CN104927403A

CN104927403A - Preparation method of high-performance lubricating oil additive

Info

Publication number: CN104927403A
Application number: CN201510340420.9A
Authority: CN
Inventors: 王文平; 李建伟; 李小龙; 赵怀华
Original assignee: Hefei University of Technology
Current assignee: Hefei University of Technology
Priority date: 2015-06-18
Filing date: 2015-06-18
Publication date: 2015-09-23
Anticipated expiration: 2035-06-18
Also published as: CN104927403B

Abstract

The invention discloses a preparation method of a high-performance lubricating oil additive. According to the method, gamma-chloropropyl triethoxysilane serves as a precursor reactant to prepare POSS-Cl, and the POSS-Cl reacts with KI to generate POSS-I with higher reactivity; then, nano-silicon dioxide is modified through a silane coupling agent; finally, a graft polymerization reaction is performed to achieve graft polymerization of silane coupling agent modified nano-silicon dioxide and the POSS-I to obtain POSS modified nano-silicon dioxide. The high-performance lubricating oil additive can effectively solve the problem that a common high-molecular polymer is not resistant to frication or high temperature and can permanently solve the problems existing in the application of a silicon dioxide composite material in lubricating oil as a lubricating oil additive.

Description

A kind of preparation method of high perofmrnace lubricating oils additive

One, technical field

The present invention relates to a kind of preparation method of high perofmrnace lubricating oils additive, is by POSS Grafted Nano-scale silicon-dioxide.

Two, background technology

Nano silicon, as lubricating oil additive, can greatly improve the frictional behaviour of lubricating oil, and nano silicon has become domestic and international study hotspot as the research of lubricating oil additive.But nano silicon specific surface area is very big, containing a large amount of hydroxyls, easily reunite, affect nano silicon lubricating oil additive performance in surface.Macromolecular compound is modified at silica particle surface by lot of domestic and international scholar, significantly improves the dispersing property of silicon dioxide granule in lubricating oil, and then plays its frictional behaviour in lubricating oil.In actual applications, lubricating oil additive generally under the state of high-temperature high-load, common macromolecule modified after silicon-dioxide easily decompose under high-temperature high-load, macromolecular compound can depart from nano silicon.Cause the agglomeration of nano silicon to continue to occur, affect the performance of its frictional behaviour in lubricating oil.

Three, summary of the invention

The present invention aims to provide a kind of preparation method of high perofmrnace lubricating oils additive, with the POSS (POSS-Cl) of γ-chloropropyl triethoxysilane for precursor reagent preparation band group chlorine, then POSS and the KI of band group chlorine is reacted, the POSS of the active stronger band I of formation reaction; Utilize APTES (KH-550) to react with the hydroxyl on nano-silicon dioxide particle surface simultaneously, make coupling agent KH-550 be grafted on nanoparticle; Finally utilize-I and amino group generation substitution reaction, prepare POSS modified manometer silicon dioxide.

Lubricating oil additive of the present invention and modified manometer silicon dioxide, have good frictional behaviour, can reduce the frictional coefficient of lubricating oil greatly, improves the performance of lubricating oil, have wide range of applications.

The preparation method of high perofmrnace lubricating oils additive of the present invention, first POSS surface is carried out to process the POSS (POSS-I) obtaining being with I, again by silane coupler modified nano silicon, silane coupler modified nano silicon and POSS-I graft polymerization is made to obtain POSS modified manometer silicon dioxide finally by graft polymerization reaction.

The preparation method of high perofmrnace lubricating oils additive of the present invention comprises surface treatment, the coupling agent modified and each unit process of graft modification:

Described surface treatment is the concentrated hydrochloric acid (mass concentration 36.5%) adding 4.88mL γ-chloropropyl triethoxysilane, 90mL dehydrated alcohol and 5mL in reactor, ultrasonic disperse 0.5h, stirring reaction 2d at 60 DEG C subsequently, obtain white solid, dry with absolute ethanol washing final vacuum, obtain POSS-Cl; Add in 80mL acetone by 1g POSS-Cl and 4g potassiumiodide, stirring reaction 6h at 30 DEG C, filters to remove solid impurity, filtrate is revolved steaming and obtains white solid; The white solid obtained is dissolved in distilled water, after filtration, collects solid product, after vacuum-drying, namely obtain POSS-I;

