CN106520271A - High-dispersibility nano anti-grinding agent preparation method - Google Patents

Abstract

The invention discloses a high-dispersibility nano anti-grinding agent preparation method, which relates to the technical field of an anti-grinding agent. The method takes vanadic anhydride as a catalyst, takes linseed oil, propylene glycol and p-toluenesulfonic acid as raw materials, takes boric acid as a modifier, the modifier having high content of hydroxy and carbonyl is prepared through a reaction under gas mixture environment, through calcining fusion and mixing of aluminium nitride, silicon carbide and chromium dioxide, the particles can be prepared, the material is modified by the modifier, the surface energy of the particles is reduced, the combination force with the metal is increased, through a principle of increasing film forming ability by polyethylene wax, the problems that service life of lubricating oil is short due to excess consumption of anti-grinding agent for forming an effective protection oil film, layering effect due to long-term placement is generated, and the dispersibility of the added lubricating oil has defect can be solved. The prepared high-dispersibility nano anti-grinding agent can form long-term effective protection oil film and can increase the usage life of the lubricating oil.

Description

A kind of preparation method of high dispersancy nano antiwear additive

Technical field

The invention discloses a kind of preparation method of high dispersancy nano antiwear additive, is related to antiwear additive technical field.

Background technology

In traditional lubrication theory, lubrication is divided into hydrodynamic lubrication and boundary lubrication.Two metals for performing relative motion Surface is separated by lubricating oil film completely, and the directly contact for not having metal, this lubricating status are called hydrodynamic lubrication；With load Increase, the oil film thickness between metal surface is gradually thinning, and when load is increased to a certain degree, continuous oil film is by metal surface Summit is destroyed, and local produces the directly contact between metal surface, and this lubricating status are called boundary lubrication.In boundary lubrication In, when metal surface is solely subjected to moderate duty, can be adsorbed on the metal surface or and metal surface if any a kind of additive Sharp wear, this additive are referred to as antiwear additive.It is continuous swift and violent with auto industry and other each industrial circle Development, it is also increasingly harsher to the antiwear additive of traditional sense.Initial antiwear additive mainly all contains the corrosion such as sulfur, phosphorus Property material, life-time service is harmful to parts itself；At the same time, the noxious emission to environment is increased containing sulfur, phosphorus.U.S.'s stone Oil association (API) ILSAC GF-4 regulations automobile engine oil requires that phosphorus content must not exceed 0.08%, and sulfur content must not exceed 0.5% (5W/XY is oily) and 0.7% (10W/XX is oily)；2009 GF-5 automobile engine oils more the control of phosphorus 0.05% Below.ILSAC specifies the wear resistence for requiring oil product is further improved on the premise of sulfur and phosphorus content is reduced, thus this to sulfur, Lube oil additive based on phosphorus constitutes significant challenge.

With the continuous development of antiwear additive, the metal nano containing nano metal chemical composition a kind of in the last few years Antiwear additive is generated, and this antiwear additive not only has good performance in terms of wear resistence, while also overcoming to ring The impact in border, but it is not enough in terms of which has two：One is that nanometer solution belongs to suspension technology, after being configured to liquid, is still a kind of unstable Fixed liquid, long-time are placed and layering effect occur, while add its dispersibility in lubricating oil to remain larger defect, therefore should Technology needs further to be improved；Two is Nano metal powder, nano-ceramic powder, in parts, engine movements parts surface, is made for a long time With producing nanoparticle aggregate, this nanometer building-up effect is carried out for a long time, and nano-particle is cumulative, is deposited into bulky grain, New abrasion, scuffing of cylinder bore can be produced to parts.Therefore, seek a kind of sulfur-bearing, phosphorus amount little, and wear resistence is excellent, the lubrication of good stability Oily antiwear additive becomes industry problem demanding prompt solution.

