CN106032482A

CN106032482A - Lubricating grease composition and preparation method thereof

Info

Publication number: CN106032482A
Application number: CN201510105344.3A
Authority: CN
Inventors: 何懿峰; 孙洪伟; 段庆华; 张建荣; 刘中其; 孔锡奎; 郑会; 姜靓; 陈政
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-03-11
Filing date: 2015-03-11
Publication date: 2016-10-19
Anticipated expiration: 2035-03-11
Also published as: CN106032482B

Abstract

A lubricating grease composition and a preparation method thereof are disclosed. The invention relates to the field of lubricating grease, and discloses a lubricating grease composition. The lubricating grease composition comprises base oil (10-80 wt%) and a thickening agent, which comprises non-Newton fluid sulfurized calcium alkyl phenate-calcium sulfonate (10-70 wt%), zircon salts of higher fatty acid (1-10 wt%), and polyurea compounds (0.5-30 wt%), and also optionally comprises one or more of non-Newton fluid calcium naphthenate (0-70 wt%), non-Newton fluid calcium salicylate (0-70 wt%), non-Newton fluid calcium oleate (0-70 wt%), zircon salts of aromatic acid (0-15 wt%), and zircon salts of micro-molecular inorganic acid and/or lower fatty acid (0-15 wt%). The invention also discloses a preparation method of the lubricating grease composition. The provided lubricating grease composition has excellent performances.

Description

Lubricant composition and preparation method thereof

Technical field

The present invention relates to a kind of lubricant composition and preparation method thereof.

Background technology

SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER has preferable detergent-dispersant performance, good acid neutralization capacity and excellence Diffusibility, be used as the detersive of lubricating oil, be widely used in modulation medium and high classes I. C. engine oil, It is particularly suited for pressurized diesel engine oil to reduce the carbon deposit of top land and the additive of marine cylinder oil, its Technology development mainly makes its high alkalization, it is simply that the calcium carbonate calcium sulfenyl phenolate with surface activity It is distributed in flux oil become a kind of colloidal dispersion system.SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is alkyl phenol warp React with CaO, vulcanize, carbonating contour alkalization technology and obtain, the Patents about preparation has CN101423483 etc..

Utilize calcium sulfonate with high base number for raw material production grease, because of its have excellence antirust and anticorrosion Property, since putting goods on the market, cause the extensive concern of domestic and international grease industry, but, although high-alkali Value complex calcium sulfonate grease has the most excellent antirust and anticorrosive property, but easy in storage process Harden, and the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it Do not promoted rapidly, meanwhile, along with people are more and more higher to the requirement of environmental conservation, sulfonate with high base number In calcium production process must through sulfonation process the pollution of environment is also increasingly subject to the concern of people.Find one Plant antirust and anticorrosive property is similar with high base number composite calcium sulfonate base grease but can alleviate the problems referred to above Grease become the big problem that people face at present.

Zirconium belongs to Group IVB as a kind of transition metal, is positioned at for the 5th cycle.Zirconium-containing compound has Excellent lubrication, is often used as lubricating additive, such as CN101113382 and JP1973038444 The oxide of zirconium is improved abrasiveness as lubricant additive；WO2007143414 and US20060063682 describes zirconium tetrafluoride can be as one of wear reducing additive component becoming lubricant； US20060254823 finds that the lubricant containing 2 thylhexoic acid zirconates shows good resistance to heavy load And abrasion resistance；US20050043189 finds that fluozirconate such as fluorine zirconic acid aluminum can be used as oxidation retarder In the lubricant；DE102004021812 finds to add the inorganic salts such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate Enter inside grease and can improve abrasion resistance.

Summary of the invention

It is an object of the invention to provide one have the most antirust and anticorrosive property, storage good security and Grease that its feed preparation process is simple and environmentally-friendly and preparation method thereof.

The present inventor finds under study for action, and calcium sulfenyl phenolate is due to containing active sulfur, at high temperature Under easily may separate out elemental sulfur and produce corrosion, therefore, when as detersive, calcium sulfenyl phenolate Antirust and anticorrosive property far below sulfoacid calcium, but calcium sulfenyl phenolate is prepared grease as thickening agent Time, but can obtain and anticorrosion the most antirust with high base number composite calcium sulfonate base grease Property.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of lubricant composition, Described lubricant composition contains base oil and thickening agent, and described thickening agent contains non-newtonian fluid alkyl monosulfide Phenol calcium sulfoacid calcium, the zirconates of higher fatty acids and polyurea compound, described thickening agent also optionally with Non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little One or more in the zirconates of molecule mineral acid and/or lower fatty acid, with described lubricant composition On the basis of weight, the content of base oil is 10 80 weight %, non-newtonian fluid calcium sulfenyl phenolate sulfonic acid The content of calcium is 10 70 weight %, and the content of the zirconates of higher fatty acids is 1 10 weight %, polyureas The content of compound is 0.5 30 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, non- The content of newton body calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, the content of the zirconates of aromatic acid is 0-15 weight %, little molecule mineral acid and/or the zirconium of lower fatty acid The content of salt is 0 15 weight %, wherein, the zirconates of described higher fatty acids be by higher fatty acids with The reaction of component A forms, and the zirconates of described aromatic acid is to be reacted with component A by aromatic acid to form, described little point The zirconates of sub-mineral acid and/or lower fatty acid is by little molecule mineral acid and/or lower fatty acid and component A reaction form, described component A be in the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide at least A kind of.

Preferably, on the basis of the weight of lubricant composition, the content of base oil is 20 70 weight %, The content of non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 20 60 weight %, the zirconates of higher fatty acids Content be 26 weight %, the content of polyurea compound is 1 20 weight %, non-newtonian fluid calcium naphthenate Content be 0-50 weight %, the content of non-newtonian fluid calcium salicylate is 0-50 weight %, non-newtonian fluid The content of calcium oleate is 0-50 weight %, and the content of the zirconates of aromatic acid is 2 10 weight %, little molecule without The content of the zirconates of machine acid and/or lower fatty acid is 2 10 weight %.

Described component A contains oxide and/or the hydroxide of zirconium, in terms of zirconium, the oxide of zirconium and/or Hydroxide is 1:0 10 with the mol ratio of zirconium alkoxide, more preferably 1:0.5 5.

Second aspect, the invention provides the preparation method of lubricant composition as above, the method Including: by thickening agent and part basis oil mix homogeneously, refine at 180 230 DEG C of constant temperature, add surplus Base oil, adds necessary additive, obtains finished product, and described thickening agent contains non-newtonian fluid alkyl monosulfide Phenol calcium sulfoacid calcium, the zirconates of higher fatty acids and polyurea compound, described thickening agent also optionally with Non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little One or more in the zirconates of molecule mineral acid and/or lower fatty acid.

The third aspect, the invention provides the preparation method of a kind of lubricant composition, and the method includes:

(1) containing newton body calcium sulfenyl phenolate, newton body and/or non-newtonian fluid sulfoacid calcium, or will contain There are newton body and/or non-newtonian fluid calcium sulfenyl phenolate, the high base number material of newton body sulfoacid calcium, and part Base oil mixes, and obtains mixture, and described high base number material is also optionally with newton body and/or non newtonian Body calcium naphthenate, newton body and/or non-newtonian fluid calcium salicylate and newton body and/or non-newtonian fluid calcium oleate In one or more；

(2) the most at least partly it is combined the reaction of zirconium: add component A, adds higher aliphatic Sour, optional aromatic acid, optional little molecule mineral acid and/or lower fatty acid, react, described group Dividing A is at least one in the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide；And/or optionally Carry out the reaction of at least part of polyurea compound: add part basis oil and monoamine, or be additionally added diamidogen, Add diisocyanate to react；

(3) add transforming agent, heat up and treat material retrogradation；

(4) carry out remaining the reaction of compound zirconium；

(5) heat up dehydration；

(6) carry out remaining the reaction of polyurea compound；

(7) it is warmed up to 180 230 DEG C of constant temperature refinings, adds surplus base oil, add necessary additive, Obtain finished product.

Fourth aspect, the invention provides the lubricant composition prepared by method as above.

The lubricant composition of the present invention, has with complex calcium sulfonate zirconio polyurea grease the most even more Excellent antirust and anticorrosive property, and there is excellent storage stability, also have and be better than complex calcium sulfonate The viscous resistance of zirconio polyurea grease, mechanical stability, water-resistance, colloid stability, abrasion resistance, Extreme pressure anti-wear and lubricating life, and also there is the performances such as excellent heat-resisting quantity.The grease of the present invention Feed preparation process simple and environmentally-friendly, constant product quality.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.

The invention provides a kind of lubricant composition, this lubricant composition have employed calcium mahogany sulfonate And/or calcium alkylbenzenesulfonate, synthesis calcium sulfenyl phenolate, optional petroleum naphthenic acid calcium and/or synthesis cycloalkanes Acid calcium, optional salicylate calcium, optional natural calcium oleate and/or synthesis calcium oleate are raw material, with Shi Hanyou is combined the polyurea compound that zirconium thickening agent, isocyanates and amine reaction produce.

Present invention also offers the preparation method of foregoing grease composition.

