阅读说明：本技术 一种含双酯基均三嗪衍生物的环保多功能材料及其制备方法与应用 (Environment-friendly multifunctional material containing diester group s-triazine derivative and preparation method and application thereof ) 是由 周文圣 周文忠 余磊 廖俊旭 赵鸿斌 于 2021-07-16 设计创作，主要内容包括：本发明公开了一种含双酯基均三嗪衍生物的环保多功能材料及其制备方法与应用。该含双酯基均三嗪衍生物具有如通式Ⅰ的结构。该含双酯基均三嗪衍生物具有制备方法简单,工艺条件温和,原料易得,合成成本低,合成产率高等特点；可作为极压、抗磨、减摩和抗腐蚀添加剂使用,可明显提高基础油的承载能力,改善其抗磨和减摩性能,是一种环境友好的多功能添加剂；其中,R为C原子数为1～30的直链、支链烷基。(The invention discloses an environment-friendly multifunctional material containing diester group s-triazine derivatives, and a preparation method and application thereof. The diester group-containing s-triazine derivative has a structure shown as a general formula I. The diester group-containing s-triazine derivative has the characteristics of simple preparation method, mild process conditions, easily obtained raw materials, low synthesis cost, high synthesis yield and the like; can be used as an extreme pressure, anti-wear, anti-friction and anti-corrosion additive, can obviously improve the bearing capacity of the base oil and improve the anti-wear and anti-friction performance of the base oil, and is an environment-friendly multifunctional additive; wherein R is a straight chain or branched alkyl with 1-30C atoms.)

1. An environment-friendly multifunctional material containing diester s-triazine derivatives is characterized by having a chemical structure shown as a general formula I:

wherein R is a straight chain or branched alkyl with 1-30C atoms.

2. A method for preparing the multifunctional environment-friendly material containing the diester group s-triazine derivative as set forth in claim 1, comprising the steps of:

(1) under the action of alkali, cyanuric chloride reacts with dialkyl amine to prepare an intermediate I, and the structural general formula of the intermediate I is as follows:

wherein R is a straight chain or branched alkyl with 1-30C atoms;

(2) under the action of alkali, 2-mercaptobenzothiazole reacts with the intermediate I to prepare an intermediate II, and the structural general formula of the intermediate II is as follows:

(3) under the action of alkali, the intermediate II reacts with diethanol amine to prepare an intermediate III, and the structural general formula of the intermediate III is as follows:

(4) under the action of alkali, the intermediate III reacts with dodecanoyl chloride to prepare the diester group-containing s-triazine derivative.

3. The method for preparing the environment-friendly multifunctional material containing the diester group s-triazine derivative as claimed in claim 2, wherein the method comprises the following steps: in the steps (1) - (4), the reaction medium of the reaction is one or a mixture of more of chloroform, dichloromethane, water, ethanol, tetrahydrofuran and acetone.

4. The method for preparing the environment-friendly multifunctional material containing the diester group s-triazine derivative as claimed in claim 2, wherein the method comprises the following steps: in the steps (1) - (4), the reaction temperature of the reaction is-5-80 ℃.

5. The method for preparing the environment-friendly multifunctional material containing the diester group s-triazine derivative as claimed in claim 2, wherein the method comprises the following steps: in the steps (1) - (4), the reaction time of the reaction is 0.5-12.0 h.

6. Use of the environmentally friendly multifunctional material comprising a diester group-s-triazine derivative as set forth in claim 1, wherein: the environment-friendly multifunctional material containing the diester-based s-triazine derivative is used as a lubricating oil (grease) additive independently or is compounded with other lubricating oil (grease) additives.

7. The use of the multifunctional environmental friendly material comprising diester s-triazine derivative as claimed in claim 6, wherein: the environment-friendly multifunctional material containing the diester-based s-triazine derivative is used as a lubricating oil (grease) additive to be added into base oil, and the addition amount of the environment-friendly multifunctional material is 0.1-10 wt% of the base oil.

Technical Field

The invention relates to an environment-friendly multifunctional material containing diester s-triazine derivatives, a preparation method and application thereof, wherein the derivatives can be widely applied to the fields of machinery, energy, environment, materials, chemical industry and the like, and are particularly suitable for being used as green environment-friendly lubricating oil (grease) additives.

Background

Due to the ever-increasing performance of modern mechanical equipment and the increasingly stringent environmental requirements, there is a need for multifunctional lubricant additives with higher performance. Meanwhile, in order to meet the requirements of environmental protection, control emission and reduce the use of phosphorus and chlorine containing additives, the trend is inevitable, and lubricating oil additives are developing towards low ash content, multiple functions and reduction of environmental pollution.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the environment-friendly multifunctional material containing the diester-based s-triazine derivative, which does not contain elements harmful to the environment and health, such as phosphorus, halogen, metal elements and the like, and has the characteristics of excellent performance and environmental friendliness.

