CN106032487A

CN106032487A - A lubricating grease composition and a preparing method thereof

Info

Publication number: CN106032487A
Application number: CN201510106512.0A
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: CN106032487B

Abstract

The invention relates to the field of lubricating grease, and discloses a lubricating grease composition. The composition comprises base oil and a thickening agent. The thickening agent comprises non-Newtonian fluid sulfurized calcium alkyl phenate-calcium sulfonate and a zirconium salt of a higher aliphatic acid, and optionally comprises one or more selected from a group consisting non-Newtonian fluid calcium naphthenate, non-Newtonian fluid calcium salicylate, non-Newtonian fluid calcium oleate, a zirconium salt of an aromatic acid, and a zirconium salt of a small-molecule inorganic acid and/or a lower aliphatic acid. Based on the weight of the composition, the content of the base oil is 10-80% by weight, the content of the non-Newtonian fluid sulfurized calcium alkyl phenate-calcium sulfonate is 10-70% by weight, the content of the zirconium salt of the higher aliphatic acid is 1-10% by weight, and contents of other optional components are respectively 0-70% by weight, 0-70% by weight, 0-70% by weight, 0-15% by weight and 0-15% by weight. A preparing method is also disclosed. The composition has excellent properties.

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, and storage good security.

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 and the zirconates of higher fatty acids, described thickening agent is also optionally with non-newtonian fluid cycloalkanes Acid calcium, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little molecule mineral acid and / or the zirconates of lower fatty acid in one or more, on the basis of the weight of described lubricant composition, The content of base oil is 10 80 weight %, and the content of non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium is 10 70 weight %, the content of the zirconates of higher fatty acids is 1 10 weight %, non-newtonian fluid calcium naphthenate Content be 0-70 weight %, the content of non-newtonian fluid calcium salicylate is 0-70 weight %, non-newtonian fluid The content of calcium oleate is 0-70 weight %, and the content of the zirconates of aromatic acid is 0-15 weight %, little molecule without The content of the zirconates of machine acid and/or lower fatty acid is 0 15 weight %, wherein, and described higher fatty acids Zirconates be to be reacted with component A by higher fatty acids to form, the zirconates of described aromatic acid is by aromatic acid and component A reaction forms, 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, described component A is the hydroxide of the oxide of zirconium, zirconium At least one in thing and zirconium alkoxide.

Preferably, on the basis of lubricant composition weight, 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 non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid water The content of poplar acid calcium is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, aromatic acid The content of zirconates be 2-10 weight %, the content of the zirconates of little molecule mineral acid and/or lower fatty acid It is 2 10 weight %.

Preferably, described component A contains oxide and/or the hydroxide of zirconium, in terms of zirconium, the oxygen of zirconium The mol ratio of compound and/or hydroxide and zirconium alkoxide is 1:0 10, 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 and the zirconates of higher fatty acids, described thickening agent is also optionally with non-newtonian fluid cycloalkanes Acid calcium, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little molecule mineral acid and / or the zirconates of lower fatty acid in one or more.

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；

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

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

(5) heat up dehydration；

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

Preferably, in step (2), the reaction of zirconium at least partly it is combined.

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

The lubricant composition of the present invention, has the most excellent with complex calcium sulfonate grease Antirust and anticorrosive property, and there is excellent storage stability, also have and be better than Composite calcium-sulfonate-batetrapolyurea lubrication The mechanical stability of fat, water-resistance, colloid stability, abrasion resistance and extreme pressure anti-wear, and also have The performances such as excellent heat-resisting quantity.The feed preparation process of the grease of the present invention is simple and environmentally-friendly, product Steady 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 zirconium thickening agent.