On the one hand, the invention provides a kind of lubricant composition, described lubricant composition contains basis Oil and thickening agent, described thickening agent contains non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, higher fatty acids Zirconates and polyurea compound, described thickening agent is also optionally with non-newtonian fluid calcium naphthenate, non newtonian Body calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little molecule mineral acid and/or lower fatty acid Zirconates in one or more, on the basis of the weight of described grease, the content of base oil is 10 80 Weight %, the content of non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 10 70 weight %, higher aliphatic The content of the zirconates of acid is 1 10 weight %, and the content of polyurea compound is 0.5 30 weight %, non-cattle The content of body calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight %, the content of non-newtonian fluid calcium oleate is 0-70 weight %, and the content of the zirconates of aromatic acid is 0-15 weight %, the content of the zirconates of little molecule mineral acid and/or lower fatty acid is 0 15 weight %, wherein, institute Stating the zirconates of higher fatty acids is to be reacted with component A by higher fatty acids to form, and the zirconates of described aromatic acid is Reacted with component A by aromatic acid and form, the zirconates of described little molecule mineral acid and/or lower fatty acid be by Little molecule mineral acid and/or lower fatty acid react with component A and form, and described component A is the oxidation of zirconium At least one in thing, the hydroxide of zirconium and zirconium alkoxide.

In the present invention, " optionally with " refer to can not contain this component containing this component, That is, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, One or more in the zirconates of little molecule mineral acid and/or lower fatty acid are optional components, the present invention's Lubricant composition can include this component, it is also possible to do not include this component.

Non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid salicylic acid Calcium, non-newtonian fluid calcium oleate or a combination thereof thing are at infrared spectrum 873cm^–1–886cm^–1There is crystal formation carbon in place Acid calcium characteristic absorption peak.Non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is by newton body sulfoacid calcium and newton Body calcium sulfenyl phenolate is converted by transforming agent and obtains, non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium total Base number is 250 450mgKOH/g, preferably 300 400mgKOH/g；Non-newtonian fluid calcium naphthenate is Being obtained by the conversion of newton body calcium naphthenate, the total base number of non-newtonian fluid calcium naphthenate is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium salicylate is by newton The conversion of body calcium salicylate obtains, and the total base number of non-newtonian fluid calcium salicylate is 250-450mgKOH/g, It is preferably 300-400mgKOH/g；Non-newtonian fluid calcium oleate is converted by newton body calcium oleate and obtains, The total base number of non-newtonian fluid calcium oleate is 250-450mgKOH/g, preferably 300-400mgKOH/g. And newton body sulfoacid calcium, newton body calcium sulfenyl phenolate, newton body calcium naphthenate, newton body calcium salicylate, Containing unformed calcium carbonate in newton body calcium oleate, at infrared spectrum 860cm^–1–865cm^–1There is nothing in place Sizing calcium carbonate characteristic absorption peak.Newton body calcium sulfenyl phenolate is synthesis calcium sulfenyl phenolate, its total alkali Value is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body sulfoacid calcium is oil sulphur Acid calcium and/or calcium alkylbenzenesulfonate, its total base number is 250-450mgKOH/g, is preferably 300-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, its Total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium salicylate is Salicylate calcium, its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g； Newton body calcium oleate is natural calcium oleate and/or synthesis calcium oleate, and its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g.Non-newtonian fluid calcium sulfenyl phenolate sulphur Acid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate and the base number of non-newtonian fluid calcium oleate mixing Weight meansigma methods for the base number of each component.

In the present invention, higher fatty acids be carbon number be fatty acid or the hydroxyl fat of 8-20, preferably 10-18 Fat acid, such as in lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic acid At least one, preferably 12-hydroxy stearic acid.

In the present invention, aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, and aromatic acid can be Substituted or unsubstituted aromatic acid, its substituent group can be alkyl, thiazolinyl, alkynyl, aryl, halo or At least one in the alkyl or aryl of perhalogeno etc., the molecular weight of aromatic acid is preferably smaller than equal to 550.Virtue Acid is preferably binary aromatic acid, for example, it is possible to selected from the unsubstituted or substituted adjacent benzene two of C1 C5 alkyl At least one in formic acid, M-phthalic acid, p-phthalic acid, biphenyl dicarboxylic acid, polyphenyls dioctyl phthalate. It is preferably phthalic acid, M-phthalic acid, p-phthalic acid, biphenyl dicarboxylic acid, and methyl replaces Biphenyl dicarboxylic acid, at least one in polyphenyls dioctyl phthalate etc..

In the present invention, the molecular weight of little molecule mineral acid or lower fatty acid is less than or equal to 250.Wherein, Little molecule mineral acid can be selected from least one in boric acid, phosphoric acid, sulphuric acid etc., preferably boric acid and/ Or phosphoric acid；Lower fatty acid can be selected from acetic acid, ethanedioic acid, propanoic acid, malonic acid, butanoic acid, succinic acid At least one in Deng, preferably acetic acid.

The present inventor has been surprisingly found that under study for action, when component A contains oxide and/or the hydrogen of zirconium During oxide, when i.e. the raw material of zirconium contains oxide and/or the hydroxide of zirconium, can further improve lubrication The viscous resistance of fat, mechanical stability, water-resistance, colloid stability and abrasion resistance, therefore, component A Preferably comprise oxide and/or the hydroxide of zirconium, wherein, in terms of zirconium, the oxide of zirconium and/or hydrogen-oxygen Compound is preferably 1:0 10, more preferably 1:0.2 8 with the mol ratio of zirconium alkoxide, the most excellent Elect 1:0.5 5 as, in the situation of the oxide of zirconium and/or hydroxide with the preferred molar ratio of zirconium alkoxide Under, it is possible to improve further grease thickening, mechanical stability, water-resistance, colloid stability and Abrasion resistance.

In the present invention, oxide and/or the hydroxide of zirconium are preferably selected from ZrO₂、ZrO(OH)₂、Zr(OH)₄ And at least one in their hydrate.ZrO(OH)₂Hydrate can be brand-new wet hydrogen oxidation Zirconium, it can pass through ZrOX₂·8H₂O (X is F, Cl, Br or I) or ZrO (NO₃)₂·2H₂O etc. Obtaining with alkali reaction, wherein, alkali can be NaOH, KOH, strong aqua ammonia etc., preferably ZrOCl₂·8H₂O React with NaOH.

In the present invention, the formula of zirconium alkoxide can be Zr (OR₁)₄, R₁Can be the alkyl of C1 C10, It is preferably the alkyl of C2 C6；It is highly preferred that zirconium alkoxide is selected from ethanol zirconium, zirconium-n-propylate, positive fourth At least one in alcohol zirconium, zirconium tert-butoxide and n-amyl alcohol zirconium.

In the present invention, polyurea compound, without particular/special requirement, can be polyurea compound commonly used in the art, Such as, the structural formula of polyurea compound can be

Wherein, n is preferably the integer of 03.

Wherein, R¹、R⁴Can be the same or different, can be alkyl, cycloalkyl or aryl, alkyl Or the carbon number of cycloalkyl can be 8 24, preferably 10 18, aryl can be phenyl or substituted phenyl, It is preferably phenyl or the alkyl of C1 C3 or the phenyl of halogen substiuted.

Wherein, R²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2 12, is preferably 28, arlydene can be phenylene or biphenylene.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or sub-cycloalkanes The carbon number of base can be 6 30, preferably 6 20, R³More preferably With-(CH₂)₆In- At least one.

In the present invention, it is possible to use single polyureas, it is possible to use mixing polyureas, such as, polyureas chemical combination Thing can be in dimerization carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds At least one.

Above-mentioned polyurea compound can use the thinkable various methods of those skilled in the art institute to obtain, example As can according to CN103060069A, CN103060070A, CN103060068A, The method that CN103060067A, US3243372 record prepares.

Described lubricating base oil can be mineral oil, artificial oil, vegetable oil or their mixture, 100 DEG C dynamic viscosity is 4 150mm²/ s, preferably 10 60mm²/s.Artificial oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc..

The lubricant composition of the present invention can also contain various additives, such as antioxidant, extreme-pressure anti-wear Agent, antirust agent etc..Wherein, antioxidant preferred arylamine kind antioxidant, account for grease gross weight 0.01 5%, preferably 0.1 2.5%, can be in diphenylamines, phenyl αnaphthylamine and di-iso-octyldiphenylamine At least one, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5 12% of grease gross weight, Preferably 0.8 8%, can be dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, two Sulfur for dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, two Molybdenum sulfide, politef, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, At least one in tungsten disulfide, selenium sulfide, fluorographite, calcium carbonate and zinc oxide；Antirust agent accounts for The 0.01 4.5% of grease gross weight, preferably 0.1 2%, can be barium mahogany sulfonate, petroleum sodium sulfonate, At least one in benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

In the present invention, " optionally with " as it was previously stated, do not repeat them here.

In the present invention, for non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, non-newtonian fluid calcium naphthenate, Non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of higher fatty acids, the zirconates of aromatic acid, little Molecule mineral acid and/or the zirconates of lower fatty acid, polyurea compound, base oil and additive as it has been described above, Do not repeat them here.

It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil Being the total amount of base oil used, in the present invention, part basis oil is excellent with the weight ratio of surplus base oil Elect 1:0.1 5 as.