Described coupling agent modified be that 5g nano silicon, 100mL toluene, 2.5mL silane coupling agent are joined ultrasonic disperse 0.5h in reactor, then stirring reaction 12h at 80 DEG C, anhydrous methanol is utilized to wash for several times after completion of the reaction, 60 DEG C of vacuum-drying 24h, obtain silane coupler modified nano silicon;

Described graft modification adds in 80mL acetone by silane coupler modified to 1g POSS-I, 2.5g nano silicon, then adds 1g NaHCO ₃as acid binding agent, at 90 DEG C, react 12h, the solid product obtained uses acetone and distilled water wash successively, obtains POSS modified manometer silicon dioxide after vacuum-drying.

Described silane coupling agent is APTES (KH-550).

The present invention is at nano-silica surface grafting POSS, there is excellent mechanical property and distinct heat resisting performance, effectively can improve the problem of common high molecular polymer not rub resistance, high temperature, improvement silicon dioxide composite material that can be lasting is as the problem of lubricating oil additive in lubricating oil application aspect.Preparation method's temperature of reaction of the present invention is low, mild condition, and aftertreatment is simple, and product performance are superior, and industrialization cost is little.

Four, accompanying drawing explanation

Fig. 1 is the synthetic route chart for silane resin acceptor kh-550.

Fig. 2 is the infrared spectrum of silicon dioxide granule and its matrix material.Wherein curve A is POSS modified manometer silicon dioxide matrix material, and curve B is silane coupler modified nano silicon; Curve C is nano silicon.Three curves of Fig. 2 are all at 1110cm ^-1there is very powerful peak in place, this is the absorption peak of Si-O key, this is because silicon-dioxide is essential substance, so this peak value is the strongest.Curve B (SiO ₂-KH-550) spectrogram in there is 3426cm ^-1the peak at place is the stretching vibration absorption peak of N-H in primary amine, 1629cm ^-1the peak at place is the in-plane deformation vibration absorption peak of N-H, and the existence at these two peaks, describes the surface that silane resin acceptor kh-550 has successfully been grafted on silicon dioxide granule.Curve A (SiO ₂-POSS) in obviously can find out 3426cm ^-1and 1629cm ^-1the strong peak at place no longer exists, and the peak values such as corresponding Si-O-Si key are still very strong, and illustrate that reaction generates new material, the POSS containing Si-O-Si makes 1110cm ^-1the unabated major cause of place's peak value.

Fig. 3 is the electron-microscope scanning figure of nano silicon (a) and POSS modified manometer silicon dioxide matrix material (b).Two figure amplify identical multiple.From basic appearance, silicon dioxide granule globulate, size distribution is more even.B figure is more uniformly dispersed relative to the particle distribution of a figure, thinks because silicon dioxide granule has modified organosilicon POSS, and so particle surface has certain sterically hindered, silicon dioxide granule is distributed comparatively even.

Fig. 4 is the POSS modified manometer silicon dioxide matrix material (SiO of different addition quantity ₂-POSS) frictional coefficient and time chart.Can significantly observe in Fig. 4, along with SiO ₂the increase of-POSS volume, frictional coefficient is along with also reducing, and when volume is 0.5wt%, frictional coefficient reaches minimum.When volume is 1wt%, become large relative to 0.5wt% frictional coefficient, so reach optimum value when volume is 0.5wt%.Think and serve except a kind of effect of microballoon bearing except having eutectic microballoon when rubbing, organosilicon inarch on silica simultaneously, makes nano composite material have excellent abrasion resistance and high temperature resistant property.In friction process, nano composite material, at the chemical redemption film of friction surface meeting formative dynamics, reduces the friction to contact surface, wearing and tearing.Nano composite material is because Van der Waals force is adsorbed in friction surface simultaneously, forms one deck physical adsorption film, can bring micro-polishing action like this, reduce surface roughness.