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

On the one hand, the invention provides a kind of lubricant composition, lubricant composition contain base oil and Thickening agent, thickening agent contains non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium and the zirconates of higher fatty acids, Thickening agent is also optionally with non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid oleic acid One or more in the zirconates of calcium, the zirconates of aromatic acid, little molecule mineral acid and/or lower fatty acid, with On the basis of the weight of lubricant composition, the content of base oil is 10 80 weight %, and non-newtonian fluid vulcanizes The content of alkyl phenol calcium sulfoacid calcium is 10 70 weight %, and the content of the zirconates of higher fatty acids is 1 10 Weight %, the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, the content of non-newtonian fluid calcium salicylate For 0-70 weight %, the content of non-newtonian fluid calcium oleate is 0-70 weight %, the content of the zirconates of aromatic acid For 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 higher fatty acids is to be reacted with component A by higher fatty acids to form, and the zirconates of aromatic acid is Being reacted with component A by aromatic acid and form, the zirconates of little molecule mineral acid and/or lower fatty acid is by little point Sub-mineral acid and/or lower fatty acid react with component A and form, and component A is the oxide of zirconium, zirconium At least one in hydroxide and zirconium alkoxide.

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 non-newtonian fluid calcium naphthenate is 0-50 weight %, non-newtonian fluid water The content of poplar acid calcium is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, aromatic acid The content of zirconates be 2-10 weight %, the content of the zirconates of little molecule mineral acid and/or lower fatty acid It is 2 10 weight %.

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 can be carbon number be 8 20, the fatty acid of preferably 10 18 or hydroxyl Base fatty acid, such as lauric acid, Palmic acid, stearic acid, 12 hydroxy stearic acids, eicosyl carboxylic acid In at least one, preferably 12 hydroxy stearic acids.

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 and 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, base oil can be mineral oil, artificial oil, vegetable oil or their mixture, 100 DEG C Dynamic viscosity is 4 60mm²/ s, preferably 10 30mm²/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.

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 thickening agent contains non-newtonian fluid calcium sulfenyl phenolate Sulfoacid calcium and the zirconates of higher fatty acids, thickening agent is also optionally with non-newtonian fluid calcium naphthenate, non- Newton body calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little molecule mineral acid and/or rudimentary fat One or more in the zirconates of fat acid.

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

In the present invention, non-newtonian fluid calcium sulfenyl phenolate sulfoacid calcium, the zirconates of higher fatty acids, non-cattle Pause body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the zirconates of aromatic acid, little molecule Mineral acid and/or the zirconates of lower fatty acid, base oil and additive be not as it was previously stated, 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 calcium sulfenyl phenolate, Niu Dunti Sulfoacid calcium, newton body calcium naphthenate, newton body calcium salicylate, newton body calcium oleate or a combination thereof thing are respectively Converted by transforming agent and obtain, such as, by newton body calcium sulfenyl phenolate, newton body sulfoacid calcium, optionally Newton body calcium naphthenate, optional newton body calcium salicylate, optional newton body calcium oleate and base 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 minute, then heats to 110-130 DEG C of dehydration.

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；

" 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. does not has step (2), only carries out in step (4) The reaction of whole compound zirconiums, is i.e. equivalent to the inventive method and is initially charged transforming agent and converts, after conversion Carry out the reaction of compound zirconium again；(ii) carry out the reaction of the compound zirconium of part, i.e. carry out in step (2) The reaction of the compound zirconium of part, carries out remaining the reaction of compound zirconium in step (4) again, is i.e. equivalent to this Inventive method carries out the reaction of the compound zirconium of part before conversion, carries out the anti-of the compound zirconium of part the most again Should；(iii) all it is combined the reaction of zirconium, in step (2), i.e. carries out the anti-of whole compound zirconiums Should, do not carry out step (4), be i.e. equivalent to the inventive method and first carry out the reaction of compound zirconium, then carry out turning Change.

This area, when preparing grease, is generally individually to be initially charged transforming agent to convert, then is combined The reaction of zirconium, during as prepared complex calcium sulfonate zirconio grease.But the present inventor sends out under study for action Existing, the method carrying out the present invention according to above-mentioned situation (ii) or (iii), carry out than according to situation (i) The method of the present invention, the most first carries out the reaction of all or part of compound zirconium, then converts, it is possible to more enter One step improves the performance of the grease prepared.This reaction being likely due to first carry out compound zirconium, it is possible to more Newton body calcium sulfenyl phenolate by oily is converted into the non-newtonian fluid calcium sulfenyl phenolate of smectic well.Cause This, it is preferable that in step (2), at least partly it is combined the reaction of zirconium.