For non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid water Poplar acid calcium, non-newtonian fluid calcium oleate or a combination thereof thing, can be by newton body sulfoacid calcium, newton body sulfuration alkane Base phenol calcium, newton body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate or a combination thereof thing Respectively by transforming agent convert obtain, such as, by newton body sulfoacid calcium, newton body calcium sulfenyl phenolate, Optional newton body calcium naphthenate, optional newton body calcium salicylate, optional newton body calcium oleate and base Plinth oil Hybrid Heating to 50 80 DEG C, the transforming agent needed for addition reacts, after all transforming agents add, 80 100 DEG C of constant temperature 60 90 minutes, then heat to 110 130 DEG C of dehydrations.

In the present invention, " optional " refer to have this raw material can also not this raw material, such as, " appoint The newton body calcium naphthenate of choosing " i.e. refer to there is newton this raw material of body calcium naphthenate, it is also possible to do not have This raw material of newton body calcium naphthenate.

(3) add transforming agent, heat up and treat material retrogradation；

(4) carry out remaining the reaction of compound zirconium；

(5) heat up dehydration；

(6) carry out remaining the reaction of polyurea compound；

" optionally with " as it was previously stated, do not repeat them here.

In the present invention, newton body calcium sulfenyl phenolate, non-newtonian fluid calcium sulfenyl phenolate, newton body sulfonic acid Calcium, non-newtonian fluid sulfoacid calcium, newton body calcium naphthenate, non-newtonian fluid calcium naphthenate, newton body salicylic acid Calcium, non-newtonian fluid calcium salicylate, newton body calcium oleate, non-newtonian fluid calcium oleate, higher fatty acids, virtue Molecule mineral acid sour, little, lower fatty acid, the oxide of zirconium, the hydroxide of zirconium, zirconium alkoxide and Base oil is not as it was previously stated, repeat them here.

In step of the present invention (1), " containing newton body calcium sulfenyl phenolate, newton body and/or non newtonian Body sulfoacid calcium, or containing newton body and/or non-newtonian fluid calcium sulfenyl phenolate, newton body sulfoacid calcium high-alkali Value material " i.e. refer to the calcium sulfenyl phenolate in high base number material and sulfoacid calcium at least one be newton body Type.

In step of the present invention (1), for the weight ratio of sulfoacid calcium and calcium sulfenyl phenolate without particular/special requirement, It is preferably 1:0.25 4.For the amount of other optional high base number materials without particular/special requirement, can basis Being actually needed the amount commonly used in the art that uses, high base number material gross weight is excellent with the weight ratio of part basis oil Elect 1:0.1 3 as.

In step of the present invention (2), " being the most at least partly combined the reaction of zirconium " i.e. includes three kinds Situation: (i) does not carry out the reaction of compound zirconium, i.e. do not carry out the reaction of compound zirconium in step (2), only In step (4), carry out the reaction of whole compound zirconiums, be i.e. equivalent to the inventive method and be initially charged conversion Agent converts, and carries out the reaction of compound zirconium after conversion again；(ii) reaction of the compound zirconium of part is carried out, i.e. In step (2), carry out the reaction of the compound zirconium of part, carry out again remaining compound zirconium in step (4) Reaction, is i.e. equivalent to the inventive method and carries out the reaction of the compound zirconium of part before conversion, enter The reaction of the compound zirconium of row part；(iii) all it is combined the reaction of zirconium, i.e. carries out in step (2) The reaction of whole compound zirconiums, does not carry out step (4), is i.e. equivalent to the inventive method and first carries out compound zirconium Reaction, then convert.

In step of the present invention (2), " optionally carrying out the reaction of at least part of polyurea compound " i.e. includes Three kinds of situations: (i) does not carry out the reaction of polyurea compound, i.e. do not carry out polyureas chemical combination in step (2) The reaction of thing, only carries out the reaction of whole polyurea compounds in step (6), is i.e. equivalent to this Bright method is initially charged transforming agent and converts, and carries out the reaction of polyurea compound after conversion again；(ii) carry out The reaction of part polyurea compound, i.e. carries out the reaction of part polyurea compound in step (2), Step (6) carries out remaining the reaction of polyurea compound again, is i.e. equivalent to the inventive method before conversion Carry out the reaction of part polyurea compound, carry out the reaction of part polyurea compound the most again；(iii) Carry out the reaction of whole polyurea compound, i.e. in step (2), carry out the anti-of whole polyurea compounds Should, do not carry out step (6), be i.e. equivalent to the inventive method and first carry out the reaction of polyurea compound, then enter Row converts.

This area, when preparing grease, is generally individually to be initially charged transforming agent to convert, then is combined Zirconium and the reaction of polyurea compound, during such as preparation sulfoacid calcium zirconio polyurea grease.But the invention of the present invention People finds under study for action, is combined situation (ii) or (iii) of the reaction of zirconium according to the carrying out of above-mentioned steps (2), And/or according to the situation (ii) of the reaction carrying out polyurea compound of above-mentioned steps (2) or (iii), enter The method of the row present invention, the most first carries out the reaction of all or part of compound zirconium and/or polyurea compound reaction, Convert again, it is possible to further improve the performance of prepared grease.This is likely due to first carry out The reaction of all or part of compound zirconium and/or the reaction of polyurea compound, it is possible to preferably by the newton of oily Body calcium sulfenyl phenolate is converted into the non-newtonian fluid calcium sulfenyl phenolate of smectic.It is therefore preferred that step (2), in, the reaction of zirconium at least partly it is combined；And/or, carry out at least part of polyurea compound Reaction.I.e., preferably first carry out the reaction of all or part of compound zirconium and/or first carry out all or part of poly- Carbamide compound reacts, then converts.

As it was previously stated, the present inventor has been surprisingly found that under study for action, when component A contains the oxidation of zirconium When thing and/or hydroxide, when i.e. the raw material of zirconium contains oxide and/or the hydroxide of zirconium, one can be entered Step improves the mechanical stability of grease, water-resistance, colloid stability, abrasion resistance and the lubrication prepared Life-span.It is therefore preferred that in step (2) and step (4), when carrying out the reaction of compound zirconium, At 85 100 DEG C, add component A, add higher fatty acids, stir 5 30 minutes, add optional Aromatic acid, optional little molecule mineral acid and/or lower fatty acid, stir 5 30 minutes, described component A Oxide containing zirconium and/or hydroxide, in terms of zirconium, the oxide of zirconium and/or hydroxide and alcoxyl The mol ratio of base zirconium is preferably 1:0 10, more preferably 1:0.2 8, the most preferably 1:0.5 5. Wherein, the addition of component A, higher fatty acids, aromatic acid, little molecule mineral acid and/or lower fatty acid is suitable Sequence can exchange.

In the present invention, higher fatty acids and optional aromatic acid and optional little molecule mineral acid and/or low The H of level fatty acid⁺The amount of total material is equal to all neutralizing the oxide of zirconium, the hydroxide of zirconium and alcoxyl H needed for base zirconium⁺Molal quantity, but the hydroxide of the oxide of zirconium, zirconium and zirconium alkoxide relative to Higher fatty acids, aromatic acid and selective little molecule mineral acid and/or lower fatty acid can excess 1 10%.

In the present invention, the addition of the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide is the most high-alkali The 1 15% of value material gross weight；With H⁺The gauge of material, higher fatty acids and optional aromatic acid and Optional little molecule mineral acid and/or the mol ratio of lower fatty acid are preferably 1:1 10.

In step of the present invention (2) and step (6), when carrying out the reaction of polyurea compound, can prepare Single polyureas, it is also possible to preparation mixing polyureas.Prepare the method for polyurea compound without particular/special requirement, permissible The various methods using those skilled in the art to commonly use, such as, can use as above CN103060069A、CN103060070A、CN103060068A、CN103060067A、 Prepared by the method that US3243372 records.Preferably, add part basis oil, monoamine, optional diamidogen, After diisocyanate, 100 120 DEG C of constant temperature 10 30 minutes, wherein, monoamine, optional diamidogen, The amount of the material of diisocyanate meets following relation: the thing of the amount of the material of diisocyanate × 2=monoamine Amount × 2 of the material of the amount+diamidogen of matter, or, diisocyanate excess, amount≤10% of excess.

The structure of described diisocyanate is OCN R³NCO, R³Can be carbon number be 6 30, preferably Arlydene, alkylidene or the cycloalkylidene of 6 20, is preferably -(CH₂)₆-etc.. Such as, described diisocyanate can be toluene di-isocyanate(TDI) (TDI), diphenylmethane diisocyanate Ester (MDI), six hexylidene diisocyanates (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI) With at least one in xylylene diisocyanate (XDI) etc..

Described monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R¹–NH₂、R⁴–NH₂, R therein¹、R⁴Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 24, Preferably 10 18, aryl can be phenyl or substituted phenyl, preferably phenyl or C1 C3 alkyl or halogen Substituted phenyl.Preferably monoamine can be selected from aniline, m-chloroaniline, parachloroanilinum and/or to toluene The arylamine of amine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, the fatty amine of 18-amine..

Described diamidogen can be fatty amine or arylamine, and structural formula is NH₂–R²–NH₂, wherein, R²Permissible Being alkylidene or arlydene, the carbon number of alkylidene can be 2 12, preferably 28, and arlydene can be sub- Phenyl or biphenylene.Preferably diamidogen can be selected from p-phenylenediamine, o-phenylenediamine, 4,4 ' biphenyl two The aromatic amine of amine and/or selected from ethylenediamine, propane diamine, the straight-chain fatty amine of 1,6 hexamethylene diamines.