Five, embodiment

Nano-meter SiO_2 used in the present invention ₂particulate material buys Aladdin reagent net, and particle diameter soccer star is even, median size 20nm.Because Nano-meter SiO_2 ₂microparticle surfaces can be large, easily there is physical absorption water, so dry according to following step: take 30g Nano-meter SiO_2 ₂particulate, puts into vacuum drying oven, and dry 1d at 100 DEG C, seals for subsequent use.

All through pre-treatment before toluene used in the present invention uses, treating processes is as follows: in reactor, first add 100ml toluene, adds the sodium Metal 99.5 being cut into fragment afterwards, stir at 120 DEG C of lower magnetic forces and spend the night, the a small amount of moisture existed in removing toluene, eventually passes underpressure distillation, seals for subsequent use.

Embodiment 1:

1, in the round-bottomed flask of 300mL, add the concentrated hydrochloric acid (mass concentration 36.5% of 4.88mL γ-chloropropyl triethoxysilane, 90mL dehydrated alcohol and 5mL, lower same), ultrasonic disperse 0.5h, stirring reaction 2d at 60 DEG C subsequently, obtain white solid, dry with absolute ethanol washing final vacuum, obtain POSS-Cl; Add in 80mL acetone by 1g POSS-Cl and 4g potassiumiodide, stirring reaction 6h at 30 DEG C, filters to remove solid impurity, filtrate is revolved steaming and obtains white solid, the white solid obtained is dissolved in distilled water, after filtration, collects solid product, at 40 DEG C, after vacuum-drying 24h, namely obtain POSS-I;

2,5g nano silicon, 100mL toluene, 2.5mL KH-550 are joined ultrasonic disperse 0.5h in 300mL round-bottomed flask, then stirring reaction 12h at 80 DEG C, anhydrous methanol is utilized to wash for several times after completion of the reaction, 60 DEG C of vacuum-drying 24h, obtain silane coupler modified nano silicon (SiO ₂-NH);

3, by 1g POSS-I, 2.5gSiO ₂-NH adds in 80mL acetone, then adds 1g NaHCO ₃as acid binding agent, at 90 DEG C, react 12h, the solid product obtained uses acetone and distilled water wash successively, obtains POSS modified manometer silicon dioxide at 60 DEG C after vacuum-drying.

Embodiment 2:

1, in the round-bottomed flask of 500mL, add the concentrated hydrochloric acid of 9.76mL γ-chloropropyl triethoxysilane, 180mL dehydrated alcohol and 10mL, ultrasonic disperse 0.5h, stirring reaction 2d at 60 DEG C, obtains white solid subsequently, dry with absolute ethanol washing final vacuum, obtain POSS-Cl; 2g POSS-Cl and 8g potassiumiodide are added in 160mL acetone, stirring reaction 6h at 30 DEG C, filter to remove solid impurity, filtrate is revolved steaming and obtains white solid, the white solid obtained is dissolved in distilled water, collect solid product after filtration, at 40 DEG C, after vacuum-drying 24h, namely obtain POSS-I;

2,10g nano silicon, 200mL toluene, 5.0mL KH-550 are joined ultrasonic disperse 0.5h in 500mL round-bottomed flask, then stirring reaction 12h at 80 DEG C, anhydrous methanol is utilized to wash for several times after completion of the reaction, 60 DEG C of vacuum-drying 24h, obtain silane coupler modified nano silicon (SiO ₂-NH);

3, by 2g POSS-I, 5gSiO ₂-NH adds in 160mL acetone, then adds 2g NaHCO ₃as acid binding agent, at 90 DEG C, react 12h, the solid product obtained uses acetone and distilled water wash successively, obtains POSS modified manometer silicon dioxide at 60 DEG C after vacuum-drying.