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 and adhesiveness, the colloid stability prepared.Therefore, Preferably, when carrying out step (2) and step (4), at 85 100 DEG C, add component A, add Enter 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, the mol ratio of the oxide of zirconium and/or hydroxide and zirconium alkoxide is preferably 1:0 10, more It is preferably 1:0.2 8, the most preferably 1:0.5 5.Wherein, component A, higher fatty acids, The addition sequence of aromatic acid, little molecule mineral acid and/or lower fatty acid 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 (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.

Described transforming agent be preferably 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 At least one in alkyl benzene sulphonate, C16-C24 alkyl phenol and water；It is more preferably selected from the fat of C1 C5 Fat alcohol, the fatty acid of C1 C5, the aliphatic ketone of C1 C5, the fatty aldehyde of C1 C5, the fat of C1 C5 Fat amine, the ether of C1 C5, boric acid, the alkyl phosphonic acid of C1 C10, the di alkyl phosphonic acid of C2 C16, The arylphosphonic acid of C6 C20, the diaryl phosphonic acids of C12 C24, the aromatic alcohol of C7 C20, C7 C20 Aromatic amine, C8 C20 alkyl benzene sulphonate, aphthenic acids, C16-C22 alkyl phenol and water at least one Kind；Further it is preferably selected from DBSA, aphthenic acids, octadecyl phenol, methanol, isopropyl At least one in alcohol, butanol, boric acid, acetic acid and water.The addition of transforming agent is preferably high base number thing The 2 30% of 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 (6), 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, part basis oil used and the weight of surplus base oil in step (6) in step (1) Amount ratio preferably 1:0.1 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, mechanical stability, water-resistance, Colloid stability and abrasion resistance.

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 of kinematic viscositys are 31mm²/ s, 30kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 17kg).

A volume be 110L 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；Adding 2.8kg 4 octadecylphenol, temperature controls at 50 DEG C, stirs 10 minutes； Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir 10 minutes；It is warmed up to 80 DEG C, permanent Temperature 90 minutes, material retrogradation.It is warmed up to 120 DEG C under stirring, keeps 45 minutes, dehydration.It is warmed up to 200 DEG C of constant temperature 10 minutes.Then, the HVI500SN lubricating base oil of 7kg is added；Treat that temperature cools down 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 37.7 weight %；Lubricating base oil 53.2 weight %；12 hydroxy stearic acids Oxygen zirconium 2.6 weight %；P-phthalic acid oxygen zirconium 6.5 weight %.

Embodiment 2

Raw material components: overbased sulfoacid calcium (total base number is 420mgKOH/g, 6kg)；Overbased Calcium sulfenyl phenolate (total base number is 420mgKOH/g, 24kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 30kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)； Ethanol zirconium (5.5kg)；Zr(OH)₄(0.65kg)；12 hydroxy stearic acids (2kg)；Phthalic acid (3.5kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 17kg).

A volume be 110L 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 420mgKOH/g, 24kg total base number are The overbased calcium sulfenyl phenolate of 420mgKOH/g and the HVI150BS lubricating base oil of 30kg, Stirring, is warmed up to 85 DEG C, addition 0.55kg ethanol zirconium and the Zr (OH) that solid content is 20 weight %₄Outstanding Turbid liquid 0.325kg, in terms of zirconium, Zr (OH)₄It is 1:5 with the mol ratio of ethanol zirconium, stirs 10 minutes； Add 0.2kg 12 hydroxy stearic acid, stir 10 minutes；Add 0.35kg phthalic acid, stir 10 Minute.At 65 DEG C, constant temperature 20 minutes, add 2.8kg 4 octadecylphenol, temperature controls 65 DEG C, stir 10 minutes, add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir 10 points Clock；It is warmed up to 85 DEG C, constant temperature 80 minutes, material retrogradation.Successively add 4.95kg ethanol zirconium and admittedly contain Amount is the Zr (OH) of 20 weight %₄Suspension 2.925kg, in terms of zirconium, Zr (OH)₄With ethanol zirconium mole Ratio is 1:5, stirs 10 minutes；Add 1.8kg 12 hydroxy stearic acid, stir 10 minutes；Add 3.15kg phthalic acid, stirs 10 minutes.It is warmed up to 110 DEG C under stirring, keeps 60 minutes, de- Water.It is warmed up to 230 DEG C of constant temperature 5 minutes.Then, the HVI500SN lubricating base oil of 17kg is added； 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 37.7 weight %；Lubricating base oil 53.2 weight %；12 hydroxy stearic acids Oxygen zirconium 2.6 weight %；Phthalic acid oxygen zirconium 6.5 weight %.

