 times, anhydrous magnesium sulfate drying filters, and filtrate obtains temephos pyrrolotriazine derivatives extreme pressure anti-wear additives after steaming and removing organic solvent under normal pressure.
4, the preparation method of temephos pyrrolotriazine derivatives extreme pressure anti-wear additives according to claim 3 is characterized in that organic solvent has benzene or toluene.
5, the preparation method of temephos pyrrolotriazine derivatives extreme pressure anti-wear additives according to claim 3 is characterized in that acid binding agent has triethylamine, pyridine, 2, N, accelerine or N, N-Diethyl Aniline.
CN 03129697 2003-07-03 2003-07-03 BIthiophosphotriazine derivative limit pressure antiwear agent and its preparation method Expired - Fee Related CN1219038C (en)

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