In step of the present invention (3), it is preferable that at 50 80 DEG C, preferably constant temperature 10 30 minutes, adds Enter required transforming agent to react, preferably add and stir 8 12 minutes after every kind of transforming agent, all turns After agent adds, 80 100 DEG C of constant temperature 60 90 minutes.

Transforming agent is preferably selected from fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, carbonic acid Calcium, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8 C20 alkane At least one in base benzenesulfonic acid, C16 C24 alkyl phenol and water；It is more preferably selected from the fat of C1 C5 Alcohol, the fatty acid of C1 C5, the aliphatic ketone of C1 C5, the fatty aldehyde of C1 C5, the fat of C1 C5 Amine, the ether of C1 C5, boric acid, the alkyl phosphonic acid of C1 C10, the di alkyl phosphonic acid of C2 C16, C6 C20 Arylphosphonic acid, the diaryl phosphonic acids of C12 C24, the aromatic alcohol of C7 C20, the aromatic amine of C7 C20, At least one in C8 C20 alkyl benzene sulphonate, C16-C22 alkyl phenol and water；The most preferably select From DBSA, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, vinegar At least one in acid and water.The addition of transforming agent is preferably the 2 30% of high base number material gross weight, More preferably the 6 22% of high base number material gross weight.

In the present invention, fatty alcohol includes straight chain, side chain and ring-type fatty alcohol, fatty acid, aliphatic ketone, Fatty aldehyde, fatty amine are in like manner.

In step of the present invention (5), it is preferable that be warming up to 110-130 DEG C, 30-60 is preferably kept to divide Clock is to realize dehydration.

In step of the present invention (7), it is preferable that be warmed up to 180 230 DEG C of constant temperature 5 30 minutes；Add Surplus base oil, treats that temperature is cooled to 100 120 DEG C, adds necessary additive, stirring, is circulated throughout Filter, homogenizing, degassing.

In the present invention, in step (1), the total amount of base oil used is used with step (2) and (6) In the total amount of base oil and step (7), the weight ratio of the total amount of base oil used is preferably 1:0.1 5: 0.1–5。

Fourth aspect, the profit that the preparation method that present invention also offers is provided by third aspect present invention prepares Grease composition.

Compared with the lubricant composition that the preparation method provided by second aspect prepares, the third aspect provides Preparation method prepare lubricant composition have more preferable viscous resistance, water-resistance, colloid stability, Abrasion resistance and lubricating life.

Embodiment

The present invention is further illustrated for below example, but and is not so limited the present invention.

In the following Examples and Comparative Examples:

Non-newtonian fluid alkyl monosulfide calcium phenolsulfonate in the lubricant composition prepared, non-newtonian fluid cycloalkanes The total content of acid calcium, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate all uses non-newtonian fluid alkyl monosulfide Phenol calcium sulfoacid calcium % represents, i.e.

Non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium %=(overbased or calcium sulfonate with high base number raw material weight Amount+overbased or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER raw material weight+overbased or overbased calcium alkyl-salicylate Raw material weight+overbased or high base number calcium salicylate raw material weight+overbased or high base number calcium oleate Raw material weight+transforming agent gross weight)/grease gross weight × 100%.Transforming agent all counts non-newtonian fluid sulfur Change in the content of alkyl phenol calcium sulfoacid calcium.

Overbased and SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is prepared according to patent CN101423483.

Overbased and calcium sulfonate with high base number is prepared according to the method for patent CN101928239A.

It is limited that overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Lander Speciality Petrochemicals share Company.

Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industry Co., Ltd.

High base number calcium salicylate is prepared according to the method for patent CN1345921.

High base number calcium oleate is prepared according to document (NLGI Spokeman, 2009,73 (2): 1 17) method.

Embodiment 1

The present embodiment is for illustrating lubricant composition prepared by the present invention.

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 24kg)；Superelevation alkali Value calcium sulfenyl phenolate (total base number is 400mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm²/ s, 30kg)；4 octadecylphenol (2.8kg)；Methanol (1kg)；Vinegar Acid (0.56kg)；Zr(OH)₄(3.9kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)； 18-amine. (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 17kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring, is warmed up to 95 DEG C, adds the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, stirs Mix 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes；Add 3.5kg p-phthalic acid, Stir 10 minutes；Add the HVI500SN lubricating base oil of 10kg and make material be down to 50 DEG C, permanent Temperature 30 minutes, adds 2.8kg 4 octadecylphenol, and temperature controls at 50 DEG C, stirs 10 minutes, Add 1kg methanol, stir 10 minutes, add the aqueous acetic acid that 2.8kg concentration is 20 weight %, Stir 10 minutes, be warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation；120 DEG C it are warmed up under stirring, Keep 45 minutes, dehydration；Add HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, Stir 4 minutes, add the 0.7kg MDI in the HVI500SN lubricating base oil being dissolved in 2kg, stir Mixing 4 minutes, the mol ratio of added MDI and 18-amine. is 1:2,120 DEG C of constant temperature 20 minutes；Finally It is warmed up to 200 DEG C of constant temperature 10 minutes.Then, remaining HVI500SN lubricating base oil is added；Treat Temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 36.8 weight %；Polyureas 2.4 weight %；Lubricating base oil 51.9 weight %； 12 hydroxy stearic acid oxygen zirconium 2.6 weight %；P-phthalic acid oxygen zirconium 6.3 weight %.

Embodiment 2

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 24kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm²/ s, 20kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)； Zirconium-n-butylate (7.83k)；Zr(OH)₄(0.65kg)；Stearic acid (1.9kg)；Phthalic acid (3.5kg)； Lauryl amine (1.31kg)；MDI(0.89kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscositys For 11mm²/ s, 27kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 6kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 24kg total base number are The SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir Mix；It is warmed up to 100 DEG C, adds HVI500SN lubricating base oil and the 0.131kg lauryl amine of 0.2kg, Stir 8 minutes, add the 0.089kg MDI in the HVI500SN lubricating base oil being dissolved in 0.2kg, Stirring 8 minutes, the mol ratio of added MDI and lauryl amine is 1:2,100 DEG C of constant temperature 10 minutes；? At 85 DEG C, addition 0.783kg zirconium-n-butylate and the Zr (OH) that solid content is 20 weight %₄Suspension 0.325kg, in terms of zirconium, Zr (OH)₄It is 1:5 with the mol ratio of zirconium-n-butylate, stirs 10 minutes, add Enter 0.19kg stearic acid, stir 10 minutes, add 0.35kg phthalic acid, stir 10 minutes； At 80 DEG C, constant temperature 10 minutes, add 2.8kg 4 octadecylphenol, temperature controls at 80 DEG C, Stir 10 minutes, add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir 10 minutes, rise Warm to 90 DEG C, constant temperature 60 minutes, material retrogradation；At 85 DEG C, successively add 7.047kg n-butyl alcohol Zirconium and the Zr (OH) that solid content is 20 weight %₄Suspension 2.925kg, in terms of zirconium, Zr (OH)₄With positive fourth The mol ratio of alcohol zirconium is 1:5, stirs 10 minutes, adds 1.71kg stearic acid, stirs 10 minutes, Add 3.15kg phthalic acid, stir 10 minutes；It is warmed up to 110 DEG C under stirring, keeps 60 minutes, Dehydration；Add HVI500SN lubricating base oil and the 1.179kg lauryl amine of 1.8kg, stir 8 minutes, Add the 0.801kg MDI in the HVI500SN lubricating base oil being dissolved in 1.8kg, stir 8 minutes, Added MDI is 1:2 with the mol ratio of 18-amine., 100 DEG C of constant temperature 10 minutes；Finally it is warmed up to 230 DEG C constant temperature 5 minutes, then, is cooled to 160 DEG C, adds remaining HVI500SN lubricating base oil, Treating that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 36.9 weight %；Polyureas 2.4 weight %；Lubricating base oil 51.9 weight %； Zirconyl stearate 2.5 weight %；Phthalic acid oxygen zirconium 6.3 weight %.

Embodiment 3

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 24kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C kinematic viscosity is 31mm²/ s, 15kg)；4 octadecylphenol (2.8kg)；Methanol (1kg)；Vinegar Acid (0.56kg)；Zirconium-n-propylate (4.0kg)；Zr(OH)₄(2.0kg)；12 hydroxy stearic acids (2kg)； 2 methyl 1,4 phthalic acid (3.8kg)；18-amine. (1.5kg)；MDI(0.7kg)；HVI500SN (100 DEG C of kinematic viscositys are 11mm to lubricating base oil²/ s, 7kg).