Embodiment 3

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 24kg)；High base number Calcium sulfenyl phenolate (total base number is 320mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 20kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)； Zirconium-n-butylate (3.13kg)；Zr(OH)₄(2.6kg)；Stearic acid (1.9kg)；M-phthalic acid (3.5kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 28kg).

A volume be 110L 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 SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g and the HVI150BS lubricating base oil of 20kg, stir Mix, be warmed up to 90 DEG C, addition 3.13kg zirconium-n-butylate and the Zr (OH) that solid content is 20 weight %₄Outstanding Turbid liquid 13kg, in terms of zirconium, Zr (OH)₄It is 1:0.5 with the mol ratio of zirconium-n-butylate, stirs 10 minutes； Add 1.9kg stearic acid, stir 10 minutes；Add 3.5kg M-phthalic acid, stir 10 minutes. At 80 DEG C, constant temperature 10 minutes；Adding 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 100 DEG C, constant temperature 60 minutes, material retrogradation.It is warmed up to 130 DEG C under stirring, keeps 30 minutes, Dehydration；It is warmed up to 180 DEG C of constant temperature 20 minutes.Then, the HVI500SN lubrication base of 28kg is added Oil；Treating that temperature is cooled to 100 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 37.8 weight %；Lubricating base oil 53.2 weight %；Zirconyl stearate 2.5 Weight %；M-phthalic acid oxygen zirconium 6.5 weight %.

Embodiment 4

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 33kg)；High base number Calcium sulfenyl phenolate (total base number is 320mgKOH/g, 6kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 20kg)；DBSA (1.2kg)；4 octadecylphenol (1.6kg)；Acetic acid (0.56kg)；Zirconium-n-propylate (4.0kg)；Zr(OH)₄(2.0kg)；12 hydroxyls Stearic acid (2kg)；Boric acid (2.32kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 28kg).

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；Transforming agent increases detergent alkylate sulphur Acid；Add Zr (OH)₄Time be additionally added zirconium-n-propylate, in terms of zirconium, Zr (OH)₄With zirconium-n-propylate mole Ratio is 1:1；P-phthalic acid is replaced with boric 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 44.0 weight %；Lubricating base oil 49.8 weight %；12 hydroxy stearic acids Oxygen zirconium 2.4 weight %；Boric acid oxygen zirconium 3.8 weight %.

Embodiment 5

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 23kg)；High base number Calcium sulfenyl phenolate (total base number is 320mgKOH/g, 6kg)；Overbased calcium salicylate (total base number For 400mgKOH/g, 10kg)；(100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 20kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Zirconium-n-propylate (4.0kg)；Zr(OH)₄ (2.0kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)；HVI500SN lubricates base (100 DEG C of kinematic viscositys are 11mm to plinth oil²/ s, 28kg)；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, adds overbased calcium salicylate； Add Zr (OH)₄Time be additionally added zirconium-n-propylate, in terms of zirconium, Zr (OH)₄It is 1 with the mol ratio of zirconium-n-propylate: 1；And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, right ' di-iso-octyldiphenylamine, stir 10 After minute, then circulating filtration, homogenizing, degassing obtain finished product；The consumption of each composition is as above.Inspection knot Fruit 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 43.7 weight %；Lubricating base oil 49.5 weight %；12 hydroxy stearic acids Oxygen zirconium 2.2 weight %；P-phthalic acid oxygen zirconium 4.4 weight %；Right, right ' di-iso-octyldiphenylamine 0.2 weight Amount %.