The invention also aims to provide a preparation method of the environment-friendly multifunctional material containing the diester group s-triazine derivative, which has the advantages of simple operation, convenient control, high production efficiency and low production cost and can be used for large-scale production.

The invention also aims to use the diester-group-containing s-triazine derivative as a multifunctional additive of lubricating oil (grease) alone or in combination with other lubricating oil (grease) additives.

The purpose of the invention is realized by the following technical scheme: an environment-friendly multifunctional material containing diester s-triazine derivatives has a chemical structure shown as a general formula I:

wherein R is a straight chain or branched alkyl with 1-30C atoms.

The other purpose of the invention is realized by the following technical scheme: the preparation method of the environment-friendly multifunctional material containing the diester group s-triazine derivative comprises the following steps:

(1) under the action of alkali, cyanuric chloride reacts with dialkyl amine to prepare an intermediate I, and the structural general formula of the intermediate I is as follows:

wherein R is a straight chain or branched alkyl with 1-30C atoms;

(2) under the action of alkali, 2-mercaptobenzothiazole reacts with the intermediate I to prepare an intermediate II, and the structural general formula of the intermediate II is as follows:

(3) under the action of alkali, the intermediate II reacts with diethanol amine to prepare an intermediate III, and the structural general formula of the intermediate III is as follows:

(4) under the action of alkali, the intermediate III reacts with dodecanoyl chloride to prepare the diester group-containing s-triazine derivative.

Preferably, in the steps (1) to (4), the reaction medium of the reaction is one or a mixture of chloroform, dichloromethane, water, ethanol, tetrahydrofuran and acetone.

Preferably, in the steps (1) to (4), the reaction temperature of the reaction is-5 to 80 ℃.

In the above-mentioned means, the reaction time of the reaction in the steps (1) to (4) is preferably 0.5 to 12.0 hours.

The invention also aims to realize the following technical scheme: the environment-friendly multifunctional material containing the diester group s-triazine derivative is used as a lubricating oil (grease) additive to be used alone or in a compound way with other lubricating oil (grease) additives.

Preferably, the multifunctional environment-friendly material containing the diester-based s-triazine derivative is added to base oil as a lubricating oil (grease) additive, and the addition amount of the multifunctional environment-friendly material is 0.1-10 wt% of the base oil.

The invention has the beneficial effects that: the multifunctional lubricating oil additive containing the diester-based s-triazine derivative has excellent thermal stability, corrosion resistance, extreme pressure performance, wear resistance and friction reduction performance, and is a lubricating oil additive with excellent comprehensive performance.

The preparation process is simple, the reaction conditions are mild, the used raw materials are cheap and easy to obtain, and the synthesis yield is high; the derivative is phosphorus-free, halogen-free and ashless, and is an environment-friendly lubricating oil additive.

Drawings

FIG. 1 is a NMR chart of example 1;

FIG. 2 is a NMR chart of example 2;

FIG. 3 is a NMR chart of example 3;

FIG. 4 is a mass spectrum of example 1;

FIG. 5 is a mass spectrum of example 2;

FIG. 6 is a mass spectrum of example 3;

FIG. 7 is a scanning electron microscope image of the surface topography of the plaque using vegetable oil base oil (a), (b), (c), (d) oil samples with 1.0% by weight of ZDDP additive (the same applies hereinafter), (e), (f) oil samples with 1.0% by weight of the additive of example 1, (g), (h) oil samples with 1.0% of the additive of example 2, and (i), (j) oil samples with 1.0% of the additive of example 3.

Detailed Description

For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.

Example 1

0.05mol (9.25g) of cyanuric chloride, 0.06mol (8.30g) of K₂CO₃And 80mL of acetone were sequentially added to a 250mL three-necked flask, and 0.05mol (6.46g) of di-n-butylamine was added dropwise in an ice bath to conduct reaction for 2.0 hours. After the reaction is finished, the reaction solution is extracted by diethyl ether in a separating funnel, washed by saturated saline, dried by anhydrous magnesium sulfate, filtered, and the filtrate is rotated and evaporated to remove the solvent, so that the 2-di-n-butylamino-4, 6-dichloro-1, 3, 5-s-triazine is obtained.