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter 24kg total base number be the calcium sulfonate with high base number of 320mgKOH/g, 6kg total base number be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and the HVI150BS lubricating base oil of 15kg, stirring；It is warmed up to 110 DEG C, add HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, stir 4 minutes, then add Enter to be dissolved in the 0.7kg MDI in the HVI500SN lubricating base oil of 2kg, stir 4 minutes, added The mol ratio of MDI and 18-amine. is 1:2,110 DEG C of constant temperature 15 minutes；At 65 DEG C, constant temperature 30 points Clock, adds 2.8kg 4 octadecylphenol, and temperature controls at 65 DEG C, stirs 10 minutes, adds 1kg Methanol, stirs 10 minutes, adds the aqueous acetic acid that 2.8kg concentration is 20 weight %, stirs 10 points Clock, is warmed up to 100 DEG C, constant temperature 70 minutes, material retrogradation；At 90 DEG C, add 4.0kg normal propyl alcohol Zirconium and the Zr (OH) that solid content is 20 weight %₄Suspension 10kg, in terms of zirconium, Zr (OH)₄And normal propyl alcohol The mol ratio of zirconium is 1:1, stirs 10 minutes, adds 2kg 12 hydroxy stearic acid, stirs 10 minutes, Add 3.8kg 2 methyl Isosorbide-5-Nitrae phthalic acid, stir 10 minutes；It is warmed up to 130 DEG C under stirring, keeps 30 minutes, dehydration；Finally it is warmed up to 180 DEG C of constant temperature 20 minutes.Then, remaining HVI500SN is added Lubricating base oil；Treating that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection The results are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 50.6 weight %；Polyureas 3.3 weight %；Lubricating base oil 33.4 weight %； 12 hydroxy stearic acid oxygen zirconium 3.6 weight %；2 methyl 1,4 phthalic acid oxygen zirconium 9.1 weight %.

Embodiment 4

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 14kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 6kg)；Naphthenate with superhigh base number calcium (total base number For 400mgKOH/g, 10kg)；(100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 25kg)；DBSA (1.2kg)；4 octadecylphenol (1.6kg)；Methanol (1kg)； Acetic acid (0.56kg)；Ethanol zirconium (2.21kg)；Zr(OH)₄(2.6kg)；12 hydroxy stearic acids (2kg)； M-phthalic acid (3.5kg)；18-amine. (1.66kg)；TDI(0.54kg)；HVI500SN lubricates base (100 DEG C of kinematic viscositys are 11mm to plinth oil²/ s, 22kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, sulfoacid calcium uses total base number For the calcium sulfonate with high base number of 320mgKOH/g, and add the superelevation alkali that total base number is 400kgKOH/g Value calcium naphthenate；Transforming agent increases DBSA；P-phthalic acid is replaced with M-phthalic acid； MDI is replaced with toluene di-isocyanate(TDI) (TDI)；Add Zr (OH)₄Time be additionally added ethanol zirconium, with zirconium Meter, Zr (OH)₄It is 1:0.5 with the mol ratio of ethanol zirconium；The consumption of each composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 36.8 weight %；Polyureas 2.4 weight %；Lubricating base oil 51.9 weight %； 12 hydroxy stearic acid oxygen zirconium 2.6 weight %；M-phthalic acid oxygen zirconium 6.3 weight %.

Embodiment 5

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 14kg)；Overbased calcium salicylate (total alkali Value is 400mgKOH/g, 10kg)；(100 DEG C of kinematic viscositys are 31 to HVI150BS lubricating base oil mm²/ s, 25kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)； 12 hydroxy stearic acids (2kg)；4,4' biphenyl dicarboxylic acid (5.1kg)；18-amine. (4.5kg)；MDI(2.1kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 18.6kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, high base number material adds Overbased calcium salicylate, transforming agent only uses 4 octadecylphenol and acetic acid, saves and adds methanol Step；P-phthalic acid is replaced with 4,4' biphenyl dicarboxylic acid；The consumption of each composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 35.8 weight %；Polyureas 7.1 weight %；Lubricating base oil 46.8 weight %； 12 hydroxy stearic acid oxygen zirconium 2.5 weight %；4,4' biphenyl dicarboxylic acid oxygen zirconium 7.8 weight %.

Embodiment 6

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 20kg)；(total base number is overbased calcium oleate 400mgKOH/g, 4kg)；(100 DEG C of kinematic viscositys are 40mm to polyalphaolefin artificial oil PAO 40²/ s, 30kg)；4 octadecylphenol (2kg)；Aphthenic acids (total acid number is 180mgKOH/g, 0.8kg)； Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)； 18-amine. (1.5kg)；MDI(0.7kg)；Polyalphaolefin artificial oil PAO 10 (100 DEG C of kinematic viscositys For 11mm²/ s, 9kg)；Dithio dibutylphosphoric acid zinc (2kg)；Dibutyl dithiocaarbamate molybdenum (1kg)；Tungsten disulfide (2kg)；Two tungsten selenide (2kg)；Right, right ' di-iso-octyldiphenylamine (0.2kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, calcium sulfenyl phenolate uses Total base number is the SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, and adds total base number and be The overbased calcium oleate of 400kgKOH/g；Use polyalphaolefin artificial oil PAO 40 (100 DEG C of motions Viscosity is 40mm²/ s) and polyalphaolefin artificial oil PAO 10 (100 DEG C of kinematic viscositys are 11mm²/s) (100 DEG C of kinematic viscositys are 31mm to replace HVI150BS respectively²/ s) and HVI500SN (100 DEG C of fortune Kinetic viscosity is 11mm²/s)；Transforming agent aphthenic acids replaces methanol；And treat that temperature is cooled to 110 DEG C, Add the dithio dibutylphosphoric acid zinc of 2kg, stir 10 minutes, add the dibutyl dithio of 1kg Carbamic acid molybdenum, stirs 10 minutes, adds the tungsten disulfide of 2kg, stirs 10 minutes, adds 2kg Two tungsten selenide, stir 10 minutes, add 0.2kg right, right ' di-iso-octyldiphenylamine, stir 10 Minute, then circulating filtration, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay It is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 37.2 weight %；Polyureas 2.5 weight %；Lubricating base oil 43.4 weight %； 12 hydroxy stearic acid oxygen zirconium 2.6 weight %；P-phthalic acid oxygen zirconium 6.4 weight %；Dithio dibutyl Zinc phosphate 2.2 weight %；Dibutyl dithiocaarbamate molybdenum 1.1 weight %；Tungsten disulfide 2.2 weight %；Two tungsten selenide 2.2 weight %；Right, right ' di-iso-octyldiphenylamine 0.2 weight %.

Embodiment 7

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 6kg)；Overbased sulfur Change alkyl phenol calcium (total base number is 400mgKOH/g, 10kg)；(total base number is overbased calcium alkyl-salicylate 300mgKOH/g, 8kg)；High base number calcium salicylate (total base number is 300mgKOH/g, 6kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 15kg)；4 octadecyl benzene Phenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12 hydroxy stearic acids (2kg)；Right Phthalic acid (3.5kg)；18-amine. (0.94kg)；Para-totuidine (0.38kg)；MDI(0.88kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 33kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, sulfoacid calcium uses total base number For the calcium sulfonate with high base number of 320mgKOH/g, add overbased calcium alkyl-salicylate and high base number bigcatkin willow simultaneously Acid calcium；Transforming agent only uses 4 octadecylphenol and acetic acid, saves the step adding methanol；Adding During 18-amine., it is additionally added para-totuidine；The consumption of each composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 36.4 weight %；Polyureas 2.4 weight %；Lubricating base oil 52.4 weight %； 12 hydroxy stearic acid oxygen zirconium 2.6 weight %；P-phthalic acid oxygen zirconium 6.2 weight %.

Embodiment 8

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 6kg)；High base number vulcanizes Alkyl phenol calcium (total base number is 320mgKOH/g, 10kg)；(total base number is high base number calcium salicylate 360mgKOH/g, 6kg)；High base number calcium oleate (total base number is 400mgKOH/g, 8kg)；HVI150BS (100 DEG C of kinematic viscositys are 31mm to lubricating base oil²/ s, 20kg)；4 octadecylphenol (2.8kg)； Acetic acid (0.56kg)；Zr(OH)₄(11.2kg)；12 hydroxy stearic acids (2kg)；Boric acid (2.32kg)； P-phthalic acid (7.6kg)；18-amine. (0.84kg)；Lauryl amine (0.58kg)；MDI(0.78kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 28kg)；Right, right ' bis-different pungent Base diphenylamines (0.2kg).

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, sulfoacid calcium uses total base number For the calcium sulfonate with high base number of 320mgKOH/g, calcium sulfenyl phenolate uses total base number to be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, add high base number calcium salicylate and high base number calcium oleate simultaneously；Convert Agent only uses 4 octadecylphenol and acetic acid, saves the step adding methanol；Add 12 hydroxy stearate After acid, it is additionally added boric acid, then adds p-phthalic acid；When adding 18-amine., it is additionally added lauryl amine； And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right ' di-iso-octyldiphenylamine, stir 10 points Zhong Hou, then circulating filtration, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Assay It is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 32.7 weight %；Polyureas 2.2 weight %；Lubricating base oil 47.0 weight %； 12 hydroxy stearic acid oxygen zirconium 2.3 weight %；Boric acid oxygen zirconium 3.5 weight %；P-phthalic acid oxygen zirconium 12.1 Weight %；Right, right ' di-iso-octyldiphenylamine 0.2 weight %.

Embodiment 9

Raw material components: non-newtonian fluid calcium sulfonate with high base number (15kg)；Overbased calcium sulfenyl phenolate is (total Base number is 400mgKOH/g, 5kg)；Naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 4kg)；Overbased calcium salicylate (total base number is 400mgKOH/g, 3kg)；Overbased calcium oleate (total base number is 400mgKOH/g, 3kg)；(100 DEG C of kinematic viscositys are HVI150BS lubricating base oil 31mm²/ s, 15kg)；Aphthenic acids (total acid number is 180mgKOH/g, 2.8kg)；Acetic acid (0.56kg)； Zr(OH)₄(6.5kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)；Acetic acid (2kg)； 18-amine. (1.5kg)；MDI(0.7kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 33kg).