Embodiment 6

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 20kg)；High base number sulfur Change alkyl phenol calcium (total base number is 320mgKOH/g, 6kg)；(total base number is overbased calcium oleate 400mgKOH/g, 4kg)；(100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 15kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12– Hydroxy stearic acid (2kg)；P-phthalic acid (3.5kg)；HVI500SN lubricating base oil (100 DEG C of fortune Kinetic viscosity is 11mm²/ s, 7kg).

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 overbased calcium oleate；The consumption of each composition is as above.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 52.6 weight %；Lubricating base oil 34.7 weight %；12 hydroxy stearic acids Oxygen zirconium 3.7 weight %；P-phthalic acid oxygen zirconium 9.0 weight %.

Embodiment 7

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 6kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 8kg)；(total base number is overbased calcium alkyl-salicylate 300mgKOH/g, 8kg)；High base number calcium salicylate (total base number is 300mgKOH/g, 8kg)；Poly- (100 DEG C of kinematic viscositys are 40mm to alhpa olefin artificial oil PAO 40²/ s, 30kg)；4 octadecyl benzene Phenol (1.8kg)；DBSA (1.0kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)； 12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)；Polyalphaolefin artificial oil PAO 10 (100 DEG C Kinematic viscosity is 11mm²/ s, 17kg).

Prepare lubricant composition according to the method for embodiment 1, except for the difference that, add high base number cycloalkanes Acid calcium and high base number calcium salicylate, transforming agent increases DBSA；Use polyalphaolefin artificial oil (100 DEG C of kinematic viscositys are 40mm to PAO 40²/ s) and polyalphaolefin artificial oil PAO 10 (100 DEG C of fortune Kinetic viscosity is 11mm²/ s) (100 DEG C of kinematic viscositys are 31mm to replace HVI150BS respectively²/ s) and (100 DEG C of kinematic viscositys are 11mm to HVI500SN²/s)；The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 8

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, 10kg)；(total base number is high base number calcium salicylate 360mgKOH/g, 7kg)；High base number calcium oleate (total base number is 400mgKOH/g, 7kg)；HVI150BS (100 DEG C of kinematic viscositys are 31mm to lubricating base oil²/ 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)；2 methyl 1,4 phthalic acid (3.8kg)；HVI500SN lubricates base (100 DEG C of kinematic viscositys are 11mm to plinth oil²/ s, 16.7kg).

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, adds high base number calcium salicylate simultaneously With high base number calcium oleate；Transforming agent increases aphthenic acids；Replace benzene two with 2 methyl 1,4 phthalic acids Formic 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 37.7 weight %；Lubricating base oil 52.8 weight %；12 hydroxy stearic acids Oxygen zirconium 2.7 weight %；2 methyl 1,4 phthalic acid oxygen zirconium 6.8 weight %.

Embodiment 9

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, 12kg)；(total base number is overbased calcium alkyl-salicylate 360mgKOH/g, 6kg)；High base number calcium oleate (total base number is 320mgKOH/g, 6kg)；HVI150BS (100 DEG C of kinematic viscositys are 31mm to lubricating base oil²/ s, 30kg)；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)；(100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 20kg)；It is right, Right ' di-iso-octyldiphenylamine (0.2kg)；Dithio dibutylamino formic acid molybdenum (4kg)；Selenium sulfide (4kg)；Benzotriazole (0.4kg).

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 calcium oleate； P-phthalic acid is replaced with 4,4' biphenyl dicarboxylic acid；And treat that temperature is cooled to 110 DEG C, add 0.2kg Right, right ' di-iso-octyldiphenylamine, stir 10 minutes, add 4kg dithio dibutylamino first Acid molybdenum, stirs 10 minutes, adds the selenium sulfide of 4kg, stirs 10 minutes, adds the benzene of 0.4kg A pair of horses going side by side triazole, stirs 10 minutes, and then circulating filtration, homogenizing, degassing obtain finished product；Each composition Consumption 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 32.9 weight %；Lubricating base oil 49.2 weight %；12 hydroxy stearic acids Oxygen zirconium 2.3 weight %；4,4' biphenyl dicarboxylic acid oxygen zirconium 7.2 weight %；Right, right ' di-iso-octyldiphenylamine 0.2 weight %；Dithio dibutylamino formic acid molybdenum 3.9 weight %；Selenium sulfide 3.9 weight %；Benzene A pair of horses going side by side triazole 0.4 weight %.