0.05mol (8.362g) of 2-mercaptobenzothiazole and 0.06mol (3.366g) of KOH are dissolved in a mixed solution of 20mL of acetone and 20mL of water to prepare a potassium salt solution of 2-mercaptobenzothiazole for later use. 0.04mol (11.04g) of 2-di-n-butylamino-4, 6-dichloro-1, 3, 5-s-triazine and 20mL of acetone are added into a 250mL three-necked bottle, the temperature is raised to 42 ℃, a potassium salt solution of 2-mercaptobenzothiazole is added dropwise, and the constant temperature reaction is carried out for 12 hours. After the reaction is finished, pouring the reaction liquid into a separating funnel, extracting with ethyl acetate, washing with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, removing the solvent from the filtrate to obtain a crude product, and performing silica gel column chromatography to obtain 2-di-n-butylamino-4- (benzothiazole-2-yl-sulfenyl) -6-chloro-1, 3, 5-s-triazine.

0.04mol (4.20g) of diethanolamine, 0.04mol (4.24g) of anhydrous sodium carbonate and 50mL of ethanol were put into a 250mL three-necked flask, and 0.03mol (12.21g) of 2-di-n-butylamino-4- (benzothiazol-2-yl-thio) -6-chloro-1, 3, 5-s-triazine was added dropwise at room temperature, followed by reaction for 0.5h and then reflux reaction for 12 h. After the reaction, insoluble matter was removed by suction filtration, the solvent was removed by rotary evaporation, the residue was dissolved in ethyl acetate, washed with saturated brine and anhydrous magnesium sulfateDrying, filtering and removing the solvent from the filtrate to obtain the intermediate 3. And reacting the intermediate 3 with the dodecanoyl chloride for 3 hours under ice bath to obtain a crude product. The crude product was purified by silica gel column chromatography to give 15.70g of a white solid in 83.3% yield. The analysis results are shown in figures 1 and 4,¹H NMR(400MHz,CDCl₃)δ8.03(d,J＝8.1Hz,1H),7.85(d,J＝7.9Hz,1H),7.51–7.45(m,1H),7.40(dd,J＝11.1,4.0Hz,1H),4.27(dt,J＝16.3,5.7Hz,4H),3.83(dt,J＝15.7,5.7Hz,4H),3.54–3.42(m,4H),2.31(t,J＝7.6Hz,4H),1.60(s,8H),1.30(d,J＝29.3Hz,36H),0.98–0.87(m,12H).MALDI-TOF-MS,m/z:calcd for C₄₆H₇₆N₆O₄S₂[M+1]⁺:840.54,found:841.560。

example 2

0.05mol (9.25g) of cyanuric chloride, 0.06mol (8.30g) of K₂CO₃And 80mL of acetone were sequentially added to a 250mL three-necked flask, and 0.05mol (12.07g) of diisooctylamine was added dropwise in an ice bath to react for 2.0 hours. After the reaction is finished, extracting the reaction solution by using ethyl ether in a separating funnel, washing the reaction solution by using saturated saline solution, drying the reaction solution by using anhydrous magnesium sulfate, filtering the reaction solution, and removing the solvent by rotary evaporation of the filtrate to obtain the 2-diisooctylamino-4, 6-dichloro-1, 3, 5-s-triazine.

0.05mol (8.362g) of 2-mercaptobenzothiazole and 0.06mol (3.366g) of KOH are dissolved in a mixed solution of 20mL of acetone and 20mL of water to prepare a potassium salt solution of 2-mercaptobenzothiazole for later use. 0.04mol (15.53g) of 2-diisooctylamino-4, 6-dichloro-1, 3, 5-s-triazine and 20mL of acetone are added into a 250mL three-necked bottle, the temperature is raised to 42 ℃, a potassium salt solution of 2-mercaptobenzothiazole is added dropwise, and the constant temperature reaction is carried out for 12 hours. After the reaction is finished, pouring the reaction liquid into a separating funnel, extracting with ethyl acetate, washing with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, removing the solvent from the filtrate to obtain a crude product, and performing silica gel column chromatography to obtain the 2-diisooctylamino-4- (benzothiazole-2-yl-sulfenyl) -6-chloro-1, 3, 5-s-triazine.