The preparation of non-newtonian fluid calcium sulfonate with high base number: volume be 30L and with heating, stirring, Adding 8kg total base number in circulation, the normal-pressure reaction kettle cooled down is the calcium sulfonate with high base number of 350mgKOH/g It is 31mm with 100 DEG C of kinematic viscositys of 5kg²The HVI150BS lubricating base oil of/s, stirring, heating rises Warm to 80 DEG C, constant temperature 10 minutes；Adding 1.7kg DBSA, temperature controls on 80 DEG C of left sides The right side, stirs 10 minutes；Add acetic acid and the aqueous solution of acetic acid weight 4 times of 0.33kg, stir 10 Minute；Being warmed up to 85 DEG C, constant temperature 90 minutes, material retrogradation becomes smectic, obtains non-newtonian fluid sulfoacid calcium Standby.

Preparing lubricant composition according to the method for embodiment 1, except for the difference that, overbased sulfoacid calcium is straight Connect and use the non-newtonian fluid sulfoacid calcium for preparing, add simultaneously overbased calcium alkyl-salicylate, calcium salicylate and Calcium oleate, transforming agent only uses aphthenic acids and acetic acid；After adding p-phthalic acid, it is additionally added acetic acid；Respectively The consumption of composition is as above.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 35.0 weight %；Polyureas 2.3 weight %；Lubricating base oil 50.3 weight %； 12 hydroxy stearic acid oxygen zirconium 2.5 weight %；P-phthalic acid oxygen zirconium 6.0 weight %；Zirconyl acetate 3.9 Weight %.

Embodiment 10

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring, heats to 100 DEG C, adds the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, Stir 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes；Add 3.5kg terephthaldehyde Acid, stirs 10 minutes；Cool to 50 DEG C, constant temperature 30 minutes；Add 2.8kg 4 octadecylphenol, Temperature controls at about 50 DEG C, stirs 10 minutes；Add 1kg methanol, stir 10 minutes；Add 2.8kg concentration is the aqueous acetic acid of 20 weight %, stirs 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 Minute, material retrogradation；It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration.

Another volume be 30L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, be warmed up to 120 DEG C, stir 4 points Clock, adds the 0.7kg MDI in the HVI500SN lubricating base oil being dissolved in 2kg, stirs 4 minutes, Added MDI is 1:2 with the mol ratio of 18-amine., 120 DEG C of constant temperature 20 minutes, obtains polyureas.

Gained polyureas is all squeezed in a upper still, stir, be finally warmed up to 200 DEG C of constant temperature 10 Minute.Then, remaining HVI500SN lubricating base oil is added；Treat that temperature is cooled to 110 DEG C, follow Ring filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

The polyureas molecular structural formula contained in component is:

Embodiment 11

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring, heats to 50 DEG C, constant temperature 30 minutes；Add 2.8kg 4 octadecylphenol, temperature Control at about 50 DEG C, stir 10 minutes；Add 1kg methanol, stir 10 minutes；Add 2.8kg Concentration is the aqueous acetic acid of 20 weight %, stirs 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 minutes, Material retrogradation.

Another volume be 50L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering the HVI500SN lubricating base oil of 5kg, be warmed up to 100 DEG C, adding solid content is 20 weight % Zr(OH)₄Suspension 19.5kg, stirs 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 points Clock；Add 3.5kg p-phthalic acid, stir 10 minutes, obtain 12 hydroxy stearic acid oxygen zirconiums and right Phthalic acid oxygen zirconium.

The 3rd volume be 50L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Enter HVI500SN lubricating base oil and the 1.5kg 18-amine. of 2kg, stir 4 minutes, add and be dissolved in 0.7kg MDI in the HVI500SN lubricating base oil of 2kg, stirs 4 minutes, added MDI It is 1:2 with the mol ratio of 18-amine., 120 DEG C of constant temperature 20 minutes, obtain polyureas.

12 hydroxy stearic acid oxygen zirconiums and the p-phthalic acid oxygen zirconium of gained are all squeezed in first still, Stirring, be warmed up to 120 DEG C under stirring, keep 45 minutes, dehydration, by the 3rd reactor gained Polyureas all squeeze in this still, stir, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, Add remaining HVI500SN lubricating base oil；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.

Embodiment 12

Volume be 160L and with the normal-pressure reaction kettle A heating, stirring, circulate, cool down in add 10kg total base number be the calcium sulfonate with high base number of 350mgKOH/g, 20kg total base number be 400mgKOH/g Overbased calcium sulfenyl phenolate and 100 DEG C of kinematic viscositys of 25kg be 31mm²The HVI150BS profit of/s Sliding base oil, stirring, heat to 60 DEG C, constant temperature 10 minutes；Add 3kg 4 octadecyl benzene Phenol, temperature controls at about 60 DEG C, stirs 10 minutes；Add the 12.5kg butanol water that concentration is 20% Solution, stirs 10 minutes；In 87 DEG C of constant temperature 70 minutes, material retrogradation.

Volume be 30L and with the normal-pressure reaction kettle B heating, stirring, circulate, cool down in add The HVI500SN lubricating base oil of 5kg, is warming up to 90 DEG C, and adding solid content is 20 weight % Zr(OH)₄Suspension 28.9kg, stirs 10 minutes, adds the Palmic acid of 2.4kg, stirs 10 minutes, Add the biphenyl dicarboxylic acid of 4.2kg, the phosphoric acid of 1kg and the ethanedioic acid of 2kg, stir 10 minutes, obtain Palmic acid oxygen zirconium, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium.

Volume be 20L and with the normal-pressure reaction kettle C heating, stirring, circulate, cool down in add 5kg100 DEG C of kinematic viscosity is 11mm²The HVI500SN lubricating base oil of/s and 1kg MDI rapidly pre-warming To 90 DEG C, quickly stirring is lower adds 0.12kg ethylenediamine, stirs 4 minutes, adds 1.08kg 18-amine. Stirring 4 minutes, added MDI, ethylenediamine are 2:1:2 with the mol ratio of 18-amine., 120 DEG C of constant temperature 20 Minute, obtain polyureas I.

Volume be 30L and with the normal-pressure reaction kettle D heating, stirring, circulate, cool down in add 10kg100 DEG C of kinematic viscosity is 11mm²The HVI500SN lubricating base oil of/s and 1.29kg MDI preheating To 90 DEG C, quickly stirring is lower adds 0.84kg 18-amine. and 0.19kg ethylenediamine, stirs 4 minutes, institute The MDI that adds, 18-amine., the mol ratio of ethylenediamine are 3.3:2:2,120 DEG C of constant temperature 20 minutes, are gathered Urea II.

Gained Palmic acid oxygen zirconium, biphenyl dicarboxylic acid oxygen zirconium, zirconium phosphate oxygen and ethanedioic acid oxygen zirconium are all squeezed into In reactor A, stirring, be warmed up to 120 DEG C under stirring, keep 30 minutes, dehydration, by institute Obtain polyureas I and polyureas II all to squeeze in reactor A, stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, it is cooled to 150 DEG C, adds the HVI500SN lubricating base oil of 8kg；Treat temperature Being cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 32.6 weight %；Palmic acid oxygen zirconium 2.7 weight %；Biphenyl dicarboxylic acid oxygen zirconium 5.6 weight %；Zirconium phosphate oxygen 2.4 weight %；Ethanedioic acid oxygen zirconium 4.0 weight %；Polyureas 4.0 weight %； Lubricating base oil 48.7 weight %.

Embodiment 13

It is 160L and with in the normal-pressure reaction kettle A heating, stirring, circulate, cool down at a volume Adding 20kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 10kg total base number are Overbased calcium sulfenyl phenolate and 100 DEG C of kinematic viscositys of 10kg of 420mgKOH/g are 31mm²/ s's HVI150BS lubricating base oil, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 2kg 4 Octadecylphenol, temperature controls at about 50 DEG C, stirs 10 minutes；Add 1kg methanol, stirring 10 minutes；Add the aqueous acetic acid that 2kg concentration is 20 weight %, stir 10 minutes；At 83 DEG C Constant temperature 80 minutes, material retrogradation.

Volume be 30L and with the normal-pressure reaction kettle B heating, stirring, circulate, cool down in add The HVI500SN lubricating base oil of 8kg, adds the Zr (OH) that solid content is 50 weight % at 95 DEG C₄ Suspension 7.7kg, stirs 10 minutes, adds the lauric acid of 2.4kg, stirs 10 minutes, adds 7.9kg M-phthalic acid, stir 10 minutes, obtain lauric acid oxygen zirconium and M-phthalic acid oxygen zirconium.

Volume be 30L and with the normal-pressure reaction kettle C heating, stirring, circulate, cool down in add 10kg100 DEG C of kinematic viscosity is 11mm²The HVI500SN lubricating base oil of/s and 1.17kg MDI preheating To 80 DEG C, quickly lower 0.84kg 18-amine., the mixture of 0.19kg ethylenediamine of adding of stirring, added MDI, monoamine, the mol ratio of diamidogen are 3:2:2,120 DEG C of constant temperature 20 minutes, obtain polyureas.