The content of the invention

Present invention mainly solves technical problem：Easily excessively disappear to form effective tempered oil film layer for traditional antiwear additive Consume and cause Working Life of Lubricating Oil shorter, long-time is placed and layering effect occurs, its dispersibility is present in adding lubricating oil A kind of problem of defect, it is proposed that preparation method of high dispersancy nano antiwear additive, the present invention is by the use of vanadic anhydride as urging Agent, with oleum lini, Propylene Glycol and p-methyl benzenesulfonic acid as raw material, using boric acid as modifying agent, the reaction system under gaseous mixture environment The high modifying agent of hydroxyl and carbonyl content is obtained, is mixed by aluminium nitride, carborundum and chromium dioxide igneous fusion, granule is obtained, Which is modified by modification liquid, reduces particle surface energy, increased the adhesion with metal, film forming is increased by Tissuemat E Property principle, solve system antiwear additive for formed effective tempered oil film layer easily consume excessively and cause Working Life of Lubricating Oil compared with Short, long-time is placed and layering effect occurs, adds the problem of its dispersibility existing defects in lubricating oil.

In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is：

（1）Count by weight, take 40～50 parts of oleum linis, 23～33 parts of boric acid, 13～16 parts of Propylene Glycol, 8～12 parts to first Benzenesulfonic acid, 1～4 part of phosphorus pentasulfide and 2～3 parts of vanadic anhydrides, first by oleum lini, boric acid, p-methyl benzenesulfonic acid and five oxygen Change two vanadium to be put in the four-hole boiling flask with agitator, thermometer and reflux, using mixing gas shielded, then by four-hole boiling flask It is placed in oil bath pan, design temperature is 90 DEG C, preheats 30～50min, the gaseous mixture is argon and monosilane by volume 2:5 Mix；

（2）After above-mentioned preheating terminates, successively Propylene Glycol, phosphorus pentasulfide in above-mentioned parts by weight are put in four-hole boiling flask, Be warming up to 190～210 DEG C, with 200r/min 4～6h of stirring reaction, subsequently naturally cool to room temperature, to four-hole boiling flask in it is mixed Compound carries out filtration under diminished pressure, collects filtrate, obtains modification liquid；

（3）Count by weight, take 30～35 parts of aluminium nitride, 20～26 parts of carborundums, 14～17 parts of chromium dioxide, 17～22 parts Above-mentioned modification liquid, 2～4 parts of Tissuemat Es, 4～8 parts of 1- methyl anyl alcohols and 5～7 parts of oxybenzoic acid phenyl esters, first will nitridation Aluminum, carborundum and chromium dioxide mix homogeneously, are put in calcining furnace, design temperature be 1000～1200 DEG C, calcining 40～ 50min, cools to room temperature with the furnace, collects calcined material；

（4）Above-mentioned calcined material is put in pulverizer and is crushed, cross 400 mesh sieves, collect the granule that sieves, will subsequently sieve granule It is put in reactor with above-mentioned modification liquid, Tissuemat E, 1- methyl anyl alcohols and oxybenzoic acid phenyl ester in above-mentioned parts by weight, Design temperature is 240～280 DEG C, stirs 2～3h with 130r/min, then discharges, will go out material and be put in ultrasonic wave concussion device, if Frequency is determined for 1.2～1.5MHz, 40～50min of concussion, collection concussion mixture, you can secure satisfactory grades scattered property nano antiwear agent.

The application process of the present invention：In mass ratio 1：9～1：10, will be high-dispersion nano antiwear additive equal with lube base oil stirring It is even, finished lube is obtained, tetra- ball friction testing machines of finished lube agent Jing do not carry out performance test, and testing result is as follows, and not The lubricating oil of process is compared, and by high-dispersion nano antiwear additive obtained in the technical scheme, wear scar diameter reduces 85～88%, It is 1～2 times of conventional ferrous alloy that surface of friction pair generates the hardness of protective layer, it is maximum improve 9.0 without seizing charge values～ 9.4%, placed at 5～7 days and layering effect do not occur.

Beneficial effects of the present invention：

（1）High dispersancy nano antiwear additive corrosivity obtained in of the invention is substantially reduced；

（2）High dispersancy nano antiwear additive obtained in of the invention can form permanently effective tempered oil film layer, and increasing lubricating oil makes Use the life-span.