0.04mol (4.20g) of diethanolamine, 0.04mol (4.24g) of anhydrous sodium carbonate and 50mL of ethanol were added to a 250mL three-necked flask, and 0.03mol (12.21g) of 2-diisooctylamino-4- (benzothiazol-2-yl-thio) -6-chloro-1, 3, 5-s-triazine was added dropwise at room temperature, reacted for 0.5h, and then refluxed for 12 h. After the reaction, suction filtration was carried outInsoluble matter was removed, the solvent was removed by rotary evaporation, the residue was dissolved in ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed from the filtrate to obtain intermediate 3. And reacting the intermediate 3 with the dodecanoyl chloride for 3 hours under ice bath to obtain a crude product. The crude product was purified by silica gel column chromatography to give 19.24g of a white solid in 86.67% yield. The analysis results are shown in FIGS. 2 and 5,¹H NMR(400MHz,CDCl₃)δ8.02(d,J＝8.1Hz,1H),7.85(d,J＝7.8Hz,1H),7.46(d,J＝7.7Hz,1H),7.39(d,J＝7.5Hz,1H),4.29–4.18(m,4H),3.82(d,J＝6.3Hz,4H),3.43(dd,J＝21.1,7.1Hz,4H),2.28(t,J＝7.3Hz,4H),1.76(d,J＝34.5Hz,2H),1.59(d,J＝4.1Hz,4H),1.24(s,48H),0.84(dt,J＝14.5,6.7Hz,18H)MALDI-TOF-MS,m/z:calcd for C₅₄H₉₂N₆O₄S₂[M+1]⁺:952.66,found:953.506。

example 3

0.05mol (9.25g) of cyanuric chloride, 0.06mol (8.30g) of K₂CO₃And 80mL of acetone were sequentially added to a 250mL three-necked flask, and 0.05mol (12.07g) of di-n-octylamine was added dropwise under ice bath to react for 2.0 hours. After the reaction is finished, extracting the reaction solution by using ethyl ether in a separating funnel, washing the reaction solution by using saturated saline solution, drying the reaction solution by using anhydrous magnesium sulfate, filtering the reaction solution, and removing the solvent by rotary evaporation of the filtrate to obtain the 2-di-n-octylamino-4, 6-dichloro-1, 3, 5-s-triazine.

0.05mol (8.362g) of 2-mercaptobenzothiazole and 0.06mol (3.366g) of KOH are dissolved in a mixed solution of 20mL of acetone and 20mL of water to prepare a potassium salt solution of 2-mercaptobenzothiazole for later use. 0.04mol (15.53g) of 2-di-n-octylamino-4, 6-dichloro-1, 3, 5-s-triazine and 20mL of acetone are added into a 250mL three-necked bottle, the temperature is raised to 42 ℃, a potassium salt solution of 2-mercaptobenzothiazole is added dropwise, and the constant temperature reaction is carried out for 12 hours. After the reaction is finished, pouring the reaction liquid into a separating funnel, extracting with ethyl acetate, washing with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, removing the solvent from the filtrate to obtain a crude product, and performing silica gel column chromatography to obtain the 2-di-n-octylamino-4- (benzothiazole-2-yl-sulfenyl) -6-chloro-1, 3, 5-s-triazine.

0.04mol (4.20g) of diethanolamine, 0.04mol (4.24g) of anhydrous sodium carbonate and 50mL of ethanol were put into a 250mL three-necked flask, and 0.03mol (1 g) of the mixture was added dropwise at room temperature2.21g) 2-di-n-octylamino-4- (benzothiazol-2-yl-sulfanyl) -6-chloro-1, 3, 5-s-triazine for 0.5h and then under reflux for 12 h. After the reaction, insoluble matter was removed by suction filtration, the solvent was removed by rotary evaporation, the residue was dissolved in ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed from the filtrate to obtain intermediate 3. And reacting the intermediate 3 with the dodecanoyl chloride for 3 hours under ice bath to obtain a crude product. The crude product was purified by silica gel column chromatography to give 19.24g of a white solid in 86.67% yield. The analysis results are shown in FIGS. 3 and 6,¹H NMR(400MHz,CDCl₃)δ8.03(d,J＝8.1Hz,1H),7.85(d,J＝7.9Hz,1H),7.54–7.44(m,1H),7.43–7.34(m,1H),4.27(dt,J＝17.0,5.7Hz,4H),3.88–3.77(m,4H),3.52–3.41(m,4H),2.30(t,J＝7.6Hz,4H),1.62(d,J＝6.6Hz,8H),1.27(d,J＝10.4Hz,52H),0.89(dd,J＝8.3,5.3Hz,12H).MALDI-TOF-MS,m/z:calcd for C₅₄H₉₂N₆O₄S₂[M+1]⁺:952.66,found:953.631。

example 4 Performance testing

The extreme pressure, wear resistance and friction reduction performance of the additive and the surface appearance of the ball-milled spots of the steel are as follows:

the diester group-containing s-triazine derivatives prepared in examples 1 to 3 and commercially available ZDDP were added to vegetable oil in an amount of 1.0% by mass to prepare test oil samples. The maximum seizure-free load (P) of the lubricating oil was evaluated by a MS-10A type four-ball friction tester manufactured by Xiamen testing machine factory with reference to GB-3142-82_BValue) and sintering load (P)_DValue). The test conditions are room temperature (25 ℃), the rotating speed is 1450r/min, and the time is 10 s. The steel balls used in the test are standard grade II GCr15 steel balls produced by Shanghai Steel ball factories, the diameter is 12.7mm, and the hardness is 59-61 RC. P_BValue sum P_DThe results of the value tests are listed in table 1.