Embodiment 3:

1, in the round-bottomed flask of 500mL, add the concentrated hydrochloric acid of 14.64mL γ-chloropropyl triethoxysilane, 270mL dehydrated alcohol and 15mL, ultrasonic disperse 0.5h, stirring reaction 2d at 60 DEG C, obtains white solid subsequently, dry with absolute ethanol washing final vacuum, obtain POSS-Cl; 3g POSS-Cl and 12g potassiumiodide are added in 240mL acetone, stirring reaction 6h at 30 DEG C, filter to remove solid impurity, filtrate is revolved steaming and obtains white solid, the white solid obtained is dissolved in distilled water, collect solid product after filtration, at 40 DEG C, after vacuum-drying 24h, namely obtain POSS-I;

2,15g nano silicon, 300mL toluene, 7.5mL KH-550 are joined ultrasonic disperse 0.5h in 500mL round-bottomed flask, then stirring reaction 12h at 80 DEG C, anhydrous methanol is utilized to wash for several times after completion of the reaction, 60 DEG C of vacuum-drying 24h, obtain silane coupler modified nano silicon (SiO ₂-NH);

3, by 3g POSS-I, 7.5gSiO ₂-NH adds in 240mL acetone, then adds 3g NaHCO ₃as acid binding agent, at 90 DEG C, react 12h, the solid product obtained uses acetone and distilled water wash successively, obtains POSS modified manometer silicon dioxide at 60 DEG C after vacuum-drying.

The mass substitution lubricating oil additives such as the POSS modified manometer silicon dioxide prepared with the present invention, take friction coefficient of lubricating oil as judgement criteria, under its different parameter, frictional coefficient and the relation of time are as Fig. 4.Can significantly observe in Fig. 4, along with SiO ₂the increase of-POSS volume, frictional coefficient is along with also reducing, and when volume is 0.5wt%, frictional coefficient reaches minimum.When volume is 1wt%, become large relative to 0.5wt% frictional coefficient, so reach optimum value when volume is 0.5wt%.Think and serve except a kind of effect of microballoon bearing except having eutectic microballoon when rubbing, organosilicon inarch on silica simultaneously, makes nano composite material have excellent abrasion resistance and high temperature resistant property.In friction process, nano composite material, at the chemical redemption film of friction surface meeting formative dynamics, reduces the friction to contact surface, wearing and tearing.Nano composite material is because Van der Waals force is adsorbed in friction surface simultaneously, forms one deck physical adsorption film, can bring micro-polishing action like this, reduce surface roughness.

Claims

1. a preparation method for high perofmrnace lubricating oils additive, is characterized in that: be with γ-chloropropyl triethoxysilane for precursor reagent prepares POSS-Cl, then POSS-Cl and KI is reacted, the active stronger POSS-I of formation reaction; Again by silane coupler modified nano silicon, silane coupler modified nano silicon and POSS-I graft polymerization is made to obtain POSS modified manometer silicon dioxide finally by graft polymerization reaction.

2. preparation method according to claim 1, comprises surface treatment, the coupling agent modified and each unit process of graft modification, it is characterized in that:

Described surface treatment is the concentrated hydrochloric acid adding 4.88mL γ-chloropropyl triethoxysilane, 90mL dehydrated alcohol and 5mL in reactor, ultrasonic disperse 0.5h, stirring reaction 2d at 60 DEG C, obtains white solid subsequently, dry with absolute ethanol washing final vacuum, obtain POSS-Cl; Add in 80mL acetone by 1g POSS-Cl and 4g potassiumiodide, stirring reaction 6h at 30 DEG C, filters to remove solid impurity, filtrate is revolved steaming and obtains white solid; The white solid obtained is dissolved in distilled water, after filtration, collects solid product, after vacuum-drying, namely obtain POSS-I;

Described coupling agent modified be that 5g nano silicon, 2.5mL silane coupling agent are added ultrasonic disperse 0.5h in toluene, then stirring reaction 12h at 80 DEG C, utilize anhydrous methanol to wash after completion of the reaction, after vacuum-drying, obtain silane coupler modified nano silicon;

Described graft modification adds in acetone by silane coupler modified to 1g POSS-I, 2.5g nano silicon, then adds 1g NaHCO ₃as acid binding agent, at 90 DEG C, react 12h, the solid product obtained uses acetone and distilled water wash successively, obtains POSS modified manometer silicon dioxide after vacuum-drying.

3. preparation method according to claim 1, is characterized in that:

Described silane coupling agent is γ-chloropropyl triethoxysilane.