Embodiment 10

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 8kg)；High base number vulcanizes Alkyl phenol calcium (total base number is 320mgKOH/g, 10kg)；(total base number is naphthenate with superhigh base number calcium 400mgKOH/g, 5kg)；Overbased calcium salicylate (total base number is 400mgKOH/g, 3kg)； Overbased calcium oleate (total base number is 400mgKOH/g, 4kg)；HVI150BS lubricating base oil (100 DEG C of kinematic viscositys are 31mm²/ s, 15kg)；4 octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(3.9kg)；12 hydroxy stearic acids (2kg)；P-phthalic acid (3.5kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 32kg).

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, and add naphthenate with superhigh base number calcium, calcium salicylate and calcium oleate； The consumption of each composition is as above.Assay is shown in Table 1.

Embodiment 11

Raw material components: overbased sulfoacid calcium (total base number is 400mgKOH/g, 9kg)；Overbased Calcium sulfenyl phenolate (total base number is 400mgKOH/g, 10kg)；Overbased calcium alkyl-salicylate (total base number For 300mgKOH/g, 5kg)；High base number calcium salicylate (total base number is 300mgKOH/g, 3kg)； High base number calcium oleate (total base number is 300mgKOH/g, 3kg)；HVI150BS lubricating base oil (100 DEG C Kinematic viscosity is 31mm²/ s, 30kg)；DBSA (2.8kg)；Acetic acid (0.56kg)； Zr(OH)₄(7.1kg)；12 hydroxy stearic acids (2kg)；Boric acid (2.32kg)；P-phthalic acid (3.5kg)； (100 DEG C of kinematic viscositys are 11mm to HVI500SN lubricating base oil²/ s, 15kg)；Right, right ' bis-different pungent Base diphenylamines (0.2kg).

Prepare lubricant composition according to the method for embodiment 1, except for the difference that, add high base number cycloalkanes Acid calcium, calcium salicylate and calcium oleate, use DBSA to replace 4 octadecylphenol；Adding It is additionally added boric acid after entering 12 hydroxy stearic acids, then adds p-phthalic acid；And treat that temperature cools down To 110 DEG C, add the right of 0.2kg, right ' di-iso-octyldiphenylamine, after stirring 10 minutes, then circulate Filtration, homogenizing, degassing obtain finished product；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 37.0 weight %；Lubricating base oil 49.9 weight %；12 hydroxy stearic acids Oxygen zirconium 2.6 weight %；Boric acid oxygen zirconium 4.0 weight %；P-phthalic acid oxygen zirconium 6.3 weight %；Right, right ' Di-iso-octyldiphenylamine 0.2 weight %.

Embodiment 12

Raw material components: non-newtonian fluid calcium sulfonate with high base number (23kg)；SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is (total Base number is 320mgKOH/g, 3kg)；Overbased calcium alkyl-salicylate (total base number is 400mgKOH/g, 4kg)； (100 DEG C of kinematic viscositys are 31mm to HVI150BS lubricating base oil²/ s, 30kg)；4 octadecyl benzene Phenol (2.8kg)；Acetic acid (0.56kg)；Zr(OH)₄(6.5kg)；12 hydroxy stearic acids (2kg)；Right Phthalic acid (3.5kg)；Acetic acid (2kg)；(100 DEG C of kinematic viscositys are HVI500SN lubricating base oil 11mm²/ s, 14kg)；Right, right ' di-iso-octyldiphenylamine (0.2kg).