TABLE 1 maximum No-seize load (P)_BValue) and sintering load (P)_DValue)

Oil sample	PB/N	PD/N
			Vegetable oil	470	784
ZDDP	647	980
			Example 1	745	980
Example 2	804	980
			Example 3	804	980

The result shows that the P of the vegetable oil is obtained by adding the diester-group-containing s-triazine derivative into the vegetable oil_BAnd P_DThe values are greatly improved, which shows that the extreme pressure performance of the lubricating oil can be greatly improved by the additive in the embodiment 1-3, and the extreme pressure performance of the additive is superior to that of the traditional additive ZDDP.

A commercially available ZDDP obtained from the diester-based s-triazine derivatives of examples 1-3 was added to vegetable oil in an amount of 1.0% by mass to prepare a test oil sample. The ball Wear Scar Diameter (WSD) was measured at a load of 392N, at a speed of 1450r/min and for a period of 30min on a four-ball friction tester, and the results are shown in Table 2 and the corresponding average friction coefficients are shown in Table 3.

TABLE 2 Steel ball scrub spot diameter (WSD)

Oil sample	WSD/mm
		Vegetable oil	1.405
ZDDP	0.782
		Example 1	0.704
Example 2	0.701
		Example 3	0.700

The results show that when the diester-group-containing s-triazine derivative is added into vegetable oil, the WSD value of the vegetable oil is obviously reduced. The additive of the embodiment 1-3 can obviously improve the wear resistance of the lubricating oil, and the wear resistance of the additive is superior to that of the traditional additive ZDDP.

TABLE 3 mean coefficient of friction

Oil sample	Coefficient of friction
		Vegetable oil	0.122
ZDDP	0.097
		Example 1	0.088
Example 2	0.081
		Example 3	0.078

The result shows that when the diester-group-containing s-triazine derivative is added into vegetable oil, the average friction coefficient of the vegetable oil is obviously reduced. The additive of the embodiment 1-3 can improve the antifriction performance of the lubricating oil, and the antifriction performance is superior to that of the traditional additive ZDDP.

FIG. 7 is a scanning electron microscope image of the surface topography of the plaque: (a) (b) a vegetable oil base oil; (c) adding 1.0 percent (mass fraction, the same below) of oil sample of the ZDDP additive; (e) and (f) adding 1.0 percent (mass fraction, the same below) of the oil sample of the additive in the example 1; (g) (h) oil sample with 1.0% of the additive of example 2 added; (i) and (j) an oil sample to which 1.0% of the additive of example 3 was added.

Thermal stability of lubricating oil additives:

the thermal stability of the additives prepared in examples 1 to 3 was examined using a TG209 type thermogravimetric analyzer manufactured by Germany Steady instruments manufacturing Ltd. The test conditions were: the nitrogen atmosphere and the temperature rise rate were 20 ℃/min, and the test results are shown in Table 4.

TABLE 4 thermal decomposition temperatures of additives

Additive agent	T1/℃	T2/℃
			Example 1	191	395
Example 2	203	411
			Example 3	219	424
ZDDP	161	300

The results show that the initial thermal decomposition temperature of the diester-group-containing s-triazine derivative synthesized in the examples is 171-219 ℃, the final thermal decomposition temperature is 395-424 ℃, and the diester-group-containing s-triazine derivative has excellent thermal stability and is suitable for general working conditions and high-temperature working conditions.

Corrosion resistance of the multifunctional lubricating oil additive:

the diester group-containing s-triazine derivatives prepared in examples 1 to 3 were added to vegetable oil in an amount of 1.0% by mass to prepare test oil samples. The corrosion test was carried out with reference to the method of GB/T5096-2017. The test results are shown in Table 5.

TABLE 5 copper sheet Corrosion test results

Additive (1.0 wt%)	Corrosion grade
		Example 1	1a
Example 2	1a
		Example 3	1a

The results show that the corrosion rating of the oil samples containing 3 additives is 1a, indicating that all 3 additives have excellent corrosion resistance.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.