Specific embodiment

Count by weight, take 40～50 parts of oleum linis, 23～33 parts of boric acid, 13～16 parts of Propylene Glycol, 8～12 parts to first Benzenesulfonic acid, 1～4 part of phosphorus pentasulfide and 2～3 parts of vanadic anhydrides, first by oleum lini, boric acid, p-methyl benzenesulfonic acid and five oxygen Change two vanadium to be put in the four-hole boiling flask with agitator, thermometer and reflux, using mixing gas shielded, then by four-hole boiling flask It is placed in oil bath pan, design temperature is 90 DEG C, preheats 30～50min, the gaseous mixture is argon and monosilane by volume 2:5 Mix, after above-mentioned preheating terminates, Propylene Glycol, phosphorus pentasulfide in above-mentioned parts by weight are put into into four-hole boiling flask successively In, 190～210 DEG C are warming up to, with 200r/min 4～6h of stirring reaction, room temperature is subsequently naturally cooled to, in four-hole boiling flask Mixture carries out filtration under diminished pressure, collects filtrate, obtains modification liquid, count by weight, take 30～35 parts of aluminium nitride, 20～26 parts Carborundum, 14～17 parts of chromium dioxide, 17～22 parts of above-mentioned modification liquids, 2～4 parts of Tissuemat Es, 4～8 parts of 1- methyl anyl alcohols and 5 ～7 parts of oxybenzoic acid phenyl esters, first by aluminium nitride, carborundum and chromium dioxide mix homogeneously, are put in calcining furnace, setting Temperature is 1000～1200 DEG C, calcines 40～50min, cools to room temperature with the furnace, collects calcined material, above-mentioned calcined material is put into powder Crushed in broken machine, crossed 400 mesh sieves, collected the granule that sieves, the granule that will subsequently sieve is above-mentioned modified with above-mentioned parts by weight Liquid, Tissuemat E, 1- methyl anyl alcohols and oxybenzoic acid phenyl ester are put in reactor, and design temperature is 240～280 DEG C, with 130r/min stirs 2～3h, then discharges, and will go out material and be put in ultrasonic wave concussion device, and setpoint frequency is 1.2～1.5MHz, is shaken 40～50min is swung, concussion mixture is collected, you can secure satisfactory grades scattered property nano antiwear agent.

Example 1

Count by weight, take 40 parts of oleum linis, 23 parts of boric acid, 13 parts of Propylene Glycol, 8 parts of p-methyl benzenesulfonic acid, 1 part of phosphorus pentasulfide And 3 parts of vanadic anhydrides, first oleum lini, boric acid, p-methyl benzenesulfonic acid and vanadic anhydride are put into agitator, thermometer And in the four-hole boiling flask of reflux, using mixing gas shielded, then four-hole boiling flask is placed in oil bath pan, design temperature is 90 DEG C, preheating 30min, the gaseous mixture is argon and monosilane by volume 2:5 mix, after above-mentioned preheating terminates, according to It is secondary that Propylene Glycol, phosphorus pentasulfide in above-mentioned parts by weight are put in four-hole boiling flask, 190 DEG C are warming up to, are stirred with 200r/min Reaction 4h, subsequently naturally cools to room temperature, and filtration under diminished pressure is carried out to the mixture in four-hole boiling flask, collects filtrate, obtains modified Liquid, is counted by weight, takes 30 parts of aluminium nitride, 20 parts of carborundums, 14 parts of chromium dioxide, 17 parts of above-mentioned modification liquids, 2 parts of polyethylene Wax, 4 parts of 1- methyl anyl alcohols and 5 parts of oxybenzoic acid phenyl esters, first by aluminium nitride, carborundum and chromium dioxide mix homogeneously, It is put in calcining furnace, design temperature is 1000 DEG C, calcines 40min, cools to room temperature with the furnace, collects calcined material, by above-mentioned calcining Thing is crushed in being put into pulverizer, crosses 400 mesh sieves, and collection is sieved granule, in will subsequently sieve granule and above-mentioned parts by weight Above-mentioned modification liquid, Tissuemat E, 1- methyl anyl alcohols and oxybenzoic acid phenyl ester are put in reactor, and design temperature is 240 DEG C, 2h is stirred with 130r/min, then is discharged, material will be gone out and be put in ultrasonic wave concussion device, setpoint frequency is 1.2MHz, concussion 40min, collects concussion mixture, you can secure satisfactory grades scattered property nano antiwear agent.