Gained lauric acid oxygen zirconium and M-phthalic acid oxygen zirconium are all squeezed in reactor A, stir, It is warmed up to 110 DEG C under stirring, keeps 45 minutes, dehydration, gained polyureas is all squeezed into reactor A In, stir, be finally warmed up to 200 DEG C of constant temperature 5 minutes.Then, the HVI500SN of 2kg is added Lubricating base oil；Treating that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection The results are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium 44.0 weight %；Lauric acid oxygen zirconium 4.1 weight %；M-phthalic acid oxygen zirconium 8.2 weight %；Polyureas 3.0 weight %；Lubricating base oil 40.7 weight %.

Embodiment 14

A volume be 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down in add Entering 24kg total base number is that the overbased sulfoacid calcium of 400mgKOH/g, 6kg total base number are The overbased calcium sulfenyl phenolate of 400mgKOH/g and the HVI150BS lubricating base oil of 30kg, It is warmed up under stirring at 50 DEG C, constant temperature 30 minutes, adds 2.8kg 4 octadecylphenol, temperature control System, at 50 DEG C, stirs 10 minutes, adds 1kg methanol, stirs 10 minutes, adds 2.8kg concentration and is The aqueous acetic acid of 20 weight %, stirs 10 minutes, is warmed up to 80 DEG C, constant temperature 90 minutes, material Retrogradation；It is warmed up to 100 DEG C, adds the Zr (OH) that solid content is 20 weight %₄Suspension 19.5kg, stirs Mix 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes；Add 3.5kg p-phthalic acid, Stir 10 minutes；It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration；Add the HVI500SN of 2kg Lubricating base oil and 1.5kg 18-amine., stir 4 minutes, adds the HVI500SN profit being dissolved in 2kg 0.7kg MDI in sliding base oil, stirs 4 minutes, and added MDI with the mol ratio of 18-amine. is 1:2,120 DEG C of constant temperature 20 minutes；Finally it is warmed up to 200 DEG C of constant temperature 10 minutes.Then, residue is added HVI500SN lubricating base oil；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, deaerate To finished product.Assay is shown in Table 1.

Embodiment 15

Lubricant composition is prepared, except for the difference that, by 4 octadecylphenol according to the method for embodiment 1 Replace with methyl propyl ketone, methanol is replaced with 18-amine., aqueous acetic acid is replaced with butyl ether.Inspection The results are shown in Table 1.

Embodiment 16

Lubricant composition is prepared, except for the difference that, at Zr (OH) according to the method for embodiment 3₄With positive third In the case of the total mole number of alcohol zirconium is constant, adjust Zr (OH)₄It is 1:10 with the mol ratio of zirconium-n-propylate. Each physicochemical property of gained fat is shown in Table 1.

Embodiment 17

Prepare lubricant composition according to the method for embodiment 3, except for the difference that, zirconium-n-propylate is replaced with Equimolar Zr (OH)₄.Each physicochemical property of gained fat is shown in Table 1.

Embodiment 18

Lubricant composition is prepared, except for the difference that, by Zr (OH) according to the method for embodiment 3₄Replace with Equimolar zirconium-n-propylate.Each physicochemical property of gained fat is shown in Table 1.

Comparative example 1

Lubricant composition is prepared according to the method for embodiment 1, except for the difference that, overbased alkyl monosulfide Phenol calcium total base number is that the overbased sulfoacid calcium of 400mgKOH/g replaces, and the grease finished product obtained is each Performance data is shown in Table 1.

In the grease that this comparative example obtains, on the basis of grease weight, consist of: non-newtonian fluid sulphur Acid calcium 36.8 weight %；Polyureas 2.4 weight %；Lubricating base oil 51.9 weight %；12 hydroxy stearic acids Oxygen zirconium 2.6 weight %；P-phthalic acid oxygen zirconium 6.3 weight %.

It will be understood by those skilled in the art that Drawing cone in-degree is the least, grease thickening performance is more Good；Extending Drawing cone in-degree the least with the difference of Drawing cone in-degree, the mechanical stability of grease can be the best； Water pouring number of dropouts is the least, and the water-resistance of grease is the best；Salt spray test the highest grade, grease antirust And anticorrosive property is the best；Water resistant spraying value is the least, and the adhesiveness of grease and water-resistance are the best；Steel mesh divides Oil value is the least, and the colloid stability of grease is the best；The absolute value of Surface hardened layer value is the least, grease Storage stability is the best；Coefficient of friction is the least, and the abrasion resistance of grease is the best；PB, PD value is the biggest, The extreme pressure anti-wear of grease is the best.

Table 1 each grease properties of sample data

Each indication test method: dropping point: GB/T 3498；Drawing cone in-degree and prolongation Drawing cone in-degree: GB/T 269；Corrosion: GB/T 7326； Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant is sprayed: SH/T0643；Steel Net point oil: SH/T 0324；Surface hardened layer value: SH/T 0370 appendix A；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202； Bearing lubrication life-span: ASTM D 3336.

Table 1 (Continued) each grease properties of sample data

Embodiment 1 and comparative example 1 are compared it can be seen that lubricant composition anti-of the present invention Rust and anticorrosive property, storage stability are substantially better than complex calcium sulfonate zirconio polyurea grease.And, this Invention lubricant composition have be better than complex calcium sulfonate zirconio polyurea grease viscous resistance, machinery peace Qualitative, water-resistance, colloid stability, abrasion resistance, extreme pressure anti-wear and lubricating life.And, this The lubricant composition of invention also has the heat-resisting quantity of excellence.

Embodiment 1 is compared with embodiment 10 and embodiment 11 respectively it can be seen that prepare in situ Lubricant composition, there is more preferable viscous resistance, water-resistance, colloid stability, abrasion resistance and profit The sliding life-span；Embodiment 1 and embodiment 11, embodiment 14 are compared it can be seen that first carry out multiple Zirconium and/or the reaction of polyurea compound, then convert, the lubricant composition prepared has preferably Viscous resistance, water-resistance, colloid stability, abrasion resistance and lubricating life；By embodiment 1 and embodiment 15 compare it can be seen that transforming agent selected from DBSA, aphthenic acids, octadecyl phenol, At least one in methanol, isopropanol, butanol, boric acid, acetic acid and water, the lubricant composition of preparation, There is more preferable viscous resistance, water-resistance, colloid stability, abrasion resistance and lubricating life；By embodiment 3 compare it can be seen that the raw material of the zirconium oxide that contains zirconium and/or hydrogen respectively with embodiment 16 18 Oxide, and the mol ratio of the oxide of zirconium and/or hydroxide and zirconium alkoxide is 1:0.5 5, it is possible to Improve further the mechanical stability of lubricant composition of preparation, water-resistance, colloid stability, wear-resistant Damage property and lubricating life.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims

1. a lubricant composition, described lubricant composition contains base oil and thickening agent, and it is special Levying and be, described thickening agent contains non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, the zirconium of higher fatty acids Salt and polyurea compound, described thickening agent is also optionally with non-newtonian fluid calcium naphthenate, non-newtonian fluid water Poplar acid calcium, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little molecule mineral acid and/or the zirconium of lower fatty acid One or more in salt, on the basis of the weight of described lubricant composition, the content of base oil is 10 80 weight %, the content of non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 10 70 weight %, high The content of the zirconates of level fatty acid is 1 10 weight %, and the content of polyurea compound is 0.5 30 weight %, The content of non-newtonian fluid calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 Weight %, the content of non-newtonian fluid calcium oleate is 0-70 weight %, and the content of the zirconates of aromatic acid is 0-15 Weight %, the content of the zirconates of little molecule mineral acid and/or lower fatty acid is 0 15 weight %, wherein, The zirconates of described higher fatty acids is to be reacted with component A by higher fatty acids to form, the zirconates of described aromatic acid Being to be reacted with component A by aromatic acid to form, the zirconates of described little molecule mineral acid and/or lower fatty acid is Being reacted with component A by little molecule mineral acid and/or lower fatty acid and form, described component A is the oxygen of zirconium At least one in compound, the hydroxide of zirconium and zirconium alkoxide.

Lubricant composition the most according to claim 1, wherein, with the weight of lubricant composition On the basis of amount, the content of base oil is 20 70 weight %, non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium Content be 20 60 weight %, the content of the zirconates of higher fatty acids is 26 weight %, polyureas chemical combination The content of thing is 1 20 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, non newtonian The content of body calcium salicylate is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, The content of the zirconates of aromatic acid is 2 10 weight %, the zirconates of little molecule mineral acid and/or lower fatty acid Content is 2 10 weight %.

Lubricant composition the most according to claim 1 and 2, wherein, described non-newtonian fluid sulfur Change alkyl phenol calcium sulfoacid calcium to be obtained by newton body sulfoacid calcium and the conversion of newton body calcium sulfenyl phenolate, The total base number of described non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 250 450mgKOH/g；Described non- Newton body calcium naphthenate is converted by newton body calcium naphthenate and obtains, described non-newtonian fluid calcium naphthenate Total base number is 250-450mgKOH/g；Described non-newtonian fluid calcium salicylate is to be turned by newton body calcium salicylate Change obtains, and the total base number of described non-newtonian fluid calcium salicylate is 250-450mgKOH/g；Described non-cattle The body calcium oleate that pauses is converted by newton body calcium oleate and obtains, and the total base number of described non-newtonian fluid calcium oleate is 250-450mgKOH/g。

Lubricant composition the most according to claim 1 and 2, wherein, described higher fatty acids For fatty acid that carbon number is 8-20 or hydroxy fatty acid.