The preparation of non-newtonian fluid calcium sulfonate with high base number: volume be 30L and with heating, stirring, Adding 15kg total base number in circulation, the normal-pressure reaction kettle cooled down is the sulfonate with high base number of 350mgKOH/g Calcium and 100 DEG C of kinematic viscositys of 5kg are 31mm²The HVI150BS lubricating base oil of/s, stirring, heating It is warmed up to 80 DEG C, constant temperature 10 minutes；Adding 2.5kg DBSA, temperature controls at 80 DEG C Left and right, stirs 10 minutes；Add acetic acid and the aqueous solution of acetic acid weight 4 times of 0.5kg, 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, calcium sulfonate with high base number is direct Using the non-newtonian fluid sulfoacid calcium prepared, calcium sulfenyl phenolate uses total base number to be 320mgKOH/g SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, add calcium naphthenate simultaneously；It is additionally added after adding p-phthalic acid Acetic acid, then adds transforming agent and converts；And treat that temperature is cooled to 110 DEG C, add the right of 0.2kg, Right ' di-iso-octyldiphenylamine, after stirring 10 minutes, then circulating filtration, homogenizing, degassing obtain finished product； 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 37.1 weight %；Lubricating base oil 48.9 weight %；12 hydroxy stearic acids Oxygen zirconium 2.6 weight %；P-phthalic acid oxygen zirconium 4.8 weight %；Zirconyl acetate 6.4 weight %；Right, right ' Di-iso-octyldiphenylamine 0.2 weight %.

Embodiment 13

A volume be 110L 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 50 DEG C, stir 10 minutes；Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stir Mix 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 Enter 7kg HVI500SN lubricating base oil, at 100 DEG C, add the Zr (OH) that solid content is 20 weight %₄ Suspension 19.5kg, stirs 10 minutes；Add 2kg 12 hydroxy stearic acid, stir 10 minutes；Add Enter 3.5kg p-phthalic acid, stir 10 minutes, obtain 12 hydroxy stearic acid oxygen zirconium and p-phthalic acids Oxygen zirconium.

Gained 12 hydroxy stearic acid oxygen zirconium and p-phthalic acid oxygen zirconium are all squeezed in a upper still, stirs Mix uniformly, be warmed up to 120 DEG C under stirring, keep 45 minutes, dehydration；It is 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.

Embodiment 14

A volume be 110L 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 at 50 DEG C, constant temperature 30 minutes；Add 2.8kg 4 octadecylphenol, temperature control System, at 50 DEG C, stirs 10 minutes；Add the aqueous acetic acid that 2.8kg concentration is 20 weight %, stirring 10 minutes；It is warmed up to 80 DEG C, constant temperature 90 minutes, material retrogradation.It is warmed up to 100 DEG C, adds and admittedly contain Amount is the Zr (OH) of 20 weight %₄Suspension 19.5kg, stirs 10 minutes；Add 2kg 12 hydroxyl hard Fat acid, stirs 10 minutes；Add 3.5kg p-phthalic acid, stir 10 minutes.It is warmed up under stirring 120 DEG C, keep 45 minutes, dehydration.It is warmed up to 200 DEG C of constant temperature 10 minutes.Then, 17kg 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 18-amine., acetic acid is replaced with ethylene glycol monobutyl ether.Assay is shown in Table 1.

Embodiment 16

Lubricant composition is prepared, except for the difference that, at Zr (OH) according to the method for embodiment 4₄With 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 4, 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 4₄Replace with Equimolar zirconium-n-propylate.Each physicochemical property of gained fat is shown in Table 1.

Comparative example 1

Lubricant composition is prepared, except for the difference that, by overbased sulfuration alkane according to the method for embodiment 1 Base phenol calcium replaces with the overbased sulfoacid calcium that total base number is 400mgKOH/g.Each physics and chemistry of gained fat 1 can be shown in Table.

In the grease that this comparative example obtains, on the basis of grease weight, consist of: non-newtonian fluid sulphur Acid calcium 37.7 weight %；Lubricating base oil 53.2 weight %；12 hydroxy stearic acid oxygen zirconium 2.6 weight %； P-phthalic acid oxygen zirconium 6.5 weight %.

Table 1 each grease properties of sample data

Each indication test method: outward appearance: range estimation；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； Stencil oil-dividing: 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.

Table 1 (Continued) each grease properties of sample data

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.