In mass ratio 1：9, high-dispersion nano antiwear additive and lube base oil are stirred, finished lube is obtained, should Tetra- ball friction testing machines of finished lube agent Jing carry out performance test, and testing result is as follows, compared with untreated lubricating oil, lead to High-dispersion nano antiwear additive obtained in the technical scheme is crossed, and wear scar diameter reduces 85%, protective layer is generated in surface of friction pair Hardness is 1 times of conventional ferrous alloy, maximum to improve 9% without seizing charge values, placed at 5 days and layering effect does not occur.

Example 2

Count by weight, take 45 parts of oleum linis, 28 parts of boric acid, 14 parts of Propylene Glycol, 10 parts of p-methyl benzenesulfonic acid, 3 part of five sulfuration two Phosphorus and 2 parts of vanadic anhydrides, are put into oleum lini, boric acid, p-methyl benzenesulfonic acid and vanadic anhydride with agitator, temperature first In the four-hole boiling flask of meter and reflux, using mixing gas shielded, then four-hole boiling flask is placed in oil bath pan, design temperature is 90 DEG C, preheating 40min, the gaseous mixture is argon and monosilane by volume 2:5 mix, after above-mentioned preheating terminates, according to It is secondary that Propylene Glycol, phosphorus pentasulfide in above-mentioned parts by weight are put in four-hole boiling flask, 200 DEG C are warming up to, are stirred with 200r/min Reaction 5h, subsequently naturally cools to room temperature, and filtration under diminished pressure is carried out to the mixture in four-hole boiling flask, collects filtrate, obtains modified Liquid, is counted by weight, takes 32 parts of aluminium nitride, 23 parts of carborundums, 15 parts of chromium dioxide, 19 parts of above-mentioned modification liquids, 3 parts of polyethylene Wax, 6 parts of 1- methyl anyl alcohols and 6 parts of oxybenzoic acid phenyl esters, first by aluminium nitride, carborundum and chromium dioxide mix homogeneously, It is put in calcining furnace, design temperature is 1500 DEG C, calcines 45min, cools to room temperature with the furnace, collects calcined material, by above-mentioned calcining Thing is crushed in being put into pulverizer, crosses 400 mesh sieves, and collection is sieved granule, in will subsequently sieve granule and above-mentioned parts by weight Above-mentioned modification liquid, Tissuemat E, 1- methyl anyl alcohols and oxybenzoic acid phenyl ester are put in reactor, and design temperature is 260 DEG C, 2h is stirred with 130r/min, then is discharged, material will be gone out and be put in ultrasonic wave concussion device, setpoint frequency is 1.3MHz, concussion 45min, collects concussion mixture, you can secure satisfactory grades scattered property nano antiwear agent.

In mass ratio 1：9, high-dispersion nano antiwear additive and lube base oil are stirred, finished lube is obtained, should Tetra- ball friction testing machines of finished lube agent Jing carry out performance test, and testing result is as follows, compared with untreated lubricating oil, lead to High-dispersion nano antiwear additive obtained in the technical scheme is crossed, and wear scar diameter reduces 85%, protective layer is generated in surface of friction pair Hardness is 1 times of conventional ferrous alloy, maximum to improve 9% without seizing charge values, placed at 5 days and layering effect does not occur.