Lubricant composition the most according to claim 4, wherein, described higher fatty acids is selected from At least one in lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic acid.

Lubricant composition the most according to claim 1 and 2, wherein, described aromatic acid is for replacing Or unsubstituted aromatic acid, substituent group is the alkane of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno At least one in base or aryl, the molecular weight of described aromatic acid is less than or equal to 550.

7. according to the lubricant composition described in claim 6, wherein, described aromatic acid is selected from unsubstituted Or the substituted phthalic acid of C1-C5 alkyl, M-phthalic acid, p-phthalic acid, biphenyl diformazan At least one in acid, polyphenyls dioctyl phthalate.

Lubricant composition the most according to claim 1 and 2, wherein, little molecule mineral acid and The molecular weight of lower fatty acid is less than or equal to 250.

Lubricant composition the most according to claim 8, wherein, described little molecule mineral acid selects At least one in boric acid, phosphoric acid, sulphuric acid, described lower fatty acid selected from acetic acid, ethanedioic acid, third At least one in acid, malonic acid, butanoic acid, succinic acid.

Lubricant composition the most according to claim 1 and 2, wherein, described component A contains The oxide of zirconium and/or hydroxide, in terms of zirconium, the oxide of zirconium and/or hydroxide and zirconium alkoxide Mol ratio be 1:0 10.

11. lubricant compositions according to claim 10, wherein, in terms of zirconium, the oxidation of zirconium The mol ratio of thing and/or hydroxide and zirconium alkoxide is 1:0.5 5.

12. lubricant compositions according to claim 1 and 2, wherein, the oxide of zirconium and/ Or hydroxide is selected from ZrO₂、ZrO(OH)₂、Zr(OH)₄And at least one in their hydrate.

13. lubricant compositions according to claim 1 and 2, wherein, described zirconium alkoxide Formula is Zr (OR₁)₄, R₁Alkyl for C1 C10.

14. lubricant compositions according to claim 13, wherein, described zirconium alkoxide is selected from At least one in ethanol zirconium, zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and n-amyl alcohol zirconium.

15. lubricant compositions according to claim 1 and 2, wherein, described polyurea compound Structural formula be

Wherein, n is the integer of 03, R¹、R⁴It is alkyl, cycloalkyl or aryl, R²It it is alkylidene Or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.

16. lubricant compositions according to claim 15, wherein, polyurea compound is dimerization At least one in carbamide compound, four polyurea compounds, six polyurea compounds and eight polyurea compounds.

17. lubricant compositions according to claim 15, wherein, R¹、R⁴It is phenyl or takes The phenyl in generation, or carbon number is the alkyl or cycloalkyl of 8 24；R²It is phenylene or biphenylene, or carbon Number is the alkylidene of 2 12；R³It is arlydene, alkylidene or the cycloalkylidene of 6 30.

18. lubricant compositions according to claim 17, wherein, R¹、R⁴It is phenyl or C1 C3 Alkyl or the phenyl of halogen substiuted, or carbon number is the alkyl or cycloalkyl of 10 18；R²Be phenylene or Biphenylene, or carbon number is the alkylidene of 28；R³It is With-(CH₂)₆In- At least one.

The preparation method of lubricant composition described in any one, the party in 19. claim 1 18 Method includes: by thickening agent and part basis oil mix homogeneously, refine at 180 230 DEG C of constant temperature, adds remaining Amount base oil, adds necessary additive, obtains finished product, it is characterised in that described thickening agent contains non- Newton body calcium sulfenyl phenolate sulfoacid calcium, the zirconates of higher fatty acids and polyurea compound, described thickening Agent also optionally with non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, One or more in the zirconates of the zirconates of aromatic acid, little molecule mineral acid and/or lower fatty acid.

The preparation method of 20. 1 kinds of lubricant compositions, it is characterised in that the method includes:

(3) add transforming agent, heat up and treat material retrogradation；

(4) carry out remaining the reaction of compound zirconium；

(5) heat up dehydration；

(6) carry out remaining the reaction of polyurea compound；

21. methods according to claim 20, wherein, in step (2), are carried out at least partly The reaction of compound zirconium；And/or, carry out the reaction of at least part of polyurea compound.

22. according to the method described in claim 20 or 21, wherein, and step (2) and step (4) In, when carrying out the reaction of compound zirconium, at 85 100 DEG C, add component A, add higher fatty acids, Stir 5 30 minutes, add optional aromatic acid, optional little molecule mineral acid and/or lower fatty acid, Stirring 5 30 minutes, described component A contains oxide and/or the hydroxide of zirconium, in terms of zirconium, zirconium The mol ratio of oxide and/or hydroxide and zirconium alkoxide is 1:0 10.

23. methods according to claim 22, wherein, in terms of zirconium, the oxide of zirconium and/or hydrogen Oxide is 1:0.5 5 with the mol ratio of zirconium alkoxide.

24. according to the method described in claim 20 or 21, wherein, and step (2) and step (6) In, when carrying out the reaction of polyurea compound, add part basis oil, monoamine, optional diamidogen, two different After cyanate, 100 120 DEG C of constant temperature 10 30 minutes, wherein, monoamine, optional diamidogen, two different The amount of the material of cyanate meets following relation: the material of the amount of the material of diisocyanate × 2=monoamine Amount × 2 of the material of amount+diamidogen, or, diisocyanate excess, amount≤10% of excess.

25. according to the method described in claim 20 or 21, wherein, in step (3), at 50 80 DEG C, Transforming agent needed for addition reacts, after all transforming agents add, at 80 100 DEG C of constant temperature 60 90 Minute.

26. according to the method described in claim 20 or 21, wherein, in step (5), is warming up to 110-130 DEG C of dehydration.

27. according to the method described in claim 20 or 21, wherein, in step (7), is warmed up to 180 230 DEG C of constant temperature 5 30 minutes；Add surplus base oil, treat that temperature is cooled to 100 120 DEG C, add Enter the additive of necessity, stirring, circulating filtration, homogenizing, degassing.

28. according to the method described in claim 20 or 21, wherein, and described newton body sulfenyl phenolate Calcium is synthesis calcium sulfenyl phenolate, and the total base number of described newton body calcium sulfenyl phenolate is 250-450mgKOH/g；Described newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, described The total base number of newton body sulfoacid calcium is 250-450mgKOH/g；Described newton body calcium naphthenate is oil ring Alkanoic acid calcium and/or synthesis calcium naphthenate, the total base number of described newton body calcium naphthenate is 250-450mgKOH/g；Described newton body calcium salicylate is salicylate calcium, described newton body bigcatkin willow The total base number of acid calcium is 250-450mgKOH/g；Described newton body calcium oleate is natural calcium oleate and/or conjunction Becoming calcium oleate, the total base number of described newton body calcium oleate is 250-450mgKOH/g.

29. according to the method described in claim 20 or 21, wherein, described transforming agent selected from fatty alcohol, Fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, Phenol, aromatic alcohol, aromatic amine, aphthenic acids, C8 C20 alkyl benzene sulphonate, C16-C24 alkyl phenol and At least one in water, the addition of transforming agent is the 2 30% of described high base number material gross weight.

30. methods according to claim 29, wherein, described transforming agent is selected from detergent alkylate In sulfonic acid, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water extremely Few one, the addition of transforming agent is the 6 22% of described high base number material gross weight.

31. according to the method described in claim 20 or 21, and wherein, the structural formula of described monoamine is R¹–NH₂、R⁴–NH₂, wherein, R¹、R⁴It is phenyl or C1 C3 alkyl or the phenyl of halogen substiuted, Or carbon number is the alkyl or cycloalkyl of 10 18.

32. methods according to claim 31, wherein, described monoamine is selected from aniline, m-chloro The aromatic amine of aniline, parachloroanilinum and/or para-totuidine and/or selected from lauryl amine, tetradecy lamine, cetylamine And/or the fatty amine of 18-amine..

33. according to the method described in claim 20 or 21, and wherein, the structural formula of described diamidogen is NH₂–R²–NH₂, wherein, R²Be carbon number be the alkylidene of 28, or phenylene or biphenylene.

34. methods according to claim 33, wherein, described diamidogen be selected from p-phenylenediamine, O-phenylenediamine, the aromatic amine of 4,4 ' benzidines and/or selected from ethylenediamine, propane diamine, 1,6 hexamethylene diamines Straight-chain fatty amine.

35. according to the method described in claim 20 or 21, wherein, and the structure of described diisocyanate For OCN R³NCO, R³Be carbon number be arlydene, alkylidene or the cycloalkylidene of 6 30.

36. methods according to claim 35, wherein, described diisocyanate is selected from toluene two Isocyanates, methyl diphenylene diisocyanate, six hexylidene diisocyanates, dicyclohexyl methyl hydride two At least one in isocyanates and an xylylene diisocyanate.

37. lubricant compositions prepared by the method described in any one in claim 20 36.