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 grease.And, the present invention Lubricant composition have and be better than the mechanical stability of complex calcium sulfonate zirconio grease, water-resistance, glue Body stability, abrasion resistance and extreme pressure anti-wear.And, the lubricant composition of the present invention also has excellent Different heat-resisting quantity.

Embodiment 1 and embodiment 13 are compared it can be seen that the lubricant composition of preparation in situ, There is more preferable viscous resistance, mechanical stability, water-resistance, colloid stability and abrasion resistance；To implement Example 1 and embodiment 13, embodiment 14 compare it can be seen that first carry out the reaction of compound zirconium, then Convert, prepare lubricant composition have more preferable viscous resistance, mechanical stability, water-resistance, Colloid stability and abrasion resistance；Embodiment 1 and embodiment 15 are compared it can be seen that convert Agent selected from DBSA, aphthenic acids, octadecyl phenol, methanol, isopropanol, butanol, boric acid, At least one in acetic acid and water, the lubricant composition of preparation, there is more preferable viscous resistance, machinery peace Qualitative, water-resistance, colloid stability and abrasion resistance；By embodiment 4 respectively with embodiment 16, implement Example 17, embodiment 18 compare it can be seen that the raw material of the zirconium oxide that contains zirconium and/or hydroxide Thing, and the mol ratio of the oxide of zirconium and/or hydroxide and zirconium alkoxide is 1:0.5 5, it is possible to enter one Step improve preparation the viscous resistance of lubricant composition, mechanical stability, water-resistance, colloid stability and Abrasion resistance.

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 and the zirconium of higher fatty acids Salt, described thickening agent is also optionally with non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-cattle One in the zirconates of body calcium oleate, the zirconates of aromatic acid, little molecule mineral acid and/or lower fatty acid or Multiple, 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 %, the zirconates of higher fatty acids Content be 1 10 weight %, the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, non-newtonian fluid The content of calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, virtue The content of the zirconates of acid is 0-15 weight %, containing of the zirconates of little molecule mineral acid and/or lower fatty acid Amount is 0 15 weight %, and wherein, the zirconates of described higher fatty acids is by higher fatty acids and component A Reaction forms, and the zirconates of described aromatic acid is to be reacted with component A by aromatic acid to form, described little molecule mineral acid And/or the zirconates of lower fatty acid be to be reacted with component A by little molecule mineral acid and/or lower fatty acid and Becoming, described component A is at least one in the oxide of zirconium, the hydroxide of zirconium and zirconium alkoxide.

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

Lubricant composition the most according to 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, described little molecule is inorganic The molecular weight of sour and described 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.

The preparation method of lubricant composition described in any one, the party in 15. claim 1 14 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 and the zirconates of higher fatty acids, described thickening agent the most optionally contains Have 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.

The preparation method of 16. 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；

17. methods according to claim 16, wherein, in step (2), are carried out at least partly The reaction of compound zirconium.

18. according to the method described in claim 16 or 17, wherein, and step (2) and step (4) In, 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 contains oxide and/or the hydroxide of zirconium, in terms of zirconium, the oxide of zirconium and/or hydroxide It is 1:0 10 with the mol ratio of zirconium alkoxide.

19. methods according to claim 18, 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.

20. according to the method described in claim 16 or 17, wherein, in step (3), at 50 80 DEG C Under, the transforming agent needed for addition reacts, after all transforming agents add, at 80 100 DEG C of constant temperature 60 90 Minute.

21. according to the method described in claim 16 or 17, wherein, in step (5), is warming up to 110-130 DEG C of dehydration.

22. according to the method described in claim 16 or 17, wherein, in step (6), is warmed up to 180 230 DEG C of constant temperature 5 30 minutes, adds surplus base oil, treats that temperature is cooled to 100 120 DEG C, add Enter the additive of necessity, stirring, circulating filtration, homogenizing, degassing.

23. according to the method described in claim 16 or 17, 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.

24. according to the method described in claim 16 or 17, 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.

25. methods according to claim 24, 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.

26. lubricant compositions prepared by the method described in any one in claim 16 25.