Example 3

Count by weight, take 50 parts of oleum linis, 33 parts of boric acid, 16 parts of Propylene Glycol, 12 parts of p-methyl benzenesulfonic acid, 4 part of five sulfuration two Phosphorus and 3 parts of vanadic anhydrides, are put into oleum lini, boric acid, p-methyl benzenesulfonic acid and vanadic anhydride with agitator, temperature first In the four-hole boiling flask of meter and reflux, using mixing gas shielded, then four-hole boiling flask is placed in oil bath pan, design temperature is 90 DEG C, 50min is preheated, the gaseous mixture is that argon and monosilane 5 are mixed by volume, after above-mentioned preheating terminates, successively Propylene Glycol, phosphorus pentasulfide in above-mentioned parts by weight are put in four-hole boiling flask, 210 DEG C are warming up to, it is anti-with 200r/min stirrings 6h is answered, room temperature is subsequently naturally cooled to, filtration under diminished pressure is carried out to the mixture in four-hole boiling flask, collected filtrate, obtain modification liquid, Count by weight, take 35 parts of aluminium nitride, 26 parts of carborundums, 17 parts of chromium dioxide, 22 parts of above-mentioned modification liquids, 4 parts of Tissuemat Es, 8 parts of 1- methyl anyl alcohols and 7 parts of oxybenzoic acid phenyl esters, first by aluminium nitride, carborundum and chromium dioxide mix homogeneously, are put into In calcining furnace, design temperature is 1200 DEG C, calcines 50min, cools to room temperature with the furnace, collects calcined material, above-mentioned calcined material is put Crushed in entering pulverizer, crossed 400 mesh sieves, collected the granule that sieves, the granule that will subsequently sieve is above-mentioned with above-mentioned parts by weight Modification liquid, Tissuemat E, 1- methyl anyl alcohols and oxybenzoic acid phenyl ester are put in reactor, and design temperature is 280 DEG C, with 130r/min stirs 3h, then discharges, and will go out material and be put in ultrasonic wave concussion device, and setpoint frequency is 1.5MHz, shakes 50min, Collect concussion mixture, you can secure satisfactory grades scattered property nano antiwear agent.

In mass ratio 1：10, high-dispersion nano antiwear additive and lube base oil are stirred, finished lube is obtained, should Tetra- ball friction testing machines of finished lube agent Jing carry out performance test, and testing result is as follows, compared with untreated lubricating oil, lead to High-dispersion nano antiwear additive obtained in the technical scheme is crossed, and wear scar diameter reduces 88%, protective layer is generated in surface of friction pair Hardness is 2 times of conventional ferrous alloy, maximum to improve 9.4% without seizing charge values, placed at 7 days and layering effect does not occur.

Claims (1)

1. a kind of preparation method of high dispersancy nano antiwear additive, it is characterised in that be specifically prepared as：

（1）Count by weight, take 40～50 parts of oleum linis, 23～33 parts of boric acid, 13～16 parts of Propylene Glycol, 8～12 parts to first Benzenesulfonic acid, 1～4 part of phosphorus pentasulfide and 2～3 parts of vanadic anhydrides, first by oleum lini, boric acid, p-methyl benzenesulfonic acid and five oxygen Change two vanadium to be put in the four-hole boiling flask with agitator, thermometer and reflux, using mixing gas shielded, then by four-hole boiling flask It is placed in oil bath pan, design temperature is 90 DEG C, preheats 30～50min, the gaseous mixture is argon and monosilane by volume 2:5 Mix；

（2）After above-mentioned preheating terminates, successively Propylene Glycol, phosphorus pentasulfide in above-mentioned parts by weight are put in four-hole boiling flask, Be warming up to 190～210 DEG C, with 200r/min 4～6h of stirring reaction, subsequently naturally cool to room temperature, to four-hole boiling flask in it is mixed Compound carries out filtration under diminished pressure, collects filtrate, obtains modification liquid；

（3）Count by weight, take 30～35 parts of aluminium nitride, 20～26 parts of carborundums, 14～17 parts of chromium dioxide, 17～22 parts Above-mentioned modification liquid, 2～4 parts of Tissuemat Es, 4～8 parts of 1- methyl anyl alcohols and 5～7 parts of oxybenzoic acid phenyl esters, first will nitridation Aluminum, carborundum and chromium dioxide mix homogeneously, are put in calcining furnace, design temperature be 1000～1200 DEG C, calcining 40～ 50min, cools to room temperature with the furnace, collects calcined material；

（4）Above-mentioned calcined material is put in pulverizer and is crushed, cross 400 mesh sieves, collect the granule that sieves, will subsequently sieve granule It is put in reactor with above-mentioned modification liquid, Tissuemat E, 1- methyl anyl alcohols and oxybenzoic acid phenyl ester in above-mentioned parts by weight, Design temperature is 240～280 DEG C, stirs 2～3h with 130r/min, then discharges, will go out material and be put in ultrasonic wave concussion device, if Frequency is determined for 1.2～1.5MHz, 40～50min of concussion, collection concussion mixture, you can secure satisfactory grades scattered property nano antiwear agent.